UNIVERSITY OF CALGARY

In Situ Heavy Oil Upgrading Through Ultra-disperse Nano-Catalyst Injection in Naturally

Fracture Reservoirs

by

Carlos Rogelio Orozco Castillo

A THESIS

SUBMITTED TO THE FACULTY OF GRADUATE STUDIES

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE

DEGREE OF MASTER OF SCIENCE

GRADUATE PROGRAM IN

CHEMICAL AND PETROLEUM ENGINEERING

CALGARY, ALBERTA

JANUARY, 2016

Carlos Rogelio Orozco Castillo, 2016

 ii

Abstract

Unconventional reservoirs are the next challenge for maintaining the worlds oil production.
Several EOR processes are under study, one promising is the In Situ Upgrading which
produces EOR and Upgrading by injection of a hot fluid, in this case vacuum residue from the
heavy oil produced, with suspended nano-catalytic particles flowing down-hole along with
dissolved hydrogen as precursor of partial Hydroprocessing of the residue. The combination of
thermal and chemical reactions with a catalyst leads to In-Situ Upgrading (ISU) of the residue
injected and the in situ oil near the surroundings of the injection well bore, while the heat
carried, the diluents, the steam and hot water generated warm up the rock and the oil in the
porous media, enhancing extraction. Testing the reactivity of the oil has to be assessed at
temperatures, pressures and time to determine the suitability of this EOR process.
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Acknowledgements

First, I thank to my family and beloved ones whom I miss every day, but their support and faith
in me, make me follow and feel proud of having them in my life.

I would like to express my gratitude to Petroleos Mexicanos (PEMEX), the National Council for
Science and Technology of Mexico (CONACYT), the Schulich School of Engineering at the
University of Calgary, and the Catalysis for Bitumen Upgrading Group (CBUG) for giving me the
opportunity, financial support, and letting me be part of the new development technologies
that can improve the Mexican oil and gas industry.

I would like to thank my supervisors Dr. Pedro Pereira Almao and Dr. Fernando Sebastian Flores
Avila, for their advice, trust and guidance through the different aspects of this thesis.

I also want to thank the staff of the CBU group, Dr. Carlos Scott, Lante Carbognani, Alejandro
Coy, Wuilder Torres, Josune Carbognani, Dr. Argenis Aguero, Dr. Azfar Hassan and all the
students and researchers of the group, whose contribution, help and guidance to this work and
experience at the university is appreciated.

Also thanks to Silvia Chavez, Francisco Da Silva, Maryam Ashtari and David Gutierrez, who were
the former office mates and to Mariana Trujillo and Sarah Alamolhoda who are the actual
mates, for their time, guidance and great environment in our daily cohabitation.

Likewise, thanks to my new friends, most of them Mexicans, that gave me the opportunity to
share with them great moments, they are: Silvia Chavez, Ricardo Suarez, Francisco Pacheco,
Mildred Castellanos, Coyolxauhqui Flores, Lauro Vargas, Carmen Munoz, Bruno Lopez, Juan
Pablo Urdaneta, and Marta Salas.

The last but not the least, thanks to Silvia Chavez and Peter Gwozdz, here in Calgary, and Jose
Antonio Gonzalez, in Mexico. For their great support and faith that they have in me. Without
them, this work had not been possible.
 iv

Dedication

Para las personas que estuvieron presentes,

acompandome en este sendero
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Table of Contents

Abstract ........................................................................................................................................................ ii
Acknowledgements ..................................................................................................................................... iii
Dedication.................................................................................................................................................... iv
Table of Contents ......................................................................................................................................... v
List of Tables ................................................................................................................................................ ix
List of Figures and Illustrations .................................................................................................................. xii
List of Symbols, Abbreviations and Nomenclature .................................................................................. xvii
1. CHAPTER ONE: INTRODUCTION ........................................................................................................... 1
2. CHAPTER TWO: LITERATURE REVIEW .................................................................................................. 4
2.1. Heavy oil properties ...................................................................................................................... 4
2.2. Refining processes ...................................................................................................................... 10
2.2.1. Desalting ................................................................................................................................. 11
2.2.2. Atmospheric distillation (topping unit) ................................................................................... 12
2.2.3. Vacuum distillation unit .......................................................................................................... 13
2.3. Naturally Fractured Reservoirs (NFR) ......................................................................................... 13
2.4. Enhanced Oil Recovery (EOR) Processes..................................................................................... 22
2.5. Chemical Processes ..................................................................................................................... 23
2.6. Gas Processes .............................................................................................................................. 27
2.7. Thermal Processes ...................................................................................................................... 30
2.7.1. Steam processes ..................................................................................................................... 32
2.7.1.1. Cyclic Steam Stimulation (CSS) ............................................................................................ 32
2.7.2. In Situ Combustion (ISC).......................................................................................................... 34
2.7.2.1. Dry combustion ................................................................................................................... 34
2.7.2.2. Wet combustion.................................................................................................................. 35
2.7.3. Steam Assisted Gravity Drainage (SAGD)................................................................................ 36
2.8. Other Processes .......................................................................................................................... 38
2.9. Chemical reactions ...................................................................................................................... 39
2.9.1. Catalyst................................................................................................................................ 40
2.9.1.1. Ultradispersed catalyst ................................................................................................... 44
2.9.2. Kinetics ................................................................................................................................ 45
2.9.3. Kinetic modelling................................................................................................................. 47
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3. CHAPTER THREE: HYDROGEN ADDITION PROCESSES ....................................................................... 52

3.1. Thermal cracking ......................................................................................................................... 52
3.2. Hydrocracking ............................................................................................................................. 54
3.3. Hydrotreating .............................................................................................................................. 57
3.3.1. Hydrodesulphurization (HDS) ................................................................................................. 59
3.3.2. Hydrodemetalization (HDM) ................................................................................................... 59
3.3.3. Hydrodenitrogenation (HDN).................................................................................................. 60
3.3.4. Hydrogenation of complex structures .................................................................................... 60
4. CHAPTER FOUR: THERMAL ASPECTS ................................................................................................. 61
4.1. Heat applied to fluid ................................................................................................................... 62
4.2. Heat applied to porous media .................................................................................................... 66
4.3. Thermodynamics of thermal cracking ........................................................................................ 68
4.3.1. Gibbs free energy .................................................................................................................... 69
4.4. Thermodynamics of hydroprocessing......................................................................................... 70
4.5. Rock wettability .......................................................................................................................... 71
4.6. Enthalpy of Reaction ................................................................................................................... 74
5. CHAPTER FIVE: IN SITU UPGRADING TRHOUGH CATALYST INJECTION ............................................ 76
5.1.1. Process Description ............................................................................................................. 76
5.1.1.1. Catalyst placement.......................................................................................................... 77
5.1.1.2. Process implementation ................................................................................................. 78
5.1.1.3. Process mechanism ......................................................................................................... 83
5.1.1.4. Operation procedure ...................................................................................................... 85
5.1.2. Surface Facilities.................................................................................................................. 87
6. CHAPTER SIX: EXPERIMENTAL SECTION ............................................................................................ 94
6.1. Process Overview ........................................................................................................................ 95
6.2. Process Material ......................................................................................................................... 95
6.3. Metal content analysis of original crude oil.............................................................................. 105
6.4. Metal content analysis of vacuum residue ............................................................................... 107
6.5. Reactivity Test Unit ................................................................................................................... 108
6.6. Sample Characterization ........................................................................................................... 111
7. CHAPTER SEVEN: RESULTS ............................................................................................................... 112
7.1. Crude Oil Kinetic Model ............................................................................................................ 112
7.1.1. Temperature and residence time effect ............................................................................... 114
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7.1.2. Upgrading results .................................................................................................................. 116

7.1.3. Quality results ....................................................................................................................... 121
7.1.3.1. Viscosity ............................................................................................................................ 122
7.1.3.2. API gravity ......................................................................................................................... 124
7.1.3.3. Microcarbon (MCR) ........................................................................................................... 126
7.1.3.4. Sulfur content ................................................................................................................... 128
7.1.3.5. P-value............................................................................................................................... 129
7.1.4. Kinetic evaluation.................................................................................................................. 131
7.1.4.1. Hydrodesulphurization ..................................................................................................... 138
7.1.4.2. Hydrodemetalization ........................................................................................................ 139
7.1.4.3. Correlation ........................................................................................................................ 141
7.2. Vacuum Residue Kinetic Model ................................................................................................ 144
7.2.1. Temperature and residence time effect ............................................................................... 145
7.2.2. Upgrading results .................................................................................................................. 146
7.2.3. Quality results ....................................................................................................................... 149
7.2.3.1. Viscosity ............................................................................................................................ 150
7.2.3.2. API gravity ......................................................................................................................... 152
7.2.3.3. Microcarbon (MCR) ........................................................................................................... 153
7.2.3.4. Sulfur content ................................................................................................................... 154
7.2.3.5. P-value............................................................................................................................... 155
7.2.4. Kinetic evaluation.................................................................................................................. 156
7.2.4.1. Hydrodesulfurization ........................................................................................................ 163
7.2.4.2. Correlation ........................................................................................................................ 164
7.3. Comparison ............................................................................................................................... 167
7.4. Stoichiometry of reactions ........................................................................................................ 173
8. CHAPTER EIGHT: CONCLUSIONS ...................................................................................................... 175
9. CHAPTER NINE: RECOMMENDATIONS ............................................................................................ 177
10. REFERENCES .................................................................................................................................. 178
A. APPENDIX: Upgrading properties and kinetic model ...................................................................... 183
A.1. Fluid upgrading properties per condition ..................................................................................... 183
A.2. Hydroprocessing kinetic model..................................................................................................... 186
B. APPENDIX: Analytical measurements and equipment ................................................................... 189
B.1. Liquid samples............................................................................................................................... 189
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B.1.1. Simulated Distillation (SIMDIST) ............................................................................................... 189

B.1.2. Density and API gravity ............................................................................................................. 191
B.1.3. Viscosity .................................................................................................................................... 192
B.1.3.1. Low temperature .................................................................................................................. 193
B.1.3.2. High temperature.................................................................................................................. 193
B.1.4. Metal Analysis ........................................................................................................................... 194
B.1.5. Micro-carbon (MCR) ................................................................................................................. 195
B.1.6. Nitrogen and Sulfur content ..................................................................................................... 196
B.1.7. Peptization value (P-value) ....................................................................................................... 196
B.1.8. Nano-particle Tracking Analysis (NTA) ...................................................................................... 197
B.2. Gas samples .................................................................................................................................. 199
B.2.1. Gas chromatography (GC)......................................................................................................... 199
B.2.2. Gas flow meter .......................................................................................................................... 200
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List of Tables
Table 2-1 type of oil classified by viscosity and density (Gray, 2015). .......................................................... 5
Table 2-2 Classification designated by the structure. Six carbon compound example (Gray, 2015). .......... 6
Table 2-3 Indications of fractures in a reservoir using production data as evidence. ................................ 17
Table 2-4 Indications of fractures in a reservoir using drilling data as evidence........................................ 18
Table 2-5 Indications of fractures in a reservoir using geological data as evidence. ................................. 18
Table 2-6 Indications of fractures in a reservoir using geophysical data as evidence. ............................... 18
Table 2-7 Type 1 NFR positive and negative problem. ............................................................................... 20
Table 2-8 Type 2 NFR positive and negative problem. ............................................................................... 21
Table 2-9 Type 3 NFR positive and negative problem. ............................................................................... 21
Table 2-10 Type 4 NFR positive and negative problem. ............................................................................. 21
Table 2-11 Chemical processes application until 2010 (Manrique, et al., 2010). ....................................... 26
Table 2-12 Gas processes application until 2010 (Manrique, et al., 2010). ............................................... 30
Table 2-13 Screening criteria differences between steam and ISC processes (Green & Willhite, 1998). .. 30
Table 2-14 Steam processes applications until 2010 (Manrique, et al., 2010). .......................................... 33
Table 2-15 SAGD projects application until 2010 (Manrique, et al., 2010). ............................................... 37
Table 2-16 ISC projects application until 2010 (Manrique, et al., 2010). ................................................... 38
Table 2-17 Catalyst used for several reaction............................................................................................. 43
Table 3-1 Hydroprocess reaction characteristics (Vasquez, 2007). ............................................................ 52
Table 3-2 Bond dissociation energies (Gray, 2015). ................................................................................... 53
Table 3-3 Thermal cracking activation energies (Gray, 2015). ................................................................... 54
Table 4-1 heat of reaction value by type. ................................................................................................... 70
Table 6-1 Ag crude oil topping and desalting. ............................................................................................ 95
Table 6-2 Lights components added to the topped oil, and properties measured. ................................... 98
Table 6-3 Recombined oil analyses. ............................................................................................................ 98
Table 6-4 SARA properties affected by biodegradation (Gray, 2015). ....................................................... 98
Table 6-5 crude oil and vacuum residue lump yield (wt %). ..................................................................... 100
Table 6-6 Analytical parameters of Ag vacuum residue. .......................................................................... 101
Table 6-7 Metal content comparison. ...................................................................................................... 101
Table 6-8 Crude oil original and added metals (Catalyst). ........................................................................ 104
Table 6-9 Vacuum residue original and added metals (catalyst). ............................................................. 104
Table 7-1 Experimental conditions. .......................................................................................................... 112
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Table 7-2 Samples obtained for each condition run. ................................................................................ 113
Table 7-3 Composition (wt. %) for each catalytic condition sample. ....................................................... 117
Table 7-4 Composition (wt. %) for each thermal condition sample. ........................................................ 118
Table 7-5 Composition (wt. %) of each partial pressure catalytic condition sample (700 cm3 of H2 to 1 cm3
of oil pumped)........................................................................................................................................... 118
Table 7-6 Comparison between thermal (19 and 20) and catalytic run, condition 360 C at 24 hrs. ...... 119
Table 7-7 Comparison between thermal (21 and 22) and catalytic run, condition 48 hrs, 340 C. ......... 120
Table 7-8 Comparison between partial pressure (25 and 26) and catalytic run, condition 360 C-72 hrs.
.................................................................................................................................................................. 120
Table 7-9 Quality variables evaluated in the reacted samples. ................................................................ 121
Table 7-10 Parameters for Arrhenius plot. ............................................................................................... 135
Table 7-11 Kinetic constants for Hydroprocessing modeling. .................................................................. 135
Table 7-12 Metal content of different samples, feed and original crude oil. ........................................... 139
Table 7-13 Raw data for viscosity correlation........................................................................................... 141
Table 7-14 Raw data for API correlation. .................................................................................................. 142
Table 7-15 Experimental conditions to evaluate. ..................................................................................... 144
Table 7-16 Samples obtained per condition run....................................................................................... 144
Table 7-17 Composition (wt %) for each catalytic condition sample. ...................................................... 148
Table 7-18 Quality variables evaluated in the reacted samples. .............................................................. 149
Table 7-19 Parameters for Arrhenius plot. ............................................................................................... 160
Table 7-20 Kinetic constants for Hydroprocessing modeling. .................................................................. 162
Table 7-21 Raw data for viscosity correlation plot. .................................................................................. 164
Table 7-22 Raw data for API correlation plot. .......................................................................................... 165
Table 7-23 Residence time required for VR to reach in-situ oil properties using correlations. ............... 166
Table 7-24 Activation energies and pre-exponential factors of the different fluids analyze. .................. 171
Table 7-25 Activation energies and pre-exponential factors for original fluids upgrading. ..................... 172
Table 7-26 Heavier fluids comparison in Arrhenius plot. ......................................................................... 173
Table 7-27 Molecular weight for each lump. ............................................................................................ 173
Table 7-28 Product coefficients for each reaction for the residue of Ag crude oil................................... 174
Table A.1-1 Ath bitumen upgrading properties (Loria, Trujillo-Ferrer, Sosa-Stull, & Pereira-Almao, 2011).
.................................................................................................................................................................. 183
Table A.1-2 Ag crude oil kinetic modeling. ............................................................................................... 183
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Table A.1-3 Ath vacuum residue upgrading properties per condition (Da Silva, 2014). .......................... 184
Table A.1-4 Ag vacuum residue kinetic model.......................................................................................... 184
Table A.1-5 Tk crude oil upgrading properties per condition (Chavez, 2015). ......................................... 185
Table A.2-1 Ath bitumen kinetic model (Loria, Trujillo-Ferrer, Sosa-Stull, & Pereira-Almao, 2011). ....... 186
Table A.2-2 Ath bitumen kinetic model from Loria experimental data (Da Silva, 2014). ......................... 186
Table A.2-3 Ath pitch kinetic model (Da Silva, 2014). ............................................................................... 186
Table A.2-4 Ath vacuum residue kinetic model (Da Silva, 2014). ............................................................. 187
Table A.2-5 Tk crude oil kinetic model (Chavez, 2015). ............................................................................ 187
Table A.2-6 Ag crude oil kinetic model. .................................................................................................... 187
Table A.2-7 Ag vacuum residue kinetic model.......................................................................................... 188
Table B.1.1-1 Component lumping by TBP. .............................................................................................. 189
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List of Figures and Illustrations

Figure 1-1 Mexico oil production in the last 10 years by type of oil (Rionda, 2014). ................................... 1
Figure 1-2 Mexican Reserves classification by type. Heavy oil sub classification (million barrels) (Rionda,
2014). ............................................................................................................................................................ 2
Figure 2-1 Density and viscosity properties by crude oil type (Gray, 2015). ................................................ 4
Figure 2-2 petroleum fractions structural composition (Le Page, 1987). ..................................................... 8
Figure 2-3 Schematic representation of an Asphaltene aggregate, with its associations (Gray, 2015). ...... 9
Figure 2-4 Residue compounds fractions depending on the process applied to the original feedstock
(Speight, 1981). ........................................................................................................................................... 10
Figure 2-5 Desalter unit diagram (Speight & Ozum, 2002). ........................................................................ 11
Figure 2-6 Atmospheric distillation diagram (Speight & Ozum, 2002). ...................................................... 12
Figure 2-7 Fracture network representation (Aguilera, 1995). .................................................................. 14
Figure 2-8 Classification of fracture contribution to porosity and permeability (Nelson, 2001). .............. 15
Figure 2-9 NFR classification by storage capacities (Aguilera, 1995). ......................................................... 16
Figure 2-10 Displacement front comparison with waterflooding and the use of polymers. ..................... 24
Figure 2-11 Displacement front for an immiscible surfactant-polymer process (Green & Willhite, 1998).
.................................................................................................................................................................... 26
Figure 2-12 Miscible displacement process (Green & Willhite, 1998). ...................................................... 29
Figure 2-13 Steamflood process (Green & Willhite, 1998). ........................................................................ 32
Figure 2-14 Huff and puff process diagram (Green & Willhite, 1998). ....................................................... 33
Figure 2-15 ISC process (Green & Willhite, 1998)....................................................................................... 35
Figure 2-16 SAGD chamber mechanism (Butler, 1994). ............................................................................. 36
Figure 2-17 Catalyst activation energy drop compare to no catalyst reactions (Bartholomew & Farrauto,
2006). .......................................................................................................................................................... 41
Figure 2-18 Solid catalyst reaction mechanism (Bartholomew & Farrauto, 2006). ................................... 41
Figure 2-19 Adsorption mechanism (Le Page, 1987). ................................................................................. 42
Figure 2-20 Activation energy intensity. ..................................................................................................... 47
Figure 2-21 Kinetic model diagram (Sanchez, Rodriguez, & Ancheyta, 2005). ........................................... 49
Figure 2-22 Kinetic model lumps upgrading. .............................................................................................. 50
Figure 3-1 Mechanism of hydrocracking reaction. ..................................................................................... 56
Figure 4-1 Influence of different production mechanism as a function of the oil type (Hoffman, 2001). . 61
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Figure 4-2 Temperature profile for convection and convection and conduction mechanism. (Prats, 1985).
.................................................................................................................................................................... 67
Figure 5-1 Different catalyst placement methods. ..................................................................................... 77
Figure 5-2 Process implementation via injection zone under catalyst zone (Weissman J. G., 1997). ........ 78
Figure 5-3 ISC with catalyst placement zone in production zone (Weissman J. G., 1997). ........................ 79
Figure 5-4 Catalytic ISU chamber (Canada Patent No. CA 2810022, 2013). ............................................... 80
Figure 5-5 Huff and puff catalytic ISU (Canada Patent No. CA 2810022, 2013). ........................................ 81
Figure 5-6 Catalytic ISU flooding. ................................................................................................................ 82
Figure 5-7 Three well pattern for catalytic ISU (Canada Patent No. CA 2810022, 2013). .......................... 82
Figure 5-8 Catalytic ISU mechanism in SAGD configuration (Canada Patent No. CA 2810022, 2013). ...... 83
Figure 5-9 Catalytic ISU mechanism in huff and puff configuration (Canada Patent No. CA 2810022,
2013). .......................................................................................................................................................... 84
Figure 5-10 Temperature, residence time, and conversion profiles at certain well displacement. ........... 85
Figure 5-11 Surface facility units needed for catalytic ISU. ........................................................................ 87
Figure 6-1 Research plan scheme ............................................................................................................... 94
Figure 6-2 Mexican oil comparison Ag (blue), Mb (green), and Tl (red). .................................................... 96
Figure 6-3 Chromatogram comparison of Mexican crude oils. .................................................................. 96
Figure 6-4 a) Ag crude oil (black) and topped Ag oil (red); b) Ag crude oil (black) and recombined Ag
crude oil (red).............................................................................................................................................. 97
Figure 6-5 Different feedstock blend simdist curve for crude oil kinetic modeling. .................................. 99
Figure 6-6 Crude oil and vacuum residue simdist curve comparison. ...................................................... 100
Figure 6-7 Ag crude oil viscosity measurement at different temperatures.............................................. 101
Figure 6-8 Ag crude oil viscosity properties. ............................................................................................. 102
Figure 6-9 Ag Vacuum residue viscosity at different temperatures. ........................................................ 102
Figure 6-10 Vacuum residue viscosity properties. .................................................................................... 103
Figure 6-11 Metal comparison for Ag crude oil. ....................................................................................... 103
Figure 6-12 Metal comparison for Ag vacuum residue. ........................................................................... 105
Figure 6-13 Ag crude oil with catalyst XPS analysis. ................................................................................. 106
Figure 6-14 Particle size distribution for Ag crude oil with catalyst. ........................................................ 106
Figure 6-15 Ag VR without catalyst XPS analysis. ..................................................................................... 107
Figure 6-16 Ag VR with catalyst added XPS analysis. ................................................................................ 107
Figure 6-17 Particle size distribution for Ag VR with catalyst. .................................................................. 108
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Figure 6-18 RTU-2 unit flow diagram. ....................................................................................................... 109

Figure 6-19 RTU-2 picture. ........................................................................................................................ 110
Figure 7-1 Residue conversion as a function of residence time and temperature................................... 115
Figure 7-2 Temperature impact to residue conversion. ........................................................................... 115
Figure 7-3 Simulated distillation curves for each product of the kinetic model experiment. .................. 116
Figure 7-4 Catalytic sample components (left axis) and API curve (right axis). ...................................... 119
Figure 7-5 Thermal condition (24 hrs, 360 C) compared with the same catalytic condition. .................. 119
Figure 7-6 Thermal condition (340 C, 48 hrs) compared with the same catalytic condition. ................. 120
Figure 7-7 Partial pressure condition (360 C, 72 hrs) compared with the same catalytic condition. ...... 121
Figure 7-8 Viscosity reduction at different temperature and residence time conditions (40 C). ........... 122
Figure 7-9 Viscosity reduction as a function of conversion. ..................................................................... 123
Figure 7-10 Viscosity as a function of residence time and conversion per temperature range. .............. 123
Figure 7-11 API gravity increase as a function of residence time (room temperature). .......................... 124
Figure 7-12 Density and API gravity correlation. ...................................................................................... 124
Figure 7-13 API gravity improvement as a function of conversion........................................................... 125
Figure 7-14 API gravity as a function of residence time and conversion per temperature. ..................... 126
Figure 7-15 MCR as a function of residence time per temperature range. .............................................. 127
Figure 7-16 Sulfur content as a function of residence time per temperature range. .............................. 128
Figure 7-17 Sulfur content reduction as a function of residue conversion. ............................................. 129
Figure 7-18 P-value as a function of residence time per temperature range. ......................................... 129
Figure 7-19 Microscopic view for evaluation of P-value........................................................................... 130
Figure 7-20 Component percentage (wt. %) vs. residue conversion (wt. %)............................................ 131
Figure 7-21 lump conversion (wt %) vs residue conversion (wt. %). ........................................................ 132
Figure 7-22 Property conversion (%) vs. residue conversion (wt. %). ...................................................... 133
Figure 7-23 First order reaction evaluation for residue Hydroprocessing of Ag crude oil. ...................... 134
Figure 7-24 first order reaction evaluation for hydrodesulphurization.................................................... 134
Figure 7-25 Arrhenius plot for Hydroprocessing. ..................................................................................... 135
Figure 7-26 Reaction diagram for crude oil residue Hydroprocessing. .................................................... 136
Figure 7-27 Arrhenius plot for global and different reaction constants. .................................................. 136
Figure 7-28 Kinetic model match and calculation of composition lumps per condition. ......................... 138
Figure 7-29 Arrhenius plot for the Hydroprocessing reaction at several temperatures. ......................... 139
Figure 7-30 Metal content comparison of different samples and original crude oil and feed................. 140
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Figure 7-31 Hydrodemetalization trend per type of metal, a) original in feed, b) added metals. ........... 141
Figure 7-32 Viscosity decreasing at certain residence time and temperature. ........................................ 141
Figure 7-33 API increasing at certain residence time and temperature. .................................................. 142
Figure 7-34 P-value comparison for each API and viscosity value. ........................................................... 143
Figure 7-35 Residue conversion as a function of residence time and temperature for VR feed. ............ 145
Figure 7-36 Temperature impact on residue conversion. ........................................................................ 146
Figure 7-37 Simulated distillation curves for each product sample of the kinetic model experiment for
VR. ............................................................................................................................................................. 147
Figure 7-38 Catalytic sample components and API curve......................................................................... 149
Figure 7-39 Viscosity reduction at different temperature and residence time conditions (80 C). ......... 150
Figure 7-40 Viscosity reduction as a function of conversion (80 C). ......................................................... 151
Figure 7-41 Viscosity as a function of residence time and conversion per temperature range. .............. 151
Figure 7-42 API gravity increase as a function of residence time (ambient temperature). ..................... 152
Figure 7-43 Density and API gravity correlation. ...................................................................................... 152
Figure 7-44 API gravity improvements as a function of conversion. ........................................................ 153
Figure 7-45 MCR as a function of residence time per temperature tested. ............................................. 153
Figure 7-46 Sulfur content as a function of residence time per temperature range. .............................. 154
Figure 7-47 Sulfur content reduction as a function of VR conversion. ..................................................... 155
Figure 7-48 P-value as a function of residence time per temperature range. ......................................... 155
Figure 7-49 Microscopic view for evaluation of P-value........................................................................... 156
Figure 7-50 Component percentage (wt %) vs. residue conversion (wt. %)............................................. 157
Figure 7-51 lump conversion (wt. %) vs residue conversion (wt. %). ....................................................... 157
Figure 7-52 lump conversion (wt. %) vs residue conversion (wt. %). ....................................................... 158
Figure 7-53 Property conversion (%) vs. residue conversion (wt %). ....................................................... 158
Figure 7-54 First order reaction evaluation for residue Hydroprocessing................................................ 159
Figure 7-55 First order reaction evaluation for hydrodesulfurization. ..................................................... 160
Figure 7-56 Arrhenius plot for residue Hydroprocessing.......................................................................... 160
Figure 7-57 Arrhenius plot for global reaction constants. ........................................................................ 161
Figure 7-58 Arrhenius plot for each reaction constant............................................................................. 161
Figure 7-59 residue Hydroprocessing diagram. ........................................................................................ 162
Figure 7-60 Components calculation vs experimental data. .................................................................... 163
Figure 7-61 Arrhenius plot for hydrodesulfurization of VR ...................................................................... 163
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Figure 7-62 Viscosity correlation plot for different residence time and temperature conditions. .......... 164
Figure 7-63 API correlation for different temperature and residence time conditions. .......................... 165
Figure 7-64 P-value comparison for different viscosity and API gravity ................................................... 165
Figure 7-65 Crude oil component vs. conversion, comparing upgrading of Loria (blue) and Orozco data
(red)........................................................................................................................................................... 167
Figure 7-66 Vacuum residue components vs conversion, comparing Da Silva (blue) and Orozco data
(red)........................................................................................................................................................... 168
Figure 7-67 Pitch and VR components vs conversion, comparing Da Silva (blue) and Orozco data (red).
.................................................................................................................................................................. 169
Figure 7-68 Crude oil components vs conversion, comparing Chavez (blue) and Orozco data (red). ..... 169
Figure 7-69 Temperature impact for upgrading in pitch and Tk crude oil................................................ 170
Figure 7-70 Arrhenius plot comparing all the kinetic models of the fluids analysed. .............................. 171
Figure 7-71 Original crude oil upgrading comparison in Arrhenius plot. ................................................. 172
Figure 7-72 Vacuum residue and pitch comparison in Arrhenius plot ..................................................... 173
Figure B.1.1-1 Chromatograph model 6890N (Agilent Technologies, 2015). ........................................... 189
Figure B.1.1-2 TBP curve and distilled fractions (Gray, 2015). ................................................................. 190
Figure B.1.1-3 Gas chromatogram (Gray, 2015). ...................................................................................... 190
Figure B.1.2-1Density meter DDM 2910 (Rudolph Research Analytical, 2015)........................................ 191
Figure B.1.2-2 Mixture density vs %V/V plot. ........................................................................................... 192
Figure B.1.3.1-1 Low temperature viscometer DV-II Pro (Brookfield Engineering, 2015). ....................... 193
Figure B.1.3.2-1 High temperature viscometer Thermosel system (Brookfield Engineering, 2015). ....... 194
Figure B.1.4-1 MARS-6 equipment for sample digestion (CEM corporation, 2015). ................................ 194
Figure B.1.4-2 IRIS Intrepid II XPS spectrometer (EVISA, 2010). ............................................................... 195
Figure B.1.5-1 Thermo scientific Muffle furnace. ..................................................................................... 196
Figure B.1.6-1 Antek 9000NS Sulfur and Nitrogen analysis (Micro analysis, Inc, 2015). .......................... 196
Figure B.1.7-1 P-value analysis for Ag crude oil. ....................................................................................... 197
Figure B.1.7-2 P-value analysis for Ag vacuum residue. ........................................................................... 197
Figure B.1.8-1 NanoSight NS300 (Malvern, 2015). ................................................................................... 198
Figure B.1.8-2 Nano particle tracking. ...................................................................................................... 198
Figure B.2.1-1 Gas chromatography SRI 8610C (Mandel, 2015)............................................................... 199
Figure B.2.2-1 MilliGascounter Type MGC-1 from Ritter (Litre Meter Limited, 2011). ............................ 200
 xvii

List of Symbols, Abbreviations and Nomenclature

1P = Proved reserves cps = Centipoise
2P = Probable reserves C = Degrees Celsius
3P = Possible reserves bbl = Barrels
API = American Petroleum Institute lb = Pound
AP = Alkali- Polymer nm = nanometer
ASP = Alkali Surfactant Polymer m = micro meter
DF = Downflow SH= Sites occupied by hydrogen
EIA = Energy Information Administration Ea = Activation Energy
EOR = Enhanced Oil Recovery Hr = Heat of reaction
FCM = First Contact Miscibility H = Enthalpy
HDS = Hidrodesulfurization S = Entropy
HDM = Hydrodemetalization rads = Rate of adsorption
HDN = Hydrodenitrogenation rdes = Rate of desorption
HDCC = Hydrodeconradson carbon k = Rate of reaction
HDA = Hydrodeasphaltene k = Permeability
IFT = Interfacial Tension Cv = Vacant site concentration
ISC = In Situ Combustion pH2 = Partial pressure of hydrogen
ISU = In Situ Upgrading A, A0 = Pre-exponential factor
IOR = Improved Oil Recovery R = gas constant
LPG = Liquefied T = Temperature
MB = Mass balance = Density
MCM = Multiple Contact Miscibility = Interfacial tension
NFR = Naturally fractured reservoir u = volumetric flow velocity
PF = Polymer flooding c = Contact angle
PV = Pore Volume = Formation dip
SimDist = Simulated Distillation = Mass flow
SP = Surfactant-Polymer = Thermal conductivity
UF = Upflow W = Mass fraction of component x
 xviii

VAPEX = Vapor Extraction

VGO = Vacuum Gas Oil
VR = Vacuum residue
WAG = Walter Alternated Gas
X = Conversion
 1

1. CHAPTER ONE: INTRODUCTION

Oil production in the world is tied to the increasing energy consumption and population
growth. Mexico is among the top ten oil producers in the world, is the third in America after
United States and Canada. The oil production in Mexico has decreased since 2005, the main
reason being, the reduce production from the Cantarell offshore reservoir and in general the
decline of the fields in the country (EIA, 2014). The production rate has been steady for the last
years due to a campaign of field and well optimization. As well as new techniques and methods
to produce the fields, new discoveries have contributed to the oil production plateau
maintenance (Figure 1-1).

Figure 1-1 Mexico oil production in the last 10 years by type of oil (Rionda, 2014).

Mexico produces all types of known oils. They are classified in three main products: 1)
superlight, an oil with API higher than 38; 2) light, oils in the range of 27 and 38 API, and 3)
heavy, oils with API lower than 27. Which correspond to 12, 34, and 54 percent, respectively,
of the total oil production being heavy oil, the most produced by the big offshore reservoirs.

The total reserves of Mexico, including proven, probable and possible (1P, 2P, and 3P), in
million barrels, using the same classification are: 32,024 for heavy oil, 17,925 for light oil, and
6,804 for superlight. From the heavy oil 6,058 correspond to proven reserves that are in
production, 10,165 million barrels of probable and 15,801 million barrels for possible (Figure
1-2). The probable or 2P reserves are volumes of oil that are adjacent to probe areas or
 2

reservoirs that are waiting for new technology, facilities construction, and development
(drilling).

For heavy oil, there is a potential amount of reserves that can be incorporated from 2P to 1P,
corresponding to 10,165 million barrels. For this reason, Petroleos Mexicanos (PEMEX) is
investing in new projects to study, analyze and determine the feasibility of actual and new
exploitation techniques for these type of reservoir fluids.

Figure 1-2 Mexican Reserves classification by type. Heavy oil sub classification (million barrels)
(Rionda, 2014).

Several techniques are under development and application in the heavy oil industry. Enhanced
oil recovery (EOR) is used as a direct process to extract this high viscosity oil. Thermal process
are the most common. Steam is the most frequently used technique to improve recovery.

Worldwide, most of the heavy crude oil are contained in sandstone formations, where most of
the EOR processes have proven to be efficient. In Mexico, the biggest and most productive
fields are naturally fractured carbonates. This characteristic is an additional challenge, due to
the two systems that compound the formation (matrix and fractures). Oil has to be extracted
from the matrix and produced via the fractured network.

Few EOR projects have been tested in this type of formations. The most used are waterflooding
and steam the most used. New developments are in progress, one of them is In Situ Upgrading
(ISU) via hot fluid injections, which take the surface refinery concepts to the reservoir. The
 3

objective is to transform the heavy oil in an upgraded quality fluid in the formation, using a
trimetallic catalyst and hydrogen injection.

Upgrading can be defined as the process through which heavier hydrocarbon fluids convert to a
better quality of oil, becoming a more valuable fluid. This improvement has the characteristics
of reducing viscosity, facilitating the fluid transportation in pipeline system, reducing the
density and increasing the API gravity, eliminating contaminants in the oil (for example: sulfur,
metals, etc) (Gray, 2015).

The ISUT, process under study in this work, proceeds via Hydroprocessing reactions, including
thermal cracking, hydrocracking and hydrotreating.

A Mexican field called Aguacate (Ag) was chosen by Petroleos Mexicanos (PEMEX) to evaluate
this new technology, it is a naturally fractured reservoir that contains an 11 API heavy oil. This
reservoir is connected to an active aquifer and is currently producing with a declining rate due
to the increase in water production caused by the difference in mobility between fluids.

This work presents the ISU technology and performs the first evaluation of the fluid reactivity to
analyze the feasibility of applying this process for this type of reservoirs. This evaluation
consists of a laboratory study that tests the reactivity of the oil to hydrogen addition and
thermal processing, helped by a trimetallic catalyst. The target is to experimentally validate a
kinetic model that can predict the upgrading of the oil API, viscosity, and decrease sulfur
content and coke at different temperatures and residence times.

In this thesis the upgrading process is proved and the kinetic model describing the
hydroprocessing of the residue to lighter cuts by a series of reactions are used to obtained
kinetic constants such as: activation energy and pre-exponential factors, which together can
help to evaluate, compare and make sensibilities of the process in a numerical reservoir
simulator.
 4

2. CHAPTER TWO: LITERATURE REVIEW

This work is focused on a novel application of an enhanced oil recovery process for heavy oil in
a naturally fractured reservoir. This process consist of hydroprocessing reactions that upgrade
the quality of the crude oil in the reservoir, using: temperature, hydrogen, catalyst, time and
pressure; evolving the surface refining concepts to reservoir engineering. This chapter provides
basic information of an eclectic variety of processes, equipment and concepts needed to
introduce the ISU process on target. Topics spanning from heavy oil fluids, refining processes,
naturally fractured formations, enhance oil recovery methods, and chemical reactions will
therefore be introduced, also state of the art information on the processes of interest involving
EOR and in reservoir upgrading.

2.1. Heavy oil properties

Several correlations have stablished by many authors relying on properties of the oil, such as
the American Petroleum Institute (API) gravity, which relates to density, and can be correlated
to viscosity (Figure 2-1). This relationship is almost linear, and classifications depend upon the
industry context of use. Figure 2-1 shows the relationship between density and viscosity by
crude oil type.

Figure 2-1 Density and viscosity properties by crude oil type (Gray, 2015).

Condensate, light oil and medium oils are fluids that can be produced by primary production.
Their production complexity comes with the reservoir formation, aquifer, production
mechanism, and rock-fluid forces. From heavy oil to bitumen, beside the mentioned
 5

complexities, the fluid properties add an additional problem for extraction. Table 2-1 shows the
classification of oil based on viscosity and density properties for a better understanding (Gray,
2015).

In order to avoid confusion, there are some terms that are used in the heavy oil context, these
are: heavy, extra-heavy oil, tar sand bitumen, oil sands and bituminous sands. Heavy oil is
already defined. Its a viscous fluid different from the conventional, with higher viscosities and
low API gravity. Extra heavy oil is a more viscous oil. At reservoir conditions it can be mobile.
Tar sands, oil sands and bituminous sands refers to the same type of reservoir. It is a sandstone
formation saturated with bitumen, solid or near solid fluid and immobile under reservoir
conditions. This material cannot be produced by conventional well or techniques (Speight,
2013). This is the case of Canadian reservoirs, In Mexico heavy and extra-heavy oil fields can be
found.

Table 2-1 type of oil classified by viscosity and density (Gray, 2015).

Gravity Density Viscosity

Material
(API) (gr/cm3) (cps)
Bitumen <10 >1 >105
Extra heavy oil <10 >1 <105
Heavy oil 10-19 0.9-1.0 102-105
Medium crude oil 19-34 0.855-0.900 -
Light crude oil >34 <0.855 -

Heavy oils are defined to have an API gravity below 20. Usually, other properties are used to
further detail this classification, for example sulfur content being higher than 2 wt %. The color
of the oil is also indicative of the quality. Darker is the heaviest and yellowish or colorless is the
lightest. The same rule applies for viscosity, the lowest the API the higher the viscosity. These
type of oils contain the non-volatile compounds. For instance: asphaltenes, resins, heteroatoms
(nitrogen, oxygen and sulfur) and contaminants (metals, etc.) (Speight, 1981).
 6

In order to evaluate the components that constitute the fluid, crude oil can be classified into
rough family groups. They are: hydrocarbons (paraffins, naphtenes, aromatics, alkenes, and
others), non-hydrocarbon (organic heteroatoms, and organometallic), and non-defined
compounds (asphaltenes, and resins).

Table 2-2 Classification designated by the structure. Six carbon compound example (Gray,
2015).

Boiling point Density @ 15 C

Class Structure
C gr/cm3
Paraffins 69 0.665

Isoparaffins 60 0.658

Aromatics 80.1 0.873

Naphthenes 80.7 0.784

Olefins 63 0.673

Hydrocarbons are the substantial compounds of the crude oil. They are formed of carbon and
hydrogen atoms, and are classified according to the structure in: single (suffix -ane), double
(-ene) or triple (-yne) bond. (Wauquier, 1995). The structure defines the density and boiling
point of the compound, as it is shown in Table 2-2, where a six carbon compound is presented
with different structures.

Alkanes or paraffins are compounds with a chain of carbon atoms. This can carry 0 to 3
hydrogen atoms. Their boiling point increase as the carbon atom number increase. For
each carbon, an increase of 25 C in the boiling point is expected, decreasing this
tendency as the complexity increases. Isomers can be formed due to branching, where
an equal number of carbon atoms are found, just the branch location gives the
alteration (Wauquier, 1995). The species found in heavy oil or bitumen are products of
bacterial degradation, where light bubble point compounds are almost removed. This
reduction in paraffinic fractions are found as a side chain in the compounds (Gray,
2015).
 7

Naphtenes or cycloparaffins are compounds containing cyclic or ring structures

(Wauquier, 1995). For example cyclohexane and steranes, derived from bacterial
degradation are abundant in heavy oils (Gray, 2015).
Aromatic, are found in a high concentration in crude oil as cyclic and polyunsaturated
molecules, at least one ring with three double bonds (Wauquier, 1995). Single ring
compounds have been degraded by bacteria but, due to upgrading processes, they are
formed again and can be found in the naphtha fraction (Gray, 2015).
Alkenes, are compounds that have the existence of one or more double bonds between
carbon atoms.
Other hydrocarbons, found in traces in the crude oil correspond to diolefins, acetylenes,
etc. those are most often subproducts from conversion process.

Non-hydrocarbon compounds that are constituted in addition to hydrogen and carbon by

metallic atoms, are classified as organic and organometallic compounds (Wauquier, 1995).
Other non-hydrocarbons containing non-metallic elements are called organic compounds.

Organic compounds:
Sulfur compounds can range from 0.1 to higher than 8 weight percent, their
presence have correlation with density, therefore with API gravity. They can be
found in the form of sulfides (cyclic and lineal sulfides), disulfides, thiols, or
thiophenes where S is inserted in aromatic rings (Wauquier, 1995). The former are
difficult to hydrogenate, the latter are easier (Gray, 2015).
Oxygen compounds, their concentration in crude oils is less than that of sulfur
compounds. They can dictate the acidity of the crude oil and can be found in
carboxylic acids (COOH), esters (COO) or rings such as phenols (OH) and furans
(Wauquier, 1995).
Nitrogen compounds are mostly found in oil fractions with boiling point over 250 C,
concentrated in resins and asphaltenes. They can take the form of an aromatic
amide, amine, or cyclic ring with bonds like carbazole and pyridine (Wauquier,
1995). This element is difficult to remove from the main structure. As the boiling
 8

point of the fraction increases, the aromatic rings in the nitrogen compound
increase (Gray, 2015).
Organometallic compounds are found in the non-defined compounds. The metals that
form this complex are nickel (N) and vanadium (V). Arrangements are from the
porphyrin family represented by a four pyrrolic ring, and the metal in the center, that
can be Ni or VO (Wauquier, 1995).

Figure 2-2 petroleum fractions structural composition (Le Page, 1987).

Figure 2-2 shows the structural characteristics of each fraction for any crude oil. As it can be
observed, as the crude oil becomes heavier or denser, the more complex it turns lighter
materials reduce while heavy compounds increase. Heavy oil can be formed from 50% of
residue, which dictates the viscosity and API quality of the oil.

The heaviest part of the crude oil constitutes the non-defined components. Actual analytical
methods cant isolate and characterize each molecule completely, because of its complexity. No
exact structures and complete definitions exists for asphaltenes and resins (Wauquier, 1995).

Asphaltenes are amorphous dark solids that do not melt before decomposition and are
soluble in aromatic naphthas or benzene (Speight, 1981). These compounds are
separated using n-heptane in toluene. If it is insoluble in pure toluene it can be either
mineral or insoluble coke material. They have the higher concentration of polar
 9

compounds, contained mostly in the residue fraction (Gray, 2015). The composite of
polynuclear aromatics layers are linked by chains of saturated compounds. The layers
are in piles, attributed to electrons of the double bonds in benzene rings (Wauquier,
1995). Besides these bonds, others can be found, such as: acid-based interactions,
hydrogen bonding, coordination complex, and Van der Waals interaction.

Figure 2-3 shows a complex schematic representation of an asphaltenes aggregation and its
aggregates (Gray, 2015). Other properties like density is around 1.2 gr/cm3, and they present
high microcarbon (MCR) percentage, due to the high concentration of poly-nuclear aromatic
carbon. The fraction soluble in heptane receives the name of maltene.

Figure 2-3 Schematic representation of an Asphaltene aggregate, with its associations (Gray,
2015).

Resins are dark-red to black semisolids with high amount of heteroatoms that are
soluble in low-boiling point liquid hydrocarbons. These compounds have high
concentration of heteroatoms (N, O, S, Ni and V) and aromatic carbon. They are also
called polar compounds or N, S, O compounds. Resins are the polar section of the
maltenes. Their molecular weight range from 500 to 1,000 (Wauquier, 1995).

The asphaltic fraction or crude oil residue is obtained from a distillation process where volatile
materials are removed. The distillation conditions are at ambient pressure and a temperature
no higher than 350 C, where thermal decomposition begins. Residue is a black viscous
 10

material, and depending on the process used to separate the volatile cuts, can be liquid
(atmospheric distillation) or solid (vacuum distillation). If this residue comes from a distillation
process with temperatures higher than 350 C it is called pitch, where thermal decomposition
affect the product.

The chemical composition of residue is very complex, high amount of resins, asphaltenes with
high molecular weight and highly aromatic structures are found. There is also a significant
amount of organometallic material, such as: vanadium and nickel. In addition, the heavier the
cut, the greater the concentration of sulfur and metals in the residue, and the decline of the
physical properties of the residue (Speight, 1981).

Thermal decomposition of oil products at temperatures higher than 350 C leads to a

deposition of carbonaceous material due to condensation reactions. Large molecules present
are not sufficiently mobile to be reached by hydrogen and to be saturated. Therefore, they
continue condensing and degrading, forming coke. The amount of coke deposition depends on
the micro-carbon content of the oil. Coke lead to several operational problems on surface
refining process. The deposition of beds of this material deactivates the catalyst beds and can
plug lines or units, due to its solid properties.

2.2. Refining processes

Figure 2-4 Residue compounds fractions depending on the process applied to the original
feedstock (Speight, 1981).
 11

Several are the processes involved in the conversion of the feedstock at surface refineries,
passing through initial treatment, separation, conversion, and upgrading of the products. The
feed has to be treated, then separated in a distillation column, and the residue treated to
obtain the vacuum residue. The processes are: desalting, atmospheric and vacuum distillation
respectively. Figure 2-4 shows the comparison among distillation processes with the original
feedstock, where the higher compounds remain, creating a heavier residue per step, and the
lighter fractions are extracted for subsequent processing.

2.2.1. Desalting
Most of the crude oils have certain amount of salt content, a value of 10 lb/1,000 bbl is taken as
a reference for surface processes (Gary & Handwerk, 2001). If the oil has a greater content, it
must be desalted. This process avoids corrosion caused by salt deposition on heat transfer
surfaces, and formation of acids due to the cracking of the NaCl bonds. Also, catalyst can be
deactivated if metals in inorganic compounds are mixed with emulsified water in the oil.

Figure 2-5 Desalter unit diagram (Speight & Ozum, 2002).

The salt in crude oil is usually dissolved in emulsified water or suspended as salt crystals in the
oil. The process principle is to use water to wash this salt. This also helps to remove suspended
solids, such as: sand, clay and soil particles, iron oxides, etc. Figure 2-5 presents a diagram of
the process, where the oil is mixed with water, then sent to a vessel in which the emulsions are
separated by an applied electrical field. The bottom is sent to disposal or to a settling tank for
separating the solids and recycle water. Cleaner oil is thus obtained as a feed for the next
 12

process. One or more stages can be used in this process. This depends on the quality of the
feed needed in subsequent units (Speight & Ozum, 2002).

A typical operating condition for oils with API gravity less than 30 are: temperature in the range
of 140 150 C, and a water wash volume between 7 10 percent (Gary & Handwerk, 2001).

The salts are dissolved in the water added, and the oil and water phases are separated in a
settling vessel helped by adding chemicals that break the emulsion or by applying an electrical
field that coalesce the droplets. With these 90 to 95 percent efficiency can be reached.

2.2.2. Atmospheric distillation (topping unit)

Figure 2-6 Atmospheric distillation diagram (Speight & Ozum, 2002).

Once the oil is desalted, it is heated to a temperature in the range of 340 C and 400 C by heat
exchangers, depending in the type and products that the refinery needs, and charged to the
atmospheric distillation unit. A proportion of the oil is converted to vapor phase, a foamy oil is
charged to the distillation tower where the oil is fractioned. The vapors (light components) go
to the top, and the non-volatile or liquid proportion goes to the bottom. This is called
atmospheric residue. For example a 350 C temperature will separate light components (< 350
 13

C) from heavier components (>350 C). Lighter components will flow to the top and can be
condensed and collected upstream. The heaviest components are sent to the vacuum
distillation unit. This temperature cannot be higher because thermal cracking would form coke.

Figure 2-6 shows a diagram of the process, where the column is divided by a number of metal
trays or plates, the more trays the more re-distillation, and better separation of the original
feed. In these plates the heavy compounds that were volatile are recaptured, and can be mixed
with the desired product (Speight & Ozum, 2002).

2.2.3. Vacuum distillation unit

Secondary or vacuum distillation is used after the feedstock has been separated. The
temperature limitation due to thermal cracking and coke formation makes this process suitable
for the extraction of light cuts of the atmospheric residue. This process recovers heavy distillate
cuts leaving the vacuum residue (VR) which contains most of the contaminants of the original
feedstock, such as: salts, sediments, sulfur, nitrogen, asphaltenes, coke, etc. (Wauquier, 1995)

To continue distilling oil fractions, temperature must be limited below 400 C. Then vacuum is
applied, this helps to decrease the concern of cracking the feed. Vacuum can achieve pressures
around 25 to 40 mmHg (Gary & Handwerk, 2001), commercial temperatures ranges 315 425
C (Speight & Ozum, 2002). This helps to avoid coke formation and increase component
recovery still flowing at ambient temperature (with viscosity lower than 280 cP at 25 C).

The light component obtained from this process is called Vacuum Gas Oil (VGO), and the
heaviest component remaining of this process is called vacuum residue (VR). An intermediate
unit between atmospheric and vacuum distillation can be used to obtain a mild separation at
low cost and an increase in space efficiency.

2.3. Naturally Fractured Reservoirs (NFR)

Naturally fractured reservoirs are located in all parts of the globe, making up a large and
increasing percentage of the reserves. These types of formations are characterized by a
compact matrix block containing fractures. This can have a positive or negative impact in fluid
flow (Aguilera, 1995) and subsequently rate of production and recovery factor.
 14

A fracture is a planar rock discontinuity at a macroscopic level, due to deformation. If they are
related to brittle failure of differential stresses exceeding the elastic limit of the rock (Ahr,
2008), subsequent geologic events altered or mineralized them. If it is due to ductile failure at
high pressure and temperatures, a highly deformed country rock band may exist. Both
processes makes this type of reservoir anisotropic (Nelson, 2001). Open or partially mineralized
fractures improve oil recovery, but totally mineralized or closed fractures create barriers where
the oil cant be extracted. This lead to a variety of effects for primary, secondary, and tertiary
recovery performance. NFR can be located in any type of structural and stratigraphic
combination. The most common lithologies are sandstones and carbonates (Aguilera, 1995)

Figure 2-7 Fracture network representation (Aguilera, 1995).

A single type of porosity and permeability are no longer the principal containing and flowing
phases, a double or secondary phase appear by the presence of fractures. Depositional or
diagenetic formations are related to primary porosity and permeability. Secondary phase is
caused through fractures created by mechanical stresses and subsequent dissolution and
cementation (Ahr, 2008). The most common representation of a fracture network is sown in
Figure 2-7, where the matrix is resembled as blocks, and the space among the blocks is the
fracture network. Other representations can be found in the literature.

Primary or matrix porosity is formed by the first sediment deposition, where the grain
arrangement and distribution, cementation, and void interconnection (effective) will dictate
this property. Induced or secondary porosity is not related to primary. It is formed by fractures
 15

and its properties depend on the solution, recrystallization, and dolomitization processes; the
latter being the most positive impact to porosity and permeability (Aguilera, 1995).

For permeability, the same treatment is applied, being primary for the matrix and secondary for
the fracture network. For the former, Darcys law is used to evaluate this parameter. For
carbonate reservoirs, the presence of vugs add additional porosity and permeability, they are
created by dissolution processes in the matrix. For secondary permeability, it is expected to be
higher than primary permeability due to the presence of unhealed, uncemented, and open
fractures. The important variables for the study of fractures are the width, length and lateral
extension. These combine with Darcys Law equation we can obtain a relationship for fracture
permeability (Aguilera, 1995).

Figure 2-8 Classification of fracture contribution to porosity and permeability (Nelson,

2001).

A classification of NFR due to permeability and porosity properties contribution from each
system, it is as follows (Nelson, 2001):

Type 1: Fractures provide reservoir porosity and permeability.

Type 2: Fractures provide reservoir permeability
Type 3: Fractures assist permeability in a producible matrix.
Type 4: Fractures have no contribution on porosity or permeability only create barriers.

In Figure 2-8, this classification is explained, where x axis corresponds to the porosity
contribution. From 100 % matrix to 0 %, while fracture porosity increases. The y axis is given the
 16

same treatment, but with a permeability property. The first three types are affected positively
by fractures, the fourth negatively due to flow barriers appearance.

For type 1, the knowledge of fracture characteristics such as width and spacing values are
critical for reserves evaluation. This type has a high initial production rate and a rapid declining
behavior, due to the oil contained in the fractures is small. For types 2 and 3, these values are
less sensible, because fractures only contribute significantly in permeability, being the volume
reserves contained in the matrix. For these types, the interaction is important to determine if
the matrix oil can be drained (Nelson, 2001). For the latter, it is important to characterize the
fractures that form barriers for field development or EOR processes evaluation and
implementation, to have a better sweep efficiency and recovery.

Type A Type B Type C

Figure 2-9 NFR classification by storage capacities (Aguilera, 1995).

An important classification of NFR related to the properties of the rock, corresponds to its
storage capacity (Figure 2-9), where fracture network have a negligible capability and matrix an
important volume with low permeability. Type A, reservoirs with permeable matrix and
permeable fractures, with matrix storage volume higher than fractures. Type B are reservoirs
with same matrix and fracture porosity, being the matrix porosity very small and permeability is
provided by the fracture media; and type C, very low porosity and permeability in the matrix,
being the fracture media, storage, and flowing capability of the reservoir. This type is
characterized by high initial production rates that decline to uneconomical levels (Aguilera,
1995).

On this type of reservoirs the matrix, with low permeability, has the significant portion of oil
reserves, while the fractures only contain a small fraction of the oil in a low pore volume with
high permeability.
 17

For reservoir characterization, some qualitative data can be used to recognize a NFR.
Depending on the source of information and the evidence found, can lead to conclude that the
findings are from a NFR. The sources are drilling (Table 2-4), geological (Table 2-5), geophysical
(Table 2-6) and production data (Table 2-3). Summarizing this evidence, we can conclude how
highly fractured the formation is (Narr, Schechter, & Thompson, 2006).

Table 2-3 Indications of fractures in a reservoir using production data as evidence.

Observation Explanation
Isolated intervals of high productivity that dont Fractures enhance permeability
correspond to matrix properties

Unexpected gas show in low permeability rock Light hydrocarbons in fracture

Dual porosity behavior in well test Fracture drainage, followed by matrix drainage

Highly productive well shows rapid decline in Fractures intersected by well are limited, so
productivity system reduces to drainage from matrix

Rapid rise in GOR/WOR, then stabilization Dual system, fractures drain first, then gas and
water enter, then matrix feeds fractures, new
steady state is achieved

Water or gas coning High vertical conductivity of fractures allows

fluids to be rapidly drawn to low pressure area
near producing well

High well to well productivity variability Fracture intersection results in variation in well
performance

Well to well hydraulic communication Movement of fluids between wells along aligned
fractures

Rapid breakthrough of injected fluids along Movement of fluids between wells along aligned
consistent trend fractures

High vertical conductivity Fractures cross-cut k-layers

Strong anisotropy in multiwall pulse test Rapid hydraulic conductivity along oriented
fracture set
 18

Table 2-4 Indications of fractures in a reservoir using drilling data as evidence.

Observation Explanation
Drilling breaks Rapid drilling progress along fractures, especially
when it is unexpected
Bit drop Open fracture

Bit chatter Bit fracture interaction

Abrupt loss of circulation fluids Mud drained into open fracture system

Table 2-5 Indications of fractures in a reservoir using geological data as evidence.

Observation Explanation
Open fractures evidence in core and image logs Fractures in the reservoir are open

Spikes in Stoneley wave log Open fractures in the reservoir

Hard rock in the reservoir Brittle rock has a tendency to respond to strain
by creation of open fractures

Same reservoir productive from fractures Subsurface fractures are a characteristic of this
elsewhere formation

Table 2-6 Indications of fractures in a reservoir using geophysical data as evidence.

Observation Explanation
Anisotropic seismic attenuation It varies as a function of raypath orientation in
accordance to fracture orientation

Shear and P-wave velocity anisotropy in VSP or It varies as a function of fracture orientation
surface seismic

Shear wave polarization in seismic, vertical seismic Birefringence due to open fractures
profile (VSP), full-wave sonic

Dynamic data used for NFR characterization provide a large scale dimension for understanding
a NFR behavior. This information can be used for geological calibration for a numerical
simulation model. Single well tests help us to calculate well average permeability, porosity, skin
factor, linear vs radial flow behavior, and dual porosity. From this we can calculate storativity,
compressibility of the system (matrix and fracture). For long time periods, barriers as faults,
 19

aquifers, and average reservoir permeability can be achieved. For multi-well or interference
tests, anisotropy, permeability, porosity, as well as connectivity of the reservoir can be
determined.

Depending on the well configuration, spacing and the data collected, for instance well logs and
tests (single and interference). An intensity or fracture network density map of the reservoir
can be built. This helps to locate fracture orientation and leads to place producer and injector
wells for improving oil recovery.

The presence of fractures brings a different behavior to fluid flow, compared to single or
conventional un-fractured formations. The high conductivity of the fracture network is higher
than the matrix. An exchange and transfer of fluids occur between matrix and fracture.
Resulting effects are (Narr, Schechter, & Thompson, 2006):

Matrix and fracture interaction (drainage and sweep).

Permeability enhancement (horizontal and vertical).
Permeability anisotropy (I, j plane).
Rapid fluid breakthrough and bypassing to connected wells via fractures.

For matrix and fracture interaction, the fluid transfer process during water injection is ruled by
viscous forces (pressure gradient) and imbibition (capillary forces), a spontaneous movement of
the liquid to the matrix. Imbibition occurs when fractures carry the wetting phase (water) and
the matrix the non-wetting phase (oil). Oil is expelled due to water imbibition on the matrix in a
countercurrent mechanism. The velocity of this process depends on the intensity of fracturing,
matrix wettability and permeability. If a gas is injected, the same process happens, acting
gravity drainage mechanism on oil displacement.

Rock sweep relies on capillary forces of the matrix, fluid transfer between fractures, matrix
blocks, and intensity and connectivity of the fractures. Relative permeability for two phases are
affected by capillary forces in both medias. Matrix values can be obtained in the lab. For
fractures, it is assumed to be two straight lines with endpoints at zero and 100% saturation,
 20

resembling pipes. There is no technical standard method for varying the relative permeability
curves of a fracture.

A rate of fluid transfer between matrix and fracture is determined by capillary imbibition or
gravity drainage. This transfer is assumed to be in a steady state condition and a function of
fluid viscosity, and pressure drop between the matrix and fracture network (Narr, Schechter, &
Thompson, 2006).

The fracture network connectivity relies on the fracture intensity, most of the times it is located
at certain parts of the reservoir. A well-developed field can show differences on well
productivity, resembling the intensity of the network. The more fracture there is in the rock,
the higher the production rate that is expected.

NFR can be easy as well as difficult to manage, depending of the type and fluid contained. The
following tables provides pros and cons for each type (Nelson, 2001). Problems can be manage
if the NFR is furnished with the correct data. For type 1 (Table 2-7 the definition of reservoir
volume and fracture intensity system is important to understand. For Type 2 (Table 2-8), matrix
and fracture interaction have to be analyzed to obtain an optimum development pattern. Type
3 (Table 2-9), have problems at secondary recovery stages, if fracture network is not known.
Type 4 (Table 2-10) can be challenging if the matrix has no good permeability and porosity
properties, additional to the fractured network that create flow barriers.

For tight reservoirs fracturing is an option if the reservoir is not highly compartmentalized. If it
is the case, several zones will be left without draining, having low recovery factors. If the matrix
has good properties, the fracture network have to be understood in order to place the wells in
an adequate pattern to sweep the formation in an optimum way.

Table 2-7 Type 1 NFR positive and negative problem.

Positive Negative
1. Larger drainage area per well 1. Rapid decline
2. Fewer wells needed for exploitation 2. Early water encroachment
3. Good correlation among wells 3. Not accurate reserve calculations
 21

4. High productivity index 4. No additional reserves in development

wells

Table 2-8 Type 2 NFR positive and negative problem.

Positive
1. Can develop low permeability matrix
2. Higher production rates than expected
3. Efficient recharge of fractures with oil
Negative
1. Poor matrix draining due to low
interaction between matrix and fractures
2. Controlled oil production rate to avoid
water breakthrough
3. Critical fracture intensity and dip
4. Fracture closure in overpressure
reservoirs may occur

Table 2-9 Type 3 NFR positive and negative problem.

Positive
1. Reserves dominated by matrix properties
2. More homogeneous distribution of
reserves
3. More stable production rates
4. Reservoir continuity
Negative
1. Highly anisotropic permeability
2. Unusual response in secondary recovery
3. Elliptical drainage areas
4. Poor correlation among well logs and
cores

Table 2-10 Type 4 NFR positive and negative problem.

Negative
1. Reservoir compartmentalization
2. Poor performance of wells compared to matrix capabilities
3. Permeability anisotropy opposite to correlation fields
 22

2.4. Enhanced Oil Recovery (EOR) Processes

Due to the proven reserves (1P), production declining worldwide, and the low restitution rate,
where the easy oil is depleting, IOR (Improved Oil Recovery) and EOR (Enhanced Oil Recovery)
processes are gaining interest to revaluate 2P reserves and make them producible (even 3P).
Most of the remaining reserves are heavy oil in many types of lithologies, such as: sandstone,
carbonate, turbidites. Several techniques have been applied in order to feed the continuing
increase in demand for oil that the increasing population of the world demands.

Primary recovery involves the production of a reservoir oil by its own energy, such as: solution
gas drive, gas cap drive, water drive, fluid and rock expansion, and gravity drainage. Improved
Oil Recovery (IOR) activities or secondary recovery techniques, which do not alter the oil and
rock properties and add additional energy to the reservoir, are the next steps for the primary
production. These processes involve waterflooding for fluid displacement, and pressure
maintenance by water and immiscible gas injection. Other operations involving IOR are:
reservoir management, reservoir characterization, and infill drilling.

Once these techniques are not efficient, EOR or tertiary recovery have to be applied to increase
the recovery factor of the reservoirs. The injection of fluids that interact with the reservoir
oil/rock system favoring the oil recovery by physical and chemical mechanisms. These
interactions can be lower interfacial tension (IFT), oil swelling, oil viscosity reduction, wettability
modifications, or favorable phase behavior.

For heavy oil reservoirs, this chronological steps of recovery can be excluded, due to the high
viscosity of the fluid the primary recovery is negligible. The oil cannot flow at economic rates
with its natural energy drive. Secondary recovery is not suitable, waterflooding cannot be
applied due to the difference in mobility between the viscous oil and the water. For that
reason, tertiary recovery is the only manner to produce this type of fluids, using thermal
processes (Green & Willhite, 1998).

To evaluate the processes, they can be divided into: type of lithology (sandstone and
carbonates) and the location of the reservoirs (onshore and offshore). We are going to focus on
carbonates. Specifically in naturally fractured reservoirs (NFR), which is the lithology of the
 23

reservoir under evaluation (Ag field). Some examples of sandstone will be given, due to the
higher frequency of chemical and thermal processes used for this type of lithology, where most
of the EOR pilot and commercial test have been applied.

A considerable proportion of the Mexican high reserve reservoirs are located in carbonates, this
type of rock exhibit a low porosity and permeability in the matrix, but it might be highly
fractured which makes the crude oil and gas production highly productive, increasing the
permeability helping the reservoir to drain at high rates. In these case the fluid flow depends in
the fracture network and the matrix will act as a fluid source. This behavior leads to low
recovery factors due to an uneven sweeping of the reservoir.

The next subject is the oil type, when we are talking about heavy oils; it implies high viscosities,
low API gravity, and low gas-oil ratio. With these properties not suitable for a commercial
production, companies focus on easier opportunities that are more efficient, economically,
been abandoned, or with low investment to its development.

It is important to notice that a better geological understanding of the reservoir formation rock
may lead to a successful EOR process implementation. Problems such as: unexpected losses of
fluids or bypassing due to channeling in high permeable zones, or fractures resulting in a non-
uniform fluid movement, or sweeping and unexpected chemical adsorption, are factors that
make an EOR process a failure. Laboratory experiments with cores and plugs, obtaining enough
log and seismic data, pressure transient and historical production, and pressure analysis add
points to understand the reservoir under study.

Several types of EOR processes have been developed and applied to a diverse range of
reservoirs from gas injection, passing to chemicals and thermal, in some cases a combination of
all them.

2.5. Chemical Processes

The chemical process are divided in three main practises: Mobility control, chemical and
miscible processes (Green & Willhite, 1998). The latter will be explained in the gas processes.
 24

For the mobility control process, chemical are used for thickening the water by using polymers
and foams for gases. This reduces the mobility of the phases in order to displace oil to a
production well, increasing the macroscopic sweep efficiency in the formation. Figure 2-10
shows how the polymer improves the water front. A uniform sweeping of the pore media is
achieved, leading to an increase in the recovery factor. The high permeability zones are
damped due to the change in mobility of the displacement fluid. The polymers improve the
mobility ratio between the water with polymer and the oil and water bank in situ.

Waterflood Polymer Flood

Figure 2-10 Displacement front comparison with waterflooding and the use of polymers.

Compared with the other EOR processes, the use of polymers have a minimal effect in the
recovery factor, they act in the macroscopic media, leaving the microscopic intact. If this
method is applied after a waterflooding process, a marginal increase in recovery factor can be
achieved.

The second type are the chemical processes that change the interfacial tension (IFT) properties
of the fluids in the reservoir. Figure 2-11 illustrates an immiscible surfactant-polymer process.
This process has proven to be effective in ultimate oil recovery among the EOR processes. This
process consist in several liquid displacement slugs. The primary slug is a micellar solution
which contains surfactants (sulfonate), co-surfactants (alcohol), oil, electrolytes, and water. The
surfactant slug is around 10% of the pore volume. This is followed by a mobility buffer that
contains polymer at a few ppm concentration, its volume is around 1 pore volume, PV.
 25

The micellar slug is designed to have a very low IFT with the oil in situ. This causes the droplets
of oil to deform and to be displaced through the porous media and coalesce, resulting in an oil
bank. It is also designed to have a good mobility control with the oil bank preventing fingering,
and increasing the macroscopic displacement efficiency (Green & Willhite, 1998).

Another chemical process uses surfactants, these are designed to increase the microscopic and
macroscopic sweep efficiency. It is a complex and expensive process that is suitable for
reservoirs with high residual oil saturation after a waterflooding. This process is sensitive to
high temperature and salinity, for this reason it is excluded from the carbonate reservoirs.

Other methods are: alkaline flooding, where alkaline chemicals are injected, reacting with the
oil creating a surfactant in situ. Others use alcohol, but havent been tested in the field.

This type of process has less contribution to the world production by EOR application in
carbonates. Most of the chemical processes such as Alkali-polymer (AP), Surfactant-Polymer
(SP) and Alkali-Surfactant-Polymer (ASP), are only applicable to sandstones. Polymer flooding is
the only chemical proven as an EOR process as part of the water flooding, mainly to help as a
sweeping and managing the water front. Most of the tests for other processes are still at
laboratory scale. No large field applications are found in literature.

Other uses of chemical as a treatment, on carbonates, are: well stimulation and wettability
modifiers, using surfactants. Investigations areas are focused in spontaneous imbibition,
wettability modifiers and interfacial tension reductions, all of them are based on surfactants.
On the other hand, the use of gels and foams are and will continue to contribute to the
optimization of some processes like water alternated gas (WAG) or gas and water flooding
(Manrique, et al., 2010).
 26

Figure 2-11 Displacement front for an immiscible surfactant-polymer process (Green & Willhite,
1998).

For sandstone the story is different. This type of technique had its peak in the middle eighties,
polymer flooding being the most important, and can be considered a mature technology.
Chemical processes are sensitive to oil prices and reservoir conditions, for that reason these
techniques are effective in shallow, low temperature sandstones, helped by good
permeabilities. Table 2-11 presents the oldest and ongoing polymer flooding projects around
the world; we can conclude that this technique produces good results.

Other chemical processes include colloidal dispersion gels, alkali, surfactant, alkali-polymer
(AP), surfactant-polymer (SP) and alkali-surfactant-polymer (ASP).

Table 2-11 Chemical processes application until 2010 (Manrique, et al., 2010).

Field Location Method Process

1 El Tordillo Argentina PF Project
2 Pelican Lake Canada PF Project
3 Daquing China PF Project
4 Gudao China PF Project
5 Gudong China PF Project
6 Karamay China PF Project
7 Jhalora India PF Project
8 Sanand India PF Project
9 North Burbank U.S. PF Project
 27

10 Carmopolis Brazil PF Project

11 Buracica Brazil PF Project
12 Canto do Amaro Brazil PF Project
13 Marmul Oman PF Project
14 Pirawarth Austia PF Project
15 Voador Brazil PF Project
16 Horsefly Lake Canada PF Project
17 Bochstedt Germany PF Project
18 Daqing China ASP Test
19 Gudong China ASP Test
20 Karamay China ASP Test
21 Liahoe China ASP Test
22 Shengli China ASP Test
23 Viraj India ASP Project
24 West-Kiehl U.S. ASP Project
25 Sho-Veltum U.S. ASP Project
26 Cambridge Minnelusa U.S. ASP Project
27 Tanner U.S. ASP Project
28 Xing Long Tai China AP Project
29 David Pool Canada AP Project

2.6. Gas Processes

The main objective of a miscible process is to displace oil reaching miscibility with an injected
fluid. There are two variations of the process. First contact miscibility (FCM), where the fluid
injected is miscible at the conditions in situ with the oil. In this process, hydrocarbon gases are
used, such as liquefied petroleum gas (LPG), in a volume between 10 to 15 % PV, then displaced
by a cheaper gas, such as dry gas, high in methane. In some cases all the slugs are displaced by
water as a second displacement fluid. First and second gas slugs are desirable to mix with the
oil, to achieve a better displacement.
 28

The second process is the multiple contact miscibility (MCM), where the properties of the oil
has to be modified with the first stages of gas injection due to mass transfer. Figure 2-12 shows
an example using CO2 as a MCM gas. Through multiple contacts, high molecular weight
components of the oil are extracted to the CO2 phase, altering the composition suitable for a
subsequent CO2 miscibility.

This process uses CO2 injected at conditions above its critical temperature (87 F). Its viscosity is
very low and the mobility ratios are unfavorable, fingering can be observed. For this reason an
alternative is to displace slugs of CO2 and water, named water alternated gas process (WAG).
This reduces the CO2 mobility by altering the relative permeability to CO2 (Green & Willhite,
1998).

Other gases suitable for this type of process are: hydrocarbon gases, nitrogen, or flue gas.
These gases need higher pressure to achieve miscibility compared with CO2. They are suitable
for deeper reservoirs that are under higher pressure.

An additional process using gases, called vapor extraction (VAPEX), is a non-thermal method
that uses gases as a solvent, reducing the viscosity of the oil, increasing its mobility. It is applied
with horizontal wells, one on the top of the other, the top being the injector of gas/solvent
mixtures stimulating the oil and produced by the lower well by gravity drainage. Due to the
solvent cost, it is an expensive process, the solvent is not recovered completely. Some
experiments are running to use VAPEX before in situ combustion (ISC), where the solvent can
be recovered with an additional in situ process called de-asphalting. The Asphaltene residue
could be the fuel source for the ISC process (Schlumberger, 2011).
 29

Figure 2-12 Miscible displacement process (Green & Willhite, 1998).

Compared with the last two methods mentioned before, gas flooding for EOR applications is
the most used for light, condensate, and volatile oil in carbonates formations.

For different reasons such as depth, high-pressure, and light oil reservoir, nitrogen flooding has
been effective, at these conditions N2 can be at miscible conditions. On the other hand
immiscible N2 has been used for pressure maintenance, cycling of condensate reservoirs, and as
a drive gas for miscible slugs. In U.S. a miscible WAG-N2 has been reported but this was
suspended at the Jay Field. In Mexico, Cantarell field, N2 injection is the only representative
project outside U.S. In this case, N2 acts as a gas cap that helps the gas expansion mechanism.
Due to the high investing capital needed for this type of project, no more examples are
reported in the literature at high scale.

Other gases such as hydrocarbon gases are used worldwide, with very low contribution to the
recovery factor. These gases are widely used as a WAG mode due to the low cost of gas, it helps
the pressure maintenance or in WAG processes.

CO2 as an EOR gas injection process has been implemented successfully. It has been used in the
U.S. in the Permian Basin. On 2008, 105 active projects were documented in the U.S., 63 being
in carbonate formations. Due to its availability in the zone this gas makes this type of projects
popular (Manrique, et al., 2010).

As it was described, there is not much experience on EOR processes in heavy oil in a naturally
fractured formation. Most of the experience is in sandstones.
 30

For sandstones, only a few projects of N2 injection are ongoing for light oils. Hydrocarbon gases
have a marginal contribution. CO2 is used for medium and light oils, due to its availability its
the most used in the U.S. Table 2-12 shows some of the projects outside of the U.S. For CO2
injection, which most of them are ongoing for several years.

Table 2-12 Gas processes application until 2010 (Manrique, et al., 2010).

Field Location Method Process

1 Buraica Brazil CO2 Project
2 Rio Pojuca Brazil CO2 Project
3 Miranga Brazil CO2 Project
4 Joffre Canada CO2 Project
5 Pembina Canada CO2 Project
6 Ivanic Croatia CO2 Test
7 Budafa Hungary CO2 Test
8 Lovvaski Hungary CO2 Test
9 Szanik Hungary CO2 Test

2.7. Thermal Processes

This type of process uses thermal energy to increase the reservoir temperature, reduce the oil
viscosity, increase mobility, and produce the oil. Three processes have been developed during
the last decades in order to produce heavy, extra heavy, bitumen and tar sands. These are,
cyclic steam stimulation, steam flooding, and In Situ Combustion (ISC). The first two use the
steam as thermal drive, and the third uses air (oxygen) to initiate combustion in the reservoir.

The main properties that are important for these processes are depth, average permeability,
and pressure of the reservoir. Table 2-13, shows the screening criteria for steam and ISC
techniques. Most of them are similar, for that reason several fields have both processes
ongoing or being tested at the same time.

Table 2-13 Screening criteria differences between steam and ISC processes (Green & Willhite,
1998).
 31

Parameter Unit Steam ISC

Oil gravity API 10-34 10-35
In situ oil viscosity cps <15,000 <5,000
Depth ft <3,000 <11,500
Pay zone ft >20 >20
Reservoir Temperature F - -
Porosity Fraction >0.20 >0.20
Average permeability md 250 35
Transmisibility md-ft/cp >5 >5
Reservoir pressure psi <1,500 <2,000
Minimum oil content fraction >0.10 >0.08
Salinity of formation brine ppm - -
Sandstone or Sandstone or
Rock type -
carbonate carbonate

Depth has its limits on steam processes at 3,000 ft, where heat losses are excessive. It can be
reduced by using insulated tubing in the well. For ISC the depth recommended is a maximum of
up to 11,500 ft, the limitation is based in the reservoir pressure, if air can be injected, more
depth can be reached. We only have to ensure that there is enough air to maintain the
combustion process.

For steam processes, where the thermal energy is transported by its latent heat, the increase in
pressure reduces this energy. Also, the temperature of the steam increases and so does the
heat loss. This reduces the reservoir volume that is contacted and heated. The maximum
pressure is 3,206.2 psi, where the steam reaches its critical pressure. The most successful steam
injection processes operates at 1,500 psi or lower. For ISC, pressure is not a technical limitation,
but it is economical. Compressors are more expensive when they require higher pressures.

Permeability in thermal processes have to be well determine. For ISC, low permeabilities are
not a problem, to the rate of air that has to be injected to maintain combustion. For steam
drive processes, this can reduce the heat front, at low permeabilities (Green & Willhite, 1998).
 32

2.7.1. Steam processes

In the steam drive or steamflood process, steam is injected and the fluids are displaced to a
production well in a specific pattern to get a better sweeping of the formation. Several
mechanisms act in this process. They are: viscosity reduction, steam flashing, oil swelling, and
steam stripping (Green & Willhite, 1998). Due to heat losses, reduction in temperature is along
the formation, condensation starts and hot water front becomes a displacement mechanism
followed by a steam front.

The difference in viscosity and density between oil and steam makes the steam move to the top
of the reservoir, as well as mobility control that leads to fingering. Some areas are not
efficiently swept by this process. Figure 2-13 shows a diagram of the process.

Figure 2-13 Steamflood process (Green & Willhite, 1998).

For steam processes, where the thermal energy is transported by its latent heat, increasing
pressure and temperature reduces the energy and increase heat losses. As a consequence, a
reduction in volume contacted and heated in the reservoir is observed. The maximum pressure
that can be reached for this process is 3,206 psi, where the steam is at critical pressure. The
most successful steam injection processes operate at 1,500 psi or lower.

2.7.1.1. Cyclic Steam Stimulation (CSS)

Cyclic steam stimulation, also called steam soak or huff and puff process operates in a single
well, most of the times vertical, in which steam is injected for certain period of time. Then, the
well is shut down, this period is called soak time, for another period of time. Figure 2-14 shows
 33

a diagram of this process. Finally, the well is opened to production until the rate declines to a
non-economical level. Again, the process is repeated as many times as the production rates are
economically feasible. Steamflooding acts by the same mechanism.

Figure 2-14 Huff and puff process diagram (Green & Willhite, 1998).

This process heats the rock around the wellbore maintaining the temperature at high levels for
a long period of time. The essential requirement for a successful CSS process is the need for a
natural reservoir energy, such as: fluid expansion, water drive, gravity drainage, or compaction.
For example; for gravity drainage reservoirs the steam is injected in the productive zone,
heating and creating a zone with high temperature. This tends to extend the whole oil column.
Beyond the radius of the heated zone, the reservoir continues at its initial temperature.

This type of methods is not popular in carbonate formations, due to the heterogeneity and
fractured network that is not easily tracked and is randomly located in the reservoir. Several
test have been developed at small scale worldwide, being only one announced for a large scale
implementation (Qarn-Alam field in Oman). No further publications have been found from this
project that could lead to a complete evaluation of this technology in the future (Manrique, et
al., 2010). On Table 2-14, the different projects tested until 2010 are shown.

Table 2-14 Steam processes applications until 2010 (Manrique, et al., 2010).

Field Location Method Process

1 Garland Wyoming Steam Project
 34

2 Yates Texas Steam Project

3 Lacq Superiur France Steam Test
4 Ikiztepe Turkey Steam Test
5 Cao-32 China Steam Test
6 Issaran Egypt Steam Test
7 Wafra Saudi Arabia and Kuwait Steam Test
8 Qarn -Alam Oman Steam Large Scale

2.7.2. In Situ Combustion (ISC)

This technique is a displacement process where an oxygen containing gas (air) is injected into
the reservoir. The oxygen reacts with the crude oil creating a high temperature combustion that
propagates as a front through the reservoir. The process fuel comes from the coke formed by
the cracking of the original oil. Enough fuel (coke) must be generated to maintain the reaction
(Green & Willhite, 1998). There are two types of combustion: dry and wet. The latter refers to
the injection of water simultaneously with the gas or alternated in slugs. The former only use
gas injection.

2.7.2.1. Dry combustion

This process occurs when oxygen reacts with the coke content of the oil in the reservoir porous
media, creating a self-combustion front that generates new coke when the original oil burns.
The ignition is induced by electrical or gas igniters, or could be spontaneous. If the oil is very
reactive. Figure 2-15 shows the frontal advance process of a thin reservoir. The injected air is
preheated to combustion temperature (600 1,200 F) as it flows through the rock behind the
combustion zone. Combustion products: water, CO2 and CO that flow ahead of the slowly
moving front. Oxygen that is not consumed and nitrogen also flows with the combustion (air)
gases. In a well-developed front, gases strip light ends from the crude oil flowing ahead of the
front. Hydrocarbons stripped condense to form a small steam plateau of hot water and light
hydrocarbon banks. Most of the oil displaced by the combustion front will be produced before
breakthrough and the oil saturation remaining after stripping is thermal cracked as the
combustion front approaches, leaving a residual deposit on the rock that is rich in carbon. This
 35

becomes the fuel of the process (coke). No more than 5 to 6% of the oil is consumed. The rate
of frontal advance is controlled by the fuel availability and the rate of oxygen delivered to the
burning front. The factors controlling the ISC process are: fuel availability, air requirement and
air flux (Green & Willhite, 1998).

Figure 2-15 ISC process (Green & Willhite, 1998).

2.7.2.2. Wet combustion

This technique was developed in order to use the residual thermal energy of the rock once the
combustion front passed through. Injecting water created an in-situ hot waterflood. Then, wet
ISC appeared, it can be referred as COFCAW that corresponds to combination of forward
combustion and waterflooding. When water and air are injected simultaneously, the water fills
part of the region behind the combustion front. As water saturation increases, it is displaced to
the heated region creating a superheated steam. This will flow to the combustion front,
forming a condensation zone that travels three times faster than the combustion front, creating
a distillation zone ahead the front. The design of a wet ISC process is similar to the dry ISC, the
difference is the use of a water/air ratio due to the discovery that air requirement could be
reduce by injection water, reducing compression costs, which helped to increase the
technology spread (Green & Willhite, 1998).
 36

2.7.3. Steam Assisted Gravity Drainage (SAGD)

SAGD is a process used in sandstones that contain heavy oil or bitumen. It consists in a two
horizontal well configurations, one over the other, separated by no more than 5 m. the bottom
well is horizontal while the top could be vertical, deviated, etc. In that case, two or more wells
have to be drilled to ensure the production along the bottom well.

Steam is injected in the top wells creating a steam saturated zone (chamber) with a
temperature corresponding to the steam. At the perimeters of the chamber, the steam
condensates transfer the heat by conduction to the surrounding zone. Both fluids, water and oil
reduce viscosity, and flow by gravity drainage to the bottom well. Figure 2-16, shows a diagram
of the mechanism. As the injection time pass, the chamber grows in all directions (Butler,
1994).

Figure 2-16 SAGD chamber mechanism (Butler, 1994).

For fractured reservoirs, some lab studies and numerical simulation models have been
developed. A lab experiment comparing vertical, horizontal and homogeneous reservoir was
developed. The results show that SAGD process are enhanced due to the fractures, helping the
chamber formation and breakthrough among wells (injector and producer) improving the
recovery (Suat Bagci, 2007). It is a promising technique that has to be proven in real reservoirs.
 37

In situ combustion (ISC), the oldest thermal recovery method used (since 1920) with mixed
results and is considered high risk due to the oxygen usage. This process is also called high
pressure air injection (HPAI), it is used in heavy and light oil reservoirs. It has proven to be an
efficient recovery method in several types of formations but with more emphasis on light oils.

Other thermal method that has been increasing since 2,000 in carbonate reservoirs is High
Pressure Air Injection (HPAI). All in light crude oil (>30 API), at least eleven in the U.S. One
example is the Buffalo field in North Dakota, it started in 1980 and it is still in operation. This
contributed in an increase of interest and the creation of new HPAI processes in the
surrounding area. This technique has proven to have high potential in the increase of the
recovery factor, revitalizing mature and waterflooded carbonate reservoirs. There are risks in
this process due to the air and oxygen components, but the mentioned projects have proven
that it can be manage and it is economically attractive. Mexico is now beginning the pilot test in
the Cardenas Field, onshore. This will dictate the future of these type of projects in NFR
reservoirs.

Table 2-15 SAGD projects application until 2010 (Manrique, et al., 2010).

Field Location Method Process

1 Crude E Trinidad Steamflood Project
2 Schoonebeek Netherlands Steamflood Project
3 Alto do Rodrigues Brazil Steamflood Project
4 Cold Lake Canada LASER Test

For sandstone, additional processes have been applied, such as: Cyclic Steam Stimulation (CSS),
steamflooding, and most recently Steam Assisted Gravity Drainage (SAGD), for heavy and extra
heavy oil during the last decades. Most of this experience has been gained in Canada, U.S.,
Venezuela, Brazil and China. Table 2-15 shows the latest ongoing projects (1-3). New
optimizations are being tested using solvents, gases, chemical additives and foams. A new
technique named Liquid Addition to Steam for Enhancing Recovery that adds C5+ liquids as a
 38

steam additive in CSS was tested in Cold Lake field, without a commercial scale expansion
(Manrique, et al., 2010).

The second process in importance using steam is SAGD. Where Canada and Venezuela are the
most experienced in this process due to their high reserves volume of extra heavy oil. Their
reservoirs are unconsolidated and have high vertical permeability, making this process a huge
success. For this reason this process is focused mainly in Canada (the McMurray formation at
Athabasca). The only con is the oil price that will dictate the expansion of this technology in the
near future (Manrique, et al., 2010). Some variations of the technology are under development,
such as: single well SAGD, additives aggregated, fast SAGD and Cross or X SAGD.

The third technology for heavy and extra heavy oil in importance is In Situ Combustion (ISC).
Table 2-16 shows the ongoing projects.

Table 2-16 ISC projects application until 2010 (Manrique, et al., 2010).

Field Location Method Process

1 Battrum Canada ISC Project
2 Suplacu de Barcu Romania ISC Project
3 Balol India ISC Project
4 Bechraji India ISC Project
5 Lanwa India ISC Project
6 Santhal India ISC Project
7 Bellevue U.S. ISC Project

Several variations of the process such as: Toe to Heel Air Injection (THAI) and In situ catalytic
version of THAI (CAPRI) are in the early stages of evaluation (Manrique, et al., 2010).

2.8. Other Processes

There are other processes in study or with very low potential, such as microbial EOR (MEOR)
and low salinity water or Smart water.
 39

MEOR process consist in the injection of anaerobic bacteria to the reservoir. This bacteria is
injected with nutrients as a feedstock, the microbial metabolic products are: bio surfactants,
acids, solvents, gases, and also enzymes. All these products modify the oil properties and its
interaction with the porous media, and other fluids in situ. As a consequence mobility is
increased. The bacteria used for this method are: halophiles, barophiles, and thermophiles that
have a good adaptation behavior to the reservoir conditions. Temperature is a variable that
affect this process. No more than 120 C can be reached, and a certain type of bacteria can
grow at that condition. Other factors such as pH and biological variables have to be evaluated
(Lazar, Petrisor, & Yen, 2007).

Low salinity or SMART water injection is a process were a designed composition and salinity of
the injection water is produced. This process has the capacity of changing wettability, helped by
temperature and spontaneous imbibition mechanism of the carbonate rock. It is now in
laboratory experimentation for heavy oil in NFR. The experiments are comparing the injection
of seawater flooding and SMART water, were significant increase in the recovery factor has
been measured, passing from 30% to 60%. Future test and laboratory experimentation are in
progress with the potential of injecting sea water treated in offshore fields (Gachuz-Muro &
Sohrabi, 2014).

2.9. Chemical reactions

Thermal processes, like steam injection, are heavy oil temporarily improved processes, where
heat only helps to make the heavy oil easy to manipulate but, once heat is lost, the oil comes
back to its original properties. In the case of ISC, upgrading is achieved but it is accompanied
with the loss of part of the crude oil as coke and products of the combustion.

In Situ Upgrading (ISU) process is a technique that change the properties of the oil
permanently. This properties are viscosity, density, API gravity, sulfur content and coke content.
Applying thermal and chemical reactions the oil is upgraded on site. The main idea comes from
surface upgrading at refineries. These concepts are taken to the reservoir in order to develop
this technique. In order to understand this process, some chemical definitions must be
reviewed.
 40

The main concept is to treat the reservoir as a reactor that needs certain conditions to obtain
sub products of the feedstock, obtaining light and heavier products via chemical reactions. In
surface refineries, subproducts, such as gasoline, fuels, etc. are the main goal of the processes.
In ISU, the objective is to upgrade the quality of the crude oil contained in the reservoir and
facilitate its mobility to increase production rate and recovery factor, as an enhanced oil
recovery method for heavy oil reservoirs.

The key factors that make this process works are thermal (thermal cracking) and hydrogen
addition (catalytic) processes. These two are explained with more detail in chapter 3 and 4. For
a better understanding, some chemical and kinetic concepts are review as follows.

2.9.1. Catalyst
The catalyst is a substance that changes the reaction rate by stimulating a different mechanism
for the reaction, affecting the rate of reaction. This substance makes it feasible to obtaining
products with a lower energy barrier affecting either the yield and/or the selectivity, and
remain un-altered at the end of the reaction. In other words, accelerate or slow the reaction or
appearance of a particular product species, using less energy without affecting the equilibrium.
It is homogeneous if the catalyst is soluble in the reactant phase and heterogeneous if it is
distinct from the reactant or medium (Le Page, 1987). Usually a catalyst is a solid, for that
reason catalytic reactions are named heterogeneous (Bartholomew & Farrauto, 2006).

The role of the catalyst enhancing the rate exponentially by reducing the activation energy or
energy barrier is shown in Figure 2-17. This energy is the minimum total kinetic energy that
molecules must bring to their collisions for a chemical reaction to occur (Petrucci, 2011). This
reduction is accomplished by providing active sites for adsorption and reaction, where the
products are created. The energy difference between reactant (A) and product (B) is the heat of
reaction orHr, that refers to a change in enthalpy. The catalyst doesnt change the initial and
final state of energy, just the rate (Bartholomew & Farrauto, 2006).
 41

Figure 2-17 Catalyst activation energy drop compare to no catalyst reactions (Bartholomew
& Farrauto, 2006).

In upgrading processes of heavy oils and residue, catalyst have three main objectives in the
presence of hydrogen (Gray, 2015):

Hydrogenation of aromatics and olefins, avoiding coke formation.

Removal of metals, such as: vanadium (V), and nickel (Ni) from residue fraction.
Sulfur, nitrogen and oxygen removal.

In refinery processes, these reactions are needed for subsequent and more complicated
processes to avoid corrosion and catalyst deactivation, etc.

Figure 2-18 Solid catalyst reaction mechanism (Bartholomew & Farrauto, 2006).

There are many mechanisms proposed that explain the catalyst behavior with a reactant. The
most accepted for a unimolecular reaction is shown in Figure 2-18, and the steps are as follow:
 42

1. Diffusion of the reactant from the whole fluid to the surface of the catalyst.
2. Diffusion from the pore entrance through the inner part of the catalyst.
3. Adsorption of reactant into the surface.
4. Reaction on the surface.
5. Desorption of the product (B).
6. Diffusion of the product from the interior of the pore to the surface.
7. Mass transfer of the product from the surface to the fluid.

Figure 2-19 Adsorption mechanism (Le Page, 1987).

In order for a catalyst to react with the reactant and begin the reaction, the reactant must be
attach to the surface. This attachment is called adsorption and can be:

Physical: the forces of attraction are weak and are Van der Waals forces. This interaction
is exothermic in the range of 1-15 kcal/mol.
Chemical: the reactants are held to the surface of the catalyst by valence forces of the
same type of the atoms bonds in molecules, causing a very reactive attachment. This
interaction of the reactant with the surface of the catalyst causes that the bonds of the
 43

reactant to be stretched, making them easier to break. This interaction is also

exothermic, in the range of 40-400 kJ/mol.

Step 3, the adsorption of the reactant into the surface is a critical step for reactions. It is
explained in Figure 2-19, where the blue line represents the chemical adsorption
(chemisorption), and the orange corresponds to physical adsorption (physisorption). The
former, needs an energy of dissociation (ED) of the molecules, for instance hydrogen (diatomic),
requires to split the molecule in order to be adsorbed by the metallic surface (heterogeneous),
being a stronger attachment compared to physical. Where Van der Waals forces act between
the metal and hydrogen molecules, no dissociation is needed. It is desirable that the reactant
be adsorbed physically first, followed by chemisorption. Lower energy is needed compared to
pure chemisorption. The highest potential energy would be reached at point B, corresponding
to a transition level (Le Page, 1987).

Table 2-17 Catalyst used for several reaction.

Reaction Catalyst
Halogenation-dehalogenation CuCl2,Pd
Hydration-dehydration Al2O3, MgO
Alkylation-dealkylation Pd, Zeolites
Hydrogenation- Co, Pt, Ni
dehydrogenation Cu, Ag, Ni
Oxidation Zeolites,
Isomerization AlCl

The catalyst have the following properties:

Large surface area: because the reactions occur at the interface, large areas are needed
in attaining a significant reaction rate. This area is usually provided by the inner porous
structure.
The catalyst can be supported or unsupported. The first one is usually referred to a
minute particles of an active material dispersed over a less active one called support.
 44

Sometimes the metal has a little amount of an active ingredient called promoter, which
increase the activity of the catalyst.
Not all the surfaces of the metal catalyze the reaction, only at certain active sites that
can form strong chemical bonds with an adsorbed reactant.

An accepted classification is in function of the reaction type, and Table 2-17 shows some
examples (Fogler, 2011).

2.9.1.1. Ultradispersed catalyst

The advantages of the dispersed metals (catalyst) is that deactivation problems are reduced
and the catalytic activity remains high.

Due to the small size of the particles, around 100 nm, it offers a high surface area where the
maximum interaction of oil and hydrogen can occur. This favors the upgrading of the crude oil
or vacuum residue in our case. This contains high concentration of metal contaminants, sulfur
and nitrogen compounds, with a high microcarbon number.

The metals used for the catalyst composition are transition metals, such as: Mo, Co, Ni, fe, Cr.
Molybdenum is the most common due to its effectiveness in promoting the conversion,
lowering the boiling point, microcarbon and elimination of sulfur (HDS). To improve the results,
two or more metals are used. These systems are selected by their reaction products and the
cost of the metals.

For a successful hydroconversion, the particle size and the high quantity per volume of reactive
oil are both key factors. The composition and the degree of dispersion at certain conditions
dictate the activity of the catalyst. The distance among particles determines the efficiency of
the reaction when efficiency decreases, the thermal control increases increasing the free radical
hydrogenation that could form coke.

The driving force of the conversion reaction is provided by the thermal activation, where the
free radicals are produced by thermolysis and are stabilized by the presence of hydrogen, or
rearranging or condensation. The catalyst in a well dispersed condition favors the uptake of
 45

hydrogen, reducing coke formation (Del Bianco, Panaratti, Di Carlo, Elmouchnino, & Fixari,
1993).

2.9.2. Kinetics
To understand the In Situ Upgrading (ISU) process, we need to review some basic definitions
involved in a reaction. These are divided in two main types, homogeneous and heterogeneous.
The former are the ones that involve only one phase (liquid or gas). The latter involves more
than one phase where the reactions usually occur at the interface between phases.

Reactions can be either irreversible, those are reactions that are unidirectional and continue
until the reactant is exhausted, or reversible, which can proceed in either way, depends on the
concentration of the reactant and products relative to the corresponding equilibrium
concentration.

For heterogeneous reactions, using a solid catalyst, the reactant is adsorbed first in the active
site of the solid surface and reacts. The adsorption mechanism is modeled by Langmuir
Hinshelwood isotherm. Considering a H2 molecule adsorbed in a vacant site SH on the catalyst
surface, is represented in the following reaction, where H2 SH is the occupied site by
hydrogen molecule (Gray, 2015).

H2 + S H H 2 S H

The rate of adsorption (rads ) is proportional to the vacant site concentration (CV ) and the
partial pressure of the hydrogen (pH2 ):

rads = k A pH2 CV

Being the rate of desorption, the reverse reaction:

rdes = k A CH2 SH

For this reaction, the difference in the above two rates give the net adsorption rate:

rads rdes = k A pH2 CV k A CH2 SH

It is important to notice that the total concentration of sites is constant, so:

 46

Ct = CV + CH2 SH

At equilibrium rads rdes = 0, so rads = rdes , then:

K A pH2 Ct
CH2 SH =
1 + K A pH2

K A the adsorption equilibrium constant, is a function of temperature and most cases decreases
with increasing temperature.

kA
KA =
k A

Once the reactant is adsorbed on the surface of the catalyst, several types of reactions are
possible (Gray, 2015).

The rate of disappearance of a reactant, for example: A, rA , being the negative sign referring
to the consumption of A species, depends of the temperature and composition. For many
irreversible reactions it is written as the product of a reaction constant k A , and a function of the
concentration of the species involved. Reaction rate is referred to the reactant.

The Swedish chemist Svante Arrhenius (1859-1927) was the first to state that the reaction rate,
k A has a dependency on temperature. This can be calculated with the following equation,
known as the Arrhenius equation (Fogler, 2011):

Where:
A= pre-exponential factor or frequency factor
k A (T) = AeERT
E= Activation energy, J/mol
Equation 1
R=gas constant=8.314 J/mol*K
T=absolute temperature, K
From the collision theory, the pre exponential factor A or A0 , is proportional to the number of
collisions that can lead to a reaction. A catalyst increases the rate and the rate constant by
increasing A by providing sites for the reaction, and/or decreasing the activation energy. This
increases the fraction of collisions resulting in the reaction (Fogler, 2011).
 47

For atoms involved in a reaction an energy is needed to distort or stretch their bonds so that
they can break and form new bonds, and also to overcome the steric and electron repulsive
forces as they come close together (Fogler, 2011). This energy is the minimum increase in
potential energy of the reactants that have to be provided to transform into products, this is
called activation energy, E. This value is obtained by experimentation, measuring the reaction
rate at several temperatures. Applying natural logarithm to Equation 1, we obtain:

1
= Equation 2
1
The activation energy now can be obtain from the plot of ln k A vs T, this plot is called Arrhenius

plot, Figure 2-20. The graph is a semi log where the y axis is in log scale. High activation energy
refers to high sensitivity of the reaction to temperature. It means that an increase of a few
degrees of temperature, will increase the reaction rate greatly and vice versa.

Figure 2-20 Activation energy intensity.

For hydrodesulfurization, a first order reaction is acceptable for high oils, but for residue a
series of first order reactions is the most acceptable mechanism. These lead to a second order
effect. Various residua analysis gives a range of 27-35 kcal/mol or 6-10 kJ/mol of activation
energy (Speight, 1981).

2.9.3. Kinetic modelling

Hydroprocesses are the secondary refinery process in importance, where large compounds are
cracked to form low molecular weight compounds. When this reactions take place in a
 48

hydrogen and catalyst environment, other reactions, such as hydrodesulphurization,

hydrodemetallization, can occur simultaneously.

Modeling kinetic reactions is required for effective process control and simulation of reaction
vessels in chemical engineering. In the case of reservoir crude oil upgrading, process control is
indispensable, in order to capture the advantages of quality, exhothermicity, dilution (heavy
fractions upgrading), and to secure no coke production or oil instability. Several approaches for
kinetic modeling of heavy hydrocarbon processing have been published. Some considering each
compound and all possible reactions and partitioning the species into few equivalent classes
called lumps.

Several kinetic reviews have been reported in literature for hydrocracking processes, but very
few kinetics models have been developed. The most recent review (Ancheyta, Sanchez, &
Rodriguez, 2005) classified the models in 1) lumping techniques, 2) based on continuous
mixtures, and 3) structured oriented lumping and single event models.

The models were evaluated with experimental data from literature. Four models representing
each of the classifications were chosen. The kinetic parameters for each model were calculated
using a non-linear regression procedure based on the Levenberg-Marquardt method, which
minimize the objective function based on the sum of errors between experimental and
calculated product yields.

The results are that, for lump models, their disadvantage is their simplicity and dependency of
the kinetic parameters on feed properties, and the use of invariant distillation ranges.
Continuous mixtures, overcome some of those disadvantages, the dependency on feed
properties is still present. Structured detail models are more detailed, expressing the chemical
transformation of molecular structure. Dependency of rate parameters on feed properties are
still present. Due to complexity of the feedstock, lumping models are the most reliable and easy
to apply.

The proposed kinetic model used for ISU process, developed by the CBU group at the University
of Calgary, is based on the studies performed by Sergio Sanchez in the Instituto Mexicano del
 49

Petroleo (Sanchez, Rodriguez, & Ancheyta, 2005). This model is adequate for the moderate
hydrocracking of heavy oils, and model relies on the lumping model. It has 5 lumps:

Vacuum Residue unconverted (VR)

Vacuum Gas Oil (VGO)
Distillates
Naphtha
Gases

Figure 2-21 Kinetic model diagram (Sanchez, Rodriguez, & Ancheyta, 2005).

For this lumps ten kinetic parameters k i are calculated, and for every reaction corresponds a
kinetic expression ri , in function of a product yield yi , and kinetic constants. The only
assumption is that all reactions are first order. The Figure 2-21 present the diagram of the
kinetic model, where the VR component is the initial reactant where the catalyst will act.
Residue converts to VGO, Distillates, Naphtha, and Gases with the kinetic constants from 1 to 4.
Followed by the conversion of VGO to Distillates, naphtha and gases with the kinetic constants
from 5 to 7, and so on.

The mathematical model have to solve a matrix with the following components:

Vacuum residue (VR):

rR = (k1 + k 2 + k 3 + k 4 )yR

Vacuum Gas Oil (VGO):

 50

rVGO = k1 yR (k 5 + k 6 + k 7 )yVGO

Distillates:

rD = k 2 yR + k 5 yVGO (k 8 + k 9 )yD

Naphtha

rN = k 3 yR + k 6 yVGO + k 8 yD k10 yN

Gases

rG = k 4 yR + k 7 yVGO + k 9 yD + k10 yN

A lab experiment must be set considering several conditions of temperature and residence
times. At least three temperature points must be granted. This experimental set up will be
explained later. From the samples taken a mass balance is obtained with the five lumps that the
model requires. The yield at different temperature and residence times will be the input of the
matrix.

The expected behavior is represented in Figure 2-22, where the VR yield decrease lineally with
respect to conversion. The behavior of VGO is to increase yield up to a maximum percentage,
where it decreases due to the conversion to lighter components. Distillates, naphtha and gases
have an increasing trend because they are the sub product of the reaction.

Figure 2-22 Kinetic model lumps upgrading.

 51

Once the yield is obtained and the matrix is filled, it can be solved by iterative methods solving
the differential equation. The best set of kinetic parameters at every temperature for each
reaction is found, applying an objective function based on the addition of the square errors
between the experimental composition and the calculated. It can be solved using least-squares
criterion with a nonlinear regression procedure.

To corroborate that the calculation has a good approach to the experimental data, a 45 degree
plot helps to ensure that the values are correct. On the other hand, the Arrhenius plot must be
presented with the kinetic parameters obtained from each temperature, looking for the
linearity of the trend.

An MSc student of the CBU Group developed a spreadsheet that automates the calculations,
making this process easier. That procedure is applied in this thesis (Da Silva, 2014).
 52

3. CHAPTER THREE: HYDROGEN ADDITION PROCESSES

Hydrogen addition processes in the ISU technology allows the manipulation of the crude oil
molecular composition, breaking bonds and adding hydrogen to those large molecular chains.
This hydrogen addition increase content in the molecule and slightly decreases density of the
fluid. In particular, makes these molecules more reactive or crackable. Other reactions
eliminate contaminants and improve quality of the fluid.

Hydrogen addition reactions are summarize in Table 3-1. The main characteristic is that the
heavier the feedstock, the higher the severity of the conditions for treatment (Vasquez, 2007).

Table 3-1 Hydroprocess reaction characteristics (Vasquez, 2007).

Operating
Process Feed Products Remarks
Conditions
Hydrogenates the feed with
72-2,320 psi
Same as 10% or less hydrocraking.
Hydrotreating All cuts 260-400 C
feed Removes sulfur, nitrogen and
0.15-10 h-1
metals
Light gases
Naphtha 1,450-2,900 psi Changes the skeletal structure
Medium and
Hydrocracking Kerosene 350-430 C of the feed, by breaking C-C
heavy cuts
Diesel fuel 0.22 h-1 bonds
Lube oils
Same as hydrocracking, but at
725-1,160 psi
Mild Medium and Kerosene lower severity
350-440 C
Hydrocraking heavy cuts Diesel oil Hydrocracks 40% or less of the
0.2-2 h-1
feed

For ISU, a mild hydrocracking is pursued, non severe conditions are targeted in order to get
mild conversions. The expectation is to convert the residue injected into original oil properties.

3.1. Thermal cracking

Thermal cracking is the first step of upgrading processes. There is a complimentary relationship
between catalytic hydrogenation and thermal cracking and condensation reactions. Most of the
residue conversion into lighter cuts is a result of this high temperature process. This mechanism
happens in the absence of catalyst through a free radical chain mechanism which, results in a
light fraction cut formation by secondary cracking of the radicals that were produced. Thermal
 53

processes lead to coke precursor formation by condensation of heavy radicals. There is the
point where catalyst and hydrogen are needed in order to intercept these radicals, saturating
them with hydrogen, reducing the tendency to condense and form coke.

The mechanism is the splitting of the carbon-carbon bonds, causing cracking. This includes
aliphatic and naphthenic ring bonds. Monoaromatic are more stable and are less thermally
crackable, as well as, resins and asphaltenes. Bond energies can provide insight of the difficulty
or amount of energy needed to apply and break certain bonds. Table 3-2 shows some examples
(Gray, 2015).

Table 3-2 Bond dissociation energies (Gray, 2015).

Energy
Chemical bond
(kJ/mol)
C-C (aliphatic) 344
C-H (primary) 411
C-H (secondary) 398
C-H (aromatic) 464
C-S 307
C-N 342
C-O 344

To achieve enough reaction rates to break a C-C bond, without catalyst, the temperature
required is 420 C. The use of metals as catalyst promote the reactions at lower temperatures
(Gray, 2015). Catalytic hydrogenation of aromatic rings into naphthenic, destabilizes carbon-
carbon bonds, making them easier to thermally break.

The key breaking step of reaction is called scission. The product generated depends on the
location of the radicle center. Additional reactions result from radical recombination or
rearrangement, due to hydrogen addition, of the decomposition of partially hydrogenated
compounds that donate hydrogen to unstable compounds during thermal cracking. In residue
conversion at thermal cracking in the presence of hydrogen and absence of catalyst,
 54

hydrogenolysis reactions (adding hydrogen) are only observed in the vapour phase (Gray,
2015).

Due to the C-S weak bond, thermal reactions on sulfur are favorable. Disulfide bonds (RS-SR)
are weaker than sulfides (R-S), which are the first chain to break serving as initiators for free
radical chain reaction. A 30% of sulfur conversion in bitumen without catalyst can be achieve,
increasing H2S. Nitrogen compounds are not affected by thermal cracking. Carboxylic acids are
reactive at temperatures higher than 250 C giving products such as carbon dioxide and
monoxide (Gray, 2015).

Table 3-3 shows some values of activation energies in thermal cracking reactions for different
type of feeds, from medium to vacuum residue, ranging from 188 to 23 kJ/mol. Higher values
correspond to of C-C bond cracking. Certain compensation exist in lower activation energies
that have higher k and pre-exponential factors (Gray, 2015).

Table 3-3 Thermal cracking activation energies (Gray, 2015).

Ln A Ea
Feed
s-1 kJ/mol
Medium crude oil 25API 31.27 224.3
Cold Lake bitumen 30.48 212.8
Atmospheric residue - 209.5
Athabasca VR (524-650 C) 25.3 188
Athabasca VR (650 C+) 32.2 230

3.2. Hydrocracking
The first approach of these reactions are based on refinery concepts, where it is mostly applied.
This process is classified as a destructive hydrogenation. The carbon-carbon bonds are broken
with a subsequent hydrogenation of those bonds; the result is a production of saturated lower
boiling point products. It is a combination of cracking, hydrogenation, isomerization, and
treating operations, where nitrogen, sulfur, and oxygen can be completely eliminated,
depending on the severity of the process (Speight, 1981). The practice uses catalyst and
 55

hydrogen. This is a thermal process that can occur at >350 C, where cracking reactions happen,
followed by the hydrogenation of those ends. The pressure can be in the range of 100 to 2,000
psi, the result is a change in the quality of the product. The diversity of products depends on
the catalyst and the conditions employed (Ancheyta & Speight, 2007).

This process is the first of the two main reactions families for petroleum transformation. It can
be applied to a wide range of feedstock, from light, medium and heavy compounds, obtaining
lighter products from each stream. Two types of process are distinguish: mild and conventional
hydrocracking. The former results in low conversions 20-40%, at low operation pressure (700-
1,160 psi), while conventional allows high conversions (70-100%) at higher pressures (1,450-
2,900 psi). The same reactions are observed in both processes, the products and quality are
different, being the conventional one that allows significant distillate products. Conventional
process is the only one capable of obtaining 100 % conversion. Mild, obtains moderate quality
and yields of medium and light distillates, with low conversions, due to catalyst, no coke
formation is observed (Leprince, 2001).

The use of catalyst reduces the temperature of the reactions from 500 C to 350 C, under
lower pressures, and increases the medium distillate cuts quality compared to a catalytic
cracking without hydrogen (Leprince, 2001).

Depending on the type of oil, naphthenic, aromatic or polyaromatic, this process has different
effects. For naphthenic hydrocarbons, is mainly of ring scission, followed by saturation of each
cracked end. All the carbon-carbon bonds are attacked. Aromatics at mild conditions are
resistant to hydrogenation. At more severe conditions the main reactions are, conversion of the
aromatic to naphthenic rings and scission within the alkyl side chain. Naphthenic are converted
to paraffins. For poly aromatics, the process is stepwise. One ring is saturated and opened at a
time, followed by the next ring, and so on (Ancheyta & Speight, 2007).

There can be three main types of reaction in hydrocracking processes, depending in the carbon-
carbon bond position in the molecular structure, these are: (Leprince, 2001)
 56

Simple hydrocracking: a carbon-carbon bond in a chain is cracked:

Hydrodealkylation: a carbon-carbon bond adjacent to a ring is cracked:

Ring opening: a carbon-carbon bond in a ring

The process works at temperatures under 420 C. The mechanism is of the carbocation type,
involving the catalysts dehydrogenating function and its acid function, with an intermediate
carbocation formation followed by its splitting after arrangement. In the end, resulting in a
highly branched product with a strong tendency of forming a more stable carbocation. The
mechanism is as follows, Figure 3-1:

Figure 3-1 Mechanism of hydrocracking reaction.

 57

1. Dehydrogenation of the paraffins (n-p) to n-olefins (n-o) on metallic sites.

1. (m) Migration of gaseous phase n-o from metallic site (M) to acid sites (A).
2. Adsorption of n-o on acid sites as carbocations.
3. Isomerization of carbocations in the acid sites.
4. Desorption of isomerized carbocations as iso-olefins (i-o) with loss of a proton.
4. (m) Migration of i-o to metallic site.
5. Cracking of carbocation giving a paraffin and an olefin
6. Hydrogenation of the olefin formed (iso) on the metallic site to paraffin.

3.3. Hydrotreating
This process is the second of the main reactions for hydrogen addition methods and can be
applied to all the range of feedstock, from light to heavy compounds. It is a non-destructive
mild processing condition reaction (Speight, 1981). This process is the most common in
refineries. The main objective is to improve the products eliminating contaminants like sulphur,
nitrogen, oxygen and metals, and improving its quality (Leprince, 2001).

Reactions with hydrogen and catalyst are used to transform heteroatomic compounds present
in the oil, resulting in saturated hydrocarbons eliminating sulfur, oxygen, and nitrogen forming
H2S, H2O and NH3, as products (Leprince, 2001).

Evaluating quality of the oil and the products from it, the higher the amount of hydrogen
content the better quality the oil. For this reason, refineries are focused in this type of
processes, and as a key factor for ISU technology. The use of catalyst and pressure make it
possible for hydrogenation at lower temperatures. If the process reaches more than 500 C,
dehydrogenation begins (Ancheyta & Speight, 2007).

Upgrading processes are based on two main factors, in chemical reactions terms. The first one
is hydrogenolysis, which refers to the elimination of elements such as sulfur, nitrogen and
metals. Those components are contaminants in the oil. The second one is residue conversion to
lighter fractions (vacuum residue > vacuum gasoil > distillates > naphtha > gases). Catalyst can
promote one or more of those processes depending on the system and operation conditions.
The most known are: (Leprince, 2001)
 58

Hydrodesulfurization (HDS).
Hydrometallization (HDM).
Hydronitrogenation (HDN).
Conradson carbon reduction (HDCC).
Asphaltene reduction (HDA).
Vacuum residue conversion (CONV).

Hydroprocessing reactions are of thermal and catalytic nature, with a close relationship
between them, they are called thermos-catalytic. Catalytic reactions correspond to
contaminant elimination reactions, such as: HDS, HDM, etc. This reactions are exothermic.
Thermal reactions involving cracking and condensation reactions are endothermic. The
combination of these reactions lead to a residue hydroconversion, which is an exothermic
reaction, the heat of reaction is in estimated ranges of 34-42 kJ per mol of hydrogen consumed
(Leprince, 2001)

This process involves, as main reactions: vacuum residue conversion (VRC) and
hidrodesulfurization (HDS), and the catalyst used mainly promotes these two reactions. The
aromatic rings and heterocyclic compounds are cracked and due to the hydrogen addition, are
hydrogenated and condensed (Leprince, 2001). These processes are part of the conversion of
the heavy fractions to lighter products with slightly modified molecular weight and lower
boiling point yields.

The cracking of the VR is consequence of the thermal energy applied to the fluid, which are at
very high temperatures. In our process this reaches 350 C, in surface refineries it can go up to
600 C. Cracking is a thermal process. No catalyst is needed or hydrogen addition, but if it is not
limited it leads to coke formation and its precipitation, which can plug the media where the
fluid flows (Leprince, 2001). For this reason catalyst is used to promote the reduction of coke
formation by interrelating hydrogenation, thermal cracking and condensation reactions.

The catalyst used for this ISU technique is solid, suspended in the liquid phase which in our case
is vacuum residue, but it can be another viscous fluid to keep the particles dispersed. These
dispersed solid catalysts are used due to their low capacity of agglomeration and deposition.
 59

When it is well dispersed and when the conditions are reached, it activates and works in the
volume where it is contained, inhibiting the condensation by capturing the radicals formed
when the thermal cracking processes and conversion is in progress (Leprince, 2001).

3.3.1. Hydrodesulphurization (HDS)

This reaction can be achieved with a thermal, chemical or hydrodesulfurization method. We will
focus on the latter. It is a catalytic process where a feedstock is conducted through a catalyst
bed at elevated temperature with hydrogen, converting the organic sulfur in to hydrogen
sulfide. This process can be classified as non-destructive, if it is applied to light crude oil. It is
destructive if the feedstock is a heavy oil or residue. For the latter, hydrocracking is desirable to
be promoted as the primary part of the desulfurization process (Speight, 1981).

This process involves sulfur content removal of the feed producing H2S as a product and
desulfurized products. In the crude oil, sulfur is found in the residue or heavy cuts. There are
two types: sulfide and thiophenic. The former is found in the asphaltenes, they can be
decomposed catalytically, but also be dissociated thermally due to the low energy of the carbon
sulfur bounds (320 kJ/mol). The latter, are only catalytically decomposed, creating parallel
reactions with or without the hydrogenation step, followed by hydrogenolysis of the carbon-
sulfur bonds (Leprince, 2001).

The catalyst use for HDS reactions are the ones that are active in their sulfide forms.
Molybdenum (alloyed with nickel or cobalt) and tungsten the most active ones. Two
mechanism observed for HDS are: hydrogenation of the aromatic rings followed by reaction of
the sulfur and direct catalytic removal of the sulfur atom in one step (Gray, 2015).

3.3.2. Hydrodemetalization (HDM)

For surface refining, this process is critical for avoiding corrosion. This are found in residue, in
the resin and Asphaltene fractions, in the form of soluble organometallic complexes such as:
porphyrin type, consisting in Ni or V atom bonded to nitrogen atoms with four heterocyclic
structures. A thermo-catalytic reaction is promoted by the partial decomposition of the
Asphaltene. The products obtained are metal sulfides (Leprince, 2001).
 60

3.3.3. Hydrodenitrogenation (HDN)

Nitrogen is in the residue fraction as a non-basic heterocyclic structure (pyrrole) and as a basic
heterocyclic (pyridine). The latter is less reactive than the former but it can be easily adsorbed
on the catalyst. In surface refining, the active time that the catalyst has is important. HDN is a
catalytic reaction. It requires a prior aromatic ring hydrogenation followed by hydrogenolysis of
the carbon-nitrogen bond (Leprince, 2001).

3.3.4. Hydrogenation of complex structures

This is an intermediate step that is important for several reactions, such as HDM and HDN,
which is an initial reaction step. Also, this promotes the HDS and decyclization reactions. These
step capture the free radicals formed by thermal cracking and affect the saturation of olefins. It
is important for avoiding coke during the reaction time (Leprince, 2001).
 61

4. CHAPTER FOUR: THERMAL ASPECTS

Thermal processes are applied in all the range of oil types, from light to heavy and in permeable
and very tight reservoirs. The acting mechanism are the same for all. It is only differentiated by
the amount of a particular mechanism effect in each reservoir. Figure 4-1 shows a diagram of
the qualitative role that a certain mechanism has for a heavy and light oil, when the
displacement fluid is hot water or steam. For light oil, thermal expansion and vaporization are
the predominant mechanism. For heavy oil, viscosity reduction has the highest effect, followed
by wettability and thermal expansion.

As an example, for high viscosity reservoirs, steam flooding is used to increase the oil
production by viscosity reduction, where oil gravity drainage gets into effect. For light oils, the
main objective is to reduce the residual oil saturation. For fractured and heterogeneous
reservoirs, thermal conduction allows that thermal heat diffusion sweeps through areas that
are not in contact by the hot fluid injected. Thermal expansion, and vaporization are the
important mechanism of recovery (Hoffman, 2001).

Figure 4-1 Influence of different production mechanism as a function of the oil type (Hoffman,
2001).
 62

As temperature increases, interfacial tension between fluids decreases, at thermodynamic

equilibrium. For light oils, the rock is generally water wet. At increased temperatures, the
thickness of the water film adsorbed changes. These variations plus capillary forces contribute
to the decrease of residual oil saturation. If the rock is oil wet, only the interfacial tension and
viscosities have relevance, which is the case of heavy oils.

For naturally fractured reservoirs, the increase in temperature has an important impact. The
combined influence of thermal expansion and the formation of a vapor phase inside the matrix,
allow the expulsion of oil, even in the absence of imbibition. The formation of emulsions (oil
and water) could have additional recovery (Burger, Sourieau, & Combarnous, 1985).

A resume list of mechanism by several authors contain (Hoffman, 2001):

Viscosity reduction.
Vaporization (distillation).
Gas (steam drive).
Thermal Expansion.
Relative permeability and capillary pressure variation.
Gravity segregation.

The application of heat in the reservoir affects the geochemical composition of mineral and
organic compounds of the oil contained in the reservoir, as well as the formation media. All
phases are affected, changing the composition of gas, oil and produced water. The results can
make toxic products, but also lead to oil upgrading, formation plugging, or mineralogical
changes of the rock composition (Speight, 1981).

4.1. Heat applied to fluid

Crude oils with gravity smaller than 20 are considered heavy, extra heavy, bitumen and tar sand
oils. The main problem of producing these fluids to be produces is the very high viscosity that
avoids mobility, even at reservoir conditions. This leads to a very low recovery, lasting years to
obtain a recovery factor of at least 11 %.
 63

This type of oil has a small amount of gas in solution, and is not enough to be a production
mechanism. Applying energy by gas or water injection is not feasible due to the differences in
mobility. The injected fluids are more mobile, causing channeling (a fast breakthrough the
production wells).

These fluids are contained in very big reservoirs, becoming an attractive prospective reserve
that needs to be produced. For that reason several techniques have been developed in order to
increase the mobility of this type of fluid by viscosity reduction.

Viscosity reduction is feasible by the use of the injection of miscible gas. Eventually becoming
inefficient due to the low solubility and mobility differences. Heat application is the most
effective process for viscosity reduction, due to the strong dependency of the viscosity with
temperature.

The crude oil flow rate has three dimensionless parameters, independent among them (Prats,
1985), these are:

The ratio of gravity to applied pressure forces:

Equation 3

The ratio of capillary pressure forces to applied pressure forces

Equation 4

The ratio of applied pressure forces to viscous forces

Equation 5

k = Permeability of the reservoir

p = Pressure drop between injectors and producers

= Crude viscosity

L = Distance between injection and production wells

u= Volumetric flow velocity (Darcy velocity or volumetric flux)

 64

= Interfacial tension between crude and water

c = Wetting contact angle

g = Acceleration constant due to gravity

= Density difference between water and crude

= Formation dip

For the gravity to pressure ratio, the parameter that can be affected due to the crude oil is the
difference in density between the oil and the displacement fluid. For capillary forces ratio,
capillary forces attach the oil to the rock system, so interfacial tension has to be reduce to near
zero, leading to dissolved crude oil in the injected fluid. For example, in water or chemical
flooding, the oil dissolved in water or emulsify, reduces the viscosity of the displacement fluid
compared to the in-situ oil.

For the viscous ratio, viscosity is the only property that can be changed, and this will change the
volumetric flow rate. In order to reduce viscosity two physical ways can be used, increasing
temperature and mixing with a solvent or lower viscosity fluid. Another form to accomplish
viscosity reduction is by thermal decomposition of the oil, for example: visbreaking, thermal
cracking, or pyrolysis. The latter destroy the oil into gases, with a carbonaceous product or
coke, and medium products with lower density than the original oil. Visbreaking is a mild
pyrolysis, no significant change is observed. For this reason viscosity reduction using thermal
processes is the most viable method applied for production of this type of reservoir (Prats,
1985).

Having a fluid injected to the reservoir different from the in-situ, generates a non-uniform
mixture where temperature and concentration gradients can induce mass fluxes. These fluxes
need a chemical potential gradient in order for diffusion to happen (Burger, Sourieau, &
Combarnous, 1985). The following equation is derived by Ficks law, that for a given mixture the
rate of mass flow of a J component due to the concentration gradient alone is:

= = Equation 6

 65

Where, and J are the density of the fluid mixture and the mass concentration of J,
respectively. wJ is the mass fraction of J and D is the coefficient of molecular diffusion of J in the
mixture. D, depends on temperature, pressure and the nature of the diffusing constituents. The
effect of pure diffusion is increased by turbulent flow of the mixture (Burger, Sourieau, &
Combarnous, 1985).

The EOR experience is concentrated in steam injection, which is the most used process in heavy
oil reservoirs. Laboratory studies indicate that at temperatures in the range of 200 350 C
during long period of time, chemical reactions will form pollutants such as H2S and CO2. The
formation water is a key factor for the formation of these components, in the absence of water
they forme at higher temperatures. Aqua-thermolysis of sulfur is an important source of H2S,
and hydrolysis produces CO2. H2S can react with a calcium carbonate matrix (CaCO3) resulting in
calcium sulfide and carbonic acid, eliminating H2S (Speight, 1981).

Injection fluids to the reservoir conveys to heat conduction carried by the fluid. In order to
calculate the thermal conductivity, k, in W/(m*k) at a certain temperature (T) in C, is
represented by Equation 7 (Gray, 2015).

= 0.1289 1.3 104 Equation 7

Thermal conductivity increases with the boiling point of crude oil or fluid use for injection, for
that reason the use of vacuum residue in ISU process is convenient. For a defined cut boiling
point temperature a different correlation can be used, expressed in Equation 8, where Tb
correspond to the average boiling point in K, and T the temperature of the fluid (Gray, 2015).

= 0.2904 (2.01 102 1.98 105 ) Equation 8

Some values for comparison in W/(m*K), are: bitumen, asphalt materials (0.16), and coke (0.4-
0.9).

As it was mentioned before, vacuum residue at room conditions is in a solid state. It needs to
be heated to 150 C in order to melt it, due to its complexity and heavy components.
Asphaltenes are also considered as a solid due to their precipitation from a paraffinic solvent,
but also have a melting point. For example, Maya VR melts at 250 C (Gray, 2015).
 66

For several calculations heat capacity, cp , is needed, a correlation provided by the API for
several heavy oils and bitumen, where a, b, and c constants are provided by the API Technical
book (API, 1983). Equation 9, represents the heat capacity in J/(g*K), where temperature (T) is
in kelvin (Gray, 2015).

= + + 2 Equation 9

4.2. Heat applied to porous media

Heat applied in a formation can travel with several mechanisms: conduction and convection, a
third one that is the combination of both, and radiation. The former will always appear
whenever a temperature gradient exist in the formation (non-isothermal). Conduction is based
on the molecular collision from the higher to the lower temperature region through a non
flowing material (motionless), such as a reservoir formation rock (Prats, 1985). This mechanism
is very slow, for example: the conduction rate through 1 square foot of rock surface is only 1
Btu/hr for a gradient of 1 F/ft. On the other hand for short distances and large areas this could
be effective (Szasz & Thomas, 1965). The mathematical expression for conduction is based on
Fouriers law is:

T
ux = x Equation 10

Where ux is the conductive heat flux in the x direction; , is the thermal conductivity of the
T
material, negative sign is due to, transfer, is in the decreasing temperature, and x is the

temperature gradient in the x direction. For y and z the directions are similar in the expression
(Prats, 1985). This equation applies for a steady state condition, but also can describe a
transient regime (Burger, Sourieau, & Combarnous, 1985).

The second mechanism is convection, this can be carried by a fluid with sensible or latent heat,
or both is faster compared to conduction, due to the carrier velocity being faster than the heat
transfer mechanism. The reason is that the heat exchange between the fluid and the formation
is fast, therefor the mass velocity of the carrier is higher (Szasz & Thomas, 1965).

The associated convective heat flux, parallel to the fluid flow, of the volumetric flux of a heated
fluid flowing in the media is mathematically described as:
 67

= ( ) Equation 11

Figure 4-2 shows and schematic that resembles the difference in having conduction heat
transfer, and not. If only convection exist, the only portion heated would be the region in the
pattern fill rectangle. On the other hand, if conduction exist, the temperature will propagate
more in the formation, contacting more volume creating a decreasing high temperature profile
(dashed line) until it reaches the reservoir temperature.

Figure 4-2 Temperature profile for convection and convection and conduction mechanism.
(Prats, 1985).

The radiation mechanism is a process in which heat is transfer by electromagnetic waves, this
transfer from a heated surface per unit of surface are is given by the Stefan-Boltzmann law, and
it is described as:

= (460 + )4 Equation 12

Where represents the Stefan-Boltzman constant, T the temperature, and the emissivity of
the surface area depending on the nature of the material. Thermal radiation through rock is
negligible, for this reason it is not taken into account as a heat transfer mechanism in porous
media (Prats, 1985).

Fluid and heat flow direction can be concurrent, countercurrent or perpendicular to each other.
Cocurrent flow, the carrier fluid drives thermal and mechanical energy, they cant be
 68

independently controlled or optimized. Countercurrent permits independent control over the

injected fluid, however, heat transport is inefficient and difficult because it relies in conduction
mechanism. And, the produced fluid carries sensible heat by convection in the opposite
direction.

For heat and mass transport in perpendicular direction to each other, mass and heat flow are
independent, and conduction is the principal heat transport mechanism in the reservoir, one
example is the cyclic steam stimulation.

The heating phase and the fluid driving phase does not need to occur simultaneously, it can be
sequential or cyclic, this makes the process efficient (Szasz & Thomas, 1965).

H2S formation due to oil decomposition and hydrogenation, can react with the matrix if it
contents calcium carbonate. Some studies have shown that the presence of mineral
components in the rock matrix contribute to the elimination of the asphaltene, such as sand
and kaolite.

The use of steam in a reservoir containing clay can lead to swelling, due to the high cation
exchange capacity of the clay and affinity to water, reducing permeability and porosity. It has
been observed that some constituents of heavy oils are strongly absorbed on the clays. This
phenomena helps as a shield avoiding water and clay interaction. Also, mortmorillonite
formation in a rock that contains clay, leads to permeability reduction due to temperature, pH,
salts in the water and the influence of other minerals in the water.

Thermal decomposition of rock components occurs at lower temperatures in a steam injection

environment, for instance, limestone release a significant CO2 production after a long term
exposure at 300 C and 1230 psi (Speight, 1981).

4.3. Thermodynamics of thermal cracking

At high temperatures thermal reactions occur in a spontaneous manner in organic compounds,
no catalyst is needed. Reactions and conversion are possible. An approach is given by Gibbs free
energy of reaction, where no dependence of the rate of reactions simplify the analysis at
certain range of temperatures and pressure.
 69

4.3.1. Gibbs free energy

The chemical reactions have two significant key features, the variations in the enthalpy of the
mixture and the Gibb free enthalpy. These characterize the reactions by the change in the state
function of the mixture

Gibbs free energy in thermodynamics, originally called available energy, is the maximum
amount of non-expansion work that can be extracted from a closed system. This maximum can
be attained only in a completely reversible process. This potential measures the process-
initiating work obtainable from an isothermal, isobaric thermodynamic system.

Gibbs energy is also the chemical potential that is minimized when a system reaches
equilibrium at constant pressure and temperature. As such, it is a convenient criterion of
spontaneity for processes with constant pressure and temperature (Grimes, 2013).

This quantity determines if a certain reaction is spontaneous or not, mathematically this is

given by the following equation (Burger, Sourieau, & Combarnous, 1985):

= Equation 13

Where G is the free energy, H correspond to the enthalpy and S is the entropy. The sign
determines if the reaction is spontaneous (negative), not spontaneous (positive) and
equilibrium (equal).

Having the following reversible reaction:

b1 J1 + b2 J2 b3 J3 + b4 J4

At a certain temperature and pressure, the reactions involving the elements 1, 2, 3, 4 shift until
a thermodynamic equilibrium is reached. The equilibrium constants in molar concentrations are
given by:

(3 )3 (4 )4
= Equation 14
(1 )1 (2 )2

The equilibrium constant depends exponentially on the free enthalpy of reaction and the
absolute temperature, giving:
 70

= Equation 15

At certain temperature T, it becomes:

= = 3 3 + 4 4 1 1 2 2 Equation 16

Where GJj is the free enthalpy of formation of compound Jj at temperature T.

If the compound formation free enthalpy is positive, the compound should decompose, since
the equilibrium constant is in favor of the elements from which it is derived. This does not
always happen and only occurs when the reaction rate is high enough (Burger, Sourieau, &
Combarnous, 1985).

4.4. Thermodynamics of hydroprocessing

As it was mentioned before, hydrotreating, aromatic hydrogenation, and hydrocraking are all
exothermic reactions. Table 4-1shows approximated values for heat of reaction.

Table 4-1 heat of reaction value by type.

Average heat of reaction at

Reaction Type
400 C (kJ/mol)

-210
Aromatics hydrogenation

-42 to -50
Naphtenes hydrocracking

-46 to -58
Paraffins hydrocracking

High increases in temperature lead to deactivation of the catalyst due to coking. On

hydrotreating catalyst the exothermicity is at its maximum. On hydrocracking, exhotermicity is
lower.
 71

Hydrogenation reactions are promoted by an increase in the hydrogen pressure and decrease
in temperature. A rise in the temperature leads to an increase in the aromatics content. Deep
hydrogenation of aromatics requires high hydrogen pressure. The heavier the aromatic
compound, the larger the number of rings, the more the thermodynamic limit toward a low
temperature at certain hydrogen pressure.

4.5. Rock wettability

Injection of hot fluids in the reservoir respond to three mechanisms for heat transfer (Jenkins &
Aronofsky, 1954):

1. Energy transfer due to physical movement of the injected fluid.

2. Thermal conduction from the warmer to the colder portions of the system.
3. Convective transfer between the injected fluid and the original reservoir fluids and the
permeable reservoir rock.

The studies assume that the first two mechanisms are the dominant, being convective
accounted for the instantaneous thermal equilibrium between the injected fluid and the
reservoir fluid and rock. This depends on the injection velocity.

Once a thermal process is ongoing, the hot front passes through a reservoir section, several
changes are observed or can appear due to the high temperature swept. Changes in fluid
composition and rock mineralogy, some accelerated physical/chemical reactions and tend to
amend reservoir properties (Escrochi, Nabipour, Ayatollahi, & Mehranbod, 2008). These
changes are: crude oil in situ upgrading, mineral alteration, wettability alteration and changes
in petrophysical properties.

Most of the EOR processes have as a consequence wettability changes, thermal being one of
them. Any change in the wettability leads directly to a modification in the relative
permeabilities of the phase in a porous media, affecting the residual saturation. This dictates
the capillary properties of the rock (Anderson, 1986).

The change in wettability induced by thermal changes is that the hotter the system, the more
water wet the rock becomes (Bennion & Thomas, 1992). Sandstones become more oil wet,
 72

while most carbonates show a more water wet behavior at high temperatures (Rao, 1999).
Others concluded the same, the higher the temperature the more water wet the carbonate
rock becomes during thermal recovery processes (Al-Hadhrame & Blunt, 2000). Sandstones
wettability change to oil wet at high temperatures, but an increase of this temperature
restitutes the water wet property. Also, limestones have this behavior (Escrochi, Nabipour,
Ayatollahi, & Mehranbod, 2008).

Beside temperature, the adsorption of crude oil components can alter the wettability of rocks
exposed to crude oil from their original water wet condition to another state (Buckey, Liu, &
Monsterleet, 1998). One of the main reasons of wettability alterations lies in the effect of
electro kinetic properties of the interfaces, and precipitation of water wet calcium carbonate
(Rao, 1999). If the deposition of organic molecules could be reversible oil wet could pass to
water wet (Al-Hadhrame & Blunt, 2000). The migration recovery is slower than the wettability
alteration time.

Asphaltene molecules are the most important wettability agents in the organic deposits of the
crude oil (Buckey, Liu, & Monsterleet, 1998), which lead to a strong oil wet condition.

The mechanical strength of the carbonate rock may be significantly impacted by thermal
processes. It has been shown through experimental studies that in a fractured carbonate,
thermal shock improves the permeability. It extends the existing fractures, but it also shows the
deterioration of permeability in the matrix, damaging the pore network reducing connectivity,
decreasing matrix permeability significantly. It can be compensated with the viscosity reduction
and less heavy oil moving throughout (Zekri & Chalal, 2001).

Other studies indicate a 30% injectivity decrease caused by thermal closure of fractures
compared to cold injection. The permeability reduces by 30 75% due to heating from 20 to
240 C (Macaulay, Kraft, Hartemink, & Escovedo, 1995).

In general, carbonate reservoir are mixed wet oil wet. Positive zeta potential of carbonate
surfaces at a typical pH (7), presents of sufficient number of negatively charged asphaltenic
molecules in oil, and high capillary pressure during oil migration into the reservoirs, and often
render mixed wettability to the reservoir rocks.
 73

Waterflooding does not lead to a significant amount of oil recovery from the matrix porosity
because the capillary pressure curve is predominantly negative. However, many light oil
fractured carbonate reservoirs have been successfully water flooded. The spontaneous
imbibition of the driving fluid into the matrix results in expulsion of the oil from the matrix into
the fractures. The presence of sulfates in the injected water is cited as one of the reason for
change of wettability allowing spontaneous imbibition (Swapan, 2007).

The acid number appears to be a crucial wetting parameter, which often dictates the wetting
nature of the rock. The rock becomes more oil wet as the acid number increases. Heavy oils and
bitumen generally have higher acid numbers. Surface active components in the crude oil may
adhere to the solid surface. On heating this process can be reversed on the calcite surfaces. The
surface active agents desorb, leaving a water wet surface. There is a critical temperature where
this desorption starts.

The effect of temperature on recovery by spontaneous imbibition has been studied in oil wet
carbonate cores from Oman. At 50 C the core did not imbibe any water indicating oil wet
nature. When heated with steam to 240 C and 50 atm, the core imbibed significant amount of
water and the recovery was in the range of 27 to 35% (Al-Hadhrame & Blunt, 2000).

Decarboxylation at higher temperature reduces the acid number and make the rock water wet.
Calcium carbonate acts as a catalyst in the organic acid decomposition or decarboxylation
process. Other clays like montmorillonite are also known to be catalyst in the process (Zhang,
2005).

Quartz surface tend to become more oil wet, whereas calcite surface tends to become more
water wet as temperature is raised. Experimental work indicated that a wettability changes
from oil to water wet at a temperature range of 150 200 C (Rao, 1999).

Another set of experiment data under steamflood, shows that there is enough reason to accept
that there is a change of wettability in the steam condition. The rate of imbibition in the
experiment was significantly higher under steam condensate condition than a similar
temperature hot water system.
 74

Hot water (225 C) is able to gradually convert the sample to water wet behavior. Their
experiments showed unambiguously that hot water can imbibe in an originally oil wet
carbonate sample. They postulated that in the field the exposure times are longer and hence
the conversion to water wetness would be more effective (Motealleh, Bert-Rik, & Bruining,
2005).

The mechanisms of heavy oil production from fractured carbonates by CSS are: viscosity
reduction due to thermal effects, imbibition of hot water in the matrix, oil swelling, gravity
drainage and internal depletion gas drive (Swapan, 2007). Experiments with core plugs
indicated that at 150 C, thermal expansion resulted in minimal recovery, imbibition played a
major role in producing oil from the matrix in to the fracture network and depletion resulted in
further appreciable production. A similar test at 250 C yielded higher productions at the
beginning due to the evolution of gas. As the core plug is heated beyond the bubble point,
further production is obtained through imbibition. In the first experiment, 58% of the recovery
was due to imbibition. This indicates the importance of imbibition in this type of processes
(Swapan, 2007).

4.6. Enthalpy of Reaction

The second key feature is the enthalpy. This thermodynamic potential consists of the internal
energy of a system plus the product of the pressure and volume of the system. It is given by the
following equation:

= + Equation 17

Using an irreversible reaction:

b1 J1 + b2 J2 b3 J3 + b4 J4

The enthalpy of reaction H is the change in enthalpy involved in the chemical transformation
of reactants 1 and 2 at certain temperature:

= 3 3 + 4 4 1 1 2 2 Equation 18
 75

Where HJj is the formation enthalpy at certain temperature of one mole of reactant or

product Jj . If enthalpy is negative, it represents an exothermic reaction where the heat is

provided by the surroundings, and if it is positive, it corresponds to an endothermic reaction
where heat is absorbed form the medium (Burger, Sourieau, & Combarnous, 1985).
 76

5. CHAPTER FIVE: IN SITU UPGRADING TRHOUGH CATALYST INJECTION

An ISU process is a technique in development that may possibly be a new alternative for heavy
and extra-heavy oils recovery with bitumen focus, and nowadays it is at laboratory scale. This
technology gathers thermal, chemical and surface processes in one, using heat, chemical
reactions and the use of nano-catalyst with the theory of surface processes. The idea is to bring
processing to the oil, rather than bringing oil to a process (Weissman J. G., 1997).

All thermal processes that involve crude oil upgrading (converting heavy cuts to lighter ones)
have the disadvantage of generating more and denser asphaltenes and produce olefins. For
surface processes it requires extra treatment. Also, when used for reservoirs, the asphaltenes
can precipitate and generate plugs in the porous media, as well as in production pipes and
surface pipelines. The oil becomes unstable if the upgrading process is not well managed. The
use of ultra-dispersed catalyst is an option to produce an upgraded stable oil with enhanced
quality that is easy to transport through pipelines once it is produced (Pereira Almao, 2012).

Heating the crude oil leads to two main processes; removal of the heavy cut, where the
asphaltenes and contaminants (metals, H2S) are present, and the vaporization of the light ends,
leading to a crude oil with less contaminants making it lighter, and with low viscosity and a
higher API. Any excess heat favour coke formation and its precipitation leads to pore plugging
(Weissman J. G., 1997).

In order to avoid these major problems, the addition of a metallic catalyst and hydrogen
promote a hydrogenation process in the reservoir.

5.1.1. Process Description

Comparing ISUT with conventional refinery catalytic processing, the former involves a
geological formation that contains hydrocarbons. This reservoir will be used as a reactor,
implementing catalytic reactions, upgrading the oil, providing an improved crude oil to surface
processes, adding value to the heavy cheap in situ crude oil (Weissman J. G., 1997). In order to
obtain a successful process the following steps are needed:

Catalyst and hydrogen placement

 77

Mobilization of the reactant (heavy oil)

Generation of the conditions for the reactions take place
Reservoir properties

5.1.1.1. Catalyst placement

Catalyst placement can be performed under several schemes depending on the type of process
that is intended. These could be (Figure 5-1): 1) cased gravel packing, 2) open-hole or inner case
gravel packing, 3) proppant injection, and 4) water flooding. These methods have to ensure that
the oil will flow through the catalyst zone during the process. Mobilization and the generation
of appropriate conditions could be achieved using thermal EOR methods already known. The
properties of the reservoir have to have the ability to place the appropriate amount of catalyst
and the capability of containing the pressure and temperature conditions needed (Weissman J.
G., 1997). The CBU group has developed a new method using nano catalyst dispersed in hot
viscous fluid, which place the catalyst in the same way as method 4.

Figure 5-1 Different catalyst placement methods.

Some problems have to be evaluated before placing the catalyst. As time progresses with the
hydro processing reactions in the wellbore, contaminants and impurities may be retained in the
catalyst zone increasing pressure drop and decreasing the production rate and lowering the
catalyst activity. Using ISC can eliminate this problem and\or fracking continuously the catalyst
packed bed (Weissman J. G., 1997).

Another way to avoid plugging is using fluid phase catalyst precursors, well distributed to be
extended in the surroundings of the well. This leads to more volume contact for upgrading oil. If
 78

plugs are formed, they will be far from the well. A concern to take into account in the dispersed
catalyst method is the need to ensure oil/catalyst contacting. Using water based injection
solutions for the catalyst could lead to clay contact, reducing permeability (Weissman J. G.,
1997).

Other solutions such as: polymer gel or monomer solutions to seal water channeling, can
control metal distribution in the reservoir. A gas phase metal compound can also be injected as
a component in an ISC process with catalyst (Weissman J. G., 1997).

5.1.1.2. Process implementation

Additional to the thermal process, using heterogeneous catalyst in ultra-dispersed form, and
hydrogen injection to the formation (reservoir), is the methodology that conducts to
hydroprocessing process. This will take the surface processing to the in situ oil. Four models
have been proposed for this process:

For the referred methods, the catalyst must be placed in the well completion, as shown in
Figure 5-1. Components like heat and hydrogen must be injected in certain form, using EOR
processes already known.

Figure 5-2 Process implementation via injection zone under catalyst zone (Weissman J. G.,
1997).

The first way to implement the technology is shown in Figure 5-2, where a catalyst bed was
placed. It is a double completion. One pipe is used to inject, and the second to produce.
 79

Separated by a packer to avoid communication between the injection and production zone
downhole. The latter pipe is placed where the catalyst bed is located. Fluid will flow normally
through the catalyst zone, perforations, and can be produced. The former is placed deeper in
the injection zone. Heated fluids, such as: hydrogen, hydrogen precursors reactant, or
combustion sustaining gases (air or oxygen) are injected below the catalyst bed. This must be
communicated by a fractured zone or to ensure good vertical permeability in the formation,
this zone is created during completion. The combination of in situ oil, catalyst, hydrogen and
heat will result in an upgrading process using hydrogenation reactions (Weissman J. G., 1997).

The second method shown in Figure 5-3, is a schematic of combustion assisted downhole
upgrading. The catalyst bed is placed and located in the production well. The fluid will flow
from the injector to the producer well. Air and water are injected creating a combustion front,
generating the thermal drive, sustaining it with continuous air injection. Combustion generates
hydrogen and carbon monoxide which travel faster than the fluids upgraded by the front, as
well as steam. Once hydrogen, steam, and oil contact the catalyst bed, hydrogenation will
begin, upgrading even more of the oil already enhanced by the ISC process. The catalyst zone
could be heated as mention in method one. This process could be managed as huff and puff,
alternating the injection well to producer after a soak time.

Figure 5-3 ISC with catalyst placement zone in production zone (Weissman J. G., 1997).

The last two methods are patented by the CBU group at the University of Calgary (Canada
Patent No. CA 2810022, 2013), that is developing the ISU Technique. The third method is based
in the SAGD configuration, where two horizontal wells are drilled one over the other, injecting
 80

hot fluids in the upper well and produce in the lower one, Figure 5-4. A SAGD configuration is
not mandatory, it can be any (vertical, deviated, etc.). There are two modalities for this method,
thermal and catalytic.

Figure 5-4 Catalytic ISU chamber (Canada Patent No. CA 2810022, 2013).

For the thermal process or Residue Assisted In Situ Upgrading (RAISUP), the reservoir is
preheated with steam or hot fluid, this will begin to build a chamber of heat, growing with the
shape of the injection zone (well perforations and configuration). The important feature is to
communicate the injector to the producer well, mobilizing the heavy oil between wells. Due to
the formation properties, the chamber tends to grow more in the horizontal than in the vertical
axis, because most of the time vertical permeability is smaller than the horizontal.

The hot fluids intended for this method are vacuum residue, crude oil from other reservoir,
diluent and steam. For this study, vacuum residue is the injection fluid. This fluid is heated on
surface to 350 C, will promote thermal cracking and upgrading in the reservoir. The heavier the
fraction injected, the more reactive it is to heat, leading to upgrading reactions due to thermal
energy.

It is expected that due to the better thermal properties of the residue, conductive heat will be
higher compared to the steam but, convective heat will be lower, this will increase the speed of
the chamber formation laterally but, decrease its vertical expansion.

At 350 C, thermal upgrading reactions are promoted, viscosity reduction, lighter cuts, as well
as an increase in API gravity are expected. The original target is to reach an upgraded oil
 81

viscosity in the range of 300 cP and an API gravity between 14 and 16. These parameters make
the oil suitable for pumping without problems through the pipeline system.

For the catalytic process or Residue Assisted In Situ Catalytic Upgrading (RAISCUP) the addition
of dispersed nano-catalyst and hydrogen are used to promote upgrading reactions via
Hydroprocessing, such as: hydrocracking, followed by hydrotreating, with additional results in
hydrodesulphurization. These in addition to thermocraking reactions.

The same well configuration is used, and the chamber formation is identical. The hydrogen
addition reactions are the complimentary in this mode.

One of the main features of this process, is to ensure that the catalyst will be retained in the
formation, creating a catalytic zone. Where at certain concentration in the formation, the
injection of catalyst will be stopped injecting only residue that will pass through the catalytic
area activating the Hydroprocessing reactions upgrading the residue.

Diluents can be used in the first stages of the process in order to communicate both wells, once
the temperature and communication are reached, the diluent is cut from the process, as well as
the steam, if it is the case.

Figure 5-5 Huff and puff catalytic ISU (Canada Patent No. CA 2810022, 2013).

The last method uses catalyst too, it is named Nano-Catalytic In Situ Upgrading (n-CISU). The
variation in this is the use of a vertical well that can be operated in a Huff and puff modality
(Figure 5-5). Injection is followed by a soak time and production in continuous receptions until
the well productivity is very low, and continuous injection mode as a catalytic flooding (Figure
 82

5-6), with one injector well and with neighbor producers. The pattern has to be evaluated in a
further reservoir simulation model, and it will depend in the formation properties and lithology.

Figure 5-6 Catalytic ISU flooding.

For the huff and puff variant, the catalyst can be injected only in the first cycles until the target
concentration is reached. Hydrogen can be injected during the soak time, ensuring that the
reservoir has enough hydrogen to be incorporated to the hydrocarbon such that, the
Hydroprocessing gets its optimal results.

Figure 5-7 Three well pattern for catalytic ISU (Canada Patent No. CA 2810022, 2013).

In catalytic flooding, the pattern has to be analyzed by sensibility in a reservoir simulation

model. Figure 5-7, shows two configurations of wells, the first one is a two injector with one
producer pattern, where the catalyst zone will be among the injectors, pushing the residue
injected to be produced in one well. The second one is one injector with two producers, where
 83

the injector is located between the producer wells. Depending on the fields pattern already
drilled, both can be applicable.

5.1.1.3. Process mechanism

Once the catalyst is placed, the conditions have to be ensured in the reservoir or reaction zone.
Pressure is provided by the reservoir depending on its depth, production time, production
mechanism, and processes done before. In laboratory experiments the pressure is not a main
issue for the process. It has been proven from 500 to 1500 psi, as it will be shown in subsequent
chapters. Hydrogen is the most concerning element to be provided in this process. The first
option is the hydrogen direct injection. It requires a number of surface facilities depending in
the process step (pilot test, implementation, etc.), and its hazardous. Using combustion to
eliminate hydrogen injection, because hydrogen is a product of the process (Weissman J. G.,
1997).

Temperature can be increased in the reservoir by hot fluid or steam injection or fire flooding
(IS), downhole steam generation, combustion, and electromagnetic stimulation. The depth of
the reservoir is a limiting variable for the use of steam, deeper formations higher reservoir
pressures, this affects the saturation steam temperature (Weissman J. G., 1997).

Figure 5-8 Catalytic ISU mechanism in SAGD configuration (Canada Patent No. CA 2810022,
2013).

For the process in study, the injection of vacuum residue (>545 C), that is the heaviest cut of
the crude oil, will be taken in consideration. For the RAISCU process (Figure 5-8), the continuous
 84

injection of VR at 350 C (1) will keep the injection point at a steady temperature. While the oil
moves downwards to the production zone (3), reactions will take place with the mixture of
hydrogen, catalyst, oil, and the heat, creating the reaction zone (2). The VR with dispersed nano
catalyst mixed with hydrogen will be in touch with the formation and the oil in situ. Thermal
energy will reduce the viscosity and thermal cracking will begin in both fluids. The catalyst will
accelerate the hydrogen intake to the cracked molecules, avoiding the appearance of coke and
asphaltene precipitation. The upgraded oil will move faster to the production well (3).
Residence time for the injected fluid is low comparing to the huff and puff and catalytic
flooding. Mild conversions and upgrading are expected.

The remaining hydrogen, not consumed, the light cuts that are evaporated due to temperature,
acting as a solvent (5), and the temperature transferred by conduction will heat the
surroundings (4), this will generate a recovery zone that the oil with lower viscosity, and
thermally cracked will move to the reaction zone (6), and will be upgraded and produced by
gravity. These factors will lead to an incremental recovery. Heavy compounds of the in situ oil
will be detached from the rock. The chamber will have a certain volume that it will reach, until
the heat losses equals the temperature of the reservoir (7). This will be the zone of influence for
the process. The more we inject, the more we increase the chamber. The vertical properties of
the rock will make the chamber to grow more and faster in that direction and vice versa.

Figure 5-9 Catalytic ISU mechanism in huff and puff configuration (Canada Patent No. CA
2810022, 2013).
 85

For a vertical well in a huff and puff modality the process is the same (Figure 5-9). The only
variance is the production time. As it was mentioned before, an injection, soak and production
stage have to be performed. Where the soaking time will allow for the reactions a higher
residence time in the reservoir, obtaining higher conversions and higher API upgraded oil. It is
expected that the recovery zone has a upgraded volume due to the greater residence time.

In a continuous modality or catalytic flooding high residence times and a temperature profiles
are expected between the injection and the producer well. Figure 5-10 shows the behavior of
temperature, time, and conversion as function of well displacement. The VR is injected at 350
C in a continuous mode. The injection point will keep at the same temperature, but the heat
losses far from the injection point will be high. For that reason the temperature will decrease
until reservoir temperature.

Figure 5-10 Temperature, residence time, and conversion profiles at certain well displacement.

The cumulative residence time will reach a plateau. The light oil will move faster as the VR
becomes lighter toward the producer well. As well as the conversion, it will reach a plateau
where temperature will be to low. As a result, residence time will not have enough inference on
the oil. On the other hand, the catalyst is left behind, and the hydrogen migrates to the top of
the reservoir. Reactions will no longer be effective far from the well.

5.1.1.4. Operation procedure

Start up

1. The well must be preheated with steam or heated oil (VGO or reservoir oil heated at 300
C) by re-circulation. In the case of SAGD configuration, the inter-well (zone between
top and bottom well) temperature must reach a minimum of 160 C.
 86

2. Heated light oil, such as VGO is mixed with dispersed catalyst and hydrogen, begins to
be injected at 350 C, increasing the formation temperature. For the case of SAGD
configuration, the fluid will begin to circulate from the top injector to the low producer,
heating the interwell zone to 250 C.
3. Once the zone reaches 250 C, VGO is changed to crude oil mixed with catalyst and
hydrogen until it reaches 350 C. Hydrogen rate is increased to an excess condition for
the upgrading process.
4. Once the zone reaches 350 C, VR begins to be injected with dispersed catalyst and
hydrogen.

Steady State operations

1. VR injection continue at a steady rate, as well as the hydrogen. Hydrogen is expected to

be consumed at a rate of 40-60 sm3 of hydrogen per m3 of oil for a 50% conversion, to
maintain excess, a 3 times consumption rate injection is desired, being 150 sm 3 of
hydrogen per m3 of oil injected. It is also expected that hydrogen dissolve in the oil, 5 to
10% of the volume.
2. Conversion will be observed in the inter-well zone, very low percentage of it will be
achieved in the injector well.
3. Residence time will depend on rock properties, such as: porosity and permeability, and
flow rate.
4. Hydroprocessing reactions are exothermic, an increase in 40 C is expected, making a
balance between heat losses and reaction exothermicity
5. Compared with SAGD, heat losses are expected to be less than steam due to the
difference in latent heat, being hydrocarbons less than steam. Heat transfer by
conduction is less effective than convection. An insulation layer between the upgrading
zones an overburden will be form with the vapors of light gases and condensed water.
The chamber size will be smaller compared to SAGD, les surface area for heat transfer.
6. The catalyst injected is intended to be deposited in the formation, very low volume will
be needed.
 87

7. The produced fluid will be a mixture of upgraded oil mixed with not consumed hydrogen
and gases of reaction. This gases will help the oil to flow easier in the producer well, as a
gas lift method. A higher rate of liquids production than injected is expected.

This technology is for conventional reservoirs, sandstone formations at shallow depths, low
pressure and temperature that contain extra-heavy oil or bitumen, like the Canadian bitumen
(Athabasca). This work is intended to demonstrate that it can be applied in naturally fractured
reservoirs with heavy and extra heavy oil, with deeper, warmer and higher pressure than the
original proposal.

5.1.2. Surface Facilities

Figure 5-11 Surface facility units needed for catalytic ISU.

As a chemical process with surface refining theory, facilities must be implemented in order to
make this process feasible. Figure 5-11 shows a schematic diagram of the facilities required for
this technology. The diagram corresponds to a vertical well injector, but also can be applied to
any configuration needed. The variations will be the preheated fluids that will be injected, as
well the fluid used as a catalyst carrier. The process units are:

1. Desalter.
2. Atmospheric distillation.
3. Vacuum distillation.
 88

4. Catalyst mixer.
5. Hydrogen and steam generator.
6. Hydrogen compressor.
7. Tank for produced fluids.
8. Catalyst warehouse.

The process will consist in the following steps:

1. Once the oil is received, it must be flow through the desalting unit to eliminate salts and
other solids, as well as water content. Then sent to the tank for the process feed.
2. In order to start up the process, a steam generator unit will be needed or a heated light
oil in order to preheat the well and the reservoir. This oil can be contained in a tank and
heated with the distillation unit furnace. As it was mentioned, several steps for
increasing temperature are needed.
3. Once the desired temperature is reached, the light oil will be changed to VR. This cut
will be generated from the field crude oil contained in the tank and separated in the
atmospheric distillation unit, which work at 350 C. This unit will separate the gases on
the top, the upgraded oil in the middle, and the residue at the bottom. The gases can be
treated in a separated unit that can recycle the hydrogen not consumed in the process,
which can be reinjected. The upgraded oil is sent to the pipeline system to process.
4. The atmospheric residue is sent to the vacuum unit, which uses vacuum to reduce the
temperature to obtain the vacuum residue. The lighter cuts will be mixed with the
upgraded oil and send to process.
5. The vacuum residue is then mixed with the nano catalyst, dispersing the metals in the
residue phase, and the mixing procedure is described in (US Patent No. 7897537B2,
2011).
6. Hydrogen is added to the mixture and injected in the well to the formation.
7. The products will be received by the producer well and stored in the tank, then the
produced upgraded oil is sent to the distillation unit and the cycle is repeated.
 89

It is possible to recover the catalyst and the hydrogen that comes back in the upgraded
produced oil, and re injected it into the process again.

The injection fluid can come from the same well, the total field oil production contained in a
tank, refinery vacuum residue, or other fields oil. Some tests must be made to evaluate
compatibility, as well as reactivity of that fluid.

It is important to notice that the upgraded oil will tend to produce less heavy cuts. This means
that the vacuum residue component of the upgraded oil will be reduced in time, due to the
residence time that the heavy components are taking in the reservoir, lighter material will be
produced. In order to keep the process going, vacuum residue from the others sources must be
taken to the process facilities.

The catalyst will be injected until a desired volume is placed in the reservoir. Once this amount
is achieved, the catalyst mixture will be cut, and only vacuum residue with hydrogen will be
injected. The catalyst bed in the reservoir will keep the reactions running.

If the upgraded oil is still out of specification for pumping to other facilities, diluent can be used
in smaller scale compared to the original heavy oil of the reservoir.

Steam injection will be only needed at the start-up of the process if it is required, otherwise
crude oil from the reservoir can be used.

Historical work in the Catalyst for Bitumen Upgrading Group (CBUG) to develop the ISU
technology, previously described and patented is reviewed.

The work developed by Alejandro Vazquez (Vasquez, 2007) shows a methodology to prepare, in
a continuous manner, ultra-dispersed catalyst of Cobalt Molybdenum and Nickel tungsten
sulphides in water-oil emulsion for Hydroprocessing. Two laboratory units were built for
preparing the catalyst-oil fluid. The particles sizes range in the hundreds nanometers with
particles as small as 50 nm. His works proved that ultradispersed catalyst is more active than
the conventional supported catalyst for Hydroprocessing reactions. That the catalyst is resistant
to sulphur and it is active during the test, with no observed deactivation. Two units were built
for this purpose.
 90

John Thompson (Thompson, 2008), follows the evaluation of the molybdenum based
Ultradispersed nano-catalyst. The analysis of the catalyst shows the first insight of the viscosity
reduction and oil upgrading at certain conditions, as well as the deposition in a sand packed
reactor, in the injection zone, where agglomeration was found due to the high concentration of
metals, without contributing to the conversion.

The study of Ultradispersed catalyst preparation continued with Carola Contreras (Contreras,
2009), who developed a continuous flow set up to produce the nano-particles by thermal
decomposition of precursor transient emulsions using aqueous salts, reaching particles sizes of
27 nm and agglomerates ranging from 350 to 500 nm. For that reason a new methodology was
proposed, achieving 10 nm size particles to a few microns, whose catalytic activity is better due
to the increase of active size.

On 2011, Vanessa Rendon (Rendon, 2011) showed that cracking reactions are favoured in the
presence of H2, also that hydrogenation reactions are followed by cracking, these being
(hydrocracking and hydrotreating) exothermic reactions.

Her experiments were the first ones using a sand pack, simulating a permeable media
(sandstone) reservoir, injecting bitumen mixed with ultradispersed catalyst and H2 in a
continuous flow under upgrading conditions. Catalyst retentions were evaluated where Ni
particles are the first at the outlet of the reactor, before Mo and W. This could be related to
particle size. Smaller Ni particles propagated in the media faster. Catalyst was found in all the
sand pack, proving the propagation of the particles. Also a retention trend was observed, at
higher temperatures and longer residence times, retention percentage increases. But it was
notice that at lower temperatures, the reaction avoided particle agglomeration. The retention
is irreversible, no catalyst was found in the samples collected after the experiment.

Another evaluation done was the use of catalytic emulsion for catalyst placement, it was
demonstrated that it reduces permeability, more than ultradispersed catalyst injection. With
catalyst injection, reduction in the permeability was shown after several pore volumes of
bitumen.
 91

Also tested was a 90 std cm3 of H2/cm3 of bitumen, which is enough for Hydroprocessing
reactions. Temperature has the main effect in permanent viscosity reduction above 300 C,
with low residence times. At constant temperature and higher residence time (severe
condition) better upgrading was obtained.

A kinetic study was performed obtaining activation energies of 189 kJ/mol. The activity of the
catalyst that remains attached in the sand pack was tested. It was found that injecting bitumen
without catalyst produces similar conversion than the one obtained when the bitumen injected
has the catalyst dispersed in it.

Herbert Loria (Loria, Trujillo-Ferrer, Sosa-Stull, & Pereira-Almao, 2011), evaluated the kinetic
modeling for Athabasca bitumen Hydroprocessing experimentally in a plug flow reactor. He
used a five lump kinetic model developed by the Mexican Petroleum Institute (Sanchez,
Rodriguez, & Ancheyta, 2005) and matched the experimental data, predicting the conversion
and the yields at different temperature and residence time conditions. With this model kinetic
parameters like activation energies and pre-exponential factors are obtained.

In the next study done by Carmen Galarraga (Galarraga, 2011), bitumen upgrading was studied
in a batch reactor using Ni-W-Mo catalyst at reservoir (Athabasca) conditions, using moderate
temperatures (320-380 C). Upgrading was observed at less severe conditions than typical
surface hydrocracking, the pressure has the least influence in the reactions (3.45 MPa). With
this data a kinetic model and correlations for quality properties where developed. For
Athabasca bitumen, an activation energy of 202 kJ/mol was calculated for the Hydroprocessing
of the residue in an irreversible first order reaction. For hydrodesulphurization, activation
energy correspond to 174 kJ/mol.

Another experiment adding sand observed that Hydroprocessing is improved, suggesting that
the dispersion of the catalyst in the sand favours the activity. Catalysts found in the surface of
the sand showed grains with sizes ranging 40 50 nm in a tubular shape that had a length of
500 nm.

Another investigator, Rohallah Hashemi (Hashemi R. , 2013), studied the feasibility of the
Injection of trimetallic catalyst (Ni-Mo-W) in a sandstone reservoir. Retention was observed
 92

with an exponential trend in the porous media, from the injection point to the horizontal
section. Analysis noted that deposition is a function of temperature, metal type, and
permeability. Athabasca bitumen was tested with upgrading results.

Lately, Alejando Coy (Coy Plazas, 2013), evaluated the feasibility of the injection of vacuum
residue as a Ultradispersed catalyst carrier, to the reservoir (sandstone), observing upgrading at
residence times similar to SAGD (>244 h). Low permeability reduction was observed and
catalyst retention was proven. The reactivity of the catalyst after several pore volumes was
tested injecting industrial VR without catalyst, obtaining upgrading.

Finally Francisco Da Silva (Francisco Javier, 2014), implemented a solvent deasphalting unit
(SDA) to obtain, from the Athabasca bitumen, a de-asphalted oil (DAO) and a pitch with good
quality. DAO, pitch, bitumen and vacuum residue were prepared with ultra-dispersed catalyst
and evaluated the upgrading due to hydroprocessing reactions. Pitch hydroprocessing shows
that upgrading is more sensitive to temperature than residence time. These products are still in
the residue fraction.

In order to evaluate the kinetics of hydroprocessing reactions, a program application was

developed, in Microsoft Excel with Visual Basic. Using as an objective function, the deviation in
the Arrhenius plot linearity. The results matched well the experimental data

The model proposed for Athabasca bitumen hydroprocessing at reservoir conditions, obtained
a 3.11% overall error and correlation coefficient of 0.978. It is observed that the main reaction
is in residue, and naphtha is not reactive, gases are a secondary product of the reactions.
Activation energies calculated range from 139 to 272 kJ/mol naphtha conversion is the most
energy demanding reaction.

For VR, the error was 3.97%, correlation coefficient of 0.997. The activation energies range
from 43.2 146.6 kJ/mol, lower than the bitumen.

For pitch activations energy range 144 276 kJ/mol. As the other fluids, naphtha is the most
demanding energy, and naphtha from VGO is negligible.
 93

Nowadays two studies are in progress for two Mexican carbonate naturally fractured reservoirs
with heavy oil. The evaluations of applicability of this technology is in analysis. These are the
first evaluations to be recorded for a reservoir aside from Athabasca. This thesis is on one of the
studies.
 94

6. CHAPTER SIX: EXPERIMENTAL SECTION

Figure 6-1 Research plan scheme

Figure 6-1 shows the research plan scheme followed for the experimental section on this thesis.
A Mexican oil was received and characterized. The results show that the fluid contains high
amounts of H2S, and solid particles, mostly salts. The oil was desalted, and topped to eliminate
those contaminants for the process.

A certain volume of the topped oil was sent to a company to be separated at a 510C cut.
Obtaining vacuum residue (510 C+), and a lighter cut (IBP 510C).

The remaining topped crude oil was recombined, in order to restitute the original properties of
the original fluid. Two samples were taken, one for a thermal reactivity test, with two different
conditions. And the second was mixed with ultra-dispersed catalyst for a catalytic reactivity test
with different conditions.

The VR was also mixed with ultra-dispersed catalyst for a catalytic reactivity test, without
thermal condition. For all product samples, a train of analytical measurements was performed.

For the two catalytic tests (crude oil and vacuum residue), a kinetic model was calculated to
obtain the kinetic parameters for further process simulation.
 95

6.1. Process Overview

In Situ Upgrading EOR process depends on the oil chemical reactivity at certain conditions of
pressure and temperature in contact with an ultradispersed catalyst and a hydrogen flow. A set
of experiments were performed for this purpose. The process involved the Ag reservoir oil and
the vacuum residue cut of the oil. The experiments were performed for both. We separated this
section in two (crude oil and vacuum residue), evaluating the results for each oil.

The conditions evaluated are:

Residence time: 24, 48, 72, 96 hrs.

Temperature: 320, 340, 360 C.
Pressure: 1450 1500 psi.
Oil and hydrogen rate are in function of the residence time.

6.2. Process Material

The Ag oil was received in the Pilot Plant lab at the University of Calgary. This oil had to be
treated before doing any experiment due to its high H2S content, as well as the percentage of
water and solids contained.

Table 6-1 Ag crude oil topping and desalting.

%wt %wt Viscosity %wt API

water Salt @25 C (cP) 510 C+
Received 11 0.3 15,327 62 11
Topped/dry 0 0 - 63 9.2
Recombined 0 0 20,194 62 11.6
Light End 0 0 - 0 49.9

Preliminary and basic measurements are done to the received fluid, such as: water content,
salt, viscosity, API and residue content, this is shown in Table 6-1. Other Mexican oils have
been evaluated in the University of Calgary before, these crude oils are named Mb and Tk, and
both are offshore oils. A simdist curve is obtained for the three fluids and compared (Figure
 96

6-2), showing that Ag (blue) and Mb (green) are quite similar but different to Tl (red), which is
assumed that it is contaminated with light material, due to the curve shape.

Figure 6-2 Mexican oil comparison Ag (blue), Mb (green), and Tl (red).

In Figure 6-3, the same fluids are compared by their chromatogram, where the peaks in the left
sides correspond to light components that form the crude oil, and the humps in the right
section correspond to heavy components. As it is mentioned before, the Tl crude oil contains
light materials from a possible contamination of solvents. The Ag and Mb, are very similar, as it
is shown by the simdist curves.

Figure 6-3 Chromatogram comparison of Mexican crude oils.

 97

In order to eliminate the H2S, the barrel of oil was introduced to an enclosure with extraction.
N2 flow was passed through the fluid in order to drag the H2S out of the oil. Once the H2S
content was reduced, it passed to a second treatment which consists of the same N2 flow, and
heat was applied. This helped the H2S content to reduce even more. Both processes took two
weeks each.

After the H2S content reduction, the oil was topped in order to eliminate the water and solids
content. The oil was washed with distillate water and then separated (at pressure and
temperature conditions) in a mild distillation process. A small amount of light ends were lost
during this process. Table 6-1 shows general properties of the oil before and after the
procedure. For the experimental section, the oil was recombined with some light hydrocarbons
in order to reproduce (as much as possible) the initial boiling range of the material. The oil
obtained proved to be equal to the original oil.

a) b)

Figure 6-4 a) Ag crude oil (black) and topped Ag oil (red); b) Ag crude oil (black) and recombined
Ag crude oil (red).

Figure 6-4 shows the original Ag crude oil compared with the topped fluid. It is observed that
the loss of light materials makes the simdist curve move up (a). On b), the recombined topped
oil match the original simdist curve, two light materials were used: condensate, mostly C5 and
C6 with a chain that goes up to C60, and an IBP-350 C fluid in a proportion of 3.82 and 4.6 %
respectively. Viscosity is matched in the same range and P-value, or stability is achieved like the
original (Table 6-2).
 98

From the recombined sample, analytical parameters are measured to discern more about the
crude oil to be upgraded. Table 6-3 shows nitrogen and sulfur content, SARA analysis, P-value
and MCR determination. From this data we can observe that Ag crude oil is stable. No
asphaltene precipitation is present at this condition, coke tendency formation is in the range of
a bitumen and topped sample (13.6-18.5 wt %), considering Athabasca bitumen as a reference.

Table 6-2 Lights components added to the topped oil, and properties measured.

Viscosity
A C Lights
Sample @ 25 C P-value
(wt %) (wt %) (wt %)
(cps)
Original 20,194 2.75
Topped >180,000
Blend 7 3.82 4.6 8.42 39,974 >2.7

Table 6-3 Recombined oil analyses.

N S SARA (wt %) MCR

Sample P-value
(wt %) (wt %) Saturates Aromatic Resins Asphaltene (wt %)
Recombined 0.38 4.25 23.3 18.5 42.8 15.4 2.75 16.4+/-0.1

Table 6-4 SARA properties affected by biodegradation (Gray, 2015).

Sample Saturate Aromatic Resin Asphaltene

Nondegraded oil 55 23 21 2
Moderately biodegraded oil 25 21 39 14
Heavily biodegraded oil (bitumen) 20 21 41 21

Comparing the SARA analysis with the ones reported for biodegraded oil (See Table 6-4),it is
observed that the Ag crude oil is similar to a heavily degraded oil (bitumen), with lower
Asphaltene content.

Once the oil was preliminary processed (H2S extraction and desalting), the ultradispersed
catalyst was added. This process involved a dilution step with toluene and the incorporation of
 99

nickel, molybdenum and tungsten salts for a total concentration of 700 ppm. This process
involves a reactor that works at 370 C and 500 psi, eliminating the water used to solubilize the
metals and the toluene used to dilute the oil (viscosity reduction). After this process the oil has
to be recombined and taken to its original properties by adding 8%wt of light ends.

The feed was sampled from the feed tank, and taken to the simulated distillation equipment to
analyze the composition. Figure 6-5 shows the comparison between feeds showing that it was
almost the same for each run.

Figure 6-5 Different feedstock blend simdist curve for crude oil kinetic modeling.

A small amount of toluene remained in the feed (around 2.5 % wt). This is the reason that the
simulated distillation curves show a flat behavior at low temperatures.

As it was mentioned before, two fluids were evaluated to obtain a kinetic model, crude oil and
the vacuum residue. The former is the original oil of the Ag reservoir, the latter is the heaviest
cut of the original oil. In order to obtain this, the original oil was sent to a company to be cut.
The oil was distilled and we obtained IBP 510 C and the 510 C + fractions, last one being the
vacuum residue cut.
 100

In Figure 6-6 we observed the simulated distillation curves corresponding to the vacuum
residue (magenta) and the crude oil (blue). The composition of each fluid in its different lumps
is shown in Table 6-5. The vacuum residue doesnt have light components, the 9.8 %
corresponding to the vacuum gas oil cut is due to the difference between 510 C and 550 C,
the former being the temperature of the distillation and the later the temperature at which we
will evaluate the process.

Table 6-5 crude oil and vacuum residue lump yield (wt %).

Temperature Crude oil Vacuum residue

Component
range (%) (%)
Naphtha IBP 216 C 4.9 0
Distillates 216 C 343 C 9.3 0
VGO 343 C 550 C 28.0 9.8
Residue 550 C + 57.8 90.2
100 100

As it is expected, the VR simdist curve is at the top and the original oil at the bottom. These
curves are the reference parameters for kinetic modeling, reactivity performance, and the in
situ upgrading evaluation.

Figure 6-6 Crude oil and vacuum residue simdist curve comparison.
 101

Analytical measurements performed in the Ag vacuum residue are shown in Table 6-6. We
observe that we have a stable vacuum residue, more stable than the crude oil, due to the
absence of light material. The MCR value is slightly higher than the values reported for VRs
from Canadian bitumen which range 24 to 27 wt % (Gray, 2015).

Table 6-6 Analytical parameters of Ag vacuum residue.

MCR N S
Sample P-value
(wt %) (wt %) (wt %)
Vacuum
3 28.8 0.86 4.45
residue

Also, the increase of heteroatoms such as nitrogen and sulfur is higher in the residue than in
the crude oil, as it is expected. Likewise, the metal content increases in the heaviest fractions,
as it is shown in Table 6-7.

Table 6-7 Metal content comparison.

Mo Ni W Fe V K
Crude oil 2.1 76.7 0 9.05 350.3 88.1
VR 12.8 141.1 0 15.9 629.9 142.9

Comparing with Canadian fluids, V is very high and Ni is slightly above 196 and 75 ppm for
Athabasca bitumen.

Figure 6-7 Ag crude oil viscosity measurement at different temperatures.

 102

The viscosity is one of the main parameters to evaluate in this experiment, and for that it is
important to evaluate its behavior at different temperatures. Ag crude oil at room conditions is
a high viscosity liquid. Measurements of viscosity, shear rate and shear stress were measure at
25, 40, 80, 100, 150, 200, and 250 C. Figure 6-7 shows the behavior of the measurements in a
semi log plot. A power trend line fits the data. At room conditions, the viscosity reaches a value
of 78, 140 cp. At 250 C it reaches 7.5 cp.

Figure 6-8 Ag crude oil viscosity properties.

Evaluating the rheology of the crude oil (Figure 6-8), two plots are set: the first one shows the
relationship between the viscosity and the change in the revolutions per minute at different
temperatures. And the second one, compares the shear stress against the shear rate. For a
Newtonian fluid, the forces are related to a viscosity tensor and do not depend on the stress
state and velocity of the flow. These are the easier fluids to model.

Figure 6-9 Ag Vacuum residue viscosity at different temperatures.

 103

Vacuum residue at room conditions is a black solid. In order to manipulate it, it has to be
heated to at least 150 C to have a viscous flowing behavior. Different viscosity measurements
are taken at 150, 200, 250, and 300 C. Figure 6-9 shows the behavior of the vacuum residue
when heat is applied. A power trend line fits the experimental points.

Evaluating the rheology of the vacuum residue, the same procedure is applied, having a
Newtonian behavior.

Figure 6-10 Vacuum residue viscosity properties.

Once the crude oil is analysed and processed, the metals (catalyst) are incorporated into the
crude oil, using an ultradispersed catalyst preparation unit called Skid. The original, first, and
final catalyst mix batches are shown in Table 6-8, where the total amount of metals added is in
average 790 ppm of a trimetallic mixture of nickel (Ni), molybdenum (Mo) and tungsten (W).

Figure 6-11 Metal comparison for Ag crude oil.

 104

Table 6-8 Crude oil original and added metals (Catalyst).

Mo Ni W Fe V K
Original 2.1 76.7 0 9.05 350.3 88.1
Feed 1 404.4 213.1 239.9 15.2 337.0 75.2
Feed 7 434.5 219.5 229.5 8 365 96
Added
Feed 1 402.3 136.3 239.9 6.2 -13.3 -12.8
Feed 7 432.4 142.8 229.5 -1.05 14.7 7.9

As it was mentioned before several batches were prepared in order to feed the pumps and
continue the experimentation. In Figure 6-11, a comparison between the first and last batch is
shown. No important differences are notice among the batches prepared.

For the vacuum residue of Ag crude oil, the same procedure and equipment is used to add the
catalyst. The difference between the crude oil and the vacuum preparation is the solvent used
to decrease the viscosity for mixing purposes. In the former toluene and in the latter gasoline is
used. This change was decided in order to avoid the solvent (toluene), which remains in the
feedstock, as it was notice in the simdist of the original crude oil

Table 6-9 Vacuum residue original and added metals (catalyst).

Mo Ni W Fe V K
Original 12.8 141.1 0.0 15.9 629.9 142.9
Feed 1 379.4 244.9 200.1 18.9 602.7 158.2
Added
Feed 1 366.6 103.9 200.1 3.0 -27.2 15.4

The concentration for the vacuum residue reached 670.6 ppm of the trimetallic catalyst, a
smaller amount than the crude oil, but was enough for the reactivity test experimentation.
Figure 6-12, shows the metals added compared with the original contained in the vacuum
residue. One important fact observed and mentioned before, is that the residue contains most
of the heteroatoms and metals of the whole crude oil. Comparing them, the relationship is 1:2,
double the metals in the vacuum residue compared to the original crude oil.
 105

Figure 6-12 Metal comparison for Ag vacuum residue.

The trimetallic catalyst is the precursor for the hydroprocessing reactions at lower
temperatures, it is a key variable that must to be kept, for this reason the metals in the crude
oil and VR plus the trimetallic catalyst added to the fluids are analyzed. The procedure is as
follows:

A sample of crude oil or VR (20 30g) is dissolved in toluene (80 gr).

This mixture is centrifuged at 8,000 rpm for 30 min.
The supernatant is separated and more toluene is added.
Additional agitation and centrifugation is applied.
The procedure is repeated three times.
The solid material in the bottom is dried at room temperature overnight and then
vacuum is applied at 80 C for 12 hrs.
Sample is analyzed with an X-ray diffraction equipment (XRD).
Sample then, is analyzed with an X-ray photoelectron Spectroscopy (XPS)
Finally, using a Nano-particle Tracking Analysis (NTA) is used.

The results are shown for the crude oil and the VR.

6.3. Metal content analysis of original crude oil

It is observed that metals and additional solids, such as: halite, anhydrite and sylvine (salts) are
in the crude oil. This shows that the desalting process has to be improved, to avoid salts and
 106

solids that could. This affects the future facilities used for the ISUT process. These solids
measured with the XRD equipment are shown in Figure 6-13.

Using the NTA equipment, the nanoparticles, that can be salts, metals, and other solids, can be
tracked and quantified. Additionally, a size distribution is calculated, providing the average
particle size measured in the sample, which is analyzed by this equipment. For the crude oil
with catalyst, the mean particle size is around 172.4 nm, 171 nm being the most repeated, with
a standard deviation of 53.5 nm. This is important because no higher particles or agglomeration
of metals is observed, the size are kept as desirable. Results are shown in Figure 6-14, where a
normal distribution is observed.

Figure 6-13 Ag crude oil with catalyst XPS analysis.

Figure 6-14 Particle size distribution for Ag crude oil with catalyst.
 107

6.4. Metal content analysis of vacuum residue

The same procedure is applied for the Ag vacuum residue with and without catalyst added.
Likewise the Ag crude oil, where salts are found in the vacuum residue (Figure 6-15 and Figure
6-16). The particle size measured has a mean length of 177.8 nm with a standard deviation of
62.2 nm. The shape of the distribution is not normal, being different sizes ranging in three
different values. Some agglomeration could be creating the highest values, and very small
particles generating lowest numbers.

Figure 6-15 Ag VR without catalyst XPS analysis.

Figure 6-16 Ag VR with catalyst added XPS analysis.

 108

Figure 6-17 Particle size distribution for Ag VR with catalyst.

6.5. Reactivity Test Unit

After the oil and VR were mixed with the ultradispersed catalyst, the reactivity test for the
kinetic evaluation can be initiated. The unit used for this purpose is the reactivity Test Unit
(RTU-2) which was built by a predecessor researchers of the CBU Group at the University of
Calgary, who used to work at lower temperatures and pressures (500 psi). For Ag, the reservoir
pressure is 110 kg/cm2 (1500 psi), for this reason the unit had to be revamped. The unit was
received with the following equipment:

1. Pump Section: 4 ISCO positive displacement pumps for high pressure and temperature.
The minimum rate delivered is 0.001 cm3/min. Each pump have a capacity of 507 cm3.
2. Feed tank: 3 kg capacity heated tank that operates at low pressure, being 80 psi the
highest value used to refill the pumps. Temperature ranged up to 180 C, being the
highest value used to manipulate viscous feed such as vacuum residue.
3. Reactors: 3 continuous flow reactors consisting on open flow one inch diameter pipes
which provide a 61.62 cm3 volume. Heated by tapes that can reach up to 700 C, if it is
desired. The reactor is isolated with a special jacked that reduce heat losses. In its inner
part, a 1/8 diameter six point thermocouple is installed, which helps to set and track
the temperature profile of the experiment (isothermal). Pressure is monitored by two
pressure gauges that show the pressure drop in the reactor, as well its stability.
 109

4. Stability tank: in order to ensure the stability of the experiment (pressure, flow rate and
temperature), three reactor volumes are flown. This volume is collected in this tank.
5. Mass balance tank: Once the stability is reached and gas rate and composition
measurements are done, the flow is switch to this tank. This tank will be drain every half
residence time to obtain samples for analytical test and mass balance evaluation.
6. Back pressure valves: this valves are set at a desired pressure, this helps to prevent the
pressure increase maintaining the experiment at a steady or stable pressure.
7. Mass gas flow controllers: this equipment controls the gas injected to the unit at a
certain flow, depending on the condition of residence time in evaluation.
8. Gas flow rate meter.
9. Gas chromatograph.
10. Labview application: this software permits to create a computational environment to
manipulate the RTU-2 from a computer. All the equipment described before can be
programed, manipulated and tracked by this program.

The RTU-2 diagram is shown in Figure 6-18.

Figure 6-18 RTU-2 unit flow diagram.

 110

Figure 6-19 RTU-2 picture.

Once explained the RTU-2 used for the kinetic model evaluation at lab scale. The procedure is
separated in two, stability and mass balance, for the former the following steps are done:

1. Input oil or vacuum residue in the feed tank. For crude oil, temperature is set at 60 C,
for VR it is set at 180 C. Tank pressure is set at 80 psi.
2. After the feed volume, pressure and temperature have been reached, refill pump.
3. With pumps filled, begin pumping the fluid at 1 cm3/min.
4. Set the heating tapes temperature to increase at the experiment temperature at a
certain ramp (4 C/min).
5. While the system begins to be filled with the feed and the temperature increases,
hydrogen flow has to be set at the experiment rate. The system pressure has to be
increase gradually using the N2 cylinder, reaching the experiment pressure.
6. Once the pressure, temperature and hydrogen flow rate are reached, the feed flow rate
has to be set, which correspond to the residence time of the experiment.
7. Now, the stability stage begins. At this time the back pressure valve is calibrated, as well
as the heating tapes in order to reach steady state conditions.
8. Before changing to the Mass Balance stage and having steady state, gas flow rate must
be measure, as well as the gas chromatogram acquisition.
 111

For the Mass Balance period, the following steps were followed:

1. Switch from stability tank to the mass balance tank making sure that the conditions are
steady.
2. When the first half of the residence time is reached, a sample is taken. It is done
switching the flow from the MB tank to the stability, sample the MB tank, reach original
conditions and switch from stability to MB tank.
3. This procedure is repeated for the second half of the residence time.

After reaching the complete residence time and sampling, temperature and pressure values are
changed to the next set of conditions to evaluate. These steps are the same for each new set of
conditions.

6.6. Sample Characterization

It is key for the experimentation to maintain the steady state of temperature and pressure
conditions and obtain at least two samples per condition, i.e. residence time. A battery of
analytical measurements are effected on these samples, which are:

Simulated Distillation.
Viscosity determination.
Density and API measurements.
Nitrogen and sulfur analysis.
Microcarbon measurement.

A brief description of these methods is found in Appendix B. The expected results due to the
hydroprocessing of the heavy oil or VR are, both fluids become lighter than the original, and
pass through the less severe condition to the most severe. This will reduce the viscosity and
density increasing the API gravity. As a Hydroprocessing reaction, sulfur content will reduce as
well as coke content (MCR) that could be formed reduces. These results will be analyze in the
next chapter.
 112

7. CHAPTER SEVEN: RESULTS

7.1. Crude Oil Kinetic Model
In this section, the analysis results of the laboratory kinetic data experimentation for Ag crude
oil with a tri-metallic ultradispersed nano-catalyst (Ni-Mo-W) and hydrogen are shown. The
conditions are a combination of the following variables: temperatures (320, 340, and 360 C),
residence time (24, 48, 72 and 96 hrs). Table 7-1 shows the combination of conditions
evaluated at laboratory in the RTU-2.

Table 7-1 Experimental conditions.

Temperature Residence time (hr)

( C ) 24 48 72 96
320 * *
340 * * *
360 * *

The reservoir conditions are at 60 C and 1,500 psi. The temperature used is higher, for that
reason pressure is the only variable representing the reservoir in this experiment.

For the crude oil, 13 conditions were evaluated, with one sample taken every half of the
residence time, giving 26 samples, as shown in Table 7-2. The feedstock is conditioned to keep
the original properties in each run, eight feed samples were mixed with light cuts and
Ultradispersed catalyst.

The first set of experiments, samples 1 to 6, were design to evaluate the reactor configuration.
These consist in changing the position of the feed line to the reactor. Two configurations were
evaluated, upflow (UF) and downflow (DF). It was demonstrated that upflow configuration is
stable regarding pressure and temperature, and mass balance. For that reason the upflow
configuration was chosen for the rest of the experiments.

The data used to develop the kinetic model corresponds to samples 7 to 18 and 23 to 24. It is
important to notice that samples 3 and 4, from the previous experiments, are taken into
account for the final kinetic modeling. The experiments are run in parallel in two reactors,
 113

optimizing time. The conditions are different for each set of samples. As it was mentioned
before, a stabilization time is established to obtain better results per condition run.

Sample 19 to 22, corresponds to conditions where no catalyst is added to the crude oil. These
runs are called thermal (T), and were done at two temperatures and residence times in order to
compare the results with a similar catalytic run condition.

Samples 25 to 26, are related to hydrogen partial pressure modification. Two ratios were
evaluated, that is 1,000 cm3 of hydrogen (at standard conditions) per cm3 of oil pumped and
700, in order to analyze how efficient the hydrogen behavior is at this condition.

The experiment evaluates the effect of temperature and residence time of the crude oil under
catalytic reaction at a reservoir condition. Product distribution, conversion and quality are
evaluated.

Table 7-2 Samples obtained for each condition run.

Time Temp
Sample Reactor Configuration
(hr) (C)
Configuration evaluation
1 24 360 1 DF
2 24 360 1 DF
3 24 360 2 UF
4 24 360 2 UF
5 24 360 1 DF
6 24 360 1 DF
7 24 340 2 UF
8 24 340 2 UF
9 72 360 1 UF
10 72 360 1 UF
11 72 340 2 UF
12 72 340 2 UF
13 48 320 1 UF
14 48 320 1 UF
15 24 320 1 UF
16 24 320 1 UF
17 48 340 2 UF
18 48 340 2 UF
23 96 340 1 UF
24 96 340 1 UF
 114

PP H2
25 72 360 1 UF
26 72 360 1 UF
Thermal
19 24 360 2 UF
20 24 360 2 UF
21 48 340 2 UF
22 48 340 2 UF

7.1.1. Temperature and residence time effect

The main objective of the ISU technology, is to upgrade the crude oil in situ. For that reason the
evaluation of the crude oil reactivity is indispensable, to start narrowing down the best possible
conditions of the future in situ upgrading process test. The conditions evaluated in lab are much
milder than the general practice on surface refining.

As a rule of thumb for lower temperatures, higher residence times are needed to achieve
higher conversions, but lower residence times are needed at higher temperatures for similar
conversions. The definition of c used to evaluate this process is introduced, in Equation 19,
show the method to calculate this parameter.

% Original cut %reacted cut Equation 19

X=
% Original cut
The general meaning of conversion is, the percentage of change of the evaluated variable. We
are evaluating the residue change or, residue conversion due to Hydroprocessing. The reacted
yield is subtracted from the original and divided by the original residue percentage, obtaining
the percentage of change. If this value is negative, the yield is increasing, which is not desired in
our process. A downgrading of the crude oil will be in course. A positive value is desired,
meaning that the residue yield is reducing.

The first parameter to evaluate comparing the residence time and temperature is residue
conversion. Figure 7-1, shows the residue conversion behavior at different conditions.

As it is expected, higher temperature and residence times or higher severities lead to a higher
residue conversion or upgrading of the crude oil. Comparing temperature vs. residence time,
temperature has greater effect on conversion.
 115

The three temperature curves have an increasing trend but tend to stabilize at higher residence
times. For further experimentation, a longer residence time must be evaluated to confirm this
assumption.

Figure 7-1 Residue conversion as a function of residence time and temperature.

A separation of 20 C is used to evaluate the behavior of the increasing temperature.

Comparing from 320 to 340 C a sligh improvement is seen, but two stabilization periods are
observed, where 340 C has greater conversion. The substantial increase is seen at 360 C,
where conversion reaches values of 46 wt % compared to 20.6 % at 340 C.

Figure 7-2 Temperature impact to residue conversion.

It is important to notice that the crude oil requires higher temperatures to obtain a substantial
conversion, less than 340 C a mild conversion process result. This temperature impact is shown
 116

in Figure 7-2, where a substantial increase in conversion comes at temperatures higher than
340 C.

7.1.2. Upgrading results

In order to evaluate the upgrading process, a simulated distillation unit was used to obtain the
curves shown in Figure 7-3. These curves shows the cumulative percentage of the component
as a function of its boiling points. The higher the percentage of component with higher boiling
points, the heavier the crude oil or product evaluated.

Figure 7-3 shows the simulated distillation curves for each of the samples analyzed. The blue
discontinuous curve represents the crude oil feed, as a reference, that helps to evaluate the
upgrading process. In order to understand the plot, if the curves of the reacted samples are
above the reference curve (blue discontinue curve), the process is downgrading the oil.
Meaning that the process is creating a heavier oil, which is not desired. On the other hand, if
the curves are below the reference curve, it means that the oil is being upgraded. The catalytic
conditions are converting the heavy ends to lighter compounds, that is, converting the heavy oil
into a lighter one.

Figure 7-3 Simulated distillation curves for each product of the kinetic model experiment.
 117

The results demonstrate that the hydroprocessing is upgrading the oil, corresponding the
lightest oil to the most severe condition, which is at a temperature of 360 C and a residence
time of 72 hrs. This reaches a residue conversion of 46 %. The less severe condition is at a
temperature of 320 C and a exposure time of 24 hours, reaching a conversion of 9 %.

It is important to notice that the flat initial section of the curves is due to the toluene left in the
feed after the catalyst mixing process, a 2 to 3 wt. %, is still remaining in the crude oil. It does
not affect the process or analysis.

As it was demonstrated, the hydroprocessing with catalyst is happening in the Ag crude oil. No
downgrading was observed and extreme severity was measured, this is important for future
plug reactor experimentation, and reactivity evaluation.

Table 7-3 Composition (wt. %) for each catalytic condition sample.

Time Temp.
Run Configuration Reactor Gases Naphtha Distillates VGO Residue
(hr) (C)
Feed - - - - 0.00 4.89 9.33 27.98 57.81
9 72 360 Upflow 1 2.01 7.66 15.65 38.09 36.59
10 72 360 Upflow 1 2.01 9.52 19.49 38.02 30.96
1 24 360 Downflow 1 0.58 7.61 15.96 33.36 42.49
2 24 360 Downflow 1 0.58 5.56 11.99 33.29 48.58
3 24 360 Upflow 2 0.80 5.20 15.94 36.81 41.24
4 24 360 Upflow 2 0.80 4.60 15.21 37.20 42.19
5 24 360 Downflow 1 0.48 5.58 10.66 30.67 52.61
6 24 360 Downflow 1 0.48 4.93 10.23 29.60 54.75
23 96 340 Upflow 1 0.92 6.60 12.25 37.89 42.35
24 96 340 Upflow 1 0.92 6.91 13.17 37.54 41.46
11 72 340 Upflow 2 0.91 5.15 11.94 36.12 45.87
12 72 340 Upflow 2 0.91 5.55 13.24 34.73 45.57
17 48 340 Upflow 2 0.71 4.96 11.22 35.17 47.94
18 48 340 Upflow 2 0.71 5.29 10.65 35.93 47.42
7 24 340 Upflow 2 0.48 3.92 11.89 32.09 51.61
8 24 340 Upflow 2 0.48 4.90 10.69 31.74 52.19
13 48 320 Upflow 1 0.77 5.75 12.07 33.92 47.50
14 48 320 Upflow 1 0.77 5.16 10.19 33.51 50.38
15 24 320 Upflow 1 0.22 4.99 10.89 31.73 52.17
16 24 320 Upflow 1 0.22 4.23 8.81 33.44 53.30
 118

Table 7-4 Composition (wt. %) for each thermal condition sample.

Time Temp.
Run Configuration Reactor Gases Naphtha Distillates VGO Residue
(hr) (C)
19 24 360 Upflow 2 0.89 6.29 16.72 36.35 39.75
20 24 360 Upflow 2 0.89 5.91 16.25 37.53 39.43
21 48 340 Upflow 2 0.46 5.47 15.33 33.68 45.05
22 48 340 Upflow 2 0.46 5.61 15.23 33.21 45.49

Table 7-5 Composition (wt. %) of each partial pressure catalytic condition sample (700 cm3 of H2
to 1 cm3 of oil pumped).

Time Temp.
Run Configuration Reactor Gases Naphtha Distillates VGO Residue
(hr) (C)
25 72 360 Upflow 1 4.32 7.53 18.34 36.84 32.97
26 72 360 Upflow 1 4.32 7.46 19.44 37.83 30.95

One important material that is extracted from the simulated distillation curves, are the yields or
components of the crude oil, original and reacted. As it was mentioned before five lumps are
used to evaluate the kinetics of the ISU Hydroprocessing reactions. This are: gases, naphtha,
distillates, VGO, Residue.

The simulated distillation curves only provide the liquid phases components. The gas
chromatograph measurement have to be added to the liquid components in order to obtain the
five lumps and complete description of the fluid produced, as well as the total conversion of the
residue. The raw data for each sample is tabulated in Table 7-3, Table 7-4, and Table 7-5, for
catalytic, thermal and partial pressure run samples respectively.

The raw data is plotted in stacked columns for a better visualization and understanding of the
components upgrading and residue conversion. Figure 7-4 show the evolution of the residue
conversion for the catalytic samples, from the most severe condition to the less severe, left to
right respectively. The residue component (blue) is always less compared to the feed (column
on the left), the lighter yields are higher and the gas component appear. It can be appreciated
at the more severe condition (360 C and 72 hrs, sample 9 and 10). The API gravity is always
higher than the feedstock, reaching values of 19, up from an initial API gravity of 10 in the feed.
 119

Figure 7-4 Catalytic sample components (left axis) and API curve (right axis).

The thermal runs 360 C for 24 hrs, and 340 C for 48 hrs and, are compared with its respective
catalytic sample in Figure 7-5 and Figure 7-6 correspondingly. In both cases, thermal runs are
obtained with slightly better upgrading. Improvement is observed in the conversion and API
(Table 7-6 and Table 7-7).

Figure 7-5 Thermal condition (24 hrs, 360 C) compared with the same catalytic condition.

Table 7-6 Comparison between thermal (19 and 20) and catalytic run, condition 360 C at 24
hrs.

Sample API Conversion (wt %)

3 14.4 28.7
4 13.6 27.0
19 15.5 31.2
20 15.2 31.8
 120

Figure 7-6 Thermal condition (340 C, 48 hrs) compared with the same catalytic condition.

Table 7-7 Comparison between thermal (21 and 22) and catalytic run, condition 48 hrs, 340 C.

Sample API Conversion (wt. %)

17 12.9 17.1
18 12.8 18.0
21 13.6 22.1
22 13.3 21.3

In order to evaluate the effect of partial pressure, one condition was repeated at 700 cm3 of
hydrogen per cm3 of crude oil, while the catalytic runs are at 1,000. Table 7-8 and Figure 7-7
show the comparison of both samples. The conversion is almost equal as well as the API gravity.
The reduction in the partial pressure of hydrogen, does not affect the reactivity of the process.
Conditions with smaller hydrogen/oil relationship should be evaluated to obtain the range of
hydrogen injection to avoid coking and ensure hydroprocessing reactions.

Table 7-8 Comparison between partial pressure (25 and 26) and catalytic run, condition 360 C-
72 hrs.

Sample API Conversion (wt. %)

9 16.4 36.7
10 18.8 46.4
25 15.5 43.0
26 16.4 46.5
 121

Figure 7-7 Partial pressure condition (360 C, 72 hrs) compared with the same catalytic
condition.

7.1.3. Quality results

Table 7-9 Quality variables evaluated in the reacted samples.

Time Temp Viscosity Density API Conversion P-value MCR N S

Sample
(hr) (C) (cP) gr\cc (%) (%) PPM PPM
Feed - - 81248.7 0.99998 9.9 0 2.75 17.91 5701 36998
16 24 320 13401.1 0.98833 11.5 7.8 2.7 - 5719 34671
15 24 320 8540.9 0.99120 11.1 9.8 2.7 14.32 5717 34191
14 48 320 5194.2 0.98438 12.1 12.8 2.5 - 5770 33037
13 48 320 2580.2 0.98051 12.7 17.8 2.5 13.42 5813 30987
8 24 340 5435.5 0.98704 11.7 9.7 - - 5783 33615
7 24 340 6578.2 0.98612 11.9 10.7 2.3 13.93 5881 33888
18 48 340 2282.2 0.97987 12.8 18.0 - - 5710 31134
17 48 340 2281.8 0.97925 12.9 17.1 2.1 12.79 5715 31772
11 72 340 1606.6 0.97363 13.7 20.6 1.1 11.99 5759 31301
12 72 340 1474.4 0.97084 14.1 21.2 - - 5738 30904
23 96 340 788.1 0.96974 14.3 26.7 2 10.94 5608 28657
24 96 340 851.4 0.96397 15.2 28.3 - - 5611 26495
3 24 360 1124.4 0.96909 14.4 28.7 1.40 12.5 5751 34470
4 24 360 1596.8 0.97437 13.6 27.0 - - 5731 34801
9 72 360 239.8 0.95610 16.4 36.7 1.15 10.49 6055 25954
10 72 360 87.6 0.94048 18.8 46.4 1.1 - 5673 23933
Thermal
19T 24 360 476.50 0.962 15.5 31.23 1.50 11.38 5572 29054
20T 24 360 705.65 0.964 15.2 31.79 5784 29629
21T 48 340 1,874.77 0.974 13.6 20.71 2.00 12.65 5669 31669
22T 48 340 1,771.62 0.976 13.3 19.98 5711 30850
 122

Partial Pressure of H2
25PP 72 360 131.90 0.962 15.5 39.25 1.00 11.76
26PP 72 360 136.43 0.956 16.4 42.80

Once we evaluate the performance of the conditions and the upgrading of the products, we
analyze the quality of the samples for catalytic, thermal, and partial pressure conditions; Table
7-9, shows the raw data of the measurements evaluated for the samples obtained per
condition.

For this section, API gravity, P-value, micro carbon, nitrogen, and sulfur content are evaluated,
to analyze the quality of the products obtained from the reactions in the RTU-2. It is important
to understand that the quality will guide us to the optimum conditions to operate in the
reservoir.

7.1.3.1. Viscosity

Figure 7-8 Viscosity reduction at different temperature and residence time conditions (40 C).

Figure 7-8 shows the viscosity reduction trend with reaction temperature at different residence
time. It is clearly observed that the higher and faster reduction is obtained at higher
temperatures (360 C). Observing that viscosity responds to temperature, the higher the
temperature, the higher viscosity reduction.
 123

Mild temperatures of 320 C and 340 C have a slower reduction in viscosity. Higher residence
time per temperature condition is needed to reach the same reduction as the more severe
temperature.

Plotting viscosity against conversion, in a semi log axis, an exponential trend is observed. The
equation can help us to predict the viscosity (40 C) at certain conversion values (Figure 7-9).
This correlation can be used for a range of 0 and 50 wt. % conversion for Ag crude oil catalytic
Hydroprocessing upgrading. This trend fits 94% of the experimental values.

Figure 7-9 Viscosity reduction as a function of conversion.

Figure 7-10 Viscosity as a function of residence time and conversion per temperature range.

Figure 7-10 shows the viscosity per temperature as a function of conversion and residence time
in a composed plot. An exponential trend as a function of temperature is observed, for
 124

viscosities determined at 40 C. With this plot we can obtain an estimation of the viscosity for a
certain residence time and temperature used, and show that the viscosity reduction is due to
the reduction of the residue component in the crude oil. As it was seen before, a more severe
condition (360 C) gives better viscosity reduction and higher conversion values. Mild
temperatures, need higher residence times to achieve a better viscosity decrease, a slower
development is observed.

It is also observed the stabilization trend at higher residence time, an experiment with higher
contact time has to be developed to assure this statement.

7.1.3.2. API gravity

Figure 7-11 API gravity increase as a function of residence time (room temperature).

Figure 7-12 Density and API gravity correlation.

 125

API gravity is a variable that is related to the density (Figure 7-12), therefore to the quality of
the oil. The higher the API value, the less dense the product. At high values, a lighter oil with
light compounds is observed and desired, less processing is required to obtain a good quality
product. Figure 7-11 shows the API values as a function of residence time for a given
temperature. As it was observed before, severe conditions provide better upgrading of the oil.
For this experiment, it ranges from 11 to 19, being a good quality improvement.

The three temperature conditions have a stabilization trend at higher residence times. At mild
temperatures, not big increase with short contact time, larger residence times is required to
obtain a good quality product.

Figure 7-13 API gravity improvement as a function of conversion.

Figure 7-13 shows a plot of API as a function of conversion, likewise viscosity, a linear relation
with 93% of correlation is obtained.
 126

Figure 7-14 API gravity as a function of residence time and conversion per temperature.

Figure 7-14 shows the variation of API gravity and conversion for the three temperatures
explored. A polynomial trend is observed for the conversion, as well as for API gravity, as a
function of the residence time, and seem to reach a plateau at larger contact time.

It is important to notice that the Hydroprocessing reactions are acting on the crude oil, we can
see the permanent viscosity reduction via thermal cracking radicals being hydrogenated, and
increasing the lighter cuts that upgrade the quality and reduce the density of the oil.

This measurement is more dispersed due to the type of sample obtained. The lighter
components or gases that come from the RTU-2, can volatilize easily at room conditions, this
loss can make the density and API gravity measurements more dispersed.

7.1.3.3. Microcarbon (MCR)

 127

Figure 7-15 MCR as a function of residence time per temperature range.

MCR is a measure of the tendency of a hydrocarbon to form coke. One of the objectives of the
catalyst is to avoid coke formation and to reduce its condensation if it is formed. As shown in
Figure 7-15, the reduction of the MCR from 18 to 10.5 wt% is an important improvement of the
process. Hydrogenation of the free radicals is proven in this stage. For higher temperatures, the
most reduction of the MCR is observed. It is important to notice that this reduction is
significant, providing certainty to the process applicability in reservoir. Lower values of MCR
corresponds to a lower tendency of coke formation after conversion, compared to thermal
processes. This means that, injection hydrogen, catalyst in a hot dense fluid will not impair the
porous media by coke deposit.

For the three temperatures tested, a stability is observed at higher residence times, where
probably, no more hydrogenation is achievable at the conditions used in the experiments. The
conditions just allowed a certain conversion value to be reached, where temperature is no
longer the first promoter of the reactions, becoming residence time the variable that allows
hydroprocessing reactions at a slower rate.

The values of MCR on thermal runs (Table 7-9) were expected to increase, due to the lack of
catalyst in the reaction but, it was the opposite. A probable reason of this result could be that
these runs were evaluated after 18 catalytic conditions. Deposition and decoration of catalyst
on the surface of the pipe walls, could act as a catalytic run, giving similar results to the catalytic
condition.
 128

7.1.3.4. Sulfur content

Figure 7-16 Sulfur content as a function of residence time per temperature range.

For surface refining, it is desirable that the feedstock has less sulfur and contaminants in order
to avoid corrosion and increments in production cost. Desulfurization is a process done in
refineries for this purpose. Hydrodesulphurization process is measured by the sulfur content of
the products against the original value. This content reduces from 37,000 ppm to 23,933 ppm
(48.9 % conversion) in the most severe case.

Figure 7-16 shows the trend for the reduction of the sulfur content as a function of the
residence time, for each temperature tested. In all cases, the sulfur is decrease, being the most
severe temperature (360 C), and the most hydro desulfurized sample.

As it was observed in the MCR property, no huge decrease is observed due to the temperature
effect. Time plays a higher role in this process, helped at the end by the thermal mechanism in
the most severe conditions. In the kinetic evaluation section, the sulfur conversion and kinetic
modeling for this contaminant elimination will be observed.

A sulfur content correlation as a function of residue conversion is shown in Figure 7-17. A linear
trend is observed with a 97% agreement, with the experimental data measured.
 129

Figure 7-17 Sulfur content reduction as a function of residue conversion.

7.1.3.5. P-value

Figure 7-18 P-value as a function of residence time per temperature range.

Peptization value or P-value is a measurement of stability of the crude oil, one an unstable fluid,
the higher the number, the more stable the oil. The instability means that at certain condition
of temperature and conversion, the asphaltene and heavy compounds can condense and
deposit, causing plugging in the porous media and/or well and/or pipeline system. A stable
product is required to avoid these issues. For this crude oil, the original value is 2.75, and the
products range from 1.1 to 2.7, being the most unstable, the product obtained at the most
severe condition.
 130

P-value is plotted against residence time for different temperatures tested, is shown in Figure
7-18. It is important to notice that for mild temperatures (320 and 340 C), we obtain stable
products but, for higher temperatures and residence times the samples become unstable,
which is not desirable.

Figure 7-19 shows the microscopic view of the samples for P-value evaluation. It shows the
original sample compared with the least and the most severe conditions. It is clearly observed
that at the most severe condition, corresponding to 72 hrs, 360 C, a value of 1.2 is obtained.
For mild conditions like 24 hrs, 320 C, the value almost reach the original value.

Original Crude oil

2.0 2.7 2.75 3.05

Sample 15: 24 hrs, 320 C

2.2 2.4 2.6 2.8

Sample 9: 72 hrs, 360 C

1.1 1.2 1.4 1.6

Figure 7-19 Microscopic view for evaluation of P-value.

It is important to note that the more light cuts created by hydroprocessing, the more unstable
the oil becomes. The light ends act as a solvent that make the asphaltenes and heavy
compounds condensate and precipitate at a certain condition. This value has to be taken into
consideration when designing the ISUT since the production of unstable materials can be
problematic and produce impairment of the reservoir.
 131

For the thermal runs, the P-value obtained is almost the same, no significant change was
observed. The same is observed for the experiments carried out at different partial pressure of
hydrogen.

7.1.4. Kinetic evaluation

The hydroprocess reactions act in the heaviest cut (vacuum residue), for that reason, the
conversion is calculated for this cut, and is the main point of comparison from now on.

Comparing the percentage of each cut against the conversion of each sample, in Figure 7-20 we
can observe that the residue conversion fits a lineal trend. Meaning that the hydrocracking
process is acting on this compound.

Figure 7-20 Component percentage (wt. %) vs. residue conversion (wt. %).

The purple curve corresponds to the vacuum gas oil component, which has a polynomial trend
that reach a steady state at a 45% conversion. The green, red and blue lines correspond to
distillates, naphtha, and gases component, all of them are increasing.
 132

Conversion can also be applied to each cut and be plotted against the conversion of the
Residue. The values calculated for cuts that increase the composition percentage are negative,
and for decreasing values they are positive.

Figure 7-21 lump conversion (wt %) vs residue conversion (wt. %).

Plotting this values, we can observe different types of trends (Figure 7-21). The first one
(yellow) and most important is the VR conversion, with a 45 degrees straight line showing the
main reaction. The second trend (gray) is the VGO behaviour showing an increase and reaching
a plateau behaviour, which is considered as a primary product of the reaction. The third trend is
shown by distillates, naphtha and gases as secondary products of the reaction formed by the
conversion of VGO to lighter ends, being gases formation the least. This analysis will help for
the kinetic parameter calculation presented later.

The conversion concept can be applied to the property changes of the oil in order to evaluate
the behavior and trend. The results are shown in Figure 7-22 where API, MCR, S, N and density,
are plot in order of change. The API gravity is the most important change increasing up to 68%
from its original value, followed by the reduction of micro carbon value and sulfur content.
From this we can see that the hydroprocess is working. Cracking of the VR reduces the viscosity
and, the hydrogenation of those cracked molecules reduces the coke content that can
precipitate, also the sulfur reduction is part of the global reaction.
 133

Figure 7-22 Property conversion (%) vs. residue conversion (wt. %).

Density and API gravity are related to each other, which is the reason that both trends are
linear. This is directly related to the hydroprocessing reaction of the oil. The sulfur content has
the same behavior. The change in nitrogen content is not significant, the conversion reaches 9%
at severe conditions.

From the above analysis we can observe that the hydrocracking process followed by
hydrogenation, are acting in the vacuum residue cut, generating lighter components, increasing
those cuts, and lightening the heavy oil.

In order to evaluate the reactions, the order of reaction is calculated. An algebraic expression of
a common reaction mechanism operating in solid phase is:

g(x) = ln(1 x) Equation 20

This equation is used with the conversion fraction as input (x). Then the results are plot against
residence time in hours. A linear trend with the origin at zero is expected in order to convey as
a first order reaction.

For the hydrocracking reaction, Figure 7-23 shows the linear trends for the three temperatures
evaluated, the three of them have a zero origin, as expected. Likewise, for the
hydrodesulphurization reaction, a first order reaction is observed.
 134

A first order reaction result means that the reaction depends only on the reactant involved in
the process, being the vacuum residue in this case. This plot will help the kinetic constants
calculations.

Figure 7-23 First order reaction evaluation for residue Hydroprocessing of Ag crude oil.

Figure 7-24 first order reaction evaluation for hydrodesulphurization.

Now that the three temperatures are plotted, the slopes are used to calculate the activation
energy and the pre-exponential factor of the global reaction. Arrheniuss plot is used to
determine those values. The following equations are needed:

Ea Ea 1 ln(k)
k(T) = Ao e RT Ln(k) = Ea = R
R T 1T
 135

The results are shown in Table 7-10. T, the values plotted are ln(k) and 1/T. this will give us a
three point plot, a trend is adjusted and the slope will provide a value to calculate the activation
energy (Figure 7-25).

Table 7-10 Parameters for Arrhenius plot.

T 1/T k
ln(k)
C K h-1 s-1
360 634.15 0.001576914 0.00796 -4.833326279
340 614.15 0.001628267 0.00308 -5.782825682
320 594.15 0.001683077 0.00254 -5.975591198

Figure 7-25 Arrhenius plot for Hydroprocessing.

The activation energy calculated gives a value of 88.77 kJ/mol, which is in the catalytic reaction
range, on the other hand, a low value is expected for hydroprocessing reactions in a heavy oil.

The CBU Group developed a excel sheet macro in order to characterize the kinetic model. As it
was mentioned before, the mathematical model is based on 5 lumps with 10 kinetic constants
that will describe the behavior of the hydro process from the vacuum residue to the next
lumps.

Table 7-11 Kinetic constants for Hydroprocessing modeling.

E
k 320 C 340 C 360 C Ln A0 R2
kJ/mol
1 0.003376 0.003174 0.006343 4.0 48.56 0.659
2 1.22E-06 1.9E-05 0.000163 63.9 382.16 0.997
 136

3 4.47E-06 6.13E-05 0.000798 69.7 404.65 0.999

4 0.000167 0.000276 0.00046 7.3 79.02 0.999
5 0.000421 0.001284 0.003995 27.8 175.52 0.999
8 0.000107 0.000156 0.000226 2.7 58.38 0.999

As it was described, the kinetic model macro has an objective function based on R2, which
calculates the best match with the lowest error. The values obtained for this program are
shown in Table 7-11.

Figure 7-26 Reaction diagram for crude oil residue Hydroprocessing.

The results show that the values of kinetic constants 6, 7, 9 and 10 are reactions that are
difficult to reach, so these reactions are eliminated. Figure 7-26 shows the reaction mechanism,
being the VGO component the main reaction product, followed by distillates and naphtha.

The global and by lump kinetic constants are plotted on an Arrhenius graph (Figure 7-27),
showing the agreement with the best correlation number.

Figure 7-27 Arrhenius plot for global and different reaction constants.
 137

Now that a good agreement is obtained, the model fits the experimental data with the
calculated values. In Figure 7-28, this match is observed for each temperature condition (320,
340, and 360 C). The figures in the right side shows a 45 degrees plot, where the experimental
data is plotted with the calculated yield of each lump, at each temperature tested. A good
match is obtained.

The plots on the left side show the calculated yields per temperature and residence time
condition tested, with this, an interpolation can be obtained. The agreement looks acceptable
for this model.

From these analysis we can conclude that the hydroprocess reactions are acting on the residue
compound in order to convert this yield into lighter components. The main reaction is the
hydrocracking followed by the hydrogenation of the cracked molecules, this also is in
agreement with the hydrodesulphurization of the oil. These reactions can be modeled with
good agreement of the experimental data in order to obtain interpolated data.

The oil responds in a positive manner to the hydrogen, catalyst, temperature, pressure and
contact time, confirming that the oil reacts and is suitable to be upgraded under such
conditions, which are the ones used for ISU technology. Procuring a moderate temperature of
340 C in order to keep asphaltenes stability, with P-value higher than 1.3, seems an adequate
choice.

An additional step, for future applications, is the development of a correlation between

temperature and residence time, in order to calculate viscosity and API gravity of upgraded
products of Ag crude oil.
 138

Figure 7-28 Kinetic model match and calculation of composition lumps per condition.

7.1.4.1. Hydrodesulphurization
Once we evaluate the kinetics of the residue hydroprocess, another elemental parameter is
analyse, the hydrodesulphurization reaction. It is a first order reaction, as it was demonstrate in
 139

Figure 7-24. With that data an Arrhenius plot is set to obtain the kinetic parameters, as it is
shown in Figure 7-29.

Figure 7-29 Arrhenius plot for the Hydroprocessing reaction at several temperatures.

From the trend line slope, we can calculate an activation energy, which value is 46.54 kJ/mol,
for the desulfurization of the Ag crude oil residue. This value is smaller compared to the
hydroprocessing that obtained 89 kJ/mol, less energy is needed to achieve the HDS reaction,
being less sensitive to temperature.

7.1.4.2. Hydrodemetalization
This hydro treating reaction is evaluated by measuring the metal content of the samples
acquired at each condition; comparing them with the original crude oil and the feed once mixed
with the catalyst.

Table 7-12 Metal content of different samples, feed and original crude oil.

Time Temp Conversion Metals (ppm)

Sample
hr C (%) Ni Mo W Fe V K
Original - - - 76.7 2.1 0.0 9.1 350.3 88.1
Feed - - - 219.5 434.5 229.5 8.0 365.0 96.0
15 24 320 9.8 37.8 102.7 27.5 20.9 195.0 58.5
7 24 340 10.7 20.9 86.2 17.4 32.2 195.4 12.9
13 48 320 17.8 9.0 54.5 14.2 8.4 123.5 30.3
11 72 340 20.6 0.0 68.4 7.4 17.9 89.0 38.8
9 72 360 36.7 0.0 39.8 7.0 6.0 93.1 0.3
 140

Figure 7-30 Metal content comparison of different samples and original crude oil and feed

The measurements are shown in Table 7-12, where temperature and residence time conditions,
and conversion can be used for this case. As it was mentioned before, a trimetallic nano-
catalyst is added to the crude oil, metals being nickel (Ni), molybdenum (Mo), and tungsten
(W). The remaining metals in the crude oil that are measured are: iron (Fe), vanadium (V) and
potassium (K).

The data is arranged by condition severity, from lowest to highest, in order to see easily a
trend. Figure 7-30 shows a column plot, where the original crude oil (orange) and the feed with
catalyst (blue), are the initial values for comparison, followed by the sample arranged as it was
mentioned before. A clear decrease in metal contents is observed. The data is divided by added
metals and original material in the feed. The latter, has a decreasing trend. We can say that
demetalization is occurring in major proportion for V and K. For iron, an increasing and
decreasing behaviour is observed, this could be due to corrosion particles in the set up or error
in the measurements, not significant increment or reduction is observed, a steady trend can be
assure.

For the added metals, reduction is observed to, but we cant conclude that it is due to
hydrodemetalization. This can also be a result of deposition of the added metals in the system,
probable condensation, and precipitation at severe conditions.

Figure 7-31 shows the decrease metal trend vs residue conversion. For the original metals in
the crude oil a Cartesian plot is set. For added metals, a semi log plot reflects a better
description of the phenomena. The latter shows a higher and faster decrease as the severity
 141

increases (conversion), while for the original, a smooth trend is observed. Vanadium is the
metal that decrease the most in the original feed. For the added metals, all decrease or
precipitate fast. This is important to take into account for future tests in fields where low
porosity and permeability are predominant.

a) b)
Figure 7-31 Hydrodemetalization trend per type of metal, a) original in feed, b) added metals.

7.1.4.3. Correlation

Figure 7-32 Viscosity decreasing at certain residence time and temperature.

Table 7-13 Raw data for viscosity correlation.

Viscosity (cP)
Temp 1 10 100 1,000 10,000
(C) Residence time (hr)
320 416.9 321.7 226.5 131.3 36.1
340 337.7 253.7 169.8 85.9 2.0
360 242.2 170.7 99.2 27.6 -43.9
 142

Table 7-13 shows the values of viscosity used in order to plot the data. The calculation response
to the residence time needed to reach a certain value of viscosity at a certain temperature.
Figure 7-32 shows the behavior of the viscosity with the temperature and residence time. As it
was observed from experimental data, the viscosity reduces at higher residence times, if we
maintain the temperature constant and vice versa.

For the API gravity, the same calculation was performed and, Table 7-14 shows the results used
for the correlation plot. Figure 7-33 shows the API behavior for the residence time and
temperature conditions evaluated. As it was observed, the API gravity increases with the
increase in residence time at a constant temperature and vice versa.

Another analytical value determined is the P-value, this help us to evaluate the stability of the
oil, where a number of 1 corresponds to an unstable material and higher values, refer to a
stable oil. Due to the severity of the conditions, P-value decreases, being the most severe
condition the most unstable.

Table 7-14 Raw data for API correlation.

API
Temp 10 15 20 25
(C) Residence time (hr)
320 - 118.0 250.6 383.1
340 - 98.9 214.5 330.1
360 - 39.1 159.2 279.4

Figure 7-33 API increasing at certain residence time and temperature.

 143

In the case of the non-reacted crude oil (original feed), the P-value correspond to 2.75. For the
most severe condition, this value dropped to 1.2, which means that the oil became unstable,
but still in a secure range. A higher severity must be avoid.

Figure 7-34 P-value comparison for each API and viscosity value.

Figure 7-34, shows the behavior of the viscosity, API, and P-value being the diameter of the
circles. A trend can be observed. The desired conditions for a lab experiment could be the green
points that maintain good upgrading and no risk of an unstable oil that could drop all the
asphaltene content, which could reduce permeability in the reservoir porous media.
 144

7.2. Vacuum Residue Kinetic Model

The first analysis is done for the Ag crude oil, where reactivity is evaluated, observing favorable
upgrading properties. ISUT process has VR as an injection fluid, for that reason it is important to
evaluate its reactivity. The ISUT theory state that the reservoir will act as a refining reactor, with
the proper conditions (pressure, temperature and residence time) will convert vacuum residue
into a lighter oil.

Table 7-15 Experimental conditions to evaluate.

Temperature Residence time (hr)

(C ) 48 72 96 120
320 * *
340 * * *
360 * *

The in-situ crude oil in the formation will be upgraded as a secondary mechanism. The
conditions evaluated for VR are shown in Table 7-15. It is important to notice that the residence
time has increased in the lowest temperature condition due to the high viscosity of the VR. At
lower temperature, residue conversion takes longer to obtain important upgrading.

Table 7-16 Samples obtained per condition run.

Time Temp
Sample Reactor
(hr) (C)
VR1 48 340 1
VR2 48 340 1
VR3 72 340 2
VR4 72 340 2
VR5 72 360 1
VR6 72 360 1
VR7 96 340 2
VR8 96 340 2
VR9 96 360 1
VR10 96 360 1
VR11 96 320 1
VR12 96 320 1
VR13 120 320 2
VR14 120 320 2
 145

Seven conditions are run, sampling every half residence time. At the end, 14 samples are
characterized and will be used as an input for mathematical kinetic modeling. The upflow
configuration is used, no thermal and partial pressure conditions are evaluated. Two reactors
are used in parallel for this experiment. Table 7-16 shows each sample condition and the
reactor used for its evaluation. 1,000 cm3 of H2 per cm3 of oil is injected.

7.2.1. Temperature and residence time effect

Using the same principle of evaluation for the crude oil, conditions and conversion calculation
(Equation 19), are the reference for the analysis.

Vacuum residue feed contains a 90% of the residue component. The conversion is expected to
be higher than in the crude oil. Figure 7-35 show the conversion evolution as a function of
residence time at each temperature tested.

Figure 7-35 Residue conversion as a function of residence time and temperature for VR feed.

Once we evaluate the crude oil and the vacuum residue, we can compare the upgrading
process at different conditions. For a temperature of 360 C a maximum conversion of 50.5 % is
obtained for the VR at 96 hrs, and 46.4 % at 72 hrs for the crude oil. The crude oil stabilization
trend is observed. Higher residence times are needed for the VR to reach that state.

For 340 C, VR reach a stabilized state at 45 hrs. In the crude oil a positive trend is still observed.
Comparing conversion values at 96 hrs, crude oil reached 28 %, and VR 25 %. At this condition,
 146

VR residence time has no important impact on residue diminish. Higher temperature is needed
to increase this process.

At 320 C, an increasing trend is observed, more runs are needed at higher contact time. A
stabilization trend is expected, as it is observed at 340 C. A value of 20% conversion is
calculated at a residence time of 96 hrs, comparing with crude oil. 18% was reached at 48 hrs
with no significant change.

Higher residence times are need to reach the same conversions obtained in the crude oil at
temperatures lower than 340 C. At 360 C, the tendency is positive, higher conversion could be
achieved compared with the crude oil.

Temperature has an important effect on residue conversion in the VR feed. Thermal cracking is
reached at higher temperatures in order to brake the carbon-carbon bonds, and subsequent
hydrogenation could take place.

As it is observed in the Ag crude oil kinetic model, temperature has a substantial impact at
values higher than 340 C, where conversion increases dramatically (Figure 7-36).

Figure 7-36 Temperature impact on residue conversion.

7.2.2. Upgrading results

Once that the impact of the conditions is analyzed, we have to review the product quality.
Figure 7-37 shows the simulated distillation curves for each sample obtained per condition.
 147

The VR upgrading is easily identified. The curves in the higher section of the plot correspond to
the VR feed before treatment. High boiling point components characterize the residue. The
blue discontinue line represent the curve for the original oil. The subsequent lines that keep the
VR shape, correspond to each of the reacted products of the VR, from the less severe condition
(near VR) to the most severe that are below the original oil curve. This means that, at severe
conditions, we obtain a lighter oil than the original oil in the reservoir. These curves correspond
to the higher temperature conditions (360 C).

Figure 7-37 Simulated distillation curves for each product sample of the kinetic model
experiment for VR.

The curves between the original oil and the VR correspond to the 320 and 340 C conditions.
Upgrading is observed, but higher temperatures are needed to reach upgrading that results in a
lighter oil than the original in the reservoir.
 148

From the curves we obtain the component percentage by lumps, to evaluate the lighter cut
formation and residue reduction. Raw data is shown in Table 7-17.

Table 7-17 Composition (wt %) for each catalytic condition sample.

Time Temp.
Run Reactor Gases Naphtha Distillates VGO Residue
(hr) (C)
Feed - - - 0.0 0.0 0.0 9.8 90.2
VR9 96 360 1 2.5 4.4 13.2 35.3 44.7
VR10 96 360 1 2.5 5.7 14.0 35.3 42.5
VR5 72 360 1 2.1 3.9 10.1 30.6 53.3
VR6 72 360 1 2.1 4.4 10.6 31.3 51.6
VR7 96 340 2 0.7 1.1 5.4 24.7 68.1
VR8 96 340 2 0.7 0.7 5.4 25.2 68.0
VR3 72 340 2 0.7 1.3 5.4 23.8 68.9
VR4 72 340 2 0.7 0.9 4.6 23.2 70.6
VR1 48 340 1 0.9 1.2 4.8 23.1 70.0
VR2 48 340 1 0.9 1.2 4.8 23.1 70.0
VR13 120 320 2 0.6 0.0 2.6 19.0 77.8
VR14 120 320 2 0.6 0.0 2.7 19.7 77.0
VR11 96 320 1 0.8 1.3 3.8 21.7 72.3
VR12 96 320 1 0.8 1.0 2.8 19.7 75.6

Figure 7-38 shows the stacked columns of the components obtained from simdist per condition
sample. From left to right corresponds the feed, and the most severe condition to the least,
respectively. The black line resembles the API gravity of the samples.

The feed column is 90 % blue, representing the residue component and 10 % VGO. The original
oil was cut at 510 C to obtain the residue feed for this experiment. The kinetic evaluation
model has a lump that goes from 550 C and higher. For this reason we observe 10 % of lighter
material in the feed (VGO). If it was cut at 555 C, no light cut would be found, and 100% could
correspond to the residue component.

The residue reduction is clearly observed at all the conditions evaluated. Lighter materials are
produced, being VGO the higher component followed by distillate, naphtha and gases. The
most severe conditions have a 53 % residue, and the rest correspond to lighter compounds.
Thermal cracking and hydrogenation is acting in the residue conversion.
 149

Compared with the original crude oil at 360 C and 72 hrs, the residue component reached a
value of 37 %, for VR it is 53%. Higher residence time is needed to achieve higher upgrading of
the residue. The components at this condition in VR are similar to the ones obtain at 360 C and
24 hrs for the original crude oil.

Figure 7-38 Catalytic sample components and API curve.

At 340 C the stabilization trend is observed, a slight reduction in the residue component, and
its proportional increase in lighter components. It is the same case at 320 C. No significant
change is observed.

Temperature plays an important role in the VR feed, residue compounds need higher
temperatures to break and be hydrogenated.

7.2.3. Quality results

The properties measured are: viscosity, density, API, P-value, MCR, Nitrogen and Sulfur content.
In Table 7-18, the raw data is shown for each condition sample.

Table 7-18 Quality variables evaluated in the reacted samples.

Time Temp Viscosity Density Conversion MCR N S

Run API P-value
(hr) (C) (cP) gr\cc (%) (wt %) (PPM) (PPM)
Feed - - 567626 1.0784 -0.4 0.0 3 28.8 8579 44568
VR5 72 360 350 1.0065 9.1 40.9 1.4 17.7 8133 31919
VR6 72 360 162 1.0001 9.8 42.8 1.3 - 8269 31001
VR9 96 360 82 0.9879 11.6 50.5 1.3 15.0 8804 27659
VR10 96 360 56 0.9801 12.7 52.9 1.2 - 8626 26983
 150

VR1 48 340 3101 1.0342 5.2 22.4 2.4 21.0 8233 38798
VR2 48 340 3101 1.0342 5.2 22.4 2.4 - 8233 38798
VR3 72 340 1983 1.0292 5.8 23.6 2.2 20.6 8084 37343
VR4 72 340 3416 1.0331 5.3 21.7 2.3 - 8227 35479
VR7 96 340 1915 1.0294 5.8 24.5 2.2 19.6 8478 33970
VR8 96 340 1219 1.0268 6.2 24.6 2.2 - 8483 33360
VR11 96 320 6374 1.0346 5.1 19.8 3 19.9 8821 36784
VR12 96 320 13825 1.0327 5.4 16.1 3 - 8621 37874
VR13 120 320 6752 1.0397 4.5 13.7 3 22.2 8467 38360
VR14 120 320 20188 1.0416 4.2 14.6 3 - 8457 37917

7.2.3.1. Viscosity
The first parameter evaluated is viscosity. Thermal energy applied to crude oil reduces viscosity.
At very high temperatures, thermal cracking happens, upgrading is observed, hydrogenation
avoids coke formation and increases the lighter compounds by hydrogenating the free radicals
left by the molecules rupture.

Figure 7-39 Viscosity reduction at different temperature and residence time conditions (80 C).

In Figure 7-39 the viscosity reduction as a function of residence time per temperature condition
is observed. A semilog plot is created, an exponential trend fits each of the temperatures
conditions. As it was seen in the crude oil, the highest reduction is at higher temperature. Due
to the high amount of residue compound where thermal energy acts. A lineal correspondence is
observed.
 151

Compared with the crude oil catalytic samples, at 360 C and 72 hrs, a similar reduction in
viscosity is obtained. At 340 C and 48 hrs, the same viscosity is obtained for both experiments,
but at higher residence times. No higher reduction is observed, as it was for the crude oil. At
320 C, a better reduction is obtained by the crude oil with a smaller residence time.

Figure 7-40 Viscosity reduction as a function of conversion (80 C).

A correlation as a function of conversion is developed. Figure 7-40 shows the exponential trend
in a semi log plot. This correlation helps for a quick calculation and estimation of viscosity at 80
C of VR at a certain conversion.

Figure 7-41 Viscosity as a function of residence time and conversion per temperature range.

Another plot was created relating viscosity with temperature, conversion and residence time at
certain temperature. Figure 7-41 shows this relationship. An exponential trend fits the
 152

experimental data for the three temperatures evaluated. A higher decrease of viscosity is
obtained at higher temperature. A stabilization state at 340 C is observed.

7.2.3.2. API gravity

An important improvement of the oil quality is observed when API gravity is calculated. The
relationship pf density and API gravity is shown on Figure 7-43.

Figure 7-42 API gravity increase as a function of residence time (ambient temperature).

Figure 7-42 shows the behavior of the API gravity as a function of residence time for given
temperatures. At low temperature conditions, a stabilization state is reached in density
upgrading. No important change is observed between 320 C and 340 C, almost the same
values are obtained, and only 1 API change was measured between both temperatures.

Figure 7-43 Density and API gravity correlation.

 153

Figure 7-44 API gravity improvements as a function of conversion.

A linear trend is observed when API is plotted as a function of conversion. The correlation is
shown in Figure 7-44. A linear relation exist between residue reduction and API gravity. The
heavy compound in this upgraded samples are still providing the quality values of the process.
It is important to notice that the residue API passed from -0.4 to a 12.73, a better quality
product compared to the in situ oil in the formation that has a value of 11 API.

7.2.3.3. Microcarbon (MCR)

MCR value is higher in the VR than in the crude oil, 28.9 % and 17.9 % respectively. This is
expected due to the higher asphaltene and heavy compounds that make up the residue of the
crude oil. VR is the residue compound of the original crude oil. Figure 7-45 shows the MCR
trend vs temperature at different tested temperatures.

Figure 7-45 MCR as a function of residence time per temperature tested.

 154

Coke reduction due to the catalytic hydrogenation reactions in the VR reduced the probability
of coke deposition from 28.9 % to 14.96 %, for the most severe condition. A linear trend fits the
experimental data at 360 C. Higher residence time is needed to reach a better reduction or
stabilization of this parameter.

For lower temperatures, 320 C and 340 C, stabilization is reached and no significant difference
is observed between both temperatures. Besides to the stabilization of the reduction of MCR,
hydrogenation of the free radicals due to the thermal cracking reaction of the residue is
observed. If hydrogenation is not active, free radicals would not be hydrogenated, and a higher
percentage of MCR would be obtained.

Hydrogenation is not increasing due to the free radicals formation stabilization, at low
temperatures, thermal cracking is not breaking more bonds for hydrogenation. For that reason,
no improvement at higher residence times is detected.

7.2.3.4. Sulfur content

For the sulfur content measurements, the trends are different (Figure 7-46) compared to the
other parameters analyzed already. For temperatures higher than 320 C, a linear trend fits the
experimental data. No stabilization is observed at 340 C and 360 C, meanwhile it is reached at
320 C. Hydrogenation of the radicals cracked by thermal cracking is taking place.
Hydrodesulfurization is one of the reactions acting in the residue conversion.

Figure 7-46 Sulfur content as a function of residence time per temperature range.
 155

Figure 7-47 Sulfur content reduction as a function of VR conversion.

A sulfur content as a function of conversion plot is created, an exponential trend fits the
experimental data with a 93 % match (Figure 7-47).

7.2.3.5. P-value
Vacuum residue is a more stable component than the original crude oil, a value of 3 was
measured while 2.75 was measured for crude oil.

Figure 7-48 shows the P-value behavior at a certain residence time for each temperature
evaluated. As it is expected and as observed in the crude oil, 360 C conditions make the fluid
unstable. A value of 1.2 was reached in a severe condition in both cases. Lower temperature
products have stable products with a stabilization state at 340 C and 320 C.

Figure 7-48 P-value as a function of residence time per temperature range.

 156

An example is shown in Figure 7-49, where sample 10 that represents the most severe
conditions, precipitation is observed at 1.2. For mild conditions, no precipitation is observed,
the value is higher than 3.

Original Vacuum residue

2.8 3 3.2
Sample 12: 96 hrs, 320 C

2 2.5 3
Sample 10: 96 hrs, 360 C

1 1.2 1.4
Figure 7-49 Microscopic view for evaluation of P-value.

7.2.4. Kinetic evaluation

Calculating the conversion, shown before, and plotting it with the yields of each cut, we
observe a linear trend of the residue reduction/conversion. This value reached up to 51%,
which means that half of the vacuum residue was converted into lighter products, having a
result of an upgraded oil.

VGO yield increases from 10% to 35% and the distillate, naphtha, and gas cuts appear, reducing
the density, and viscosity, and increasing the API gravity value. Figure 7-50 shows the behavior
of the yields with respect to the conversion of the vacuum residue yield.

Calculating the conversion of the yields and plotting against the residue conversion (Figure
7-51), we can see the same three trends of the crude oil. A 45 degrees angle corresponding to
the reduction of the VR yield, the increasing polynomial behavior of the VGO as a first product
 157

of the reaction, and the polynomial increasing tendency of the distillates, naphtha and gases,
which appears as a secondary products of the reaction (Figure 7-52).

Figure 7-50 Component percentage (wt %) vs. residue conversion (wt. %).

Figure 7-51 lump conversion (wt. %) vs residue conversion (wt. %).

Comparing with the crude oil, the trends are better seen in the VR reactions. This is due to the
creation of lighter yields such as distillates, naphtha and gases; that the VR feed does not
contain.
 158

As in the crude oil, naphtha generation is not very significant VGO and distillates are the cuts
that give the new properties of the oil.

Figure 7-52 lump conversion (wt. %) vs residue conversion (wt. %).

Analysing the properties conversion (Figure 7-53), the micro carbon content of the vacuum
residue is improved with a reduction of almost 47%, as well as the sulfur content reduction of
40%. This proves that hydrogenation of the cracked molecules are taking place, helped by the
catalyst.

Figure 7-53 Property conversion (%) vs. residue conversion (wt %).

In this case the API gravity conversion value obtained is positive, increasing from -0.4 to 12.7, a
32% conversion is observed.
 159

In a lower manner, density is improved. This is expected due to the nature of the upgrading
process. Nitrogen content also reduces but not in a significant way, as observed in the crude oil.

From this, we can conclude that the hydroprocessing is taking place, beginning with the
cracking of the VR that conveys to the rupture of the heaviest molecules that are hydrogenated,
by the excess hydrogen in the system, reducing the MCR content and sulfur content.

Now, we can evaluate the reaction order to obtain the kinetic parameters from the Arrhenius
plot. We used the same equation (Equation 20) to determine if it is a first order reaction
process. Figure 7-54 shows the three conditions evaluated that have a linear trend that pass
through the origin. It implies that the process is again a first order reaction that only takes into
account the reactant.

For the desulfurization process, it is also a first order reaction. Both process are related to the
vacuum residue conversion only. Figure 7-55 shows three temperature conditions evaluated
with a linear trend. It is important to notice that the agreement of the regression correlation is
better for the vacuum residue evaluation than the crude oil. A better correlation is obtained.

From the order of reaction analysis we obtain the data to calculate the Arrhenius parameters.
Table 7-19 shows the calculations results that will be input to the plot. The trend line has a
better fit compared to the crude oil. Figure 7-56 shows the trend line that fits the three points
of temperature evaluated.

Figure 7-54 First order reaction evaluation for residue Hydroprocessing.

 160

Figure 7-55 First order reaction evaluation for hydrodesulfurization.

From this data we obtained that the activation energy for the hydroprocessing reaction of the
vacuum residue is 131.74 kJ/mol, which is in the range of catalytic reactions. Comparing this
value with the crude oil, it is higher. This is expected due to the percentage of vacuum residue
yield (90%), and more energy is needed to convert this component into lighter products.

Table 7-19 Parameters for Arrhenius plot.

T 1/T k
-1
ln(k)
C K h s-1
360 634.15 0.001576914 0.007547 -4.886605146
340 614.15 0.001628267 0.002967 -5.820203938
320 594.15 0.001683077 0.0014 -6.571283042

Figure 7-56 Arrhenius plot for residue Hydroprocessing.

 161

Using the macro explained before, using the same Arrhenius plot and the data that it provides,
the calculated activation energy is 139.2 kJ/mol. Which compared with the value calculated
before, is almost the same. The fit is shown in Figure 7-57, and the trend line has a very good
match.

Figure 7-57 Arrhenius plot for global reaction constants.

The match of the kinetic constants for each of the reactions are shown in Figure 7-58, where
good r2 values are obtained.

Figure 7-58 Arrhenius plot for each reaction constant.

The calculated values obtained per reaction are shown in Table 7-20, were the activation
energy of the vacuum residue converted to VGO, reaches a value of 128.1 kJ/mol.
 162

Table 7-20 Kinetic constants for Hydroprocessing modeling.

EA
320 C 340 C 360 C Ln A0 R2
kJ/mol
1 0.00099 0.00237 0.00509 19.1 128.1 1.00
2 0.00020 0.00055 0.00144 22.7 153.8 1.00
3 0.00002 0.00013 0.00074 45.3 276.5 1.00
4 0.00006 0.00012 0.00041 20.0 147.1 0.95
5 0.00044 0.00105 0.00241 19.0 131.8 1.00
8 0.00061 0.00107 0.00183 9.9 85.8 1.00

From this evaluation we observed that the reactions for the 5 lumps are the same as for the
crude oil, being the main reaction is the conversion of the vacuum residue. Figure 7-59 shows
the mechanism of reaction for the vacuum hydroprocessing.

Figure 7-59 residue Hydroprocessing diagram.

The same calculation is performed for each temperature condition matching the experimental
data with an acceptable agreement. Figure 7-60 shows the calculation and fit of the
experimental data, and the comparison between the calculated and measured yield per lump.

a)
 163

b)

c)
Figure 7-60 Components calculation vs experimental data.

7.2.4.1. Hydrodesulfurization
Sulfur removal process is evaluated kinetically for the VR. Figure 7-61 show the linear trend that
the reactions have at three different temperatures (320 C, 340 C and 360 C). Compared with
the crude oil, a better agreement and linearity is observed in the VR desulfurization results.

Figure 7-61 Arrhenius plot for hydrodesulfurization of VR

 164

The activation energy calculated produces 94.49 kJ/mol, this being smaller than the residue
Hydroprocessing of 132 kJ/mol. The crude oil kinetics also observed a smaller value for sulfur
removal.

7.2.4.2. Correlation
From these analysis we can conclude that the vacuum residue of Ag oil is reactive. We can
obtain an upgraded oil applying certain temperature, residence time, catalyst, and hydrogen;
keeping those changes at room conditions. The energy to be applied is higher than the crude oil
but keeps in the catalytic reaction range. The vacuum residue of the Ag reservoir is suitable for
the ISU technology.

For the VR, as for the crude oil, the viscosity and API gravity correlation were calculated. For
viscosity Table 7-21 and Figure 7-62, shows the behavior of this parameter for the conditions
evaluated. It is observed that higher residence times are needed to reach the same viscosity
calculated for the crude oil.

Table 7-21 Raw data for viscosity correlation plot.

Viscosity (cP)
Temp 1 10 100 1,000 10,000
(C) Residence time (hr)
320 566.4 452.8 339.2 225.6 112.0
340 403.8 305.1 206.5 107.9 9.2
360 252.0 170.5 89.1 7.7 -73.7

Figure 7-62 Viscosity correlation plot for different residence time and temperature conditions.
 165

Figure 7-63 and Table 7-22, show the calculated parameters for the API gravity. Likewise,
viscosity, and higher residence times are need to obtain the same values calculated for the
crude oil.

Table 7-22 Raw data for API correlation plot.

API
Temp 4 5 10 15 20 25
(C) Residence time (hr)
320 20.11 75.60 353.08 630.56 908.03 1,185.51
340 - 0.92 44.99 274.55 504.11 733.67 963.23
360 - 164.00 - 124.00 76.00 276.00 476.00 676.00

Figure 7-63 API correlation for different temperature and residence time conditions.

Figure 7-64 P-value comparison for different viscosity and API gravity
 166

Analyzing the P-value (Figure 7-64), the VR seems to be more stable than the crude oil, a value
of 3 compared to 2.75 was measured. The same conclusion is reached. At more severe
conditions the products become unstable, but the vacuum upgraded oil is more stable than the
original oil. No higher severity must be reached.

The ISU process expects to upgrade the VR up to the in situ crude oil. The property to achieve is
density, for consequence API gravity. A value of 11 API is targeted. Using the correlations
mentioned before, is reached at a conversion of 46.5 %. With this value, a viscosity of 90 cps at
80 C is obtained. Table 7-23 show the residence times calculated with correlations at each
temperature condition, in order to reach in-situ oil properties.

On Figure 7-62, the red dotted line corresponds to a value of 90 cps. Depending on the
temperature reached, a certain residence time is needed to obtain that conversion and
viscosity. For a condition of 300 C and 360 C, a residence time of 450 and 90 hrs respectively is
required.

For API gravity (Figure 7-63), the red dotted line corresponds to a value of 11 API, at the same
temperature conditions than those for viscosity a residence time of 520 and 120 hrs
respectively are required.

These conditions lead to a stability value of 1.3, which is still secure for the ISU process (Figure
7-64).

Table 7-23 Residence time required for VR to reach in-situ oil properties using correlations.

Viscosity @ 80C API

Target 90 11
Temperature Residence time
(C) (hr)
320 344.4 408.6
340 211.0 320.5
360 92.8 116.0
 167

7.3. Comparison
Now that the hydroprocessing evaluation and modeling of Ag field crude oil and vacuum
residue is achieved, it is important to evaluate the differences results with previous CBUG
experiments. As it was mentioned before, several studies have been developed, the latest
kinetic models for bitumen were evaluated for Bitumen (Loria, Trujillo-Ferrer, Sosa-Stull, &
Pereira-Almao, 2011), a derivate pitch, and vacuum residue (Da Silva, 2014). Da Silvas re-
evaluation of Lorias data for bitumen, is the one used for this comparison.

Table A.1-1 (Apendix A) shows the upgraded bitumen data using 1,200 ppm of metal
concentration. The conditions range for temperature: 320 C 380 C, for a residence time of 9
51 hrs. No API or viscosity data is provided. Conversion ranges from 9.2 wt. % to 50.3 wt. % at
the most severe condition (Loria, Trujillo-Ferrer, Sosa-Stull, & Pereira-Almao, 2011). Figure 7-65
shows (blue) the components corresponding to the bitumen and (red) the components of Ag
crude oil, against the residue conversion of each fluid. For this figure, residue, VGO, and
distillates are shown. We can observe that the trends are similar but, Ag crude oil is heavier or
has less light compounds than the bitumen. For that reason the residue conversion is parallel.
The VGO trend is similar, and both tend to reach a plateau or stability at higher conversions,
while distillates tend to continue increasing.

Figure 7-65 Crude oil component vs. conversion, comparing upgrading of Loria (blue) and
Orozco data (red).

For the naphtha component, both trends are increasing, being higher yield in the Ag crude oil,
as well as the gaseous component. With this three last lumps, we can conclude that the residue
 168

conversion first pass to VGO, and the VGO at certain point begins to decompose to lighter
components, or the residue begins to convert directly to lighter compounds and VGO begins to
stay stable.

Figure 7-66 Vacuum residue components vs conversion, comparing Da Silva (blue) and Orozco
data (red).

The same treatment is used for the vacuum residue comparison. In Figure 7-66 we can observe
that the vacuum residue obtained from the bitumen has more light compounds compared to
the Ag VR (Table A.1-3 and Table A.1-4). Parallel trends are observed for residue and VGO
components, but for distillates, both behaviors overlap. The same production and degree of
production of this compound is created as the conversion becomes higher. All trends, except
residue, have a positive trend. Ag VR VGO lump tends to reach a stabilization, but further
experimental points would have to be gathered to confirm this trend.

Naphtha production of Ag VR has a rapid increase as the conversion increase. VGO has not
reached a plateau. This means that most of this components comes directly from the residue
conversion, same situation occurs with the gas lump.

The next comparison is between Ag VR and the pitch derivate from the bitumen (Figure 7-67).
The lumps upgrading are parallel. Pitch has less light compounds than the VR that was obtained
from the same bitumen, this means that the distillation or cutting of this bitumen was not deep
performed, as was for the Ag VR. For this reason, Ag VR is more alike to the pitch than the
bitumen VR.
 169

Figure 7-67 Pitch and VR components vs conversion, comparing Da Silva (blue) and Orozco data
(red).

In the CBU group, another Mexican reservoir is being analyzed for the same process
application, this is an offshore field and a crude oil kinetic model was also produced (Chavez,
2015). This reservoir is denominated Tk. Figure 7-68 shows the comparison of both Mexican
oils. The behavior of the curves are not similar, the distillates and VGO lumps of Tk crude oil
have similar initial percentage. VGO stabilizes at high conversions and distillates continue
increasing. Both curves begin to separate at a conversion of 50 %. A high severity was used for
the kinetic model of Tk.

Figure 7-68 Crude oil components vs conversion, comparing Chavez (blue) and Orozco data
(red).

The high amount of light components of Tk can be explained due to its production mechanism,
this fluid is extracted using solvents that are concentrated in the medium components, such as
distillate lump in this case, to reduce viscosity and make the extraction easier. For that reason,
 170

the other trends are quite similar, but are affected by the solvent in the oil. We can say that
both crude oils will behave similarly at original conditions.

Once we analyzed the behavior of conversion and lumps for each fluid studied by the CBU
group, we can compared the kinetic values obtained from their mathematical models. All these
evaluations were done with the Excel program mentioned before. The global kinetics can be
obtained using the Arrhenius plot and know the activation energy and pre- exponential factor
to calculate the behavior at certain temperature. In Figure 7-70, the Arrhenius plot is set with
the kinetic parameters for each fluid evaluated: Bitumen (blue), VR (black), Pitch (orange) (Da
Silva, 2014), crude oil (brown) from Tk (Chavez, 2015), crude oil (light blue), and VR (yellow)
from Ag.

Pitch Tk crude oil

Figure 7-69 Temperature impact for upgrading in pitch and Tk crude oil.

From the pitch and the Tk crude oil experimental data, additional plot (Figure 7-69) were made.
As it is observed in the Ag crude oil and VR experiment data, temperature has an important
impact when it is higher than 340 C. Figure 7-69 shows pitch and Tk crude oil behavior. Each
line represents residence time as a function of temperature and conversion. As it is observed
for pitch, the conversion increase greatly at temperatures higher than 350 C, for lower values,
conversion shows a slight improvement. For Tk crude oil, all the experiments currently available
were performed at temperatures higher than 350 C. For that reason, conversion has a linear
upgrading tendency.
 171

We can conclude that temperature at higher values than 340 C has an important impact on
upgrading, and mild conversions are achieved at lower temperatures. Thermal cracking
increases its reactivity at temperatures higher than 350 C, breaking bonds and allowing
hydrogenation and upgrading without coke problems.

From Figure 7-70 we can identify 4 trends that have an almost parallel, these are: pitch, VR of
Ag, crude oil (CO) of Tk, and Athabasca bitumen. Vacuum residue from Athabasca and crude oil
from Ag, have different trends. Using Figure 7-70 we can say that the four parallel slopes have a
similar trend and higher activation energies. The last two have different slope, meaning the
lowest activation energy. As we can observe in Table 7-24, the parallel trends have higher
activation energies than the ones that have a lower negative plot.

Figure 7-70 Arrhenius plot comparing all the kinetic models of the fluids analysed.

We can say that the ones with higher activation energy are more sensitive to temperature than
those with lower values, or that more energy is needed to make the reaction happen.

Table 7-24 Activation energies and pre-exponential factors of the different fluids analyze.

Ea Ao
Fluid
kJ/mol
Bitumen (At) 160.2 4.70E+11
Pitch (At) 153.5 1.97E+10
VR (Ag) 2 139.2 2.31E+09
VR (Ag) 1 131.7 5.14E+08
CO (Tk) 125.6 2.18E+08
 172

CO (Ag) 1 88.7 9.81E+04

CO (Ag) 2 60.4 6.50E+02
VR (At) 44.8 2.75E+01

Comparing the original fluids, bitumen, crude oil from Tk and Ag, we can observe that Tk and
bitumen require higher activation energy than Ag crude oil, bitumen being the highest. Table
7-25 and Figure 7-71 show this comparison.

Figure 7-71 Original crude oil upgrading comparison in Arrhenius plot.

Table 7-25 Activation energies and pre-exponential factors for original fluids upgrading.

Ea Ao
Fluid
kJ/mol
Bitumen (At) 160.2 4.7E+11
CO (Tk) 125.6 2.2E+08
CO (Ag) 1 88.7 9.8E+04
CO (Ag) 2 60.4 6.5E+02

Comparing Ag VR with VR and pitch from Athabasca bitumen, the Ag VR has similar behavior to
the pitch. As it was seen before, the pitch has less light components than the VR from the same
bitumen, having similar heavier compounds like the Ag VR. Figure 7-72 and Table 7-26, show
the parallel and like trend of Ag VR and pitch, and the corresponding activation energy, being
similar in the heaviest components.
 173

Table 7-26 Heavier fluids comparison in Arrhenius plot.

Ea Ao
Fluid
kJ/mol
Pitch (At) 153.5 2.0E+10
VR (Ag) 2 139.2 2.3E+09
VR (Ag) 1 131.7 5.1E+08
VR (At) 59.8 6.2E+02

Figure 7-72 Vacuum residue and pitch comparison in Arrhenius plot

7.4. Stoichiometry of reactions

Once the kinetic model has a good agreement with the experimental data, the reactions have
to be balanced in order to use them in any fluid software. In order to do this a stoichiometry
balance using molecular weights of the lumps is used. These values are shown in Table 7-27.

Table 7-27 Molecular weight for each lump.

TBP MW
Lump Component
(C) gr/gr-mol
Gases C1-C4 26.9
Naphtha IBP-216 C5-C12 101.11
Distillates 216.1-343 C13-C20 215.5
VGO 343.1-550 C21-C44 442.5
Residue >550.1 C45+ 839.13
 174

Table 7-28 Product coefficients for each reaction for the residue of Ag crude oil.

Reaction Equation Coefficient

VR + H2
1 VGO 1.90089

VR + H2
2 Distillate 3.9032

VR + H2
3 Naphtha 8.319116

VR + H2
4 Gases 31.269

VGO + H2
5 Distillate 2.0627

8 D + H2 Naphtha 2.151279

For the crude oil, six reactions are matched with the experimental data according to the kinetic
model proposed (Sanchez, Rodriguez, & Ancheyta, 2005). These reactions with their
corresponding stoichiometry coefficient for the products are shown in Table 7-28.

For reservoir simulation, these equations with their corresponding kinetic parameters have to
be used, because the model only accept one fluid model. In this case is the original oil
contained in the reservoir that will be reacting, for this reason this kinetic model has to be
applied.
 175

8. CHAPTER EIGHT: CONCLUSIONS

EOR processes are highly applicable for single porosity reservoirs, such as sandstones, where
porosity and permeability make the sweeping effect easier, helped by several mechanisms to
increase the oil recovery factor. For naturally fractured carbonate reservoirs, little experimental
support is found in literature, with most of the experience found at laboratory scale.

A novel technology is being proposed that could be applicable for this type of reservoirs, In Situ
Upgrading via hot fluid injection. This EOR methodology takes refinery concepts underground,
using the reservoir as a reactor to make hydroprocessing reactions happen at high pressure,
temperature, and residence time. The concept is to inject the heavy fraction of the crude oil
(residue) and convert it into original crude oil.

Heat capacity of the residue is higher than other fluids actually used. This heat can help to
extract the oil contained in the matrix due to expansion and extraction of the rock, and
vaporization of some of the fluid inside the porous media. Additionally, the heat will help to
reduce viscosity and begin cracking the in situ crude oil, producing the conversion chain
reaction in the presence of catalyst and hydrogen.

The fluid tested from Ag reservoir was upgraded at several severity conditions, being the lowest
at 320 C and 24 hrs residence time obtaining a conversion of 7 %, and for the most severe
around 40 % at 360C and 72 hrs. For the residue, the conversion ranged from 13 % to 50 % at
320 C and 120 hrs, and 360 C and 96 hrs, respectively.

Hydrotreating was observed in the reduction of the sulfur content, lowering of micro-carbon
(MCR) percentage and metal elimination (V, Fe). Nitrogen content remains constant indicating
that the conditions are not suitable for the elimination of this element. In this process the Ni-
Mo-W trimetallic nano catalyst serves to provoke a mild Hydroprocessing of the fluids.

The catalyst added to the crude oil and vacuum residue in concentrations of 780 ppm and 671
ppm respectively, are sufficient to provoke the hydroprocessing reactions in the Ag crude oil
and vacuum residue and it was found that the particle sizes of catalyst incorporated via
preparation method range between of 177.8 nm and 172 nm, respectively.
 176

Activation energies calculated for hydroprocessing of the crude oil and residue are in the
catalytic range, being lower than it is found in literature for thermal cracking. Activation energy
is lower for the crude oil (89 kJ/mol) and higher for the vacuum residue (131 kJ/mol).

A kinetic model was established with good agreement to the experimental data for both fluids.
Using a 5 lumps reaction model, which is useful for a future reservoir numerical simulation
model, that can help to evaluate this process.

Comparing upgrading of Ag fluids with Canadian and Mexican reservoir oils, same trends are
observed. Using the same catalyst at different conditions, no significant variations different
from the composition of each fluid is found. This findings allow concluding that from the crude
oil reactivity side, the ISU process seems to be of universal application, however rock impact
ono the process, as well as the presence of different fluids in the reservoir (water, salts and
gases) may have a significant effect on performance than the characteristics of the bitumen or
crude oils to be produced.
 177

9. CHAPTER NINE: RECOMMENDATIONS

For future work, it is important to evaluate and set a thermal kinetic model of the Ag reservoir
to ensure the catalytic activity. Due to the thermal points evaluated, no significant change is
observed between thermal and catalytic conditions, in particular the micro-carbon content that
should differ in trend. As it is well known, coke formation via thermal process is expected, even
at residue conversion of 25%. It was not observed in the experiments contained in this work.

Stability of the oil is an important concept that has to be taking into account for a real scale
process. The P-value observed has a trend where at higher severity, a lower value of stability is
obtained. This means that at higher conversions, more light material is produced and the
asphaltene stability is affected. This can provoke a precipitation that could lead to plugging in
the porous media. Conversion has to be kept at mild percentages to avoid this probable
problem. As a rule of thumb, a 40% residue conversion may be the most appropriate to target.
This has to be verified.

For future application, a core plug reactor has to be set to evaluate the interaction of the
catalyst, hydrogen, crude oil, and vacuum residue at certain condition or severity must be
performed. Also evaluation of hydroprocessing reactions and their products for the upgrading
process must be performed.
 178

10. REFERENCES

Agilent Technologies. (2015). Library. Retrieved from Agilent Technologies Life Science and Chemical
Analysis: http://www.chem.agilent.com/Library/specifications/Public/5989-3290EN.pdf

Aguilera, R. (1995). Naturally fractured reservoirs. Tulsa, Oklahoma: Pennwell publishing company.

Ahr, W. M. (2008). Geology of carbonate reservoirs. Hoboken, New Jersey: John Wiley and Sons, Inc.

Al-Hadhrame, H. S., & Blunt, M. J. (2000). Thermally induced wettability ateration to improve oil
recovery in fractured reservoirs. Society of Petroleum Engineers, SPE 59289.

Al-Rashdi, Y. S., Al Bulushi, S., Al Kindi, A., & Azri, N. (2014). Preparing a challenging fractured carbonate
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 183

A. APPENDIX: Upgrading properties and kinetic model

A.1. Fluid upgrading properties per condition

Table A.1-1 Ath bitumen upgrading properties (Loria, Trujillo-Ferrer, Sosa-Stull, & Pereira-
Almao, 2011).

Condition
Temp (C) 0 320 350 350 360 360 360 380
Residence time (h) 0 25.4 16 51 16 30 36 9
Fraction Distribution (%)
Gases - 0 0.1 0.5 1 0.5 1.9 2.2 3.1
Naphtha IBP-216 C 3.4 3.9 4.7 5.3 6 7 7.5 9
Distillates 216-343 C 13.5 15.4 19.8 20.7 21.3 22.7 24.1 25.9
VGO 343-550 C 32.5 34.6 37.1 38.6 38.9 39.5 41 36.9
Residue >550 C 50.7 46 39 34.5 33.4 28.8 25.3 25.2
Conversion (%) 0 9.2 23.1 31.9 34.2 43.2 50.1 50.3

Table A.1-2 Ag crude oil kinetic modeling.

Condition
Temp (C) 0 320 320 340 340 340 340 360 360
Residence
(h) 0 24 48 24 48 72 96 24 72
time
Quality
API () 9.9 11.5 12.1 11.7 12.8 14.1 15.2 13.6 18.8
Viscosity @ 40 (cP) 81,248 13,401 5,194 5435.5 2282.2 1474.4 851.4 1596.8 87.6
Fraction Distribution (%)
Gases - 0 0.22 0.77 0.48 0.71 0.91 0.92 0.8 2.01
Naphtha IBP-216 C 4.89 4.23 5.16 4.9 5.29 5.55 6.91 4.6 9.52
Distillates 216-343 C 9.33 8.81 10.19 10.69 10.65 13.24 13.17 15.21 19.49
VGO 343-550 C 27.98 33.44 33.51 31.74 35.93 34.73 37.54 37.2 38.02
Residue >550 C 57.81 53.3 50.38 52.19 47.42 45.57 41.46 42.19 30.96
Conversion (%) 0 7.8 12.8 9.7 18 21.2 28.3 27 46.4
 184

Table A.1-3 Ath vacuum residue upgrading properties per condition (Da Silva, 2014).

Condition
Temp (C) 0 320 380 380 380 395
Residence time (h) 0 30 20 40 50 24
Quality
API ( ) 2.4 4.1 3.5 5.9 8.9 5.4
Viscosity @ 100 C (cP) 78,400 2,760 3,557 641 75 949
Fraction Distribution (%)
Gases - 0 0 0 0.2 0.4 0.3
Naphtha IBP-216 C 0.7 1 1 1.8 3.2 1.7
Distillates 216-343 C 0.6 2.4 1.8 5.5 10.9 4.6
VGO 343-550 C 27.1 32 31.2 37.8 46.5 37.6
Residue >550 C 71.4 64.7 65.9 54.7 39 55.8
Conversion (%) 0 9.4 7.6 23.3 45.4 21.8

Table A.1-4 Ag vacuum residue kinetic model.

Condition
Temp (C) 0 320 320 340 340 340 360 360
Residence time (h) 0 96 120 48 72 96 72 96
Quality
API () -0.4 5.4 4.2 5.2 5.3 6.2 9.8 12.7
Viscosity @ 80 C (cP) 567,626 13,825 20,188 3101 3416 1219 162 56
Fraction Distribution (%)
Gases - 0 0.8 0.6 0.9 0.7 0.7 2.1 2.5
Naphtha IBP-216 C 0 1 0 1.2 0.9 0.7 4.4 5.7
Distillates 216-343 C 0 2.8 2.7 4.8 4.6 5.4 10.6 14
VGO 343-550 C 9.8 19.7 19.7 23.1 23.2 25.2 31.3 35.3
Residue >550 C 90.2 75.6 77 70 70.6 68 51.6 42.5
Conversion (%) 0 16.1 14.6 22.4 21.7 24.6 42.8 52.9
 185

Table A.1-5 Tk crude oil upgrading properties per condition (Chavez, 2015).

Condition
Temp (C) 0 340 340 360 360 360 360 380 380
Residence time (h) 0 24 72 24 48 72 96 24 72
Quality
API () 12.17 14.89 16.41 16.24 18.03 19.15 20.76 20.86 25.63
Viscosity @ 40 C (cP) 71,703 288.25 171.89 117.26 57.33 45.01 25.32 19.85 8.02
Fraction Distribution (%)
Gases - 0.0 0.1 0.0 1.3 0.3 0.8 0.7 2.9 1.4
Naphtha IBP-216 C 3.7 4.9 6.0 5.6 7.8 8.9 9.6 11.6 15.0
Distillates 216-343 C 24.3 27.6 28.1 29.0 31.4 31.5 35.0 35.7 38.7
VGO 343-550 C 23.8 28.2 29.3 30.3 32.7 32.6 34.1 32.4 30.9
Residue >550 C 48.3 39.1 36.5 33.9 27.8 26.2 20.7 17.3 13.9
Conversion (%) 0.0 18.9 24.4 29.8 42.3 45.7 57.2 64.1 71.1
 186

A.2. Hydroprocessing kinetic model

Table A.2-1 Ath bitumen kinetic model (Loria, Trujillo-Ferrer, Sosa-Stull, & Pereira-Almao, 2011).

Pre-
Activation
Temperature (C) exponential
k Energy R2
Factor
320 350 360 380 s-1 kJ/mol
1 0.00214 0.00845 0.01324 0.0265 21.47 136 0.9983
2 0.00131 0.0061 0.00951 0.03093 27.24 167 0.9949
3 0.0003 0.00113 0.00251 0.0113 30.63 192 0.966
4 0.00006 0.00073 0.00085 0.00902 43.01 261 0.9683
5 0.0067 0.00282 0.00181 0.00045 21.59 145 0.9998
6 0.00491 0.00141 0.00073 0.00014 29.6 190 0.9952
8 0.00105 0.00046 0.00032 0.00007 20.15 146 0.9979

Table A.2-2 Ath bitumen kinetic model from Loria experimental data (Da Silva, 2014).

Pre-exponential Activation
Temperature (C)
k Factor Energy
R2
320 350 360 380 s-1 kJ/mol
1 0.002200 0.008990 0.013440 0.029450 22.2 139.5 1
2 0.001140 0.004960 0.007610 0.027960 27.3 168.3 0.987
3 0.000410 0.001770 0.003260 0.010980 27.4 174.3 0.99
4 0.000060 0.000710 0.001800 0.009370 45.5 272.9 0.999
5 0.000670 0.003150 0.004930 0.016140 26.8 168.3 0.995
6 0.000000 0.000020 0.000060 0.000380 51.8 324 1
8 0.000000 0.000040 0.000230 0.010150 112.0 633.3 1

Table A.2-3 Ath pitch kinetic model (Da Silva, 2014).

Pre-exponential Activation
Temperature (C)
k Factor Energy R2
320 350 380 s-1 kJ/mol
1 0.000610 0.001700 0.009150 21.8 144.4 0.972
2 0.000160 0.000590 0.004000 26.3 173.3 0.982
3 0.000060 0.000290 0.001580 26.6 179.8 0.999
4 0.000000 0.000010 0.000170 42.0 276 0.992
5 0.000030 0.000140 0.000630 23.6 168.3 1
8 0.000000 0.000180 0.013650 85.6 487.9 1
 187

Table A.2-4 Ath vacuum residue kinetic model (Da Silva, 2014).

Pre-exponential Activation
Temperature (C)
k Factor Energy R2
320 380 395 s-1 kJ/mol
1 0.001260 0.004410 0.007920 8.8 76.6 0.979
2 0.000600 0.001240 0.001660 1.3 43.2 0.988
3 0.000120 0.000370 0.000460 2.8 58.1 1
4 0.000010 0.000090 0.000210 17.8 146.6 0.995
5 0.000420 0.001450 0.002170 6.6 70.8 0.996
8 0.000000 0.000920 0.003920 59.8 362.7 1

Table A.2-5 Tk crude oil kinetic model (Chavez, 2015).

Pre-exponential Activation
Temperature (C)
k Factor Energy R2
340 360 380 s-1 kJ/mol
1 0.002698 0.004398 0.008030 11.8 90.7 0.9939
2 0.000773 0.002929 0.007277 29.6 186.9 0.9919
3 0.000813 0.001647 0.003724 17.7 126.6 0.9964
4 0.000090 0.000302 0.000758 25.6 177.8 0.9962
5 0.000002 0.000002 0.000003 0 68.2 1
6 0.000007 0.000052 0.000356 53.3 332.3 1
8 0.000041 0.000237 0.001211 45.2 281.9 1

Table A.2-6 Ag crude oil kinetic model.

Pre-exponential Activation
Temperature (C)
Factor Energy
k R2
-1
320 340 360 h kJ/mol
1 0.003376 0.003174 0.006343 4.03 48.56 0.659
2 1.22E-06 1.9E-05 0.000163 63.9 382.16 0.997
3 4.47E-06 6.13E-05 0.000798 69.7 404.65 0.999
4 0.000167 0.000276 0.00046 7.3 79.02 0.999
5 0.000421 0.001284 0.003995 27.8 175.52 0.999
8 0.000107 0.000156 0.000226 2.7 58.38 0.999
 188

Table A.2-7 Ag vacuum residue kinetic model.

Pre-exponential Activation
Temperature (C)
k Factor Energy R2
320 340 360 h-1 kJ/mol
1 0.00099 0.00237 0.00509 19.1 128.1 1.00
2 0.00020 0.00055 0.00144 22.7 153.8 1.00
3 0.00002 0.00013 0.00074 45.3 276.5 1.00
4 0.00006 0.00012 0.00041 20.0 147.1 0.95
5 0.00044 0.00105 0.00241 19.0 131.8 1.00
8 0.00061 0.00107 0.00183 9.9 85.8 1.00
 189

B. APPENDIX: Analytical measurements and equipment

B.1. Liquid samples

B.1.1. Simulated Distillation (SIMDIST)

High temperature simulated distillation process is called due to the emulation of the physical
process, which is cost and time consuming that can be performed in a laboratory scale. The
equipment use by the CBU group is Agilent gas chromatograph model 6890N, shown in Figure
B.1.1-1.

Figure B.1.1-1 Chromatograph model 6890N (Agilent Technologies, 2015).

This equipment separates a fluid by individual components as a function of their boiling point
temperature. The results are distillation curves that represent the cumulative weight or volume
fraction at certain temperature, from lower to higher temperature range. As temperature
increase, more liquid is distillate, so the cumulative volume increases with temperature. From
this data, the crude oil can be fractions into different ranges of boiling points (lumps), having
their own true boiling point (TBP) curve (Gray, 2015). For this work five lumps are used, shown
in Table B.1.1-1.

Table B.1.1-1 Component lumping by TBP.

TBP
Lump Component
(C)
Gases C1-C4
Naphtha IBP-216 C5-C12
Distillates 216.1-343 C13-C20
VGO 343.1-550 C21-C44
Residue >550.1 C45+
 190

A true boiling point (TBP) curve is shown in Figure B.1.1-2, where the continue line represent
the whole crude curve, and the dashed lines the beginning and end of each fraction, lump at
convenience.

Figure B.1.1-2 TBP curve and distilled fractions (Gray, 2015).

The gas chromatogram also provides individual molecules insight of a crude oil. Figure B.1.1-3
shows an example of the individual characterization of the hydrocarbons compounds, where
each pick represents one of them. As the retention time increases, the picks represent heavier
compounds, being the residue the lump observed at the middle of the plot and the picks the
lighter molecules. Several reference methods are applied to obtain accurate data from this
equipment, being the ASTM one of them.

Figure B.1.1-3 Gas chromatogram (Gray, 2015).

 191

The equipment works with a column oven with an operation temperature range from 36 to 750
C. The column is coated with a nonpolar stationary phase, and uses a gas chromatograph. The
detection and measurement of the components is performed by a flame ionization detector
(FID).

The methodology of sample preparation consists in a 0.15 gr sample diluted with 20 ml of

carbon disulfide (CS2), both weights have to be recorded. Once the sample is homogenized, it is
transfer to a 2 ml vial. This is placed in the Algerie equipment, a 1 microliter volume is sample
and is eluted with helium as a carrier gas into the FID. The gas chromatograph obtains the data
and is process with specialize software.

B.1.2. Density and API gravity

Density measurements and API gravity calculations are obtained from a Density meter DDM
2910 from Rudolph Research Analytical Company. This equipment works with a mechanical
oscillating U-tube method that support a full range of fluids viscosities and densities from 0 to 3
gr/cm3, and temperature from 0 to 95C. The equipment is shown in Figure B.1.2-1.

Figure B.1.2-1Density meter DDM 2910 (Rudolph Research Analytical, 2015).

The density measurement for heavy hydrocarbons necessarily have to be diluted to avoid
plugging of the equipment or leftovers from each measurement. Three samples are prepared
with 0.05, 0.10 and 0.15 gr of hydrocarbon material, diluted with 10 gr of toluene. Once the
sample is homogenise, it is injected to the equipment, filling the U-tube without bubbles in it.
The sample have to be filtered before injecting, to avoid solids that can affect the
measurement.
 192

This procedure is performed per sample. Once the density of each sample is obtained, a four
point plot is set. Figure B.1.2-2 shows the trend observed for each sample measurements, the s
axis corresponds to percentage of V/V, calculated with Equation 22, and Y axis corresponds to
the measured density of the mixture. The slope corresponds to the density of the hydrocarbon.
With this value, divided by water density at standard conditions, we calculate the API gravity
with Equation 21.

141.5 Equation 21
API = 131.5
specific gravity
For ISU technology, density will decrease as a function of the cracking of heavy molecules and
the addition of hydrogen to those chains. The higher the amount of hydrogen added the lower
the density, therefore the API gravity and upgrading of the crude oil.

+
( ) ( )

% = + 100 Equation 22

( )

Figure B.1.2-2 Mixture density vs %V/V plot.

B.1.3. Viscosity
Viscosity is one of the main targets for the upgrading process, reducing it will help and improve
the exploitation, extraction and transportation of the fluid. The viscosity measured in the labs
correspond to dynamic viscosity in centipoise (cP). As it was mentioned before, viscosity
 193

correlates to density and therefore to molecular weight and the type of components that
constitute the crude oil evaluated.

For viscosity measurements, two equipment are used, one for low to medium viscosity (low
temperature), and for high viscosity (high temperature)

B.1.3.1. Low temperature

Figure B.1.3.1-1 Low temperature viscometer DV-II Pro (Brookfield Engineering, 2015).

For low temperature a Brookfield DV-II Pro viscometer is employed (Figure B.1.3.1-1). It is
coupled with a thermal bath that reach a temperature of 100 C. The measurement mechanism
is to drive a spindle that contacts a film of fluid sample, measuring the torque of a calibrated
spring. The result is determined by the rotational speed, the size and shape of the spindle, the
sample thickness in contact, and the torque measured. This provide a value of viscosity in
centipoise, and shear rate and shear stress values.

B.1.3.2. High temperature

For high temperature, the same apparatus is used coupled with a thermosel system (Figure
B.1.3.2-1) that heats a chamber at a programmable temperature that can reach 300 C. This
equipment is enclose, and fill with nitrogen and vacuum to have an inert environment avoiding
oxidation and degradation during the measurements at high temperatures.
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Figure B.1.3.2-1 High temperature viscometer Thermosel system (Brookfield Engineering,

2015).

B.1.4. Metal Analysis

This is a basic measurement in ISU process via hot fluid injection with catalyst. It is important to
know the concentration added to the sample to ensure the good performance of the process.
The metal content analysis consists of two sections, an elimination of hydrocarbon content to
leave only the metal concentration for the measurements, this step is called digestion; and the
second one is the metal detection via plasma in an Inductively Couple Plasma (ICP) device.

Digestion section consist in adding two types of acid to a 0.25 to 0.30 gr of sample. The acids
are 10.5 ml of nitric acid, 1 ml of phosphoric acid and 25 microliters of cobalt as a standard
solution (1,000 ppm). This mixture is encapsulated and introduce to a Microwave Accelerated
Reaction System (MARS 6), shown in Figure B.1.4-1.

Figure B.1.4-1 MARS-6 equipment for sample digestion (CEM corporation, 2015).
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The temperature ramp is set to begin at room conditions to 210 C, heating 10 C per minute,
and a 20 minutes plateau at that high temperature, followed by cooling stage. Once it is cooled
down, the sample is extracted and diluted using deionized water and transferred to a vessel.

The next step is to take the sample and analyzed in the ICP (Figure B.1.4-2), the liquid is
atomized in a pressurized argon plasma, which separates each particular element allowing its
quantification, previous calibration with a solution with Ni, Mo, W, Fe, V and Co at 20 ppm
each. A correction using cobalt should be performed to ensure and lower the error of the
measurement.

Figure B.1.4-2 IRIS Intrepid II XPS spectrometer (EVISA, 2010).

B.1.5. Micro-carbon (MCR)

MCR or carbon residue is the remaining content after evaporation and pyrolysis of crude oil
samples at certain conditions. This is related to the coke formation tendency of the oil at
thermal degradation conditions (Hassan, Carbognani, & Pereira-Almao, 2008). This
measurement is performed in a muffle furnace (Figure B.1.5-1) with an inert environment,
using pure nitrogen to eliminate oxygen. In the interior an aluminum and stainless steel base
that can support 26 vial samples, is covered with a glass with a 1/8 orifice. The vials are filled
with a 0.2-0.3 gr of sample. The system is purge by 45 min with a flow of 900 cc/min of nitrogen
and then it is heated until it reach 500 C and stand by for 20 min, with a 10C/min ramp.

Once the samples are cool down, they are weighted and obtain a percentage of carbon residue
remaining. This percentage represents the probably coke formation that the sample can form.
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Figure B.1.5-1 Thermo scientific Muffle furnace.

B.1.6. Nitrogen and Sulfur content

For the standard elemental analysis (nitrogen and sulfur) the equipment use is Antek 9000NS
(Figure B.1.6-1). A sample is introduced and combusted near 1,100 C, in combination with
oxygen, this convert chemical bound nitrogen and sulfur into NO and SO 2. The gases are send to
a membrane that dries the sample removing water and then the detector quantify the
components using chemiluminescence and ultraviolet fluorescence for nitrogen and sulfur
respectively (Micro analysis, Inc, 2015).

Figure B.1.6-1 Antek 9000NS Sulfur and Nitrogen analysis (Micro analysis, Inc, 2015).

B.1.7. Peptization value (P-value)

This measurement resemble the flocculation potential of asphaltene, forming solids, and its
proportional to stability. It is a visual detection via microscope and an imaging software.
Peptization is the process responsible of stable dispersion of colloidal particles formation in a
dispersed medium.
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The procedure consist in one gram of sample, heated at 100 C in a mineral oil bath for 30
minutes with a stirring magnet. Each time step a sample is collected and observed in the
microscope, an additional millilitre of hexadecane is added. The equation is as follows:

16
= 1 + 1 Equation 23

In the microscope, deposits of asphaltenes (grape shape) are expected. You continue the
procedure until you observe clear precipitation.

2.0 2.5 2.7

2.8 3.05
Figure B.1.7-1 P-value analysis for Ag crude oil.

2.8 3.0 3.2

Figure B.1.7-2 P-value analysis for Ag vacuum residue.

In Figure B.1.7-1 and Figure B.1.7-2, crude oil and vacuum residue, respectively are analyzed by
microscopy being the values obtained 2.75 and 3 for crude oil and vacuum residue.

B.1.8. Nano-particle Tracking Analysis (NTA)

The equipment used for tracking Nano particles is Malvern NanoSight NS300 uses the
technology of Nanoparticle Tracking Analysis (NTA). This technology employs the properties of
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both light scattering and Brownian motion in order to obtain the size distribution and
concentration measurement of particles in liquid suspension.

A laser beam is passed through the sample chamber, and the particles in suspension in the path
of this beam scatter light in such a manner that they can easily be visualized via 20x
magnification microscope onto which is mounted a camera. The camera operates at 30 frames
per second (fps), capturing a video file of the particles moving under Brownian motion. The
software tracks many particles individually and using the Stokes-Einstein equation calculates
their hydrodynamic diameters (Malvern, 2015).

Figure B.1.8-1 NanoSight NS300 (Malvern, 2015).

Figure B.1.8-2 Nano particle tracking.

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Due to the nature of the fluids used, they have to be dissolved in toluene to make them clearer
and fluid for the tracking mechanism, Figure B.1.8-2, shows a picture of the particle tracking
environment.

B.2. Gas samples

B.2.1. Gas chromatography (GC)

For gas analysis a Mandel SRI 8610C equipment is employed (Figure B.2.1-1). Measurements
are performed after the stabilization period, every three pore volumes of reactor. Three
measurements are taken. The gas produced by the hydroprocess at certain conditions for the
kinetic model are send to the GC equipment, gas has to be flowing for a certain amount of time
to ensure that the gas that the GC is sampling is part of our process.

Figure B.2.1-1 Gas chromatography SRI 8610C (Mandel, 2015).

The equipment has four detectors: one Flame Photometric Detector (FPD), one Flame
Ionization Detector (FID) and two Thermal Conductivity Detectors (TCD). TCD1 uses helium as a
carrier, allowing detection of multiple hydrocarbon compounds, carbon monoxide, carbon
dioxide, and hydrogen at high concentrations. TCD2 uses argon as a carrier, allowing the
measurement of hydrogen at low concentrations (SRI Instruments, 2014).

FID detector uses a flame that ionized the eluted compounds and produces ions (positive and
negative), these are collected by electrodes. This detect compounds with hydrogen and carbon
bonds. FPD flame is used to produce photons of different wavelengths, detecting them by a
photomultiplier tube (PMT) to select compounds containing sulfur and phosphorus as the
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combust in the hydrogen flame (SRI Instruments, 2014). This equipment is calibrated using a
certified mixture standard for all detectors.

The data is send to a specialize software that allows to see the four detectors in real time, as
well as to manually integrate the information data for further processing.

B.2.2. Gas flow meter

Once the gas flow is deviated to the GC, a volumetric gas flow meter is connected in continuous
mode to measure the rate of gases being produce by the process. The equipment is a
MilliGascounter Type MGC-1 from Ritter (Figure B.2.2-1). It is designed for small amount of gas
rates, and is suitable for inert and aggressive gases. The operation range goes from 1 ml/h to
1l/h.

Figure B.2.2-1 MilliGascounter Type MGC-1 from Ritter (Litre Meter Limited, 2011).

The measurement principle consist in a two chambers cell that is filled with the bubbling gas in
the apparatus, once it is filled it tip, beginning the next measurement. A counter equipped with
a magnetic device record the tips, therefore, the gas rate measurement. Each chamber needs
3.28 l to be filled with the bubbling gas. The equipment is filled with a silicone oil Silox, it
doesnt react with aggressive gases (Litre Meter Limited, 2011).