RemovalofCO2froma HydrogenPlant

Department of Chemical Engineering

Robert St. Pierre, Phung-Minh Dai, Mark Dalton

[TYPETHECOMPANYADDRESS]

2008

Removal of CO2 from a Hydrogen Plant

By: Robert St. Pierre, Phung-Minh Dai, and Mark Dalton

Department of Chemical Engineering University of Saskatchewan 2007-2008

Abstract
Husky Energys Lloydminster Upgrader wanted to determine if removing carbon dioxide from their Hydrogen plant would be economical using current technology. A computer model of the plant was developed using the HYSYS process simulator for this purpose. The model was used to predict the effects of removing the CO2 on the existing plant. From the effects seen in the model the savings related to lowering the heating costs could be determined. To remove the CO2 from the process stream an absorption system using Monoethanolamine (MEA) was designed. The removal system consists of a 15 tray absorber, a 17 stage regenerator, and a 12 stage MEA guard absorber along with several pumps and heat exchangers. The system is able to remove 35 tonnes per hour of CO2 at 94 percent purity, with the remainder being water. The capital cost of this project is approximately $9.82 million. The economics of the project were not found to be favourable. The total savings from removing the CO2 from the gas stream are approximately $859,000 per year. The cost to operate the amine system is around $16.9 million per year. If a value of $50.43 per tonne CO2 is applied then the net cash flow is zero. If a value of $67.33 per tonne CO2 is applied then the project will break even after 25 years. It is RPMs recommendation that Husky conduct an investigation to determine the value they can place on the CO2 product before moving forward with this project.

Acknowledgements
RPM is pleased to acknowledge the following people for their contributions and guidance: Tristan Koroscil, Senior Unit Contact Engineer Husky Upgrader Bob Brierly, Senior Staff Process Engineer Husky Upgrader Les Alberts, Gas Treating Specialist, Dow Chemical Canada Dr. Hui Wang, U of S Chemical Engineering Assistant Professor Dr. Richard Evitts, U of S Chemical Engineering Associate Professor Dr. Ding-Yu Peng, U of S Chemical Engineering Professor Dr. Gordon Hill, U of S Chemical Engineer Department Head Trey Brown, Vice President of Process Engineering, New Point Gas Services

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Table of Contents
Abstract ................................................................................................................................ i Acknowledgements............................................................................................................. ii List of Tables ..................................................................................................................... vi List of Figures ................................................................................................................... vii Nomenclature ................................................................................................................... viii 1. 2. Introduction ................................................................................................................. 1 Literature Survey: Alternative Processes .................................................................... 2 2.1 2.2 2.3 3. Membrane Separation ......................................................................................... 2 Hot Potassium Carbonate.................................................................................... 3 Amine Separation................................................................................................ 4

Detailed Qualitative Process Description .................................................................... 7 3.1 3.1.1 3.1.2 3.2 HYSYS Simulation............................................................................................. 7 Detailed Model Specifications ........................................................................ 7 Tail Gas Flow Rate Assumption ................................................................... 22 AMSIM Simulation .......................................................................................... 25

4. 5. 6. 7. 8.

Equipment Specification and Design ........................................................................ 29 Plant Safety Analysis................................................................................................. 31 Economic Analysis .................................................................................................... 33 Conclusions and Recommendations .......................................................................... 36 References ................................................................................................................. 37

Appendix A: Sample Calculations................................................................................... 39

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A.1 Membrane Size ..................................................................................................... 40 A.2 Absorber Size and Cost......................................................................................... 41 A.3 Regenerator Size and Cost .................................................................................... 42 A.4 Condenser Heat Exchanger Size ........................................................................... 44 A.5 Centrifugal Pump Size and Cost ........................................................................... 45 A.6 Amine Holding Tank Size..................................................................................... 47 A.7 Depreciation .......................................................................................................... 48 A.8 Combo Gas Savings .............................................................................................. 48 A.9 Combustion Air...................................................................................................... 48 A.10 Steam Losses....................................................................................................... 49 Appendix B: Safety Document ........................................................................................ 50 B.1 Amine Plant Design Criteria ................................................................................. 51 B.2 HAZOP/Safety Considerations ............................................................................. 52 B.3 Plant Safety ........................................................................................................... 59 B.4 Process Safety Management System..................................................................... 62 B.5 Chemical Hazard Information ............................................................................... 63 B.6 MSDS .................................................................................................................... 65 B.6.1 Hydrogen, H2 ................................................................................................. 65 B.6.2 Monoethanolamine, MEA ............................................................................. 67 B.6.3 Methane, CH4 ................................................................................................ 75 B.6.4 Carbon Dioxide, CO2 .................................................................................... 79 B.6.5 Carbon Monoxide, CO.................................................................................... 85 B.6.6 Nitrogen, N2 ................................................................................................... 91 iv

B.7 Dow Fire and Explosion Index.............................................................................. 93 Appendix C: EconExpert Equipment Costing Results .................................................... 95 C.1 Towers ................................................................................................................... 96 C.2 Heat Exchangers.................................................................................................... 98 C.3 Pumps .................................................................................................................. 100 C.4 Storage Vessel ..................................................................................................... 101 C.5 Process Vessels ................................................................................................... 101 Appendix D: Cash Flow Analysis................................................................................... 104 Appendix E: HYSYS Reports......................................................................................... 107 Appendix E1.1: PSA Tail Gas With CO2 ................................................................ 108 Appendix E1.2: Reformer Furnace With CO2 ......................................................... 112 Appendix E2.1: PSA Tail Gas Without CO2 ........................................................... 124 Appendix E2.2: Reformer without CO2 .................................................................. 127 Appendix F: AMSIM Reports ....................................................................................... 139

List of Tables
Table 1: Summary of Process Changes ........................................................................... 22 Table 2: Summary of Equipment Sizing and Specifications ............................................ 29 Table B. 1: Chemical Hazard Information Summary ...................................................... 64 Table C. 1: Ulrich Equipment Costing .......................................................................... 103 Table D. 1: Cash Flow Analysis .................................................................................... 105 Table D. 2: Cash flows at Different Carbon Tax Rates ................................................. 106 Table F. 1: Composition Profile of CO2 in Absorber A................................................. 140 Table F. 2: Vapour Phase Properties in Absorber A...................................................... 140 Table F. 3: Liquid Phase Properties in Absorber A ....................................................... 141 Table F. 4: Composition Profile of CO2 in Regenerator................................................ 141 Table F. 6: Liquid Phase Properties in the Regenerator ................................................ 142

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List of Figures
Figure 1: CO2 Removal Processes Comparison ................................................................. 4 Figure 2: HYSYS Simulation Section 1 ............................................................................. 8 Figure 3: Specified Inlet Gas Compositions ...................................................................... 9 Figure 4: HYSYS Simulation Section 2 ........................................................................... 11 Figure 5: HYSYS Simulation Section 3 ........................................................................... 12 Figure 6: HYSYS Simulation Section 4 ........................................................................... 15 Figure 7: Specified Combo Gas Composition ................................................................. 18 Figure 8: Plant 30 Block Diagram ................................................................................... 24 Figure 9: Amine System Flow Diagram ........................................................................... 27 Figure 10: Cumulative Discounted Cash Flow at Different Carbon Tax Rates in $/tonne CO2 Emitted .................................................................................................... 35

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Nomenclature
Symbol A cP CBM CP D ed,em ed,gt Description heat exchanger surface area purchased equipment cost Bare Module Cost heat capacity diameter electric motor efficiency gas turbine efficiency pump efficiency quantity factor molar flow of carbon dioxide bare module factor, material factor pressure factor height of column molar flux of carbon dioxide number of stages pressure electric motor power gas turbine power rate of heat transfer volumetric flowrate tray spacing temperature of the cold stream at inlet temperature of the cold stream at outlet temperature of the hot stream at inlet temperature of the hot stream at outlet overall heat transfer coefficient shaft power Units m2 $ $ kJ/kgoC m kJ/s kJ/s

FaBM FM FP Hcol jCO2 nact P Pem Pgt Q

fq FCO2

mol/s

m mol/m2s barg kJ/s kJ/s J/s m3/s m o C o C o C o C W/m2oC kW

q s Tci Tco Thi Tho U

Ws

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1. Introduction
The purpose of this project was to remove CO2 from a methane reformer gas stream located at Husky Energys Lloydminster Upgrader. An economic opportunity was seen in removing this CO2 for two main reasons. First, the CO2 produced in the reforming and shift reactions is currently part of the fuel gas for the reformer furnace and by removing the CO2, and thereby reducing the heating requirements, there are potential savings in the reformer furnace. The second reason is that the CO2 produced by the removal process could then be used by Husky for their enhanced oil recovery (EOR) projects. The project itself has three major objectives which needed to be achieved in order for the project to be deemed a success. First a working model of the current Hydrogen plant using simulation software had to be completed. The CO2 removal system then had to be designed, the equipment sized, and the costs estimated. Finally, the effects of the CO2 removal on the Hydrogen plant, including savings due to lower combo gas flows and changes to any additional flows or conditions, had to be determined. From the changes observed in the system economics could be performed to determine the projects feasibility.

2. Literature Survey: Alternative Processes

2.1 Membrane Separation
One of the technologies examined for the CO2 removal project was membrane technology. Membrane separation works by gas molecules permeating through a thin membrane due to a pressure gradient across the membrane. Different species permeate the membrane at different speeds due to a large number of factors including the size of the molecule, the speed of sorption onto the membrane, the ability of the molecule to dissolve in the membrane, the rigidity of the membrane lattice, and many other factors. These factors can be summarized by the permeability of the species which is obviously different for each component through each membrane. Although membranes can produce the high purities that would be desirable the main design challenge is due to the large membrane area caused by the high flow rate of the gas stream. In order to find out if a membrane solution would be feasible a preliminary calculation was performed. This calculation assumed that only CO2 would permeate the membrane, an assumption that would be unacceptable for further design. The calculation also assumed that the membrane had the highest permeability that could be found for CO2 based on Scotts Industrial Membrane Separation Technology, which was a permeability of 2700 Barrer. (Scott) The next assumption made was that the permeate gas stream was a perfect vacuum, thereby creating the greatest flux. The final

assumption was that the membrane has a thickness of 1mm. For a 600 kgmol/hr separation of CO2 the minimum surface area, based on the calculated flux of 5.87x10-4 mol/m2s, was found to be 283,736m2 which is far beyond the range of feasibility. Due to the extremely large ideal area needed the membrane system was not pursued further. A summary of the calculation is shown in Appendix A.

2.2 Hot Potassium Carbonate

Another alternative technology that was considered was using a physical solvent, namely hot potassium carbonate. As displayed in Figure 1 the hot potassium carbonate process could be used based on the composition of our process gas stream as seen in Appendix E1.1. However, the hot potassium carbonate process requires a high contactor temperature which was not ideal for our process system. The contactor temperature required for the process is 110oC and the process gas stream is cooled from 170oC to 69oC by raw gas air coolers. Therefore in order to utilize the hot potassium carbonate process the gas stream would need to be reheated to 110oC. This additional energy required is undesired as the energy costs for the process were recognized as a potential downfall of the project. Therefore alternative solvents were considered, such as primary and secondary amines. Other physical solvents are used in industry other than potassium carbonate such as Dow Chemicals patented Selexol. Selexol is a popular physical solvent in industry that could possibly be utilized for this system. However because Selexols composition is proprietary to Dow, simulation and comparison with this solvent was not possible. If

this project is to be explored further it is RPMs recommendation that Selexol or another physical solvent be considered for the process.

Figure 1: CO2 Removal Processes Comparison (Maddox)

2.3 Amine Separation

The third technology explored was using an amine solvent such as Monoethanolamine or Diethanolomine to absorb the CO2 from the gas stream. As can be seen in the Figure 1 the primary and secondary amines are mainly utilized for smaller acid gas concentrations but can be used in our process as the volume of CO2 is within the threshold. Amine solvents are common in industry to sweeten acid gas streams by removing H2S and/or CO2.

The amine process comprises of a contacting tower operating at a high pressure and low temperature. These conditions are ideal for our process as the hydrogen gas stream operates at 24oC and 2200 kPag at our tie in point. Following absorption in the contactor the CO2 can be captured by desorbing the CO2 from the amine solution in a regeneration tower at a low pressure and high temperature. The amine solution can then be recycled back into the contactor tower to absorb more CO2. When amine solvents are used to absorb CO2 the process occurs through reactive absorption. When the gas and absorbent are contacted a reversible chemical reaction occurs, unlike the more common physical absorption like when water is used as a solvent. When designing an absorption column which undergoes a reversible chemical reaction new complexities are added to the task. Upon further research it was discovered that simulating reversible chemical reactions, are best handled by computer-aided calculations. (J. D. Seader) There are several amine solutions that can be used to absorb CO2, each with different strengths and drawbacks. The following is a list of potential amine solutions that could be utilized: Monoethanolamine (MEA) Diethanolamine (DEA) Methyldiethanolamine (MDEA) Triethanolamine (TEA) Diglycolamine (DGA) Diisopropanolamine (DIPA)

MEA was chosen in the design because it is the strongest base of the listed amines and therefore reacts most rapidly with the acid gases. The rapid reaction was deemed beneficial to limit the size of our absorber tower. Also it was discovered that, MEA has the lowest molecular weight of the common amines (and) it theoretically has the largest carrying capacity for acid gases on a unit weight or volume basis. (Maddox) The large carrying capacity was an important factor in choosing MEA because it would enable the system to use less solvent. A smaller amount of solvent will result in a lower energy requirement to regenerate the amine.

3. Detailed Qualitative Process Description

3.1 HYSYS Simulation

A major part of the project was determining the effects of the CO2 removal on the existing system. In order to accurately examine how the rest of Plant 30 would react to the changes in the system, a HYSYS simulation for the current plant was constructed. The model deals with the Hydrogen plant from the feedstock until directly after the pressure swing adsorption (PSA) unit. The following section will go through, in detail, how the HYSYS simulation works, what assumptions have been made, and how the model was used to examine how removing the CO2 from after the reformer will affect the rest of the system. The names of streams and unit operations within the HYSYS simulation will be referred to in parentheses the first time they are mentioned.

3.1.1

Detailed Model Specifications

The simulation uses the Peng-Robinson equation of state as the fluid package for the simulation. It is used by HYSYS to calculate the thermodynamic properties associated with the streams.

Figure 2: HYSYS Simulation Section 1

The model begins with the inlet natural gas (Nat gas in) which is at 43oC and 3500 kPa pressure. The gas flows at 23.5 tonnes per hour. The composition of the stream was provided by Husky and can be seen below in Figure 3.

Figure 3: Specified Inlet Gas Compositions

The inlet gas is mixed with recycle Hydrogen at 500oC and 4581 kPa in a mixer (MIX-101). The recycle H2 is flowing at a rate of 290 std m3 per hour. The mixture is then heated by convection section gas in a heat exchanger (Hydrocarbon Preheat Coil) to 350oC. The heat exchanger is modelled with no pressure drop, no heat losses, and the Ft correction factor is not calculated. The size of the heat exchanger is modelled as 60 m2 which is not representative of the actual exchanger, which is much larger. The area, however, does not matter because the discrepancy between the actual area and the specified area will be taken into account by the UA term. The UA term was found to be 80900 kJ/oC-h, which is based on the outlet temperature specification for the inlet stream and duty estimates for the heat exchanger from the P&IDs provided by Husky of 7.13MW.

In the plant the heated inlet gas stream (Past Sulphur Guard) will move through a sulphur guard unit to eliminate any H2S, however in the HYSYS model the system is ignored. The sulphur guard system is ignored because it does will not have an effect on the system when it is changed. It also does not appreciably change operating conditions of the inlet gas stream, which does not contain H2S, and so it has not been included in the model. After the sulphur guard the gas is mixed with steam in a static mixer (30-MX002) in a molar ratio of 3.348 mol steam to 1 mol of inlet gas. This is accomplished by the set function (SET-3). The actual molar ratio used is 3.6 mol of steam per mol of methane. Methane makes up 93 percent of the inlet gas stream and so 93 percent of 3.6, or 3.348, is used as the set point value. The steam is at a temperature of 330oC and is produced by flue gas in the Steam Superheat Coil. An explanation of the Steam Superheat Coil can be found later in this section. The mixed gas stream from 30-MX-002 (To Convection Section) then moves to a recycle function (RCY-2). The recycle function allows for the HYSYS model to iterate until interdependent parts of the model converge. In this case the interdependent parts of the model are the inlet gas stream and three of the four convection section heat exchangers. After the iteration is complete the stream (To Convection Section-2) enters the third preheat heat exchanger (Mixed Feed Preheat Coil).

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Figure 4: HYSYS Simulation Section 2

The next heat exchanger heats the mixed feed stream from 350oC to 450oC before entering the reformer. The exchanger, again, does not model Ft correction factor, heat loss, or pressure drop. The exchanger heat duty was estimated at 14.32 MW. From the duty spec and outlet temperature a UA value of 151,700 kJ/oC-h was calculated for the exchanger. After the feed has been heated the gas enters the reformer furnace on the tube side. The tube side of the reformer furnace (30-F-001-A) is modelled as a conversion reactor. The reformation reaction converts hydrocarbons and steam to CO and H2. A reformer shift reaction also occurs within the reformer which converts CO and steam to

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CO2 and H2. The components and mole balances for the multiple reforming reactions and the shift reaction can be seen in Appendix E..2 and E2.2. The reforming reaction is assumed to occur for all of the higher hydrocarbons with 100 percent conversion. Methane is converted with 72.8 percent conversion and the shift reaction is assumed to have 58 percent conversion. These conversions were determined by trial and error in order to have the proper methane concentration in the stream out of the reactor (To Waste HEX) on a water free molar basis, as given in the simplified process flow diagram provided by Husky. The water free composition is checked by splitting the water from the stream and checking the composition. This is done by the hypothetical splitter (X-100) and checked with the top stream. (Hypothetical) The stream is then remixed (MIX-100) before being sent to the waste heat exchanger. (To Waste HEX2) The liquid stream on the reformer (DNE2) does not exist but is required by HYSYS to operate.

Figure 5: HYSYS Simulation Section 3

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The waste heat exchanger (E-103) cools the gas from 795oC to 365oC by using steam from the 4500kPa steam drum. The steam flow is set at 5600 kgmol/h or 100,900 kg/h and was specified because it gives a saturated vapour at the exit of the exchanger. (To SD1) The steam enters as a saturated liquid at 4500 kPa and 258.5oC and exits the exchanger at 259.9oC as a vapour. The exchanger itself has a tube side pressure drop of 1200 kPa based on the flow diagrams and a shell side assumed pressure drop of zero. No heat loss modelled and the Ft correction factor is not calculated. Again the default area of heat transfer is 60 m2 and the UA value is 493,200 kJ/oC-h. The UA value was found by using the outlet temperature gas stream and specifying a value for the steam flow rate. From the reformer waste heat exchanger the gas then moves to the shift converter. The shift converter (30-R-004) is a reactor that uses the shift reaction seen above to convert CO and steam to Hydrogen and CO2. The reactor is modeled as a conversion reactor, again because kinetic reaction data was not available. A conversion of 65.5 percent gives the proper composition for the tail gas stream after the PSA unit (PSA Tail Gas-1) and so it is used. The outlet temperature of the gas stream is 403oC, as calculated by the heat of reaction. The liquid flow (DNE3) out of the reactor does not exist but must be included for HYSYS to operate. The shift gas now moves to through a pair of heat exchangers. The next step in the process is a series of two heat exchangers which, in order, are the shift waste heat exchanger (30-E-004) and the boiler feed water pre-heater. (30-E005) Both exchangers do not model heat loss and do not have a pressure drop over either the tube or shell side. The water flow rates are 230,000 kg/h and 125,000 kg/h for the shift waste heat exchanger and the boiler feed water pre-heater respectively. The water

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for the shift waste heat exchanger (From P1) enters at a specified 125 oC and exits at 162.1oC. The boiler feed water (From P2) enters at the same specified temperature of 125 oC and exits at a temperature of 174.7 oC. The overall heat transfer coefficients, UA, are 204,600 kJ/oC-h and 421,700 kJ/oC-h for the shift waste heat exchanger and the boiler feed water pre-heater respectively. Both the inlet temperatures and the flow rates of both exchangers are specified in the Husky process flow diagrams. The pressure of both water streams is 5200kPa which is specified in the process P&IDs. The gas stream proceeds from the boiler feed water preheater to the first condensate drum, the hot condensate drum. (30-D-007) The drum is modelled as a component splitter that removes water from the stream. The splitter removes 2 percent of the water in the stream and sends it to the dearator which is not shown in the HYSYS model. The stream exits at 177.1oC and proceeds to the fin fan cooler section. The raw gas coolers (30-E-007 A/B/C/D/E/F) are a set of large fans that lower the temperature by moving air over a large number of tubes. The coolers are simply modelled as a cooler. The cooler lowers the temperature of the gas stream from 177.1oC to a 50oC, as stated in the Plant 30 documents supplied by Husky. The model predicts a power of 40.67 MW which is feasible because they are designed for 56.72 MW. The power was specified by setting the outlet temperature of the stream to 50 oC and copying the calculated power.

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Figure 6: HYSYS Simulation Section 4

After the raw gas coolers the next step is through a second condensate drum. (30D-080) The drum, like the other drum, is modelled as a component splitter and removes 50 percent of the water in the stream, which amounts to 24,140 kg/h. The number is just an estimate since no flow data was supplied and the flow will not have an appreciable effect on the rest of the system. The next stage in the process is another heat exchanger. The heat exchanger that follows the condensate drum is the raw gas trim cooler. (30-E-008) The cooler uses 20oC water at 550kPa to lower the gas temperature from 50oC to 23oC. The water used, according to the model, flows at a rate of 667,700 kg/h which may not be accurate since the water removed by the condensate drum may not be accurate. The water on the outlet of the exchanger is specified in the flow diagrams as 15

being 23oC. A pressure drop of 99kPa on the tube side and 210kPa on the shell side are assumed from the process flow sheets. The exchanger, like all of the others within the model, uses a default heat transfer area of 60m2 and has a UA value of 778,800 kJ/oC-h. The next step for the gas is the final cold condensate drum. (30-D-008) The drum is again modelled as a splitter and removes all of the water left in the stream. The water, like in the last condensate drum, goes to the dearator which is not modelled at a flow of 241,400 kg/h. The gas then moves to the PSA unit where the gas is purified. The pressure swing absorption unit (30-PK-004) is made up of 13 process vessels that purify the Hydrogen. The unit is quite complex and for this reason it was decided that it should be modelled as a mole and heat balance. The Hydrogen product stream (Hydrogen Product) is assumed to be 99.5 percent pure, with the remaining .5 percent being CO. The stream is specified as having a temperature of 25oC and a pressure of 2180kPa. The flow rate of the stream is determined from the inlet gas flow rate using the set function (SET-2) which makes the molar flow of the outlet hydrogen stream 2.48 times the molar flow of the inlet gas stream; a specification which was provided by Husky. The PSA tails gas (PSA Tail Gas-1) has a specified pressure of 40kPa and a calculated temperature of 17.29oC. The flow rate of the gas is approximately 48,400 std m3/h which does not agree with the value specified by Husky of 35,000 std m3/h, this is discussed later in Section 3.1.2. The compositions of the stream are determined by the mole balance and reflect the compositions of the actual gas stream. The removed CO2 (CO2 Out) also attaches to the PSA unit in the model simply because the tie in point for the CO2 removal system is directly before the PSA unit and the system does not have an appreciable affect on the stream composition beyond removing CO2.

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The tail gas from the PSA unit still has a large heating value and so is sent back to the reformer furnace as a feed for the burners. The tail gas can be sent to vent if it is deemed necessary and so a tee (TEE-100) has be placed in the model. The tee currently assumes that no gas is sent to vent, however it is available if more accurate process information is obtained. The tail gas then moves through a second recycle function. (RCY-1) The function, like the other recycle, allows HYSYS to iterate. In this case the recycle function is used to ensure that the temperature around the loop that begins and ends with the mixed feed preheat coil (Mixed Feed Preheat Coil) is consistent. The tail gas (PSA Tail Gas-2) is now sent to the reformer burners. The furnace part of the reformer (30-F-001-B) is modeled, in a similar fashion to the tube side of the reformer, as a conversion reactor. The combustion section of the reformer has three main feed streams: the PSA tail gas, a combo gas make-up stream, and combustion air. The combo gas (Combo Gas) enters at a temperature of 55oC and a pressure of 146.3kPa. The flow rate is also specified at 3900 std m3/h. The composition of the combo gas was provided in a similar format to that of the inlet gas stream and can be seen below in Figure 7.

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Figure 7: Specified Combo Gas Composition

The combustion air (Combustion Air) is assumed to be 79 mol percent Nitrogen and 21 mol percent Oxygen. The air is preheated to 300oC in a section prior to the reformer and is not modeled. The pressure of the stream is 102.8kPa. The gas flow is regulated by an adjust function (ADJ-1) which changes the flow rate of the combustion air so that 2 percent oxygen is in the reformer flue gas stream. (Waste Gas) The flow rate of the air predicted by the model is 194,000 kg/hr which is the same value that Husky provided for the stream. Once the three feeds are added to the reformer the combustible products are converted. All of the combustible products are assumed to have 100 percent conversions in the reactor. The reaction stoichiometry for the reformer furnace can be in Appendix E1.2 or E2.2 in the HYSYS reports.

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The energy from the reformer combustion section is used for the energy for the tube side of the reformer. The energy from the combustion reactions that is not used to heat the gas stream to the reformers 800oC temperature is shown by HYSYS as an energy stream. (Q-100) There is also a similar stream (Q-102) providing energy to the tube section of the reformer in 30-F-001-A. At steady state the energy produced by the combustion reaction should be equivalent to the energy consumed by the tube side of the reformer plus the heat loss to the atmosphere. This is taken into account by setting the energy of the tube side stream using a set function (SET-1) with a less than one multiplier that acts as an efficiency factor. The heat transfer efficiency factor was set by adjusting the value until an outlet temperature of 795oC was observed from the tube side reformer. (To Waste HEX) The factor was found to be .8641 which, according to Ulrich, is in an acceptable region for an industrial furnace (Ulrich, 149). It was assumed that this factor would remain constant when the CO2 was removed because the reformer should be running at the same temperature and therefore should have similar heat transfer within the tubes. The flue gas from the combustion section of the reformer is at a high temperature of 800oC and so is used for heating other process streams. The gas has a flow rate of 246,600 kg/h and is at a pressure of 40kPa. The composition of the stream is approximately 17 percent CO2, 18 percent H2O, 63 percent Nitrogen, and 2 percent Oxygen. The gas first moves to steam generation coil I (Steam Generation Coil I) to produce steam for the steam drum 30-D-003. The water enters as a saturated liquid at 5200kPa with a flow rate of 441,700 kg/h as specified on the P&IDs. The exchanger, like all of the others, does not model heat loss or the Ft correction factor. There is no pressure

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loss over the tube side which contains the flue gas and a 50kPa drop over the shell side, again specified in the P&IDs. The UA value is specified at 91,180 kJ/oC-h which is based off of the heat duty specification of 11.78MW. The outlet gas (WG to MFPC) has a temperature of 668.4oC. The outlet steam has a vapour fraction of .0512. The gas stream then moves through the mixed feed preheat coil, which is described above, and is cooled to 558.3oC. The next step is another steam generation exchanger. The second steam exchanger (Steam Superheat Coil) takes steam from the steam drum 30-D-003 and heats it so that it can be used elsewhere and to mix with the inlet feed gas in 30-MX-002. The exchanger does not have a pressure drop for the shell or tube side, it does not model heat loss, and the Ft correction factor is not calculated. The UA value of 80,050kJ/oC-h was found by specifying the flow of steam to elsewhere in the plant, (To Steam Turbines) the flow rate of steam into the mixer, (Steam) and the temperature of the steam out of the exchanger at 330oC as specified in the process flow diagram. Once the UA value was determined an adjust function (ADJ-5) was introduced to change the inlet flow rate of the stream until the temperature of the outlet steam was 330oC. The flow specification on the other stream was also removed so that changes in the inlet flow rate would not cause an error. In the exchanger the gas is cooled to 498.5oC. The gas then moves through the first heat exchanger (Hydrocarbon Preheat Coil) and is cooled to 432.2oC. The flue gass final destination is steam generation coil II (Steam Generation Coil II) which cools the gas to 332.9oC. The heat exchanger, in the nature of this simulation, does not show pressure drop over the shell or tube side, does not calculate the Ft correction factor, and does not model heat loss. The UA value of 273,500kJ/oC-h was

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determined from the heat transfer specification that 8.26MW of power are transferred to the steam stream. The vapour fraction of the outlet stream predicted is .0917. Several additional adjust functions exist within the model, each with its own purpose when adjusting the model after the CO2 is removed from the system. First is the adjust function (ADJ-4) for the stream before the sulphur guard. (Past Sulphur Guard) Although the sulphur guard is not modeled in the simulation the temperature through the guard must be maintained or the reaction, if one is needed, to remove the sulphur will not occur. The adjust therefore adjusts the combustion air flow until the proper temperature of 350oC is obtained. This works against the adjust to maintain the flue gas composition at 2 percent Oxygen (ADJ-1) and therefore if ADJ-4 is being used ADJ-1 should be ignored and vice versa. Another adjust function used after the CO2 is removed connects the combo gas and the outlet flow from the tube section of the reformer. (To Waste HEX) This adjust function (ADJ-2) adjusts the combo gas flow rate so that the temperature of the reformer outlet is 795oC, the normal exit gas temperature. Once the CO2 is removed the combo gas flow rate will have to be changed so that the outlet temperature of the tubes is maintained. This lowering of combo gas flow rate is the source of revenue for this project and so the adjust function allows for it to be accurately predicted. Once the CO2 is removed several process conditions change. These changes generally are temperatures and flow rates in the initial section of the simulation leading up to the tube side reformer. The flow rates of the combo gas and combustion air are also changed to make sure process conditions are maintained as much as possible, specifically the outlet temperature of the reformer and the temperature of the sulphur guard stream.

21

Detailed analysis of these changes can be seen in the HYSYS reports in Appendix E2. A summary of the major process changes can be seen below in Table 1.

Table 1: Summary of Process Changes With CO2 Savings (M Initial Removed $CAD) (kg/hr) (kg/hr) Combo Gas 982.2 831.2 1207784 Combustion Air 194000 232580.217 -306873 Steam Produced 1.5787E+05 1.5771E+05 -7.69E+04 CO2 Emitted 63998 27760 n/a

3.1.2

Tail Gas Flow Rate Assumption The major assumption made by the model revolves around the flow of the PSA

tail gas stream. The value for the tail gas was provided as being 35,000 std m3/h however the model predicts a value of 48,400 std m3/h. The issue was discussed with our industrial contact and he said to assume the losses were due to leaks in the reformer and to send the appropriate amount to vent. It was decided to not follow these directions for the following reasons: 1. Despite there being many leaks in a reformer, especially because it operates at below atmospheric pressure and viewing ports are not completely sealed, it does not seem feasible that over 25 percent of the stream is being sent to vent. A leak of this size would have been noticed at some point during the operation and it would be a major safety concern. 2. According to the model the flow rate of 35,000 std m3/h does not produce the energy needed to heat the stream from 450oC to 795oC, the actual normal operating temperature of the tube side reformer outlet.

22

3. The combustion air flow rate predicted by the model agrees with the higher tail gas flow rate and matches both that flow rate and the outlet gas composition of two percent excess oxygen. The air flow at the measured composition is not matched at 35,000 std m3/h. 4. The measurement for the tail gas flow occurs on the FD fan in the reformer, but the P&IDs do not indicate if that flow rate is used to control the operation or if the outlet gas composition is. It is likely the outlet gas composition that is used since a feedback loop could be applied. This means that a broken or improperly calibrated flow meter on the tail gas could go undetected by the operators. 5. The specifications given for the Hydrogen gas stream, inlet gas stream, and composition of the tail gas stream fully define the flow of the PSA tail gas. As can be seen below the reformer process up to the PSA unit can be seen as a black box process. If a balance of Carbon atoms is done over the process it can be seen that since the inlet flow rate and composition is defined, as is that of the Hydrogen gas outlet, and the compositions of the tail gas stream the flow rate is also defined. Also seen below is a rough calculation using the molar flow of methane as being the only source of carbon with the other hydrocarbons assumed as being negligible.

23

H2O In

H2 Out 99.5% H2 .5% CO F2 = 3456 kgmol/h PSA Tail Gas 44.5% CO2 17.6% CH4 6.6% CO F3 = 3456 kgmol/h

Natural Gas in 93% CH4 F1 = 1393 kgmol/h H2O Out

Figure 8: Plant 30 Block Diagram

F1 yCH 4 = F2 yCO + F3 yCO2 + F3 yCH 4 + F3 yCO (1393 kgmol )(.93) = 3456 kgmol (.005) + F3 (.445) + F3 (.176) + F3 (.066) h h F3 = 1860 kgmol h Conversion gives 43,990
std m 3 h

The other hydrocarbons in the natural gas feed will increase the flow of the stream, however it can be seen that the flow is fully defined by the conditions given.

24

3.2 AMSIM Simulation

The design of our CO2 extraction process using an amine solution was completed using a computer simulation as recommended by Seader. It is necessary to use a computer simulation to accomplish the task of modeling the CO2 extraction system because the absorption of gas into the solution is a reversible chemical reaction. AMSIM, AMine treating unit SIMulator, was utilized to simulate and design the CO2 extraction process. AMSIM is a software package developed by Schlumberger that simulates the steady state removal of acid gas from process streams using aqueous amine solutions and physical solvents. In our application no H2S was present in our process gas stream, therefore only CO2 was absorbed by the process. In order to calculate the mass transfer process of the amine treating unit, AMSIM uses a non-equilibrium stage model. The fundamental concept that AMSIM uses is that the rate of absorption and desorption is considered as a mass-transfer rate process. (Schlumberger) To simultaneously solve the non-linear stage equations for temperature, composition and phase rates for each stage of the column AMSIM uses a modified Newton-Raphson method. The Kent and Eisenberg approach is used as a basis to model the equilibrium solubility of acid gases in amine solutions. AMSIM also validates the solubility model with experimental data and proprietary information. Utilizing AMSIM the following process was designed to remove the CO2 from the reformer gas stream. The tower contacting the aqueous MEA with the gaseous reformer stream is illustrated as Absorber A. Absorber A is simulated to be 9.14 m high and 2.74 m in diameter consisting of 15 bubble cap trays and operates at 2164 kPa and 38oC. Bubble cap trays were chosen to allow a longer interaction time of the amine

25

solution and process gas resulting in a more complete absorption. The amine solution, which is 30% by weight MEA, circulates at a rate of 407 m3/hr. Following Absorber A the rich amine is depressurized in a vertical flash drum sized to be 6.75 m high and 2.25 m in diameter. 31 kmol/hr of gas is flashed off and sent to the PSA tails gas. The rich amine then flows through a lean/rich amine plate and frame heat exchanger increasing the temperature from 69.6 oC to 83.5 oC. Once the rich amine is heated it flows into the regenerator tower. The regenerator tower which is used to regenerate the rich MEA and capture the absorbed CO2, is 10.36 m high and 3.2 m in diameter consisting of 17 sieve trays. Sieve trays were chosen as they resulted in the greatest amount of CO2 captured when simulated with valve or bubble cap and are the most cost effective. The overhead vapour flow from the regenerator is 1221kmol/hr which consists of 67% CO2 and 33% H2O on a molar basis. An overhead condenser condenses the water using a plate and frame heat exchanger with a surface area of 261 m2. Following the condenser 864.9 kmol/hr of acid gas is captured consisting of 94.1% of CO2 and 5.8% water. Once the water is removed the CO2 can then be used by Husky for enhanced oil recovery. Once the amine is regenerated in the tower the lean amine flows through the lean/rich amine heat exchanger decreasing the temperature from 125 oC to 107 oC. The lean amine is further cooled by another plate and frame heat exchanger that is sized to be 203 m2. This solvent cooler reduces the temperature of the amine to 37.8 oC before reentering the contactor tower, Absorber A.

26

Figure 9: Amine System Flow Diagram

27

Absorber B, the MEA Guard, was added to the simulation in order to ensure no MEA would be entrained in the process gas stream and contaminate the PSA unit. This tower uses water as a solvent to absorb MEA from the lean gas stream. The water is recycled until the MEA concentration increases to 7% by weight at which time it can then be replaced. The MEA guard is modeled to be 7.31 m high and 1.68 m in diameter using 12 bubble cap trays. The lean gas stream then moves to a water knockout drum which removes any water in the stream. The lean gas stream then moves to the PSA unit for Hydrogen purification.

28

4. Equipment Specification and Design

The equipment sizing was done using the text by Ulrich. Sample calculations are summarized in Appendix A. Table 2 is a summary of the equipment sizing. EconExpert, a Ulrich based web tool, was used along with the September 2007 Final CEPCI value of 528.2 (Chemical Engineering Journal, Jan 2008) to find the Total Capital Cost for the new amine system. This cost was determined to be approximately $9.82 million. A break down of the equipment costs are shown in Table C.1 and a summary of EconExpert results is shown in Appendix C.

Table 2: Summary of Equipment Sizing and Specifications Towers Absorber Regenerator MEA Guard Diameter (m) 2.74 3.20 1.68 Height (m) 9.14 10.36 7.32 # of Trays 15 17 12 Material St-St St-St St-St Operating P (barg) 22 2.2 2.1

Heat Exchangers Regenerator Reboiler Regenerator Condenser Lean/Rich Amine Solvent Cooler Pumps Pump REGEN to ABS (220 to 2164 kpa) Pump for MEA Guard (2100 to 2150 kpa)

Type Shell & Tube Plate&Frame Plate&Frame Plate&Frame Pump Shaft Power (kW) 15.8 1.06

Sub Type Kettle Reboiler Flat Plate Flat Plate Flat Plate Suction P (barg) 2.2 2.1

Surface Area (m2) 481 261 1725 203 Type Centrifugal Centrifugal

Material St-St St-St St-St St-St Material St-St St-St

29

Storage Vessels Amine Holding Tank Process Vessels Amine Flash Drum Condenser Drum

Volume (m3) 33 Orientation Vertical Vertical

Material St-St Sub Type no packing or trays no packing or trays Diameter (m) 2.25 1.40 Height (m) 6.75 2.50 Material St-St St-St

30

5. Plant Safety Analysis

A plant safety analysis was conducted for the proposed amine plant. A full report is included in Appendix B. The Plant Safety Analysis conducted includes: HAZOP of the overall plant design Inherently Safe Design Process Safety Management System Chemical Hazard Information and MSDS Dow Fire and Explosion Index

Highlights of the HAZOP recommendations include the selection of stainless steel material because MEA is highly corrosive. HAZOP analysis can be found in Appendix B.2. MSDS and Chemical Hazard Information for the materials in the stream are included in Appendix B.6 and Table B.1. Other recommendations include the addition of secondary pumps in situations of no-flow. As well, the use of inert gas to purge storage and process drums to reduce corrosion, amine degradation, and prevent build up of explosive mixtures. Finally, minimizing the amine flow (407m3/hr) reduces hazardous material handling onsite.

31

The Process Safety Management System highlights include employee safety training in the areas of personal protective equipment, steam use, hazardous material handling for MEA, gas detection, and emergency evacuation. Documentation is important especially in new employee cases and the inclusion of operating manuals, equipment specifications, and frequency of maintenance are important. These are summarized in Appendix B.4 and B.5. Inherently Safe Design analysis using the concept of Intensification is summarized in Appendix B.3. The amine system is designed for a minimum amine flow and this minimizes the amount of amine on site. The Dow F&EI determined that the amine system would have a degree of hazard of 166 which is a severe risk since it is greater than 159. Since the reformer furnace uses the same chemicals in similar amounts Husky should already be capable of dealing with the risk. A summary of the analysis is shown in Appendix B.7.

32

6. Economic Analysis
The economics for this project were assessed based on methods taught in an engineering economics class. The capital cost for the project was determined in Section 4. The method for determining the operating costs, savings, depreciation, and taxation can be found in this section. Operating costs were a major component of the overall cash flow for this project. The cost of the electrical power needed to run the motors for the pumps was 5.062/kWh. (Saskpower) The system requirements for power were calculated to be 16.86 kW resulting in a cost of $7,500 per year. A cost of $323,000 of MEA was calculated based on 70 m3 of MEA in the process at a cost of MEA of $6.86 per liter. The cost of steam at the Husky Lloydminster Upgrader is $28.86 per ton. The steam necessary in the reboiler to regenerate the amine is 64,140 kg/hr resulting in a cost of $16.2 million per year. An additional operating cost of $253,000 per year resulted from a cost of additional operators based on the additional equipment. Depreciation for this project was determined using a sum of the years digits approach. The depreciation schedule was set so that the plant would be fully depreciated after 10 years. The values for the depreciation can be seen along with the overall cash flow in Table D.1.

33

The savings for this system were calculated based on the HYSYS model explained in Section 3. After the CO2 has been removed several changes are made to operating conditions at various points in the plant. These changes result in both direct and indirect costs. The main savings are associated with a reduced need for combo gas within the process. The main losses are due to lower steam production and increased need for combustion air. Calculations for these amounts can be seen in Appendix A.8 through A.12. The combo gas savings amount to $1.208 million per year. The expenses from steam losses and combustion air are $59,000 and $307,000 per year respectively. Combining these values gives total revenues of $859,000 per year. The cash flow analysis was based off several different specified conditions. First it was decided to use a one year build time so the separation system begins operation at the beginning of year one. The operating costs are higher in year one because additional amine must be purchased to fill the tower in year one, whereas only a portion of the amine is replaced in the subsequent years and is estimated as the amount in the amine holding tank. The tax rate used was 41% which is based on 28% federal tax and 13% provincial tax. (Canada Revenue Agency) The interest rate used to discount the cash flow is 8% which is simply based on what was decided to be an acceptable MARR value. The results of the cash flow analysis can be seen in Table D.1 or Figure 10. Due to the high operating cost the system shows a negative cash flow. For this reason an internal rate of return was not calculated. Also, because of the negative cash flow, it was decided to place a value on the CO2 to determine at what cost the system would become feasible. Several values were placed on the removed CO2 and the results can be seen in Figure 10. The important points to note are the point where the projects

34

revenues match the operating costs at a combined carbon dioxide tax and value of $50.43 per tonne and the point at which the project has a break even point of 25 years, at a value of $67.33 per tonne.

20 CumulativeDiscountedCashFlow(MMCAD$)

40 0 10 20 30 40 50.43 67.33

60

80

100

120

140 0 5 10 Time(Years) 15 20 25

Figure 10: Cumulative Discounted Cash Flow at Different Carbon Tax Rates in $/tonne CO2 Emitted

35

7. Conclusions and Recommendations

A HYSYS model of the existing Hydrogen plant was constructed and used to predict the effect of CO2 removal. The model predicted savings of $859,000 per year based on reduced combo gas needed as fuel for the reformer, additional combustion air needs, and slightly lowered steam production. A CO2 extraction process utilizing a Monoethanolamine based solvent was designed and simulated using AMSIM. The system is successful in capturing 35.9 tonnes/hr of CO2 which comprises 91.3% of the CO2 in the original stream. The total capital costs necessary for this project is estimated at $9.82 Million US. Using Huskys current prices this project will reach a break even point after 25 years with a combined value or tax on CO2 of $67/tonne. If Husky wants to explore this project further RPM recommends that an internal study should be conducted to determine the monetary value they can place on the CO2. If the value of CO2 is economically feasible it is recommended that detailed design be done for this project.

36

8. References
Airgas. 23 February 2008 <http://www.airgas.com/documents/pdf/1013.pdf>. BOC. 23 February 2008 <http://www1.boc.com/uk/sds>. Canada Revenue Agency. Corporation Tax Rates. Canada Revenue Agency. 2008. CRA. 02 March 2008 <http://www.craarc.gc.ca/tax/business/topics/corporations/rates-e.html>. J. D. Seader, Ernest J. Henley. Separation Process Principles. United States of America: John Wiley & Sons, Inc., 2006. Maddox, Dr. Robert N. and D. John Morgan. Gas Conditioning and Processing Volume 4: Gas Treating and Sulfur Recovery. Oklahoma: Campbell Petroleum Series, 2006. Saskatchewan, University of. "CEPCI Value." Chemical Engineering Journal (January 2008). SaskPower. 02 March 2008 <http://www.saskpower.com/services/busrates/oilfields/doc1.shtml>. Schlumberger. "AMSIM User's Manual." (2003). Scott, K. Industrial Membrane Seperation Technology. New York: Chapman and Hall, 1996. Ulrich, Gael D. Chemical Engineering Process Design and Economics a Practical Guide. Durham : Process Publishing, 2004.

37

University of Queensland Australia. 23 February 2008 <http://www.cheque.uq.edu.au/ugrad/theses/1998/DaveA/dow.html>. Valley National Gas Website. 23 Feburary 2008 <http://www.vngas.com>. Whitaker Oil Company. 23 February 2008 <http://www.whitakeroil.com/MSDS/MEA.pdf>.

38

Appendix A: Sample Calculations

39

The calculations from Ulrich may be slightly different compared with EconExpert due to the subjective reading of values from the graphs in the textbook.

A.1 Membrane Size

The flux of the CO2 through a membrane was calculated to see if a membrane system would be feasible. The permeability value is based off of values given in Scotts Industrial Membrane Separation Technology, the partial pressure defined by the HYSYS simulation, and an assumed membrane thickness.
jCO2 = jCO2 = P ( pi p L ) L (2700barrer )(3.347 10 16 mol m2 s
mol m m 2 sPa

barrer .001m

Pa )(650kpa 1000 kPa 0kPa)

jCO2 = 5.874 10 4

A CO2 removal of 600 kgmol/h, about 70% of the CO2 in the stream, was used as a basis to judge if the system could meet removal specifications.

j CO2 =

FCO2 A 600 kgmol h 1 h mol 1000 kgmol 3600 s A

mol 5.874 10 4 2 = m s A = 283736m 2 A = 284000m 2

40

A.2 Absorber Size and Cost

Using Figure 5.44b pg. 387 in Ulrich, Assuming a vertical vessel with the following data taken from the AMSIM nact = 15 D = 2.743 m s = 0.6096 m Hcol = 9.144 m

From Figure 5.44b gives a purchased equipment cost, cP = $8.5 x104.

Since P < 4 barg use Figure 5.45.

Using stainless steel material due to the corrosive MEA material gives a Material Factor, FM = 4.0 and a P = 22 barg gives a Pressure Factor, FP = 2.25.

Therefore, the Pressure Factor-Material Factor product, FP x FM = 9.

Using Figure 5.46 with a vertical vessel orientation gives a Bare Module Factor, FaBM = 18. Figure 5.44 states that: CBM = cP x FaBM CBM = ($8.5 x 104)(18) C BM = $1.53 x 106

41

Costing the trays using Figure 5.48 gives a Bare Module Cost, CBM = (cPss x FBM) * nact * fq CBM = ($4 x 103 ) * (2.2) * (15) * (1.125) CBM = $1.485 x 105

Total Cost of Absorber and trays = $1.53 x 106 + $1.485 x 105

Total Cost of Absorber and trays ~ $1.6785 x 106

A.3 Regenerator Size and Cost

Using Figure 5.44b pg. 387 in Ulrich, Assuming a vertical vessel with the following data taken from the AMSIM, nact = 17 D = 3.2 m s = 0.6096 m Hcol = 10.3632 m

From Figure 5.44b gives a purchased equipment cost, cP = $9.2 x104

Since P < 4 barg use Figure 5.45 Using stainless steel material due to the corrosive MEA material gives a Material Factor, FM = 4.0 and a P = 0.206 barg gives a Pressure Factor, FP = 1.

42

Therefore, the Pressure Factor-Material Factor product, FP x FM = 4.0.

Using Figure 5.46 with a vertical vessel orientation gives a Bare Module Factor, FaBM = 9.5.

Figure 5.44 states that: CBM = cP x FaBM CBM = ($9.2 x 104)(9.5) C BM = $8.74 x 105

Costing the trays using Figure 5.48 gives a Bare Module Cost, CBM = cPss * FBM * nact * fq CBM = ($5.5 x 103 ) * (2.2) * (18) * (1.17) CBM = $2.5483 x 105

Total Cost of Regenerator and trays = $8.74 x 105 + $2.5483 x 105

Total Cost of Regenerator and trays ~ $1.1288 x 106

43

A.4 Condenser Heat Exchanger Size

Q = UATlm Where the following data was taken from AMSIM, Thi = 89.4oC Tho = 48.9oC Tci = 23oC Tco = 49oC CP = 4.501 kJ/kgoC

Tlm = Tlm

(Thi Tco ) (Tho Tci ) ln((Thi Tco ) / (Tho Tci )) (89.4 49)o C (48.9 23)o C = o o ln((89.4 49 ) C / (48.9 23) C )

Tlm = 32.6 o C

The surface area, A:

18695.89 x10 3 W A= W (2200 2 )(32.6C ) m C

A = 261 m2

44

A.5 Centrifugal Pump Size and Cost

(Regenerator to Absorber 220 to 2164 kPa) Using equation 4.94 pg. 248 in Ulrich,
Ws =

q P

i
kg m )(9.81 2 )(10.3632m) 3 m s

P = gh = (1028.939 P = 1.0461x10 5

kg ms 2

m3 m3 q = 407 = 0.11306 hr s

Assume efficiency, i = 0.75 Therefore, shaft power, Ws = 15.8 kW.

Using Figure 4.2 pg.121 in Ulrich gives electric motor efficiency, ed,em = 0.93, and gas turbine efficiency, ed,gt = 0.26.

Power, P, is calculated from equation 4.95 pg. 248 in Ulrich,

q p

Pem =

i d ,em

(0.11306

m3 kg )(1.0461x10 5 ) s ms 2 = 18 kW (0.75)(0.93)

Pgt =

q p

i d , gt

(0.11306

m3 kg )(1.0461x10 5 ) s ms 2 = 64.2 kW (0.75)(0.26)

Using Figure 5.49 pg. 390 in Ulrich,

45

Therefore, shaft power, Ws = 15.8 kW yields a Purchased Cost (electric motor included), cP = $1.7 x 104 with FM = 1.9 for stainless steel. The calculation is based on a radial/centrifugal pump because axial flow or regenerative units are ultimately negligible on economics (Ulrich 248).

Using Figure 5.50 pg. 391 in Ulrich, Suction Pressure, Pi = 2.2 barg give a Pressure Factor, Fp = 1.

Using Figure 5.51 pg. 391 in Ulrich gives the Pressure Factor-Material Factor Product, FP x FM = 1 * 1.9 = 1.9 which give a Bare Module Factor, FaBM = 4.9.

Using Figure 5.49 pg. 390 gives a Bare Module Cost, CBM = cPss * FaBM CBM = ($1.7 x 104)(4.9)
CBM = $8.82 x 104

46

A.6 Amine Holding Tank Size

Determine volume of Absorber and Regenerator and add 25% for piping and assume need a tank to hold 20% of the amine volume in the system.

Volume of Absorber: Where the following data was taken from AMSIM, D = 2.743 m H = 9.144 m
V ABS V ABS 2.743m = r H = (9.144m) 2 = 54.04m 3
2 2

Volume of Regenerator: Where the following data was taken from AMSIM, D = 3.048 m H = 10.3632 m
VRe gen VRe gen 3.048m = r H = (10.3632m) 2 = 75.62m 3
2 2

Total Estimated Volume of MEA, VMEA = 1.25 * ( VABS + VRe gen ) VMEA = 1.25 * ( 54.04m 3 + 75.62m 3 )

VMEA = 162 m3

47

If the tank is to hold 20% of the Total Estimated Volume of MEA the volume of the tank, VT = 33 m3.

A.7 Depreciation
Years Left Po Sum of Years 10 $9,824,869 D= 10 + 9 + 8 + 7 + 6 + 5 + 4 + 3 + 2 + 1 D = $1,786,340 D=

A.8 Combo Gas Savings

The combo gas savings are calculated on the basis of reduced energy consumption per year and rely on the cost of natural gas per unit energy.
& EComboGas = FComboGas H ComboGas % Re duction h day 1GJ 3 kJ & EComboGas = (3900 m )(35891 m3 )( )(24 )(365 )(.1534) h 1000000kJ day year & E = 188128 GJ
ComboGas Year

& Savings = EComboGas NaturalGasCost

GJ 1 Savings = 188128 year $6.42 GJ

Savings = $1.208 10 6

A.9 Combustion Air

The costs of combustion air are based solely on the amount of steam that is needed to run the ID fans for the air and ignores the cost of heating the air. So for the 20% increase in air flow the associated cost can be seen below.

48

Air Losses = Steam In Steam Cost % Increase

1 Air Losses = (6.1 tonne )($28.86 tonne )(.19899)(24 h 1 Air Losses = $307,000 year

h day )(365 ) day year

A.10 Steam Losses

The losses associated with steam are calculated by using the internal steam cost and the flow rate of steam in the vapour phase for the two steam flows that are affected by the flue gas.

Steam Losses = (Steam In Vapour Fraction) Steam Cost

1 Steam Losses = [(24.52 tonne )(.0918) (6.503)(1)] ($28.86 tonne )(24 h 1 Steam Losses = $59,200 year

h day )(365 ) day year

49

Appendix B: Safety Document

50

B.1 Amine Plant Design Criteria

Design for minimal MEA in the outlet stream of the amine system to the PSA unit. MEA in the PSA unit will degrade the catalyst used. Design for specified pressure to the PSA unit. The PSA unit runs at 2200 kPa and is black boxed because it is beyond the scope of this project and there is not enough information to determine effects to the PSA unit. Maximize removal of CO2 before the PSA unit to maximize savings. 30 wt% MEA is corrosive so stainless steel material will be used for the design of the amine system. Design for a no flow situation (pump cavitation or failure) and purchase (2) secondary pumps for the amine system.

51

B.2 HAZOP/Safety Considerations Identify Hazards by considering the following Process Parameters:
i) Flow:

design for a no flow situation (pump cavitation/failure) and purchase secondary pumps for the amine system

ii) Time:

Consider designing tanks with level transmitters to prevent overflow (next phase of project-detailed plant design and layout)

Consider time and volume when fill a tank

iii) Frequency:

Consider frequency of loading amine to the holding tank (next phase of project-detailed plant design) how many times per year is necessary

iv) Mixing:

N/A

v) Pressure:

Design for specified pressure to the PSA unit . The PSA unit runs at 2200 kPa and is black boxed (beyond the scope of the project). There is not enough information to determine effects to the PSA unit.

Absorber operates at high pressure/low temperature (2164-2200 kPa, 38-70C). Consider piping that can withhold the high pressure to the flash drum and then to the Regenerator

vi) Composition:

52

30 wt% MEA is corrosive and stainless steel material will be used in the AMSIM design for the amine system

High CO2 concentrations will come out of the tops of the regenerator and if the project is to go ahead a CEI will have to be completed on potential of CO2 cloud forming around the plant

vii) Viscosity:

liquid is used, no slurries or solids, only potential for freezing if system is down, consider insulation, or placing knock-out tank indoors

viii) Temperature:

Consider steam traps and safety training for use of high pressure steam in the regenerator reboiler, steam will condense and when restarted can cause condensate induced-water hammer

Consider condensate induced water hammer, training in prepping condensate lines, making sure lines are properly drained of cooled liquid before proceeding with any opening or prep of lines

Regenerator operates at low pressure/high temperature (200-220 kPa, 90125C). Consider piping that can withhold the high temperature corrosive amine to the Absorber.

ix) pH:

30 wt% MEA is corrosive and stainless steel material will be used in the AMSIM design for the amine system

The amines in water solution are basic. (Maddox)

x) Separation/absorption:

53

Occurs inside absorber and regenerator columns. Consider using material that can withstand high temperature and high pressure with corrosive amine. Stainless steel material is chosen for vessels and equipment

xi) Level:

Consider designing tanks with level transmitters to prevent overflow (next phase of project-detailed plant design and layout)

Consider time and volume when fill a tank, consider the dielectric constant for amine (MEA) material

xii) Speed:

Pumps have moving parts, consider operator maintenance manuals for the pumps (next phase of project-detailed plant design and layout)

xiii) Information:

Documentation such as operating manuals, equipment specifications, design criteria, and MSDS to communicate details of amine system to new users

xiv) Reaction:
Amine+ Amine + H+ CO2 + H2O H2O HCO3- + H+

OH- + H+

HCO3- CO3= + H+
Absorption reaction is exothermic: 2MEA+CO2 MEACOO-+MEAH+

54

xv) Operation:

General Operating Problems :

Failure to Sweeten Gas:

1) Solution circulation too low 2) Regenerator temporarily overloaded after foaming episode 3) Poor regeneration due to : i. Tray Damage ii. Too cold in reboiler iii. Too low pressure iv. Insufficient regenerator stripping 4) Foaming 5) Gas flow too high 6) Acid gas content too high 7) Leak in contactor dP cell 8) Amine concentration too low 9) Contactor pressure too low or temperature too high (Maddox).
Corrosion:

According to Polderman et al. Corrosion will be most severe at places where the highest concentrations of acid gases encounter the highest temperatures. These points will include the amine-amine heat exchanger, the stripping column and the reboiler. (Maddox).

55

Stress corrosion is prevalent in amine systems. This generally is associated with residual stresses which result from localized heating during vessel construction, such as welds in absorbers, strippers and piping. Stress relieving all major equipment and piping will help to alleviate stress corrosion (Maddox).

Solution Degradation:

Amine solutions will slowly oxidize when exposed to air or oxygen. The products of these oxidation reactions are generally considered to cause corrosion problems. The oxidation can be minimized by use of an inert gas blanket on amine storage containers and surge drums (Maddox).

Consider purging storage containers and surge drums with inert gas to reduce oxidation

Foaming:

Foaming can cause several different problems. Plant gas through put may be severely reduced and sweetening efficiency may decrease to the point that pipeline specifications cannot be met. Also amine losses may be significantly increased (Maddox).

Causes of Foaming problems in amine units: 1) Suspended solids including iron sulphide 2) Hydrocarbon liquids 3) Condensed hydrocarbons: i) ii) Dew point shift Retrograde behavior

56

4) Amine degradation products 5) Almost any foreign material such as corrosion inhibitors, valve grease, or even impurities in make-up water 6) Heavily gas overloaded tower 7) Methanol buildup in regenerator 8) Coatings on some filter cartridges 9) Amine contamination during shipping 10) Excessive antifoam addition 11) Coatings on metal and plastic tower packing 12) Other and unknown causes (Maddox).
General Considerations: Inlet Scrubbing:

Most troubles in the contactor section are from entrained solids or entrained hydrocarbons

Insufficient inlet scrub of the sour gas can cause foaming, corrosion, and reboiler tube burnout because of excess amounts of foreign material in the amine solution

The process already has a sulphur guard in place to scrub the sour gas upon inlet

Amine Losses:

A sweet gas scrubber will help eliminate amine losses from unexpected foaming or surges. (Maddox).

57

Piping Design:

High velocity causes erosion of pipes advisable to: 1) Maintain liquid velocity below 0.9 m/s [3 ft/sec] in all piping unless stainless or other appropriate alloy is used. 2) Avoid the use of screwed fittings whenever practical. 3) Use welded fittings with long radius ells; avoid tees when possible. 4) When making up pipe with valves, instruments, etc., avoid the use of dissimilar metals to avoid bimetallic corrosion (Maddox).

58

B.3 Plant Safety

i) Safe Design:

See design criteria and HAZOP above

ii) Pollution Prevention:

Project is to remove the CO2 and will be used to inject into the ground for the tertiary method called enhanced oil recovery (EOR)

iii) Lifecycle Analysis of Products:

N/A. Project is to remove CO2 and use of it is beyond the scope of this project phase.

iv) Inherently Safe Design:

Goal: to eliminate all hazards in the process using the 10 concepts that follow:
1. Intensification:

Use very small amounts of hazardous material so that if there is a leak the hazard will be small. Design to minimize the amine flow in the system and the amount of amine in the holding tank to minimize the amount of amine on-site.
2. Substitution:

Replace hazardous materials with less hazardous ones. Design to use 30 wt% amine and dilute with water

3. Attenuation:

Use hazardous material under the least hazardous conditions. Design to minimize loss of amine to reduce the frequency of off-loading corrosive amine (MEA) by tank truck

59

4. Limitation:

Limit the effects of failures by equipment design or by change in condition rather than adding on protective equipment. N/A

5. Simplification:

Simpler plants provide fewer opportunities for error and less equipment that can fail. Design based on a typical amine system

6. Knock on Effect:

Design so that a domino effect doesnt happen. N/A. There is no inherent domino effect that could occur in the process.

7. Avoid Incorrect Assembly:

N/A. There is no assembly required at this stage of the project (beyond scope of this project phase)

8. Status Clear:

It should be possible to see, at a glance, if valves are open or shut, if levels are ok, if correctly assembled. N/A. There is no process controls in the design at this stage of the project (beyond scope of this project phase)
9. Control:

Control systems should be in place. N/A. There is no process controls in the design at this stage of the project (beyond scope of this project phase)

60

10. Survival:

If a hazard occurs personnel should be protected. Determine a fire, explosion, and emergency evacuation plan

61

B.4 Process Safety Management System

Employee safety training which includes: Personal Protective Equipment(PPE) for hearing protection, protective clothing, eye protection, and proper footwear (steel toed CSA approved) Hazards of Steam Hazardous materials (eg. MEA) used on-site, how and where to locate the MSDS sheets on the materials and on-site via National Fire Protection Agency (NFPA) signs Gas detector training Documentation such as operating manuals, equipment specifications, design criteria to communicate details of amine system to new users Employee training in fire, explosion, and emergency evacuation plans Maintenance plans for equipment being installed

62

B.5 Chemical Hazard Information

Definitions: LD-50/LC-50:

Lethal Dose 50. The dose that kills half (50%) of the animals tested.
LEL/UEL:

Lower/Upper Explosive Limit. Is the limiting/maximum concentration (in air) that is needed for the gas to ignite and explode.
TLV:

Threshold Limit Value. The reasonable level to which a worker can be exposed without adverse health effects.
IDLH:

Immediately Dangerous to Life or Health. The exposure to airborne contaminants that is likely to cause death or immediate or delayed permanent adverse health effects or prevent escape from such an environment.

63

Table B. 1: Chemical Hazard Information Summary LD-50 or LC-50 Component (route/species) Hydrogen H2 No known toxicological effects from this product Oral: believed to be >1.00-2.00g/kg(rat) moderately toxic Inhalation: Not determined Dermal: >1.00g/kg (rabbit) slightly toxic No known toxicological effects from this product

LEL/UEL Flammability Range: 4-75 vol% in air

TLV/Exposure Limits No known toxicological effects from this product

Reactivity Can form explosive mixture with air. May react violently with oxidants.

Monoethanolamine

MEA

Flammable Limits %: 5/17

6 ppm STEL-ACGIH; 3 ppm TWA-OSHA; 6 ppm STEL-OSHA; 3 ppm TWA-ACGIH

Reacts violently with: Air, water, heat, strong oxidizers, acids,

Methane

CH4

Flammability Range: 5-15 vol% in air

No known toxicological effects from this product ACGIH TLV. STEL: 54000 mg/m3 15 minute(s). Form: All forms; STEL: 30000 ppm 15 minute(s). Form: All forms; TWA: 9000 mg/m3 8 hour(s). Form: All forms; TWA: 5000 ppm 8 hour(s). Form: All forms PEL-OSHA: 50 ppm TWA; TLV-ACGIH: 25 ppm TWA No known toxicological effects from this product

Can form explosive mixture with air. May react violently with oxidants.

Carbon Dioxide

CO2

IDLH: 40000ppm

Non-Flammable

Stable

Carbon Monoxide Nitrogen

CO N2

1807 ppm/4H (rat) No known toxicological effects from this product

12.5%/74% Non-Flammable

Stable; Incompatible with oxidizers Stable under normal conditions

64

B.6 MSDS
B.6.1 Hydrogen, H2 (BOC)

65

66

B.6.2 Monoethanolamine, MEA (Whitaker Oil Company)

67

68

69

70

71

72

73

74

B.6.3 Methane, CH4 (BOC)

75

76

77

78

B.6.4 Carbon Dioxide, CO2 (Airgas):

79

80

81

82

83

84

B.6.5 Carbon Monoxide, CO (Valley National Gas Website)

85

86

87

88

89

90

B.6.6 Nitrogen, N2 (BOC)

91

92

B.7 Dow Fire and Explosion Index (Univ. of Queensland)

93

94

Appendix C: EconExpert Equipment Costing Results

95

Equipment Costing Source: Econ Expert: www.ulrichvasudesign.com/econ.html (usask05, design05)

C.1 Towers
Absorber

Regenerator

96

MEA Guard

97

C.2 Heat Exchangers

Regenerator Reboiler

Regenerator Condenser Plate & Frame HX

98

Lean/Rich Heat Exchanger

Solvent Cooler Plate & Frame HX to Absorber:

99

C.3 Pumps
Pump from Regenerator to Absorber (220 to 2164 kpa)

Pump for MEA Guard (2100 to 2150kPa)

100

C.4 Storage Vessel

Amine Holding Tank

C.5 Process Vessels

Amine Flash Drum

101

Condenser Drum

102

Table C. 1: Ulrich Equipment Costing

Equipment Towers

Cost $ US

Absorber Regenerator MEA Guard

Heat Exchangers Regenerator Reboiler Regenerator Condenser Plate & Frame HX Lean/Rich Amine Plate & Frame HX Solvent Cooler Plate & Frame HX Pumps Pump REGEN to ABS (220 to 2164 kpa) Pump for MEA Guard (2100 to 2150 kpa) Storage Vessels

1420847 1115933 406301 977485 80076 356583 66607 133408 48964 146487 406530 140121 $ 5,299,342 $ 937,469 $ 6,236,811 $ 249,472 $ 3,338,585
$ 9,824,869

Amine Holding Tank Process Vessels Amine Flash Drum Condenser Drum
Total Bare Module Cost

Contingency and Fee

Total Module Cost

Auxiliary Facilities
Installation Costs Total Capital

103

Appendix D: Cash Flow Analysis

104

Table D. 1: Cash Flow Analysis

After Tax Cash Flow (M CAD$) -9824.9 -12942.9 -6382.6 -6098.6 -5814.5 -5530.5 -5246.5 -4962.4 -4678.4 -4394.4 -4110.4 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3

year

Depreciation (M CAD$)

Savings (M CAD$)

CO2 Tax (M $/kg)

Yearly Operating Costs (M CAD$)

Net Cash Flow (M CAD$) -9824.87 -18909.3 -8093.02 -7914.39 -7735.76 -7557.12 -7378.49 -7199.85 -7021.22 -6842.59 -6663.95 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32 -6485.32

Tax Savings (M CAD$)

Net Expenses (M CAD$) -9824.9 -11156.5 -4774.9 -4669.5 -4564.1 -4458.7 -4353.3 -4247.9 -4142.5 -4037.1 -3931.7 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3 -3826.3

Discounted After Tax Cash Flow (M CAD$)

Cumulative ATCF (M CAD$) -9825 -21809 -27281 -32122 -36396 -40160 -43466 -46362 -48889 -51088 -52992 -54633 -56152 -57559 -58862 -60068 -61185 -62219 -63177 -64063 -64884 -65644 -66348 -67000 -67603 -68162

Cumulative ATCF (MM CAD$) -9.825 -21.809 -27.281 -32.122 -36.396 -40.160 -43.466 -46.362 -48.889 -51.088 -52.992 -54.633 -56.152 -57.559 -58.862 -60.068 -61.185 -62.219 -63.177 -64.063 -64.884 -65.644 -66.348 -67.000 -67.603 -68.162

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

-1786.34 -1607.71 -1429.07 -1250.44 -1071.80 -893.17 -714.54 -535.90 -357.27 -178.63

859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34 859.34

9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35 9523.35

-17123 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868 -16868

7752.8 3318.1 3244.9 3171.7 3098.4 3025.2 2951.9 2878.7 2805.5 2732.2 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0 2659.0

-11984 -5472 -4841 -4274 -3764 -3306 -2896 -2528 -2198 -1904 -1641 -1519 -1407 -1303 -1206 -1117 -1034 -958 -887 -821 -760 -704 -652 -603 -559

105

Table D. 2: Cash flows at Different Carbon Tax Rates Carbon Tax ($/tonne) Year 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

10

20

30

40

50.43

67.33

Cumulative ATCF (MM CAD$) -9.825 -9.825 -21.81 -21.81 -32.10 -30.49 -41.40 -38.31 -49.80 -45.33 -57.39 -51.65 -64.24 -57.31 -70.41 -62.40 -75.98 -66.95 -80.98 -71.02 -85.49 -74.66 -89.54 -77.91 -93.29 -80.91 -96.77 -83.70 -99.98 -86.28 -103.0 -88.66 -105.7 -90.87 -108.3 -92.92 -110.6 -94.81 -112.8 -96.57 -114.8 -98.19 -116.7 -99.70 -118.5 -101.1 -120.1 -102.4 -121.6 -103.6 -122.9 -104.7

-9.825 -21.81 -28.89 -35.21 -40.87 -45.90 -50.39 -54.38 -57.92 -61.05 -63.82 -66.27 -68.53 -70.63 -72.57 -74.37 -76.03 -77.57 -79.00 -80.32 -81.54 -82.67 -83.72 -84.69 -85.59 -86.42

-9.825 -21.81 -27.28 -32.12 -36.40 -40.16 -43.47 -46.36 -48.89 -51.09 -52.99 -54.63 -56.15 -57.56 -58.86 -60.07 -61.18 -62.22 -63.18 -64.06 -64.88 -65.64 -66.35 -67.00 -67.60 -68.16

-9.825 -21.81 -25.68 -29.03 -31.93 -34.42 -36.54 -38.34 -39.86 -41.12 -42.16 -43.00 -43.77 -44.49 -45.16 -45.77 -46.34 -46.87 -47.36 -47.81 -48.23 -48.62 -48.98 -49.31 -49.62 -49.90

-9.825 -21.81 -24.00 -25.80 -27.27 -28.43 -29.32 -29.98 -30.44 -30.73 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86 -30.86

-9.825 -21.81 -21.29 -20.58 -19.71 -18.72 -17.62 -16.43 -15.18 -13.88 -12.55 -11.19 -9.935 -8.771 -7.694 -6.696 -5.772 -4.916 -4.124 -3.391 -2.712 -2.083 -1.501 -0.961 -0.462 0.000

106

Appendix E: HYSYS Reports

107

Appendix E1.1: PSA Tail Gas With CO2

------------------------------------------------------------------------------PSA Tail Gas-1 (Material Stream): Conditions, Properties, Composition, Attachments ------------------------------------------------------------------------------Material Stream: PSA Tail Gas-1 Fluid Package: Basis-1 Property Package: Peng-Robinson CONDITIONS Overall 1.0000 17.29 40.00* 2047 5.163e+004 91.28 -1.962e+005 175.7 -4.016e+008 --Vapour Phase 1.0000 17.29 40.00 2047 5.163e+004 91.28 -1.962e+005 175.7 -4.016e+008 ---

Vapour / Phase Fraction Temperature: (C) Pressure: (kPa) Molar Flow (kgmole/h) Mass Flow (kg/h) Std Ideal Liq Vol Flow (m3/h) Molar Enthalpy (kJ/kgmole) Molar Entropy (kJ/kgmole-C) Heat Flow (kJ/h) Liq Vol Flow @Std Cond (m3/h) PROPERTIES

Overall Molecular Weight 25.22 Molar Density (kgmole/m3) 1.658e-002 Mass Density (kg/m3) 0.4181 Act. Volume Flow (m3/h) 1.235e+005 Mass Enthalpy (kJ/kg) -7778 Mass Entropy (kJ/kg-C) 6.967 Heat Capacity (kJ/kgmole-C) 34.06 Mass Heat Capacity (kJ/kg-C) 1.350 Lower Heating Value (kJ/kgmole) 2.328e+005 Mass Lower Heating Value (kJ/kg) 9232 Phase Fraction [Vol. Basis] --Phase Fraction [Mass Basis] 4.941e-324 Partial Pressure of CO2 (kPa) 17.81 Cost Based on Flow (Cost/s) 0.0000

Vapour Phase 25.22 1.658e-002 0.4181 1.235e+005 -7778 6.967 34.06 1.350 2.328e+005 9232 1.000 1.000 --0.0000

108

Act. Gas Flow (ACT_m3/h) 1.235e+005 Avg. Liq. Density (kgmole/m3) 22.43 Specific Heat (kJ/kgmole-C) 34.06 Std. Gas Flow (STD_m3/h) 4.840e+004 Std. Ideal Liq. Mass Density (kg/m3) 565.6 Act. Liq. Flow (m3/s) --Z Factor 0.9992 Watson K 10.54 User Property --Partial Pressure of H2S (kPa) 0.0000 Cp/(Cp - R) 1.323 Cp/Cv 1.325 Heat of Vap. (kJ/kgmole) --Kinematic Viscosity (cSt) 34.21 Liq. Mass Density (Std. Cond) (kg/m3) --Liq. Vol. Flow (Std. Cond) (m3/h) --Liquid Fraction 0.0000 Molar Volume (m3/kgmole) 60.32 Mass Heat of Vap. (kJ/kg) --Phase Fraction [Molar Basis] 1.0000 Surface Tension (dyne/cm) --Thermal Conductivity (W/m-K) 4.211e-002 Viscosity (cP) 1.430e-002 Cv (Semi-Ideal) (kJ/kgmole-C) 25.74 Mass Cv (Semi-Ideal) (kJ/kg-C) 1.021 Cv (kJ/kgmole-C) 25.71 Mass Cv (kJ/kg-C) 1.019 Cv (Ent. Method) (kJ/kgmole-C) --Mass Cv (Ent. Method) (kJ/kg-C) --Cp/Cv (Ent. Method) --Reid VP at 37.8 C (kPa) --True VP at 37.8 C (kPa) --Liq. Vol. Flow - Sum(Std. Cond) (m3/h) 0.0000 COMPOSITION Overall Phase COMPONENTS Methane MOLAR FLOW (kgmole/h) 360.5000

1.235e+005 22.43 34.06 4.840e+004 565.6 --0.9992 10.54 ----1.323 1.325 --34.21 ----0.0000 60.32 --1.0000 --4.211e-002 1.430e-002 25.74 1.021 25.71 1.019 ----------0.0000

Vapour Fraction 1.0000 MOLE FRACTION 0.1761 MASS FLOW (kg/h) 5783.4649 MASS FRACTION 0.1120 LIQUID VOLUME FLOW (m3/h) 19.3172 LIQUID VOLUME FRACTION 0.2116

109

Ethane Propane CO CO2 Hydrogen H2O Nitrogen Oxygen i-Butane n-Butane i-Pentane n-Pentane n-Hexane Ethylene tr2-Butene 1-Butene Helium Propene Total Vapour Phase COMPONENTS Methane Ethane Propane CO CO2 Hydrogen H2O Nitrogen Oxygen i-Butane n-Butane i-Pentane n-Pentane n-Hexane Ethylene tr2-Butene 1-Butene

0.0000 0.0000 136.7177 911.3458 613.9684 0.0000 23.7409 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.8802 0.0000 2047.1530

0.0000 0.0000 0.0668 0.4452 0.2999 0.0000 0.0116 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 1.0000

0.0000 0.0000 3829.5870 40108.0559 1237.7603 0.0000 665.0549 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 3.5233 0.0000 51627.4464

0.0000 0.0000 0.0742 0.7769 0.0240 0.0000 0.0129 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 1.0000

0.0000 0.0000 4.7906 48.5961 17.7180 0.0000 0.8247 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0284 0.0000 91.2751

0.0000 0.0000 0.0525 0.5324 0.1941 0.0000 0.0090 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 1.0000 Phase Fraction 1.000 LIQUID VOLUME FRACTION 0.2116 0.0000 0.0000 0.0525 0.5324 0.1941 0.0000 0.0090 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

MOLAR FLOW (kgmole/h) 360.5000 0.0000 0.0000 136.7177 911.3458 613.9684 0.0000 23.7409 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

MOLE FRACTION 0.1761 0.0000 0.0000 0.0668 0.4452 0.2999 0.0000 0.0116 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

MASS FLOW (kg/h) 5783.4649 0.0000 0.0000 3829.5870 40108.0559 1237.7603 0.0000 665.0549 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

MASS FRACTION 0.1120 0.0000 0.0000 0.0742 0.7769 0.0240 0.0000 0.0129 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

LIQUID VOLUME FLOW (m3/h) 19.3172 0.0000 0.0000 4.7906 48.5961 17.7180 0.0000 0.8247 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

110

Helium Propene Total UNIT OPERATIONS FEED TO Tee: TEE-100 UTILITIES

0.8802 0.0000 2047.1530

0.0004 0.0000 1.0000

3.5233 0.0000 51627.4464

0.0001 0.0000 1.0000

0.0284 0.0000 91.2751

0.0003 0.0000 1.0000

PRODUCT FROM Balance: 30-PK-004

LOGICAL CONNECTION

( No utilities reference this stream )

------------------------------------------------------------------------------Hyprotech Ltd. Aspen HYSYS Version 2006 (20.0.0.6728)

111

Appendix E1.2: Reformer Furnace With CO2

------------------------------------------------------------------------------30-F-001-A (Conversion Reactor): Design, Reactions, Worksheet ------------------------------------------------------------------------------Conversion Reactor: 30-F-001-A

CONNECTIONS Inlet Stream Connections Stream Name To Reformer Outlet Stream Connections Stream Name To Waste HEX DNE2 Energy Stream Connections Stream Name Q-102 PARAMETERS Physical Parameters Delta P 0.0000 kPa User Variables REACTION DETAILS Reaction: Component Methane H2O CO Hydrogen Meth Reform Mole Weight 16.04 18.02 28.01 2.016 Stoichiometric Coeff. -1.000 -1.000 1.000 3.000 From Unit Operation Mixed Feed Preheat Coil Heat Exchanger

To Unit Operation Component Splitter: X-100

From Unit Operation

Vessel Volume ---

Optional Heat Transfer: Heating Duty Energy Stream 3.160e+008 kJ/h Q-102

112

Reaction: Component Ethane H2O CO Hydrogen Reaction: Component Propane H2O CO Hydrogen Reaction: Component CO H2O CO2 Hydrogen Reaction: Component 1-Butene H2O CO Hydrogen Reaction: Component Ethylene H2O CO Hydrogen Reaction: Component i-Butane H2O

Eth Reform Mole Weight 30.07 18.02 28.01 2.016 Prop Reform Mole Weight 44.10 18.02 28.01 2.016 Reformer Shift Mole Weight 28.01 18.02 44.01 2.016 1-butene ref Mole Weight 56.11 18.02 28.01 2.016 ethyl ref Mole Weight 28.05 18.02 28.01 2.016 i-but ref Mole Weight 58.12 18.02 Stoichiometric Coeff. -1.000 -4.000 Stoichiometric Coeff. -1.000 -2.000 2.000 4.000 Stoichiometric Coeff. -1.000 -4.000 4.000 8.000 Stoichiometric Coeff. -1.000 -1.000 1.000 1.000 Stoichiometric Coeff. -1.000 -3.000 3.000 7.000 Stoichiometric Coeff. -1.000 -2.000 2.000 5.000

113

CO Hydrogen Reaction: Component i-Pentane H2O CO Hydrogen Reaction: Component n-Butane H2O CO Hydrogen Reaction: Component n-Hexane H2O CO Hydrogen Reaction: Component n-Pentane H2O CO Hydrogen Reaction: Component Propene H2O CO Hydrogen Reaction: Component i-pent ref

28.01 2.016

4.000 9.000

Mole Weight 72.15 18.02 28.01 2.016 n-but ref Mole Weight 58.12 18.02 28.01 2.016 n-hex ref Mole Weight 86.18 18.02 28.01 2.016 n-pent ref Mole Weight 72.15 18.02 28.01 2.016 propene ref Mole Weight 42.08 18.02 28.01 2.016 tr-but ref Mole Weight

Stoichiometric Coeff. -1.000 -5.000 5.000 11.000

Stoichiometric Coeff. -1.000 -4.000 4.000 9.000

Stoichiometric Coeff. -1.000 -6.000 6.000 13.000

Stoichiometric Coeff. -1.000 -5.000 5.000 11.000

Stoichiometric Coeff. -1.000 -3.000 3.000 6.000

Stoichiometric Coeff.

114

tr2-Butene H2O CO Hydrogen REACTION RESULTS FOR : Extents Name Meth Reform Eth Reform Prop Reform Reformer Shift 1-butene ref ethyl ref i-but ref i-pent ref n-but ref n-hex ref n-pent ref propene ref tr-but ref Balance Components Methane Ethane Propane CO CO2 Hydrogen H2O Nitrogen Oxygen i-Butane n-Butane i-Pentane Rank 0 0 0 1 0 0 0 0 0 0 0 0 0 Reformer

56.11 18.02 28.01 2.016

-1.000 -4.000 4.000 8.000

Specified % Conversion 72.80 100.00 100.00 58.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

Use Default No Yes Yes No Yes Yes Yes Yes Yes Yes Yes Yes Yes

Actual % Conversion 72.80 100.0 100.0 ------100.0 100.0 100.0 100.0 100.0 -----

Base Component Methane Ethane Propane CO 1-Butene Ethylene i-Butane i-Pentane n-Butane n-Hexane n-Pentane Propene tr2-Butene

Reaction Extent (kgmole/h) 964.9 29.16 8.390 616.4 0.0000 0.0000 0.1789 0.4969 2.016 0.2413 0.3407 0.0000 0.0000

Total Inflow (kgmole/h) 1325 29.16 8.390 0.0000 2.569 12.27 4706 23.74 0.0000 0.1789 2.016 0.4969

Total Reaction (kgmole/h) -964.9 -29.16 -8.390 446.4 616.4 3748 -1679 0.0000 0.0000 -0.1789 -2.016 -0.4969

Total Outflow (kgmole/h) 360.5 0.0000 0.0000 446.4 619.0 3760 3027 23.74 0.0000 0.0000 0.0000 0.0000

115

n-Pentane n-Hexane Ethylene tr2-Butene 1-Butene Helium Propene CONDITIONS Name Vapour Temperature (C) Pressure (kPa) Molar Flow (kgmole/h) Mass Flow (kg/h) Std Ideal Liq Vol Flow (m3/h) Molar Enthalpy (kJ/kgmole) Molar Entropy (kJ/kgmole-C) Heat Flow (kJ/h) PROPERTIES

0.3407 0.2413 0.0000 0.0000 0.0000 0.8802 0.0000

-0.3407 -0.2413 0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000 0.8802 0.0000

To Reformer 1.0000 449.9883 3501.0000 6111.7508 108305.6690 160.8581 -1.875e+005 184.1 -1.1458e+09

DNE2 0.0000 794.9993 3501.0000 0.0000 0.0000 0.0000 -1.007e+005 174.5 0.0000e-01

To Waste HEX 1.0000 794.9993 3501.0000 8237.2949 108306.4336 231.9613 -1.007e+005 174.5 -8.2978e+08

Q-102 ----------------3.1598e+08

Name To Reformer Molecular Weight 17.72 Molar Density (kgmole/m3) 0.5960 Mass Density (kg/m3) 10.56 Act. Volume Flow (m3/h) 1.025e+004 Mass Enthalpy (kJ/kg) -1.058e+004 Mass Entropy (kJ/kg-C) 10.39 Heat Capacity (kJ/kgmole-C) 44.71 Mass Heat Capacity (kJ/kg-C) 2.523 Lower Heating Value (kJ/kgmole) 1.857e+005 Mass Lower Heating Value (kJ/kg) 1.048e+004 Phase Fraction [Vol. Basis] --Phase Fraction [Mass Basis] 4.941e-324 Partial Pressure of CO2 (kPa) 1.472 Cost Based on Flow (Cost/s) 0.0000 Act. Gas Flow (ACT_m3/h) 1.025e+004 Avg. Liq. Density (kgmole/m3) 37.99 Specific Heat (kJ/kgmole-C) 44.71 Std. Gas Flow (STD_m3/h) 1.445e+005

DNE2 13.15 0.3926 5.162 0.0000 -7661 13.27 38.97 2.964 1.609e+005 1.224e+004 --4.941e-324 0.0000 0.0000 ----38.97 0.0000

To Waste HEX 13.15 0.3926 5.162 2.098e+004 -7661 13.27 38.97 2.964 1.609e+005 1.224e+004 --4.941e-324 263.1 0.0000 2.098e+004 35.51 38.97 1.948e+005

116

Std. Ideal Liq. Mass Density (kg/m3) 673.3 Act. Liq. Flow (m3/s) --Z Factor 0.9770 Watson K 18.97 User Property --Partial Pressure of H2S (kPa) 0.0000 Cp/(Cp - R) 1.228 Cp/Cv 1.272 Heat of Vap. (kJ/kgmole) 5.007e+004 Kinematic Viscosity (cSt) 2.059 Liq. Mass Density (Std. Cond) (kg/m3) 741.0 Liq. Vol. Flow (Std. Cond) (m3/h) 146.2 Liquid Fraction 0.0000 Molar Volume (m3/kgmole) 1.678 Mass Heat of Vap. (kJ/kg) 2826 Phase Fraction [Molar Basis] 1.0000 Surface Tension (dyne/cm) --Thermal Conductivity (W/m-K) 7.302e-002 Viscosity (cP) 2.175e-002 Cv (Semi-Ideal) (kJ/kgmole-C) 36.39 Mass Cv (Semi-Ideal) (kJ/kg-C) 2.054 Cv (kJ/kgmole-C) 35.15 Mass Cv (kJ/kg-C) 1.983 Cv (Ent. Method) (kJ/kgmole-C) 36.24 Mass Cv (Ent. Method) (kJ/kg-C) 2.045 Cp/Cv (Ent. Method) 1.234 Reid VP at 37.8 C (kPa) --True VP at 37.8 C (kPa) --Liq. Vol. Flow - Sum(Std. Cond) (m3/h) 146.2

466.9 0.0000 --14.89 --0.0000 1.271 1.277 3.920e+004 0.7359 --0.0000 1.000 2.547 2982 0.0000 0.0000 0.1432 3.799e-003 30.65 2.331 30.51 2.320 ----------0.0000

466.9 0.0000 --14.89 --0.0000 1.271 1.277 3.920e+004 5.299 ----0.0000 2.547 2982 1.0000 --0.1885 2.736e-002 30.65 2.331 30.51 2.320 30.49 2.319 1.278 ----0.0000

------------------------------------------------------------------------------30-F-001-B (Conversion Reactor): Design, Reactions, Worksheet ------------------------------------------------------------------------------Conversion Reactor: 30-F-001-B

CONNECTIONS Inlet Stream Connections

117

Stream Name Combo Gas PSA Tail Gas-2 Combustion Air Outlet Stream Connections Stream Name waste gas DNE Energy Stream Connections Stream Name Q-100 PARAMETERS Physical Parameters Delta P 0.0000 kPa User Variables REACTION DETAILS Reaction: Component Methane Oxygen CO2 H2O Reaction: Component Ethane Oxygen CO2 H2O Reaction: Component Propane Meth Combust

From Unit Operation RCY-1 Recycle

To Unit Operation Heat Exchanger: Steam Generation Coil I

From Unit Operation

Vessel Volume ---

Optional Heat Transfer: Cooling Duty Energy Stream 3.657e+008 kJ/h Q-100

Mole Weight 16.04 32.00 44.01 18.02 Eth combust Mole Weight 30.07 32.00 44.01 18.02 Prop combust Mole Weight 44.10

Stoichiometric Coeff. -1.000 -2.000 1.000 2.000

Stoichiometric Coeff. -1.000 -3.500 2.000 3.000

Stoichiometric Coeff. -1.000

118

Oxygen CO2 H2O Reaction: Component Hydrogen Oxygen H2O Reaction: Component Oxygen CO2 H2O 1-Butene Reaction: Component Oxygen CO2 H2O Ethylene Reaction: Component i-Butane Oxygen CO2 H2O Reaction: Component Oxygen CO2 H2O i-Pentane Reaction: Component H2 combust

32.00 44.01 18.02

-5.000 3.000 4.000

Mole Weight 2.016 32.00 18.02 1-but combust Mole Weight 32.00 44.01 18.02 56.11 ethylene comust Mole Weight 32.00 44.01 18.02 28.05 i-but combust Mole Weight 58.12 32.00 44.01 18.02 i-pent combust Mole Weight 32.00 44.01 18.02 72.15 n-but combust Mole Weight

Stoichiometric Coeff. -2.000 -1.000 2.000

Stoichiometric Coeff. -6.000 4.000 4.000 -1.000

Stoichiometric Coeff. -3.000 2.000 2.000 -1.000

Stoichiometric Coeff. -1.000 -6.500 4.000 5.000

Stoichiometric Coeff. -8.000 5.000 6.000 -1.000

Stoichiometric Coeff.

119

Oxygen CO2 H2O n-Butane Reaction: Component Oxygen CO2 H2O n-Hexane Reaction: Component Oxygen CO2 H2O n-Pentane Reaction: Component Propene Oxygen CO2 H2O n-hex combust

32.00 44.01 18.02 58.12

-6.500 4.000 5.000 -1.000

Mole Weight 32.00 44.01 18.02 86.18 n-pent comust Mole Weight 32.00 44.01 18.02 72.15 propene combust Mole Weight 42.08 32.00 44.01 18.02

Stoichiometric Coeff. -9.500 6.000 7.000 -1.000

Stoichiometric Coeff. -8.000 5.000 6.000 -1.000

Stoichiometric Coeff. -1.000 -4.500 3.000 3.000

Reaction: tr2-but combust Component Oxygen CO2 H2O tr2-Butene Reaction: Component

Mole Weight 32.00 44.01 18.02 56.11

Stoichiometric Coeff. -6.000 4.000 4.000 -1.000

Mole Weight

Stoichiometric Coeff.

120

REACTION RESULTS FOR : Extents Name Meth Combust Eth combust Prop combust H2 combust 1-but combust ethylene comust i-but combust i-pent combust n-but combust n-hex combust n-pent comust propene combust tr2-but combust CO Combust Balance Components Methane Ethane Propane CO CO2 Hydrogen H2O Nitrogen Oxygen i-Butane n-Butane i-Pentane n-Pentane n-Hexane Ethylene tr2-Butene Rank 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Combust

Specified % Conversion 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

Use Default Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes

Actual % Conversion 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Base Component Methane Ethane Propane Hydrogen 1-Butene Ethylene i-Butane i-Pentane n-Butane n-Hexane n-Pentane Propene tr2-Butene CO

Reaction Extent (kgmole/h) 391.6 3.619 1.653 370.6 1.400e-002 0.2444 5.982e-002 4.084e-003 8.196e-002 3.305e-003 9.938e-003 0.3504 2.801e-003 136.8

Total Inflow (kgmole/h) 391.6 3.619 1.653 136.8 911.4 741.2 0.0000 5336 1412 5.982e-002 8.196e-002 4.084e-003 9.938e-003 3.305e-003 0.2444 2.801e-003

Total Reaction (kgmole/h) -391.6 -3.619 -1.653 -136.8 542.8 -741.2 1544 0.0000 -1247 -5.982e-002 -8.196e-002 -4.084e-003 -9.938e-003 -3.305e-003 -0.2444 -2.801e-003

Total Outflow (kgmole/h) 0.0000 0.0000 0.0000 0.0000 1454 0.0000 1544 5336 165.5 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

121

1-Butene Helium Propene CONDITIONS Name Vapour Temperature (C) Pressure (kPa) Molar Flow (kgmole/h) Mass Flow (kg/h) Std Ideal Liq Vol Flow (m3/h) Molar Enthalpy (kJ/kgmole) Molar Entropy (kJ/kgmole-C) Heat Flow (kJ/h) Name Vapour Temperature (C) Pressure (kPa) Molar Flow (kgmole/h) Mass Flow (kg/h) Std Ideal Liq Vol Flow (m3/h) Molar Enthalpy (kJ/kgmole) Molar Entropy (kJ/kgmole-C) Heat Flow (kJ/h) PROPERTIES

1.400e-002 1.020 0.3504

-1.400e-002 0.0000 -0.3504

0.0000 1.020 0.0000

Combo Gas 1.0000 55.0000 146.3250 164.9437 982.2490 5.8716 -1.617e+004 142.2 -2.6663e+06 waste gas 1.0000 800.0000 40.0000 8501.0097 246596.8774 295.4778 -8.404e+004 216.8 -7.1444e+08

PSA Tail Gas-2 1.0000 17.2199 40.0000 2047.1530 51627.4464 91.2751 -1.962e+005 175.7 -4.0156e+08

Combustion Air 1.0000 300.0000 102.8000 6724.0000 193989.2181 224.2517 8248 171.1 5.5463e+07

DNE 0.0000 800.0000 40.0000 0.0000 0.0000 0.0000 -8.404e+004 216.8 0.0000e-01

Name Combo Gas Molecular Weight 5.955 Molar Density (kgmole/m3) 5.362e-002 Mass Density (kg/m3) 0.3193 Act. Volume Flow (m3/h) 3076 Mass Enthalpy (kJ/kg) -2715 Mass Entropy (kJ/kg-C) 23.88 Heat Capacity (kJ/kgmole-C) 31.48 Mass Heat Capacity (kJ/kg-C) 5.286 Lower Heating Value (kJ/kgmole) 3.988e+005 Mass Lower Heating Value (kJ/kg) 6.697e+004 Phase Fraction [Vol. Basis] --Phase Fraction [Mass Basis] 4.941e-324

PSA Tail Gas-2 25.22 1.658e-002 0.4182 1.235e+005 -7778 6.966 34.05 1.350 2.328e+005 9232 --4.941e-324

Combustion Air 28.85 2.157e-002 0.6222 3.118e+005 285.9 5.932 30.84 1.069 0.0000 ----4.941e-324

DNE 29.01 4.483e-003 0.1300 0.0000 -2897 7.475 38.36 1.322 0.0000 ----2.122e-314

waste gas 29.01 4.483e-003 0.1300 1.896e+006 -2897 7.475 38.36 1.322 0.0000 ----2.122e-314

122

Partial Pressure of CO2 (kPa) 1.267e-002 Cost Based on Flow (Cost/s) 0.0000 Act. Gas Flow (ACT_m3/h) 3076 Avg. Liq. Density (kgmole/m3) 28.09 Specific Heat (kJ/kgmole-C) 31.48 Std. Gas Flow (STD_m3/h) 3900 Std. Ideal Liq. Mass Density (kg/m3) 167.3 Act. Liq. Flow (m3/s) --Z Factor 1.000 Watson K 25.94 User Property --Partial Pressure of H2S (kPa) 0.0000 Cp/(Cp - R) 1.359 Cp/Cv 1.360 Heat of Vap. (kJ/kgmole) 7195 Kinematic Viscosity (cSt) 29.15 Liq. Mass Density (Std. Cond) (kg/m3) --Liq. Vol. Flow (Std. Cond) (m3/h) --Liquid Fraction 0.0000 Molar Volume (m3/kgmole) 18.65 Mass Heat of Vap. (kJ/kg) 1208 Phase Fraction [Molar Basis] 1.0000 Surface Tension (dyne/cm) --Thermal Conductivity (W/m-K) 0.1298 Viscosity (cP) 9.309e-003 Cv (Semi-Ideal) (kJ/kgmole-C) 23.16 Mass Cv (Semi-Ideal) (kJ/kg-C) 3.890 Cv (kJ/kgmole-C) 23.14 Mass Cv (kJ/kg-C) 3.886 Cv (Ent. Method) (kJ/kgmole-C) 23.12 Mass Cv (Ent. Method) (kJ/kg-C) 3.882 Cp/Cv (Ent. Method) 1.362 Reid VP at 37.8 C (kPa) --True VP at 37.8 C (kPa) --Liq. Vol. Flow - Sum(Std. Cond) (m3/h) 0.0000

17.81 0.0000 1.235e+005 22.43 34.05 4.840e+004 565.6 --0.9992 10.54 --0.0000 1.323 1.325 --31.30 ----0.0000 60.31 --1.0000 --4.210e-002 1.309e-002 25.74 1.021 25.71 1.019 ----------0.0000

0.0000 0.0000 3.118e+005 29.98 30.84 1.590e+005 865.1 --1.000 6.042 --0.0000 1.369 1.370 5891 48.58 ----0.0000 46.37 204.2 1.0000 --4.360e-002 3.022e-002 22.53 0.7808 22.52 0.7805 22.48 0.7791 1.372 ----0.0000

0.0000 0.0000 ----38.36 0.0000 834.6 0.0000 --6.967 --0.0000 1.277 1.277 --2.347 --0.0000 1.000 223.1 --0.0000 0.0000 7.160e-002 3.052e-004 30.05 1.036 30.04 1.036 --------1.630e+005 0.0000

6.842 0.0000 1.896e+006 28.77 38.36 2.010e+005 834.6 ----6.967 --0.0000 1.277 1.277 --328.8 ----0.0000 223.1 --1.0000 --7.326e-002 4.276e-002 30.05 1.036 30.04 1.036 --------1.630e+005 0.0000

------------------------------------------------------------------------------Hyprotech Ltd. Aspen HYSYS Version 2006 (20.0.0.6728)

123

Appendix E2.1: PSA Tail Gas Without CO2

------------------------------------------------------------------------------PSA Tail Gas-1 (Material Stream): Conditions, Properties, Composition, Attachments ------------------------------------------------------------------------------Material Stream: PSA Tail Gas-1 Fluid Package: Basis-1 Property Package: Peng-Robinson CONDITIONS Overall Vapour Phase Vapour / Phase Fraction 1.0000 1.0000 Temperature: (C) 31.98 31.98 Pressure: (kPa) 40.00* 40.00 Molar Flow (kgmole/h) 1231 1231 Mass Flow (kg/h) 1.570e+004 1.570e+004 Std Ideal Liq Vol Flow (m3/h) 47.74 47.74 Molar Enthalpy (kJ/kgmole) -6.438e+004 -6.438e+004 Molar Entropy (kJ/kgmole-C) 167.7 167.7 Heat Flow (kJ/h) -7.924e+007 -7.924e+007 Liq Vol Flow @Std Cond (m3/h) ----PROPERTIES Overall Molecular Weight 12.75 Molar Density (kgmole/m3) 1.577e-002 Mass Density (kg/m3) 0.2011 Act. Volume Flow (m3/h) 7.805e+004 Mass Enthalpy (kJ/kg) -5048 Mass Entropy (kJ/kg-C) 13.15 Heat Capacity (kJ/kgmole-C) 31.59 Mass Heat Capacity (kJ/kg-C) 2.477 Lower Heating Value (kJ/kgmole) 3.873e+005 Mass Lower Heating Value (kJ/kg) 3.036e+004 Phase Fraction [Vol. Basis] --Phase Fraction [Mass Basis] 4.941e-324 Partial Pressure of CO2 (kPa) 3.086 Cost Based on Flow (Cost/s) 0.0000 Act. Gas Flow (ACT_m3/h) 7.805e+004 Avg. Liq. Density (kgmole/m3) 25.78 Specific Heat (kJ/kgmole-C) 31.59 Std. Gas Flow (STD_m3/h) 2.910e+004 Vapour Phase 12.75 1.577e-002 0.2011 7.805e+004 -5048 13.15 31.59 2.477 3.873e+005 3.036e+004 1.000 1.000 --0.0000 7.805e+004 25.78 31.59 2.910e+004

124

Std. Ideal Liq. Mass Density (kg/m3) 328.8 Act. Liq. Flow (m3/s) --Z Factor 0.9999 Watson K 15.10 User Property --Partial Pressure of H2S (kPa) 0.0000 Cp/(Cp - R) 1.357 Cp/Cv 1.358 Heat of Vap. (kJ/kgmole) --Kinematic Viscosity (cSt) 60.91 Liq. Mass Density (Std. Cond) (kg/m3) --Liq. Vol. Flow (Std. Cond) (m3/h) --Liquid Fraction 0.0000 Molar Volume (m3/kgmole) 63.42 Mass Heat of Vap. (kJ/kg) --Phase Fraction [Molar Basis] 1.0000 Surface Tension (dyne/cm) --Thermal Conductivity (W/m-K) 7.500e-002 Viscosity (cP) 1.225e-002 Cv (Semi-Ideal) (kJ/kgmole-C) 23.28 Mass Cv (Semi-Ideal) (kJ/kg-C) 1.825 Cv (kJ/kgmole-C) 23.27 Mass Cv (kJ/kg-C) 1.824 Cv (Ent. Method) (kJ/kgmole-C) --Mass Cv (Ent. Method) (kJ/kg-C) --Cp/Cv (Ent. Method) --Reid VP at 37.8 C (kPa) --True VP at 37.8 C (kPa) --Liq. Vol. Flow - Sum(Std. Cond) (m3/h) 0.0000 COMPOSITION Overall Phase COMPONENTS Methane Ethane Propane CO CO2 MOLAR FLOW (kgmole/h) 360.5000 0.0000 0.0000 136.7177 94.9458

328.8 --0.9999 15.10 ----1.357 1.358 --60.91 ----0.0000 63.42 --1.0000 --7.500e-002 1.225e-002 23.28 1.825 23.27 1.824 ----------0.0000

Vapour Fraction 1.0000 MOLE FRACTION 0.2929 0.0000 0.0000 0.1111 0.0771 MASS FLOW (kg/h) 5783.4649 0.0000 0.0000 3829.5870 4178.5362 MASS FRACTION 0.3684 0.0000 0.0000 0.2440 0.2662 LIQUID VOLUME FLOW (m3/h) 19.3172 0.0000 0.0000 4.7906 5.0628 LIQUID VOLUME FRACTION 0.4046 0.0000 0.0000 0.1003 0.1060

125

Hydrogen H2O Nitrogen Oxygen i-Butane n-Butane i-Pentane n-Pentane n-Hexane Ethylene tr2-Butene 1-Butene Helium Propene Total Vapour Phase COMPONENTS Methane Ethane Propane CO CO2 Hydrogen H2O Nitrogen Oxygen i-Butane n-Butane i-Pentane n-Pentane n-Hexane Ethylene tr2-Butene 1-Butene Helium Propene Total Hyprotech Ltd.

613.9684 0.0000 23.7409 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.8802 0.0000 1230.7530

0.4989 0.0000 0.0193 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0007 0.0000 1.0000

1237.7603 0.0000 665.0549 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 3.5233 0.0000 15697.9267

0.0788 0.0000 0.0424 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 1.0000

17.7180 0.0000 0.8247 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0284 0.0000 47.7418

0.3711 0.0000 0.0173 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0006 0.0000 1.0000 Phase Fraction 1.000 LIQUID VOLUME FRACTION 0.4046 0.0000 0.0000 0.1003 0.1060 0.3711 0.0000 0.0173 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0006 0.0000 1.0000

MOLAR FLOW (kgmole/h) 360.5000 0.0000 0.0000 136.7177 94.9458 613.9684 0.0000 23.7409 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.8802 0.0000 1230.7530

MASS FLOW MASS FRACTION (kg/h) 0.2929 5783.4649 0.3684 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1111 3829.5870 0.2440 0.0771 4178.5362 0.2662 0.4989 1237.7603 0.0788 0.0000 0.0000 0.0000 0.0193 665.0549 0.0424 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0007 3.5233 0.0002 0.0000 0.0000 0.0000 1.0000 15697.9267 1.0000 Aspen HYSYS Version 2006 (20.0.0.6728)

MOLE FRACTION

LIQUID VOLUME FLOW (m3/h) 19.3172 0.0000 0.0000 4.7906 5.0628 17.7180 0.0000 0.8247 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0284 0.0000 47.7418

126

Appendix E2.2: Reformer without CO2

------------------------------------------------------------------------------30-F-001-A (Conversion Reactor): Design, Reactions, Worksheet ------------------------------------------------------------------------------Conversion Reactor: 30-F-001-A

CONNECTIONS Inlet Stream Connections Stream Name To Reformer Outlet Stream Connections Stream Name To Waste HEX DNE2 Energy Stream Connections Stream Name Q-102 PARAMETERS Physical Parameters Delta P 0.0000 kPa User Variables REACTION DETAILS Reaction: Component Methane H2O CO Hydrogen Meth Reform Mole Weight 16.04 18.02 28.01 2.016 Stoichiometric Coeff. -1.000 -1.000 1.000 3.000 From Unit Operation Mixed Feed Preheat Coil Heat Exchanger

To Unit Operation Component Splitter: X-100

From Unit Operation

Vessel Volume ---

Optional Heat Transfer: Heating Duty Energy Stream 3.160e+008 kJ/h Q-102

127

Reaction: Component Ethane H2O CO Hydrogen Reaction: Component Propane H2O CO Hydrogen Reaction: Component CO H2O CO2 Hydrogen Reaction: Component 1-Butene H2O CO Hydrogen Reaction: Component Ethylene H2O CO Hydrogen Reaction: Component i-Butane H2O

Eth Reform Mole Weight 30.07 18.02 28.01 2.016 Prop Reform Mole Weight 44.10 18.02 28.01 2.016 Reformer Shift Mole Weight 28.01 18.02 44.01 2.016 1-butene ref Mole Weight 56.11 18.02 28.01 2.016 ethyl ref Mole Weight 28.05 18.02 28.01 2.016 i-but ref Mole Weight 58.12 18.02 Stoichiometric Coeff. -1.000 -4.000 Stoichiometric Coeff. -1.000 -2.000 2.000 4.000 Stoichiometric Coeff. -1.000 -4.000 4.000 8.000 Stoichiometric Coeff. -1.000 -1.000 1.000 1.000 Stoichiometric Coeff. -1.000 -3.000 3.000 7.000 Stoichiometric Coeff. -1.000 -2.000 2.000 5.000

128

CO Hydrogen Reaction: Component i-Pentane H2O CO Hydrogen Reaction: Component n-Butane H2O CO Hydrogen Reaction: Component n-Hexane H2O CO Hydrogen Reaction: Component n-Pentane H2O CO Hydrogen Reaction: Component Propene H2O CO Hydrogen Reaction: Component i-pent ref

28.01 2.016

4.000 9.000

Mole Weight 72.15 18.02 28.01 2.016 n-but ref Mole Weight 58.12 18.02 28.01 2.016 n-hex ref Mole Weight 86.18 18.02 28.01 2.016 n-pent ref Mole Weight 72.15 18.02 28.01 2.016 propene ref Mole Weight 42.08 18.02 28.01 2.016 tr-but ref Mole Weight

Stoichiometric Coeff. -1.000 -5.000 5.000 11.000

Stoichiometric Coeff. -1.000 -4.000 4.000 9.000

Stoichiometric Coeff. -1.000 -6.000 6.000 13.000

Stoichiometric Coeff. -1.000 -5.000 5.000 11.000

Stoichiometric Coeff. -1.000 -3.000 3.000 6.000

Stoichiometric Coeff.

129

tr2-Butene H2O CO Hydrogen REACTION RESULTS FOR : Extents Name Meth Reform Eth Reform Prop Reform Reformer Shift 1-butene ref ethyl ref i-but ref i-pent ref n-but ref n-hex ref n-pent ref propene ref tr-but ref Balance Components Methane Ethane Propane CO CO2 Hydrogen H2O Nitrogen Oxygen i-Butane n-Butane i-Pentane Rank 0 0 0 1 0 0 0 0 0 0 0 0 0 Reformer

56.11 18.02 28.01 2.016

-1.000 -4.000 4.000 8.000

Specified % Conversion 72.80 100.00 100.00 58.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

Use Default No Yes Yes No Yes Yes Yes Yes Yes Yes Yes Yes Yes

Actual % Conversion 72.80 100.0 100.0 ------100.0 100.0 100.0 100.0 100.0 -----

Base Component Methane Ethane Propane CO 1-Butene Ethylene i-Butane i-Pentane n-Butane n-Hexane n-Pentane Propene tr2-Butene

Reaction Extent (kgmole/h) 964.9 29.16 8.390 616.4 0.0000 0.0000 0.1789 0.4969 2.016 0.2413 0.3407 0.0000 0.0000

Total Inflow (kgmole/h) 1325 29.16 8.390 0.0000 2.569 12.27 4706 23.74 0.0000 0.1789 2.016 0.4969

Total Reaction (kgmole/h) -964.9 -29.16 -8.390 446.4 616.4 3748 -1679 0.0000 0.0000 -0.1789 -2.016 -0.4969

Total Outflow (kgmole/h) 360.5 0.0000 0.0000 446.4 619.0 3760 3027 23.74 0.0000 0.0000 0.0000 0.0000

130

n-Pentane n-Hexane Ethylene tr2-Butene 1-Butene Helium Propene CONDITIONS Name Vapour Temperature (C) Pressure (kPa) Molar Flow (kgmole/h) Mass Flow (kg/h) Std Ideal Liq Vol Flow (m3/h) Molar Enthalpy (kJ/kgmole) Molar Entropy (kJ/kgmole-C) Heat Flow (kJ/h) PROPERTIES

0.3407 0.2413 0.0000 0.0000 0.0000 0.8802 0.0000

-0.3407 -0.2413 0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000 0.8802 0.0000

To Reformer 1.0000 449.9139 3501.0000 6111.7508 108305.6690 160.8581 -1.875e+005 184.1 -1.1458e+09

DNE2 0.0000 795.0129 3501.0000 0.0000 0.0000 0.0000 -1.007e+005 174.5 0.0000e-01

To Waste HEX 1.0000 795.0129 3501.0000 8237.2949 108306.4336 231.9613 -1.007e+005 174.5 -8.2978e+08

Q-102 ----------------3.1600e+08

Name To Reformer Molecular Weight 17.72 Molar Density (kgmole/m3) 0.5961 Mass Density (kg/m3) 10.56 Act. Volume Flow (m3/h) 1.025e+004 Mass Enthalpy (kJ/kg) -1.058e+004 Mass Entropy (kJ/kg-C) 10.39 Heat Capacity (kJ/kgmole-C) 44.71 Mass Heat Capacity (kJ/kg-C) 2.523 Lower Heating Value (kJ/kgmole) 1.857e+005 Mass Lower Heating Value (kJ/kg) 1.048e+004 Phase Fraction [Vol. Basis] --Phase Fraction [Mass Basis] 4.941e-324 Partial Pressure of CO2 (kPa) 1.472 Cost Based on Flow (Cost/s) 0.0000 Act. Gas Flow (ACT_m3/h) 1.025e+004 Avg. Liq. Density (kgmole/m3) 37.99 Specific Heat (kJ/kgmole-C) 44.71 Std. Gas Flow (STD_m3/h) 1.445e+005

DNE2 13.15 0.3926 5.162 0.0000 -7661 13.27 38.97 2.964 1.609e+005 1.224e+004 --4.941e-324 0.0000 0.0000 ----38.97 0.0000

To Waste HEX 13.15 0.3926 5.162 2.098e+004 -7661 13.27 38.97 2.964 1.609e+005 1.224e+004 --4.941e-324 263.1 0.0000 2.098e+004 35.51 38.97 1.948e+005

131

Std. Ideal Liq. Mass Density (kg/m3) 673.3 Act. Liq. Flow (m3/s) --Z Factor 0.9770 Watson K 18.97 User Property --Partial Pressure of H2S (kPa) 0.0000 Cp/(Cp - R) 1.228 Cp/Cv 1.272 Heat of Vap. (kJ/kgmole) 5.007e+004 Kinematic Viscosity (cSt) 2.059 Liq. Mass Density (Std. Cond) (kg/m3) 741.0 Liq. Vol. Flow (Std. Cond) (m3/h) 146.2 Liquid Fraction 0.0000 Molar Volume (m3/kgmole) 1.678 Mass Heat of Vap. (kJ/kg) 2826 Phase Fraction [Molar Basis] 1.0000 Surface Tension (dyne/cm) --Thermal Conductivity (W/m-K) 7.301e-002 Viscosity (cP) 2.175e-002 Cv (Semi-Ideal) (kJ/kgmole-C) 36.39 Mass Cv (Semi-Ideal) (kJ/kg-C) 2.054 Cv (kJ/kgmole-C) 35.15 Mass Cv (kJ/kg-C) 1.983 Cv (Ent. Method) (kJ/kgmole-C) 36.22 Mass Cv (Ent. Method) (kJ/kg-C) 2.044 Cp/Cv (Ent. Method) 1.234 Reid VP at 37.8 C (kPa) --True VP at 37.8 C (kPa) --Liq. Vol. Flow - Sum(Std. Cond) (m3/h) 146.2

466.9 0.0000 --14.89 --0.0000 1.271 1.277 3.920e+004 0.7359 --0.0000 1.000 2.547 2982 0.0000 0.0000 0.1432 3.799e-003 30.65 2.331 30.51 2.320 ----------0.0000

466.9 0.0000 --14.89 --0.0000 1.271 1.277 3.920e+004 5.299 ----0.0000 2.547 2982 1.0000 --0.1885 2.736e-002 30.65 2.331 30.51 2.320 30.49 2.319 1.278 ----0.0000

------------------------------------------------------------------------------30-F-001-B (Conversion Reactor): Design, Reactions, Worksheet ------------------------------------------------------------------------------Conversion Reactor: 30-F-001-B

CONNECTIONS Inlet Stream Connections

132

Stream Name Combo Gas PSA Tail Gas-2 Combustion Air Outlet Stream Connections Stream Name waste gas DNE Energy Stream Connections Stream Name Q-100 PARAMETERS Physical Parameters Delta P 0.0000 kPa User Variables REACTION DETAILS Reaction: Component Methane Oxygen CO2 H2O Reaction: Component Ethane Oxygen CO2 H2O Reaction: Component Propane Meth Combust

From Unit Operation RCY-1 Recycle

To Unit Operation Heat Exchanger: Steam Generation Coil I

From Unit Operation

Vessel Volume ---

Optional Heat Transfer: Cooling Duty Energy Stream 3.657e+008 kJ/h Q-100

Mole Weight 16.04 32.00 44.01 18.02 Eth combust Mole Weight 30.07 32.00 44.01 18.02 Prop combust Mole Weight 44.10

Stoichiometric Coeff. -1.000 -2.000 1.000 2.000

Stoichiometric Coeff. -1.000 -3.500 2.000 3.000

Stoichiometric Coeff. -1.000

133

Oxygen CO2 H2O Reaction: Component Hydrogen Oxygen H2O Reaction: Component Oxygen CO2 H2O 1-Butene Reaction: Component Oxygen CO2 H2O Ethylene Reaction: Component i-Butane Oxygen CO2 H2O Reaction: Component Oxygen CO2 H2O i-Pentane Reaction: Component H2 combust

32.00 44.01 18.02

-5.000 3.000 4.000

Mole Weight 2.016 32.00 18.02 1-but combust Mole Weight 32.00 44.01 18.02 56.11 ethylene comust Mole Weight 32.00 44.01 18.02 28.05 i-but combust Mole Weight 58.12 32.00 44.01 18.02 i-pent combust Mole Weight 32.00 44.01 18.02 72.15 n-but combust Mole Weight

Stoichiometric Coeff. -2.000 -1.000 2.000

Stoichiometric Coeff. -6.000 4.000 4.000 -1.000

Stoichiometric Coeff. -3.000 2.000 2.000 -1.000

Stoichiometric Coeff. -1.000 -6.500 4.000 5.000

Stoichiometric Coeff. -8.000 5.000 6.000 -1.000

Stoichiometric Coeff.

134

Oxygen CO2 H2O n-Butane Reaction: Component Oxygen CO2 H2O n-Hexane Reaction: Component Oxygen CO2 H2O n-Pentane Reaction: Component Propene Oxygen CO2 H2O n-hex combust

32.00 44.01 18.02 58.12

-6.500 4.000 5.000 -1.000

Mole Weight 32.00 44.01 18.02 86.18 n-pent comust Mole Weight 32.00 44.01 18.02 72.15 propene combust Mole Weight 42.08 32.00 44.01 18.02

Stoichiometric Coeff. -9.500 6.000 7.000 -1.000

Stoichiometric Coeff. -8.000 5.000 6.000 -1.000

Stoichiometric Coeff. -1.000 -4.500 3.000 3.000

Reaction: tr2-but combust Component Oxygen CO2 H2O tr2-Butene Reaction: Component

Mole Weight 32.00 44.01 18.02 56.11

Stoichiometric Coeff. -6.000 4.000 4.000 -1.000

Mole Weight

Stoichiometric Coeff.

REACTION RESULTS FOR :

Combust

135

Extents Name Meth Combust Eth combust Prop combust H2 combust 1-but combust ethylene comust i-but combust i-pent combust n-but combust n-hex combust n-pent comust propene combust tr2-but combust CO Combust Balance Components Methane Ethane Propane CO CO2 Hydrogen H2O Nitrogen Oxygen i-Butane n-Butane i-Pentane n-Pentane n-Hexane Ethylene tr2-Butene 1-Butene Rank 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Specified % Conversion 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Use Default Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Actual % Conversion 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Base Component Methane Ethane Propane Hydrogen 1-Butene Ethylene i-Butane i-Pentane n-Butane n-Hexane n-Pentane Propene tr2-Butene CO Reaction Extent (kgmole/h) 386.8 3.059 1.397 360.8 1.184e-002 0.2066 5.057e-002 3.452e-003 6.928e-002 2.794e-003 8.400e-003 0.2961 2.368e-003 136.8

Total Inflow (kgmole/h) 386.8 3.059 1.397 136.8 94.96 721.5 0.0000 6390 1692 5.057e-002 6.928e-002 3.452e-003 8.400e-003 2.794e-003 0.2066 2.368e-003 1.184e-002

Total Reaction (kgmole/h) -386.8 -3.059 -1.397 -136.8 535.8 -721.5 1512 7.994e-013 -1223 -5.057e-002 -6.928e-002 -3.452e-003 -8.400e-003 -2.794e-003 -0.2066 -2.368e-003 -1.184e-002

Total Outflow (kgmole/h) 0.0000 0.0000 0.0000 0.0000 630.7 0.0000 1512 6390 468.8 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

136

Helium Propene CONDITIONS Name Vapour Temperature (C) Pressure (kPa) Molar Flow (kgmole/h) Mass Flow (kg/h) Std Ideal Liq Vol Flow (m3/h) Molar Enthalpy (kJ/kgmole) Molar Entropy (kJ/kgmole-C) Heat Flow (kJ/h) Name Vapour Temperature (C) Pressure (kPa) Molar Flow (kgmole/h) Mass Flow (kg/h) Std Ideal Liq Vol Flow (m3/h) Molar Enthalpy (kJ/kgmole) Molar Entropy (kJ/kgmole-C) Heat Flow (kJ/h) PROPERTIES

0.9984 0.2961

0.0000 -0.2961

0.9984 0.0000

Combo Gas 1.0000 55.0000 146.3250 139.4231 830.2727 4.9631 -1.617e+004 142.2 -2.2538e+06 waste gas 1.0000 800.0000 40.0000 9002.2071 248998.0490 296.1206 -4.229e+004 211.1 -3.8073e+08

PSA Tail Gas-2 1.0000 31.9294 40.0000 1230.7530 15697.9267 47.7418 -6.439e+004 167.7 -7.9244e+07

Combustion Air 1.0000 300.0000 102.8000 8057.8742 232471.8488 268.7376 8248 171.1 6.6465e+07

DNE 0.0000 800.0000 40.0000 0.0000 0.0000 0.0000 -4.229e+004 211.1 0.0000e-01

Name Combo Gas Molecular Weight 5.955 Molar Density (kgmole/m3) 5.362e-002 Mass Density (kg/m3) 0.3193 Act. Volume Flow (m3/h) 2600 Mass Enthalpy (kJ/kg) -2715 Mass Entropy (kJ/kg-C) 23.88 Heat Capacity (kJ/kgmole-C) 31.48 Mass Heat Capacity (kJ/kg-C) 5.286 Lower Heating Value (kJ/kgmole) 3.988e+005 Mass Lower Heating Value (kJ/kg) 6.697e+004 Phase Fraction [Vol. Basis] --Phase Fraction [Mass Basis] 4.941e-324 Partial Pressure of CO2 (kPa) 1.267e-002

PSA Tail Gas-2 12.75 1.577e-002 0.2012 7.804e+004 -5048 13.15 31.59 2.477 3.873e+005 3.036e+004 --4.941e-324 3.086

Combustion Air 28.85 2.157e-002 0.6222 3.736e+005 285.9 5.932 30.84 1.069 0.0000 ----4.941e-324 0.0000

DNE 27.66 4.483e-003 0.1240 0.0000 -1529 7.631 36.10 1.305 0.0000 ----2.122e-314 0.0000

waste gas 27.66 4.483e-003 0.1240 2.008e+006 -1529 7.631 36.10 1.305 0.0000 ----2.122e-314 2.803

137

Cost Based on Flow (Cost/s) 0.0000 Act. Gas Flow (ACT_m3/h) 2600 Avg. Liq. Density (kgmole/m3) 28.09 Specific Heat (kJ/kgmole-C) 31.48 Std. Gas Flow (STD_m3/h) 3297 Std. Ideal Liq. Mass Density (kg/m3) 167.3 Act. Liq. Flow (m3/s) --Z Factor 1.000 Watson K 25.94 User Property --Partial Pressure of H2S (kPa) 0.0000 Cp/(Cp - R) 1.359 Cp/Cv 1.360 Heat of Vap. (kJ/kgmole) 7195 Kinematic Viscosity (cSt) 29.15 Liq. Mass Density (Std. Cond) (kg/m3) --Liq. Vol. Flow (Std. Cond) (m3/h) --Liquid Fraction 0.0000 Molar Volume (m3/kgmole) 18.65 Mass Heat of Vap. (kJ/kg) 1208 Phase Fraction [Molar Basis] 1.0000 Surface Tension (dyne/cm) --Thermal Conductivity (W/m-K) 0.1298 Viscosity (cP) 9.309e-003 Cv (Semi-Ideal) (kJ/kgmole-C) 23.16 Mass Cv (Semi-Ideal) (kJ/kg-C) 3.890 Cv (kJ/kgmole-C) 23.14 Mass Cv (kJ/kg-C) 3.886 Cv (Ent. Method) (kJ/kgmole-C) 23.12 Mass Cv (Ent. Method) (kJ/kg-C) 3.882 Cp/Cv (Ent. Method) 1.362 Reid VP at 37.8 C (kPa) --True VP at 37.8 C (kPa) --Liq. Vol. Flow - Sum(Std. Cond) (m3/h) 0.0000

0.0000 7.804e+004 25.78 31.59 2.910e+004 328.8 --0.9999 15.10 --0.0000 1.357 1.358 --51.08 ----0.0000 63.41 --1.0000 --7.500e-002 1.028e-002 23.28 1.825 23.27 1.824 ----------0.0000

0.0000 3.736e+005 29.98 30.84 1.905e+005 865.1 --1.000 6.042 --0.0000 1.369 1.370 5891 48.58 ----0.0000 46.37 204.2 1.0000 --4.360e-002 3.022e-002 22.53 0.7808 22.52 0.7805 22.48 0.7791 1.372 ----0.0000

0.0000 ----36.10 0.0000 840.9 0.0000 --6.557 --0.0000 1.299 1.299 3.433e+004 2.408 --0.0000 1.000 223.1 1241 0.0000 0.0000 7.018e-002 2.985e-004 27.78 1.004 27.78 1.004 --------2.042e+005 0.0000

0.0000 2.008e+006 30.40 36.10 2.129e+005 840.9 ----6.557 --0.0000 1.299 1.299 3.433e+004 350.4 ----0.0000 223.1 1241 1.0000 --7.294e-002 4.345e-002 27.78 1.004 27.78 1.004 --------2.042e+005 0.0000

------------------------------------------------------------------------------Hyprotech Ltd. Aspen HYSYS Version 2006 (20.0.0.6728)

138

Appendix F: AMSIM Reports

139

Table F. 1: Composition Profile of CO2 in Absorber A

Stage Amine Sol. [Fraction] Vapor [Fraction] 1 0.022656 0.011879 2 0.02514 0.018135 3 0.029085 0.027852 4 0.035361 0.042966 5 0.044617 0.066199 6 0.052562 0.098851 7 0.056291 0.1255 8 0.058416 0.137557 9 0.059852 0.144295 10 0.060906 0.148791 11 0.061711 0.152062 12 0.062343 0.15455 13 0.062871 0.156513 14 0.063431 0.158226 15 0.064456 0.160386 AMSIM 7.2 --- Copyright by Oilphase-DBR, Schlumberger Canada Ltd.

Table F. 2: Vapour Phase Properties in Absorber A

Mass Flow Pressure Temperature [ kPa ] [C] [ kg/h ] 1 2163.6 39.7 22174.9 2 2166.2 42.7 23530.5 3 2168.8 47.4 25642 4 2171.4 54.4 29053.8 5 2174 63.2 34577 6 2176.6 69.8 42741.5 7 2179.2 72.8 49796.9 8 2181.8 74.5 53185.8 9 2184.5 75.7 55153 10 2187.1 76.5 56496.9 11 2189.7 77.1 57488.7 12 2192.3 77.6 58245.7 13 2194.9 77.7 58822.1 14 2197.5 76.7 59210.2 15 2200.1 70.4 59235.9 AMSIM 7.2 --- Copyright by Oilphase-DBR, Schlumberger Canada Ltd. Stage Vol. Flow [ m3/h ] 5544.1 5635 5773.5 5995.3 6320.1 6689 6955.6 7086.8 7163.7 7215.1 7251 7275.6 7287.3 7267.6 7111.8 Molar Flow [ kmol/h ] 4554.758 4591.706 4642.399 4725.238 4860.23 5056.142 5222.87 5303.828 5351.418 5384.172 5408.421 5426.863 5440.412 5447.056 5434.766 Mol. Weight [ kg/kmol ] 4.869 5.125 5.523 6.149 7.114 8.453 9.534 10.028 10.306 10.493 10.629 10.733 10.812 10.87 10.899 Density [ kg/m3 ] 3.99972 4.17575 4.44134 4.84608 5.47097 6.38986 7.15928 7.50496 7.69896 7.83042 7.92837 8.00566 8.07193 8.14714 8.32927

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Table F. 3: Liquid Phase Properties in Absorber A

Mass Pressure Temperature Flow [ kPa ] [C] [ kg/h ] 1 2163.6 39.7 420406.8 2 2166.2 42.7 422518.3 3 2168.8 47.4 425930.1 4 2171.4 54.4 431453.3 5 2174 63.2 439617.8 6 2176.6 69.8 446673.2 7 2179.2 72.8 450062.1 8 2181.8 74.5 452029.3 9 2184.5 75.7 453373.2 10 2187.1 76.5 454365 11 2189.7 77.1 455122 12 2192.3 77.6 455698.4 13 2194.9 77.7 456086.5 14 2197.5 76.7 456112.2 15 2200.1 70.4 455473.2 AMSIM 7.2 --- Copyright by Oilphase-DBR, Schlumberger Canada Ltd. Stage Vol. Flow [ m3/h ] 409.9 411.3 413.6 417.3 422.7 427.2 430.9 433.1 434.7 435.8 436.7 437.3 437.7 437.5 435.5 Molar Flow [ kmol/h ] 18023.88 18074.58 18157.42 18292.41 18488.32 18655.05 18736.01 18783.6 18816.35 18840.6 18859.04 18872.59 18879.23 18866.94 18809.79 Mol. Weight [ kg/kmol ] 23.325 23.376 23.458 23.586 23.778 23.944 24.021 24.065 24.095 24.116 24.133 24.146 24.158 24.175 24.215 Density [ kg/m3 ] 1025.582 1027.243 1029.801 1033.813 1040.047 1045.676 1044.576 1043.682 1043.072 1042.622 1042.284 1042.045 1041.978 1042.501 1045.839

Table F. 4: Composition Profile of CO2 in Regenerator

Stage Amine Sol. [Fraction] Vapor [Fraction] 1 0.000665 0.941076 2 0.059573 0.666759 3 0.055604 0.539271 4 0.050837 0.398938 5 0.046309 0.29988 6 0.04242 0.237417 7 0.039191 0.194647 8 0.036465 0.163104 9 0.034147 0.138419 10 0.032144 0.118575 11 0.030382 0.102133 12 0.028796 0.088182 13 0.027346 0.076009 14 0.025995 0.065202 15 0.02471 0.055401 16 0.023481 0.046308 17 0.02095 0.037835 AMSIM 7.2 --- Copyright by Oilphase-DBR, Schlumberger Canada Ltd.

141

Table F. 5: Vapour Phase Properties in the Regenerator

Pressure Temperature Mass Flow Vol. Flow [ kPa ] [C] [ kg/h ] [ m3/h ] 1 199.9 48.9 36737.6 11477.1 2 206.2 92 43279.6 17837.9 3 207.1 101 46380.6 21455.7 4 208 108.6 51643.5 27281.1 5 208.9 113.2 56016.7 32668.1 6 209.8 115.9 58180.4 36198.7 7 210.7 117.7 59093.7 38464.8 8 211.7 119 59557.6 40086.8 9 212.6 120 59852.7 41352.5 10 213.5 120.8 60060.2 42367.7 11 214.4 121.5 60253.3 43230.2 12 215.3 122.2 60440.2 43979.1 13 216.3 122.7 60619.5 44642.8 14 217.2 123.2 60796.7 45242.4 15 218.1 123.7 60971.3 45794.2 16 219 124.1 61145.9 46313.3 17 219.9 125 61490.7 46824.8 AMSIM 7.2 --- Copyright by Oilphase-DBR, Schlumberger Canada Ltd. Stage Molar Flow [ kmol/h ] 864.864 1220.853 1440.796 1805.303 2148.032 2376.248 2526.154 2636.715 2725.796 2799.826 2864.872 2923.255 2976.664 3026.364 3073.336 3118.448 3159.503 Mol. Weight [ kg/kmol ] 42.478 35.45 32.191 28.607 26.078 24.484 23.393 22.588 21.958 21.451 21.032 20.676 20.365 20.089 19.839 19.608 19.462 Density [ kg/m3 ] 3.20096 2.42627 2.1617 1.89302 1.71473 1.60726 1.53632 1.48572 1.44738 1.41761 1.39379 1.37429 1.35789 1.34381 1.33143 1.32028 1.31321

Table F. 6: Liquid Phase Properties in the Regenerator

Pressure Temperature Mass Flow Vol. Flow [ kPa ] [C] [ kg/h ] [ m3/h ] 1 199.9 48.9 6545.1 6.6 2 206.2 92 464022.1 449 3 207.1 101 469290.5 456.8 4 208 108.6 473650.3 463.4 5 208.9 113.2 475807 468.6 6 209.8 115.9 476718.3 472.3 7 210.7 117.7 477181.5 475.1 8 211.7 119 477476.4 477.3 9 212.6 120 477683.7 479.1 10 213.5 120.8 477876.6 480.7 11 214.4 121.5 478063.4 482.2 12 215.3 122.2 478242.7 483.5 13 216.3 122.7 478419.8 484.7 14 217.2 123.2 478594.3 485.8 15 218.1 123.7 478768.9 486.9 16 219 124.1 479113.6 488.1 17 219.9 125 417622.9 427.8 AMSIM 7.2 --- Copyright by Oilphase-DBR, Schlumberger Canada Ltd. Stage Molar Flow [ kmol/h ] 355.989 19354.28 19718.78 20061.51 20289.73 20439.63 20550.19 20639.28 20713.31 20778.35 20836.73 20890.14 20939.84 20986.82 21031.93 21072.98 17913.48 Mol. Weight [ kg/kmol ] 18.386 23.975 23.799 23.61 23.451 23.323 23.22 23.134 23.062 22.999 22.943 22.893 22.847 22.805 22.764 22.736 23.313 Density [ kg/m3 ] 998.6405 1033.371 1027.448 1022.022 1015.443 1009.263 1004.37 1000.343 996.9533 994.0457 991.4991 989.213 987.1263 985.1855 983.3416 981.529 976.2471

142