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Article
Partial upgrading of heavy crude oil by slurry-phase
hydrocracking with analytical grade and ore catalysts
Alexander Quitian, and Jorge Ancheyta
Energy Fuels, Just Accepted Manuscript DOI: 10.1021/acs.energyfuels.6b01648 Publication Date (Web): 25 Oct 2016
Downloaded from http://pubs.acs.org on October 31, 2016

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Page 1 of 33 Energy & Fuels

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4 Partial upgrading of heavy crude oil by slurry-phase hydrocracking with analytical grade
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6 and ore catalysts
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9 Alexander Quitian,, Jorge Ancheyta*
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11 Facultad de Qumica, Universidad Nacional Autnoma de Mxico, Ciudad Universitaria,
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Coyoacn, Mexico D.F. C.P. 04510
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16 Instituto Mexicano del Petrleo, Eje Central Lzaro Crdenas Norte 152 Col. San Bartolo
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18 Atepehuacan, Mexico D.F. C.P 07730, Email: jancheyt@imp.mx
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20
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22 ABSTRACT
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A heavy crude oil of 13 API and a viscosity of 6100 cSt at 37.8C was used to study the effect
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27 of different hydrocracking catalysts at low severity conditions in a slurry-phase batch reactor.
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29 The evaluated catalysts were Mo and Fe analytic grade oxides and ores (molybdenite, hematite
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32 and magnetite) from different Mexican mine sites. The effect of the concentration of catalysts on
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34 heavy oil upgrading was studied in the range of 0 to 13333 ppm of active metal (Mo or Fe). The
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36 results showed that the required minimum concentration of catalyst to obtain upgraded crude oil
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39 with suitable properties for transportation (API gravity> 16 and viscosity at 37.8 C <250 cSt) is
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41 5000 ppm. At the evaluated operating conditions, coke formation is not observed and the
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selectivity towards gases is low. Mo showed better hydrogenation capacity than Fe, which is
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46 observed by an increase in the light fraction composition and reduction of the heavy vacuum
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48 gasoil and vacuum residue. Depending on the concentration, type and active metal content of the
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51 catalysts, vacuum residue conversion in the range of 37-49% was obtained.
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55 Keywords: dispersed catalyst, ore, heavy crude oil, upgraded crude oil, hydrocracking
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1
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3 1. INTRODUCTION
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6 Heavy crude oils have low API gravity and high viscosity which make difficult their
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8 transportation by pipeline. Handling high viscosity heavy crude oils involves high costs of
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operation and capital investment in transportation facilities and pumping that together with the
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13 low value of the heavy crude oils reduces the profitability of production processes. In some cases,
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15 the required specifications for transportation of crude oils by pipeline depend on existing
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infrastructure as well as on the agreement between the oil producer and the company that
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20 provides the transportation service by pipeline. It is widely accepted that crude oils must have
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22 API gravity higher than 16 and viscosity lower than 250 cSt at 37.8C for their feasible
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25 transportation by pipeline1,2.
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27 The most used commercial approaches to achieve the required flow properties of heavy crude oils
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29 are heating and dilution. In the former, heavy oils are heated along the jacketed pipeline using
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32 steam or flue gases. Various heating stations are needed along the pipeline in order to maintain
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34 the required temperature. Heating not only has high requirements of energy but it can also
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enhance sedimentation of water and solids present in crude oil that may cause plugging of piping
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39 and damage of pumping systems.35
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41 Dilution consists of mixing the heavy crude oil with lighter streams (light crude oils or diluents),
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44 thus improving its flow properties. The advantage of using diluents such as light naphtha is that
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46 they can be recovered by atmospheric distillation and their reusing is possible. However, heavy
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48 oil may be incompatible with the diluent that can cause sedimentation of water, solids and even
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51 asphaltenes thus provoking damage and blockages in the pumping and piping systems.68
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53 Other more direct manners to achieve the required flow properties of heavy crude oils is by
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55 transforming them into lighter hydrocarbons (upgraded crude oil) through thermal or catalytic
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58 reactions. Such approaches, called partial upgrading processes, are classified as:
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3 i. Carbon rejection that favors the thermal breakage of hydrocarbons with high molecular
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6 weight and reduces the vacuum residue fraction of crude oils. The yield of upgraded crude
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8 oils is low due to high formation of byproducts such as coke and gaseous hydrocarbons (C1-
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C5). This type of processes is the most used because of its relatively low operating costs and
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13 investment. Pyrolysis, thermal cracking and visbreaking belong to this category.911
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15 ii. Hydrogen addition that favors the hydrogenation reactions of high molecular weight
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molecules of heavy oil in the presence of catalysts and hydrogen donors. Also, the vacuum
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20 residue fraction is reduced, and the formation of coke and volatile gases is inhibited which
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22 increases the yield of the upgraded crude oil. Aquathermolysis and hydrocracking are the
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25 most common hydrogen addition processes for upgrading of flow properties of crude oils. 12
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29 Hydrocracking processes are commonly carried out at temperature of 360-480C, hydrogen
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32 partial pressure of 3-15 MPa and reaction time of 1-6 hours for batch operation. Hydrogen
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34 consumption is about 50-360 m3/m3 depending on the severity of the reaction. 16,17 According to
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the type of catalyst, hydrocracking can be operated with:
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39 a. Supported catalysts, consisting of transition metal sulfides that favor hydrogenation
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41 reactions. They are supported on Al2O3 or SiO2 that promote the reactions of thermal
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44 breakage. Such catalysts are used in commercial fixed-bed or ebullated-bed reactors.
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46 b. Slurry-phase catalyst, wherein the catalyst precursors are added together with the feed as
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48 powder-finely divided or as metal salts soluble in water or in oil. Catalyst precursors
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51 become metal sulfides that are more stable and catalytically more active due to the
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53 presence of hydrogen and hydrogen sulfide produced by the cracking and
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55 hydrodesulfurization reactions at operating conditions. The catalyst precursors are
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58 generally oxides, sulfides, salts or organometallic complexes of transition metals.
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3 In general, hydrocracking reactions with supported catalysts occur at lower severity reaction
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6 conditions than with slurry-phase catalysts due to the presence of acid sites in the supports. But in
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8 both processes, the most used transition metals are in order of higher catalytic activity: Mo, W,
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Ni, V, Co, Cr and Zn. 18,19
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13 The coke formed during hydrocracking and the metals present in heavy crude oil cause rapid
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15 deactivation of catalyst. For supported catalysts, deactivation is a critical issue that requires
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continuous replacement of catalyst. In some cases, it is necessary to use more than two reactors to
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20 maintain continuous operation.2022
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22 With slurry-phase catalyst precursors, coke formation decreases as the particle size is closer to
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25 the molecular size of the metal sulfides. Smaller particle size ensures greater activity, and
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27 nanometric sizes can be obtained by using water and oil soluble precursors.23
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29 Currently the low oil prices and the high costs of soluble catalysts do not make profitable their
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32 commercial use. In order to reduce operating costs, some slurry-phase hydrocracking processes
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34 use low cost precursors such as ores or "throw-away" material in the form of finely divided
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powders, which contain high concentration of catalytically active transition metals (usually Fe,
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39 Ni and V). The studied ores are mainly hematites and limonites.2426 Other inexpensive materials
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41 include fly ash from the combustion of petroleum coke, red mud from aluminum production,
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44 coke breeze preparation from metallurgical coke, fine coke from flexi-coking, etc.18
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46 Slurry-phase hydrocracking of heavy crude oil is studied at low severity reaction conditions in
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48 batch operation using ores as catalyst precursor, which were obtained from different Mexican
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51 mines. The objective of this research is to explore the utilization of different ore catalysts to
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53 upgrade the flow properties of a heavy crude oil that allow its pumping by pipeline (>16 API and
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55 <250 cSt at 37.8C).
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3 2. EXPERIMENTAL
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6 2.1. Materials
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8 The properties of the heavy crude oil used as feedstock are shown in Table 1. The ore catalysts
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used were molybdenite, hematite A, hematite B and magnetite. These ores were recovered from
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13 different Mexican mining sites located and exploited in the states of Sonora, Colima, Durango
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15 and Chihuahua respectively.
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For comparison purposes, analytical grade powders of molybdenum trioxide (MoO3) and ferric
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20 oxide (Fe2O3) (Sigma Aldrich) are also used as catalysts, which compositions are shown in
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22 Tables 2 and 3 respectively.
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25 2.2. Preparation and characterization of ore catalysts
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27 Rock samples of the different ores were crushed, pulverized and sieved to a size less than 5
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29 microns. Subsequently, all samples used as catalyst powder were dried at 120 C for 2 hours
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32 before being the experiments.
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34 The composition of the dried powder ores was determined by X-ray fluorescence (XRF) and the
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results are summarized in Table 4. XRF analyses were performed on a Siemens D500
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39 diffractometer with Cu anode and graphite mono-chromed, using CuK radiation (=1.450589).
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41 Diffraction sweeps were performed in the range of 2 angles between 0-5 and 10-70 with a
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44 scan rate of 0.5 min-1. The crystalline phases were identified with reference to the standard data
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46 of JCPDS powders using a specific software installed in the diffractometer for the peak
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48 identification.
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51 2.3. Hydrocracking of heavy crude oil
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53 Reactions of slurry phase hydrocracking with the catalyst powders were conducted in batch
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55 operation using a stirred Parr reactor of series model 4848, equipped with measuring and control
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58 systems of pressure, temperature and stirring speed.
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3 In previous work, the best operating conditions to achieve the desired values of API gravity and
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6 viscosity using the same heavy oil, reaction system and powdered molybdenum trioxide in
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8 analytical grade as catalyst were defined, which are initial pressure, temperature, and reaction
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time of 3.92 MPa, 380C and 4 h respectively1. These conditions are used here to study the effect
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13 of type and concentration of catalysts in the range of 0-13333 ppm.
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15 The batch reactor was pressurized with hydrogen at room temperature. Subsequently, it is heated
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to the reaction temperature (380C) at a heating rate of 5 C/min and then the initial pressure
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20 (3.92 MPa) is reached at the same time. Afterwards stirring rate (800 rpm) is initiated and this
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22 moment is considered as the beginning of the reaction.
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25 At the end of the reaction time (4 h), the reactor was rapidly cooled to room temperature. After,
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27 liquid and gaseous products were quantified. If there is formation of solids or sediments, they
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29 were separated from the liquid by decantation, washed with toluene and dried at 110C and
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32 finally their mass was quantified. Hydrogen consumption was calculated with the gas
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34 composition, the weight of produced gas and the amount of hydrogen loaded to the reactor.
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2.4. Product characterization
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39 After each experiment, liquid, gas and solid (coke or insoluble in toluene) samples were taken,
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41 measured and analyzed. Liquid samples were analyzed in terms of API gravity, viscosity,
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44 simulated distillation and elemental analysis. Density and viscosity were determined in an Anton
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46 Parr densimeter/viscometer model SVM3000. Simulated distillation was measured using an
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48 Agilent 7890A gas chromatograph according to ASTM D7169 method. Elemental analyses
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51 (carbon, hydrogen, sulfur, nitrogen and oxygen) were performed with a Pekin Elmer Model
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53 Series II CHNS-O Analyzer 2400.
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55 Gas samples were analyzed by gas chromatography using an Agilent Gas Chromatograph Model
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58 6890 according to the UOP-539 standard for refinery gases.
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3 The elemental analyses of coke were performed according to the ASTM D 3178, 3177 and 3179
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6 methods for the determination of carbon and hydrogen, sulfur and nitrogen respectively.
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8 The distribution of molecular weights of coke were determined by gel permeation
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chromatography (GPC) in an Agilent HP 1100 Series HPLC System using a PL aquagel-OH
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13 MIXED-H Column. The coke was diluted in a concentration of 1 g/lt using as eluent
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15 tetrahydrofuran with a flow rate of 1 ml/min.
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Nuclear magnetic resonance of 1H and 13
C was performed on a Bruker BioSpin GmbH
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20 Spectrometer that was operated at 300 MHz for proton and 75 MHz for carbon.
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22 Deuteriochloroform (CDCl3) was used to dissolve the coke. The calculation of structural
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25 parameters was done with methods reported in the literature.27,28
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27 The morphology and microstructures of coke were determined by X-ray diffraction using a
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Siemens D500 diffractometer with nickel-filtered CuK radiation (=1.5418) at 35 kV and 35
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32 mA with an angular scanning of 2 in the range between 0-80 and a scanning speed of
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34 0.02/min. The interlayer spacing and microcrystalline parameters of coke were calculated using
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37 the Braggs Law and other equations reported elsewhere for such materials.2931
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39 Thermogravimetric analyzes (TGA) and differential thermogravimetric analyzes (DTA) of coke
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41 were conducted in a TA Instrument's 2950 Thermogravimetric analyzer with a heating rate of 10
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44 C/min from 20C to 1100C using nitrogen.
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46 3. RESULTS AND DISCUSSION
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The analytic grade oxides or ore catalysts inhibit the formation of coke as shown in Figure 1.
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51 Coke is formed at low catalyst concentration (up to 9 wt%), and it is null above 5000 ppm.
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53 Analytical grade oxides exhibited slightly lower tendency to form coke than ore catalysts. During
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slurry-phase hydrocracking, free radicals are formed from thermal breakage of C-C bonds of high
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3 molecular weight hydrocarbons. The catalyst accelerates hydrogenation rate of the formed
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6 radicals, however, if the amount of catalyst is insufficient, the high complexity and poly-
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8 aromaticity free radicals undergo condensation reactions that lead to coke formation. This coke is
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deposited on the reactor walls and agitator as well as on the dispersed catalyst causing its
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13 deactivation, however, for certain concentration of catalyst (> 5000 ppm in this study), then there
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15 is not coke deposition.25,26,32
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Elemental analyses of coke obtained with (2500 ppm molybdenite) and without catalyst are
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20 shown in Table 5. They indicate that both cokes have almost the same chemical composition and
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22 aromaticity (H/C ratio). The distribution of molecular weights of cokes obtained by GPC/SEC are
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25 shown in Table 5. The calculated polydispersity index resulted to be low and identical
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27 (PDI=1.25), which indicates that both cokes have compounds with common chemical structure.
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29 The high average molecular weights and the low H/C ratios indicate a high degree of aromaticity
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32 in the carbonaceous compounds.
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34 The NMR spectra of the cokes are presented in Figure 2, and the corresponding structural
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parameters are reported in Table 5. These results confirm that both cokes have similar chemical
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39 structure, i.e., about 95-98 aromatic rings and 5 carbons by aliphatic chains. These similar
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41 structures are the result of thermal hydrocracking and condensation of asphaltenes reactions and
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44 indicate that ores do not catalyze reactions of thermal breakage but they only inhibit coke
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46 formation.
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48 Figure 3 and Table 5 show the results of X-ray diffraction, the calculated interlayer spacing and
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51 microcrystalline parameters for cokes obtained with and without catalyst. The average staking
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53 height of graphene layers Lc is a good indication of graphitizability due to the hydrocracking. The
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55 feature of diffractions peaks (002) and (100) in both cokes has a typical turbostratic crystalline
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58 structure in which the coke is made of graphite-like microcrystallites, bounded by cross linking
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3 network, consisting of several graphite-like layers, stacked nearly parallel and equidistant with
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6 each layer having a random orientation.
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8 The TGA and DTA results are shown in Figure 4. The thermal behavior of both cokes is similar
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and occurs in three stages, which are typical of coke obtained at low temperatures by thermal
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13 cracking: 1) From room temperature to 400C there is a minimum loss of weight and thus no
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15 release of light volatiles or thermal cracking reactions is observed; 2) between 400C and 600C
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there is high loss of volatile, however, there is not highly evolved gas. Weight losses are mainly
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20 due to intermolecular associations, destroy of weaker chemical bonds and rupture of alkyl chains
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22 to generate gaseous molecules; and 3) above 600C, where more volatiles are produced
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25 constantly until no more gases are released. In this point, the stronger bonds are broken, the
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27 molecules of coke are fully destroyed and consequently gaseous molecules are obtained until a
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29 heavier coke prevails as final product of coke pyrolysis.
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32 Similar behavior than coke is exhibited by gases yield, which is inhibited as the concentration of
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34 catalyst is increased (Figure 1). At concentrations greater than 5000 ppm, the amount of gas
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formed remains constant at about 2 wt.%. Gas formation is mainly due to thermal breakage of C-
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39 C bonds of paraffinic compounds present in the fraction of saturates and from the aliphatic chains
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41 arising during thermal cracking of fractions of aromatics, resins and asphaltenes. The aliphatic
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44 chains undergo decomposition reactions and hydrogen abstraction that lead to gas formation.
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46 This type of reactions is inhibited by the presence of hydrogen and catalyst.33
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48 The composition of gases (C1-C2, C3-C4, C5+) is quite similar with all the used catalysts (Table 6).
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51 At high catalyst concentration, it is slightly lower. Hydrogen sulfide exhibits the opposite
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53 behavior, which indicates that higher concentration of catalyst favors the selectivity towards the
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55 hydrodesulfurization reactions and therefore increasing the production of H2S.
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3 API gravity and viscosity of the upgraded crude oils present similar tendencies as can be
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6 observed in Figures 5 and 6, respectively. Above 5000 ppm, constant values of these properties
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8 are achieved. Analytical grade oxides increased more the API gravity and reduced more the
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viscosity as compared with ores. In general, analytical MoO3 exhibited the best performance
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13 among all the catalyst studied. Molybdenite was the best among the ore catalysts. Above 5000
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15 ppm, the upgraded crude oils have suitable properties for their transportation by pipeline (<250
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cSt at 37.8C).
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20 The removal of sulfur is presented in Figure 7. The trends are the same than for the other
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22 properties. However, it is important to highlight that the maximum level of hydrodesulfurization
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25 with analytical grade oxides is between 13-16%, while for the ore catalysts is between 7-11%.
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27 These values of HDS are considerably lower than those typically obtained with supported
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29 catalysts. 20,3436
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32 This fact could be of great importance when designing a commercial process, since the gas
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35 product stream is typically sent to a sweeting unit to remove the hydrogen sulfide and then to a
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37 purification unit to be able to recycle a high purity hydrogen stream. Having low level of HDS
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39 and hence low production of H2S would indicate that both sweeting and purification units can be
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42 either eliminated or designed to work for the new required efficiency, which will reduce the
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44 investment and operation costs.
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47 Hydrogen consumption is reported in Figure 8. With analytical grade oxides, higher hydrogen
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49 consumptions are obtained than with ores, which agrees with the flow properties and selectivity
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52 towards the different reactions discussed above. The consumption of hydrogen increases as the
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54 concentration of catalyst also increases, which reaches a maximum value after 5000 ppm. For all
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56 the catalyst, the consumed hydrogen is relatively low (100-160 ft3/bbl) which is due to the low
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3 severity reaction conditions used in the experiments. The formation of free radicals depends only
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6 on the nature of feed and temperature, since the dispersed catalysts have very low activity for the
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8 thermal cracking reactions. There is also a low breaking of C-C bonds by thermal cracking,
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therefore, using catalyst concentrations higher than 5000 ppm with a hydrogen excess do not
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13 allow for an additional hydrogenation. In this research, the slurry-phase hydrocracking has been
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15 mainly focused on reducing the viscosity at low pressure and temperature with ore catalysts. This
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approach is new and there is only few information about hydrogen consumption at these
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20 conditions. Matzamura et al.26 studied the slurry-phase hydrocracking of Brazilian Marlim
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22 vacuum residue at 8 MPa, 440C and 4 h using limonite from Australia (56.6 wt% iron) and
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25 Brazil (45.5 wt% iron) in concentrations of 3 wt%. They reported hydrogen consumptions of 960
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27 and 1118 ft3/bbl respectively. Du et al.37 obtained a hydrogen consumption of 181 ft3/bbl in the
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29 slurry-phase hydrocracking of a vacuum residue of Karamay crude oil (API gravity of 14.48 and
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32 viscosity at 80C of 901.6 cSt) at 8 MPa, 400C and 1 h using 500 ppm of a dispersed oil soluble
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34 molybdenum. It is then seen that the hydrogen consumption determined in this work is lower than
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those reported in the literature, which is mainly due to the differences in reaction conditions.
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39 All the previous results indicate that the enhancement of flow properties and reduction of sulfur
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42 content of the crude oil through slurry-phase hydrocracking is greater as the content of active
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44 metal (Mo or Fe) in the ore catalyst is higher. Therefore, higher amount of active metal in the
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mineral catalyst allows for higher hydrogenation and hydrogenolysis, which can be also
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49 corroborated by the higher hydrogen/carbon ratio of the upgraded oils compared with that of the
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51 hydrocracking without catalyst (Table 7).
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In summary, the flow properties, HDS and hydrogen consumption hardly change at catalyst
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56 concentrations higher than 5000 ppm. This behavior is typical of hydrocracking processes using
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3 catalyst in slurry phase without acid sites (unsupported) since they are limited by the formation of
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6 free radicals and the amount of catalyst.38 Firstly, a homolytic breaking of chemical bonds (C-C,
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8 C-S, C-N) occurs due to temperature in the presence of hydrogen (thermal hydrocracking) that
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leads to the formation of free radicals. The hydrogen sulfide released during HDS converts metal
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13 oxide (in this case analytic grade oxide or ore) into active metal sulfide, which catalyzes the
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15 reactions of dissociation of hydrogen and hydrogenation of free radicals.32,39
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At concentration of metal active lower than 5000 ppm, there is not enough amount of catalyst to
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20 inhibit the condensation reactions of free radicals, which cause a rise in the formation of coke and
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22 gas. By contrast, above 5000 ppm of active metal, there is a sufficient amount of catalyst to
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25 hydrogenate the radicals formed by thermal breakage, accordingly, the properties of upgrade
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27 crude oil and hydrogen consumption are similar because reaction temperature limits the
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29 formation of free radicals.4042
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32 For both analytical grade oxides and ores, Mo-based catalysts have better ability to hydrogenate
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34 than Fe-based catalysts, which is a well-known fact reported for supported catalyst. The reasons
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for this are not very well-known yet but it is attributed to the electron configuration of
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38 4345
39 molybdenum and its lower binding energy with sulfur. These characteristics allow for
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41 having greater number of vacant sites to interact with unpaired electrons of free radicals and with
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44 hydrogen. Analytic grade catalysts (MoO3 and Fe2O3) have better performance than ore catalysts
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46 due to their purity. When hydrodesulfurization reactions occur, the produced hydrogen sulfide
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48 causes the sulfurization of the catalyst precursor, so that the metal oxides in the ores are
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51 transformed into metal sulfides which are catalytically more stable. The produced metal sulfides
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53 have an irregular crystal structure that facilities the hydrogenation reactions of formed free
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55 radicals by thermal cracking.44,46 Ores and their sulfides species have a perfectly developed
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58 lattices in their crystalline structure, vacancies of active metal and a random distribution of the
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3 various non-active catalytically compounds. These features may prevent adsorption, dissociation
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6 and subsequent transport of hydrogen to free radicals. 25,47,48
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8 The compositions of upgraded crude oils determined by simulated distillation for different
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catalysts using 5000 ppm of concentration of active metal are shown in Table 8. It is clearly seen
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13 that the composition of light straight-run naphtha does not change while those of the other
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15 fractions (except vacuum residue) increase as compared with that of the feed. At low severity
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reaction conditions, fractions of kerosene and vacuum gasoils are mainly formed from the
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20 hydrocracking of the vacuum residue fraction and the medium and heavy straight-run naphtha are
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22 produced by the hydrocracking of middle fractions. The values of residue conversion are typical
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25 of those obtained at low severity conditions (<50%).
26
27 CONCLUSIONS
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29 The analytic grade oxides and ores catalysts have the ability to inhibit the gas and coke formation
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32 caused by decomposition and condensation reactions, promote the hydrogenation and slightly
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34 enhance the hydrogenolysis of the free radicals formed primarily by thermal cracking of C-C
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bonds.
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39 The ability of powdered ores and analytic grade oxides to upgrade flow properties increases
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41 according to their active metal purity and decreases as the catalyst concentration is reduced at
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44 values lower than 5000 ppm. The type and active metal content also affect the flow properties of
45
46 the upgraded oils. Catalysts rich in molybdenum allow for greater conversion to lighter fractions
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48 and therefore an increase of the H/C ratio as compared with catalysts rich in iron. Higher content
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51 of active metal in the catalysts also favors the hydrogenation and hydrogenolysis reactions
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53 causing an increase of lighter fractions and H/C ratio.
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3 The upgrading of flow properties in the slurry-phase hydrocracking at low severity reaction
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6 conditions with the studied powdered catalysts is due to the conversion of residue fraction into
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8 middle distillates fractions and then into light, medium and heavy straight-run naphtha.
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13 ACKNOWLEDGEMENTS
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15 The authors thank The Mexican Institute of Petroleum for the financial support. A. Quitian also
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thanks Consejo Nacional de Ciencia y Tecnologa (CONACYT) for the PhD Scholarship.
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3 REFERENCES
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3 Table 1. Properties of heavy crude oil
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5 Property Method Value
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7 Specific gravity @ 60/60F ASTM D1298 0.9812
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10 API gravity ASTM D287 12.71
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12 Viscosity, cSt ASTM D7042
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14 25.0C 22791
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16 37.8C 6110
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18 54.4 C 1518
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20 Insolubles in C7, wt% ASTM D3279 18.78
21
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23 Simulated distillation, C ASTM D7169
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25 IBP 67.8
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27 10 vol% 222.0
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29 25 vol% 343.3
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31 50 vol% 501.2
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33 75 vol% 605.8
34
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36 90 vol% 679.8
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38 FBP 739.4
39
40 CHNS/O
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42 Elemental analysis, wt% Elemental
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44 Analyzer
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46 C 83.01
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49 H 9.66
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51 O 1.52
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53 N 0.54
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55 S 5.27
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3 Table 2. Composition of molybdenum trioxide of analytic grade
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6 Component Content (wt%)
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8 MoO3 99.5
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11 (AsO4)3 0.001
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13 (SiO4)4- 0.001
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16 Cl- 0.002
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18 Pb 0.005
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NH4+ 0.002
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23 NO3- 0.003
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25 (PO4)3- 0.000005
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28 (SO4)2- 0.02
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3 Table 3. Composition of ferric oxide of analytic grade
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6 Elements Content (wt%)
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8 Fe 71.3
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11 O 28.6
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13 Ca, C, P, Si, Mg, N, Al, Ti, Na, V, S, K, Cl, Mn,
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Ce, Ba, Co, Zn, Cu, Sr, Y, Ni, Rb, B, Cd, Dy, <0.002
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18 Sn, Tm
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3 Table 4. Composition (wt%) of the ores catalysts
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6 Element Molybdenite Magnetite Hematite A Hematite B
7 Mo 41.76 0.00 0.00 0.00
8 Fe 1.05 55.90 72.06 53.02
9 O 1.79 16.63 16.71 17.84
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S 19.63 0.09 0.27 0.09
12 C 10.95 8.25 3.07 8.70
13 B 21.94 0.00 1.65 0.00
14 Cu 0.91 0.01 0.02 0.01
15 Si 0.73 2.32 0.19 2.29
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Al 0.33 0.30 0.14 0.32
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18 Ca 0.21 11.28 5.19 12.32
19 Zn 0.13 0.01 0.01 0.01
20 Mg 0.12 0.65 0.05 0.65
21 K 0.12 0.09 0.01 0.08
22 Rh 0.09 0.00 0.00 0.00
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Na 0.09 0.13 0.1 0.13
25 Ag 0.02 0.00 0.00 0.00
26 Pb 0.02 0.00 0.00 0.00
27 Ti 0.01 0.20 0.01 0.20
28 W 0.01 0.00 0.00 0.00
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Se 0.01 0.00 0.00 0.00
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31 Ar 0.01 0.00 0.00 0.00
32 Mn 0.01 0.03 0.05 0.03
33 Ce 0.01 0.02 0.00 0.02
34 Pr 0.01 0.00 0.00 0.00
35 Nb 0.01 0.00 0.00 0.00
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In 0.01 0.00 0.00 0.00
38 Nd 0.01 0.00 0.00 0.00
39 V 0.00 0.10 0.00 0.11
40 Y 0.00 0.01 0.00 0.01
41 Sn 0.00 0.00 0.36 0.00
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Dy 0.00 0.00 0.03 0.00
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44 Cr 0.00 0.00 0.02 0.00
45 Tm 0.00 0.00 0.02 0.00
46 Ni 0.00 0.01 0.02 0.01
47 CI 0.00 0.07 0.01 0.07
48 P 0.00 3.39 0.01 3.57
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50 Sr 0.00 0.01 0.00 0.01
51 N 0.00 0.46 0.00 0.46
52 Ba 0.00 0.02 0.00 0.02
53 Co 0.00 0.02 0.00 0.02
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5 Without With 2500 ppm
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catalyst of molybdenite
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8 Elemental Analysis 81.21 81.19
9 Carbon, wt% 81.21 81.19
10 Hydrogen, wt% 8.46 8.48
11 Oxygen, wt% 3.40 3.52
12 Nitrogen, wt% 1.02 1.01
13 Sulfur, wt% 5.91 5.80
14 H/C 1.241 1.245
15 Molecular Weight
16 Weight average molecular weight (Mw), g/mol 35,140 34,858
17 Number average molecular weight (MN), g/mol 44,074 43,596
18
Polydispersity Index (PDI) 1.25 1.25
19
20
Proton NMR
21 Fraction of aromatic hydrogen (Har) 0.11 0.11
22 Fraction of alpha aliphatic hydrogen (H) 0.18 0.18
23 Fraction of aliphatic hydrogen other than alpha (Hd) 0.71 0.71
24 Fraction of aliphatic hydrogen (Hal) 0.89 0.89
25 Fraction of aromatic carbon (Car) 0.33 0.33
26 Fraction of aliphatic carbon (Cal) 0.67 0.67
27 13
Carbon NMR
28 Numbers of carbons by aliphatic chain 4.94 4.94
29 Wt% of aromatic carbon 27.79 27.76
30 Wt% of unbridged aromatic carbon substituted by alkyl groups 11.41 11.40
31
Wt% of unbridged and no-substituted aromatic carbon 11.17 11.19
32
33
Wt% of unbridged aromatic carbon 22.58 22.59
34 Number of aromatic carbons 1020.65 1008.51
35 Number of unbridged aromatic carbons 829.26 820.78
36 Number of aromatic rings 96.70 94.86
37 % substitution of aromatic carbons in aromatic rings by
50.54 50.45
38 unbridged alkyl groups
39 Number of alkyl substituents on the aromatic carbons 419.10 414.12
40 Number of aliphatic carbons 2072.24 2047.57
41 Number of aliphatic hydrogens 3318.51 3290.28
42 Number of internal quaternary carbons and / or methylene
43 631.86 627.05
bridges and / or biaryl
44
Aromaticity factor 0.33 0.33
45
46 Interlayer spacing and microcrystalline parameters
47 d002, 3.48 3.46
48 d100, 2.14 2.14
X-Ray data
49 2002, deg. 25.6 25.7
50 2100, deg. 42.2 42.2
51 Lc, 14.69 16.95
52
Microcrystalline parameter
La, 31.74 36.62
53 Effective Dimension L, 22.65 26.13
54 Table 5. Properties of cokes
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Table 6. Composition of gas product (mol%) as function of the concentration and type of catalyst
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7 Concentration
Analytical Analytical Hematite Hematite
8 of catalyst Molybdenite Magnetite
MoO3 Fe2O3 A B
9 (ppm)
10 C1-C2 26.56 26.56 26.56 26.56 26.56 26.56
11 C3-C4 6.05 6.05 6.05 6.05 6.05 6.05
0
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13 C5+ 0.11 0.11 0.11 0.11 0.11 0.11
14 H 2S 1.51 1.51 1.51 1.51 1.51 1.51
15 C1-C2 14.41 e14.82 13.92 13.51 14.21 14.09
16
C3-C4 2.26 2.44 2.17 2.97 2.92 2.11
17 3333
18 C5+ 1.18 0.79 0.92 0.89 0.61 0.77
19 H 2S 7.62 7.54 7.04 7.15 6.92 7.06
20
C1-C2 12.07 12.41 11.86 11.33 12.78 12.13
21
22 C3-C4 1.97 2.13 1.96 3.47 2.63 4.80
5000
23 C5+ 0.79 0.64 0.77 0.81 0.57 0.86
24
H 2S 7.91 8.91 7.79 8.83 9.28 7.84
25
26 C1-C2 11.37 10.90 11.15 12.06 11.58 10.33
27 C3-C4 2.01 2.08 2.12 2.77 2.22 3.89
28 6665
C5+ 0.71 0.66 0.63 0.47 0.53 0.72
29
30 H 2S 8.31 7.96 8.23 9.61 9.29 9.07
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3 Table 8. Elemental analysis of upgraded oils as function of type of catalyst using 0 and 5000 ppm
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6 of metal active.
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8 Concentration
9 C H O N S
10 of catalyst Upgrade Oil H/C
11 (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
12 (ppm)
13
14
Without
0 81.84 11.35 1.82 0.52 4.47 1.654
15 catalyst
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17 Analytical
18 5000 81.30 11.86 1.87 0.51 4.46 1.740
19 MoO3
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21 Analytical
22
5000 81.22 11.74 1.90 0.53 4.61 1.724
Fe2O3
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24 5000 Molybdenite 81.18 11.70 1.84 0.53 4.75 1.719
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26 5000 Hematite A 81.41 11.48 1.82 0.55 4.74 1.682
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28 5000 Hematite B 81.49 11.30 1.78 0.52 4.91 1.654
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5000 Magnetite 81.34 11.57 1.86 0.43 4.80 1.697
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3 Table 9. Composition of upgraded oils as function of type of catalyst using 5000 ppm of metal
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6 active.
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8 Analytical Analytical Hematite Hematite
9 Distillation fraction Feed Molybdenite Magnetite
MoO3 Fe2O3 A B
10
11 LSRN 0.10 0.10 0.10 0.10 0.10 0.10 0.10
12 MSRN 5.87 9.97 8.85 8.85 8.04 7.34 7.97
13 HSRN 2.33 3.96 3.94 3.70 4.05 3.94 3.52
14
JF 7.30 12.84 12.88 12.13 11.55 11.88 11.46
15
16 K 5.61 8.99 8.71 8.41 8.06 8.42 8.04
17 SRGO 3.73 6.73 6.52 6.38 6.19 6.39 6.20
18 LVGO 17.35 22.32 22.04 22.02 22.32 21.00 21.30
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20 HVGO 17.30 14.04 14.79 14.97 15.12 14.89 15.76
21 VR 40.41 21.03 22.17 23.44 24.56 26.04 25.64
22 VRC, % - 48.98 46.23 43.15 40.44 36.83 37.82
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26 LSRN: Light straight-run naphtha (<71C), MSRN: Medium straight-run naphtha (71-177C),
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28 HSRN: Heavy straight-run naphtha (177-204C), JF: Jet fuel (204-274C), K: Kerosene (274-
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33 HVGO: Heavy vacuum gasoil (454-538C), VR: Vacuum residue (>538C), VRC: Vacuum
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3 FIGURE CAPTIONS
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6 Figure 1. Coke and gas yields as function of type and concentration of catalyst. () Analytic
7
8 molybdenum trioxide (MoO3), () Analytic ferric oxide (Fe2O3), (*) Molybdenite, ()
9
10
Magnetite (--) Hematite A, () Hematite B.
11
12
13 Figure 2. Nuclear resonance magnetic of cokes without catalyst and with catalyst. (A) Proton
14
15 13
NMR of coke without catalyst, (B) Carbon NMR of coke without catalyst, (C)
16
17 13
18
Proton NMR of coke with 2500 ppm of molybdenite, (D) Carbon NMR of coke
19
20 with 2500 ppm of molybdenite.
21
22 Figure 3. XRD of cokes without catalyst and using 2500 ppm of molybdenite. (---) Coke with
23
24
25 2500 ppm of molybdenite, () Coke without catalyst.
26
27 Figure 4. TGA and DTA curves of cokes without catalyst and 2500 ppm of molybdenite.
28
29 Figure 5. API gravity of upgrading crude oils as function of type and concentration of catalyst.
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31
32 () Analytic molybdenum trioxide (MoO3), () Analytic ferric oxide (Fe2O3), (*)
33
34 Molybdenite, () Magnetite (--) Hematite A, () Hematite B.
35
36
37
Figure 6. Viscosity at 37.8C of upgrading crude oils as function of type and concentration of
38
39 catalyst. () Analytic molybdenum trioxide (MoO3), () Analytic ferric oxide
40
41 (Fe2O3), (*) Molybdenite, () Magnetite (--) Hematite A, () Hematite B.
42
43
44 Figure 7. Hydrodesulfurization of upgrading crude oils as function of type and concentration of
45
46 catalyst. () Analytic molybdenum trioxide (MoO3), () Analytic ferric oxide
47
48 (Fe2O3), (*) Molybdenite, () Magnetite (--) Hematite A, () Hematite B.
49
50
51 Figure 8. Hydrogen consumption as function of type and concentration of ore catalyst. ( ) 0
52
53 ppm, ( ) 3333 ppm, ( ) 5000 ppm, ( ) 6665 ppm.
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