Energy Fuels 2010, 24, 15021510 Published on Web 02/08/2010

: DOI:10.1021/ef901339k

Mechanism of Catalytic Aquathermolysis: Influences on Heavy Oil by Two Types of Efficient Catalytic Ions: Fe3 and Mo6
Yuanqing Wang, Yanling Chen,*, Jing He, Pei Li, and Chao Yang

Faculty of Resources, China University of Geosciences, Wuhan 430074, Peoples Republic of China, and Faculty of Materials Science and Chemical Engineering, China University of Geosciences, Wuhan 430074, Peoples Republic of China Received November 11, 2009. Revised Manuscript Received January 23, 2010

In this paper, we have used thin-layer chromatography-flame ionization detection (TLC-FID), elemental (EL) analysis, 1H nuclear magnetic resonance (1H NMR), and gas chromatography/mass spectroscopy (GC/MS) to analyze the changes in heavy oil, reaction water, and pyrolytic gas during catalytic aquathermolysis comprehensively, and then describe the same and different influences on heavy oil during the aquathermolysis catalyzed by two types of typical efficient catalytic ions: Fe3 and Mo6. The results showed that, using these two ions, seven types of actions were observed during the reaction: pyrolysis; depolymerization; hydrogenation; isomerization; ring opening; oxygenation, alcoholization, and esterification; and reconstruction. It was also found that the former caused more changes in the resin, saturated hydrocarbon, and oxygen-containing groups, whereas the latter led to more changes in the asphaltene, aromatic hydrocarbon, and sulfur-containing groups. of the heavy oils.2-4 However, further research results show that these changes can regress rapidly. This is because the heteroatoms S, N, and O in the heavy oil molecules can interact with other groups via hydrogen bonding or van der Waals forces and polymerize to form larger molecules, thus leading to rapid viscosity regression. Termination of this regression is a key factor in reducing the viscosity of heavy oil. These results also show that aquathermolysis has little effect on extra-heavy oil only in the presence of the injection steam.5 Hence, several research groups conducted intense studies on aquathermolysis catalyzed by several types of catalysts, such as transition-metal ion salts, transitional metallic compounds, and some solid superacids.6-26 They noted
(2) Clark, P. D.; Hyne, J. B. Steam-Oil Chemical Reactions: Mechanisms for the Aquathermolysis of Heavy Oil. AOSTRA J. Res. 1984, 1, 1520. (3) Hyne, J. B. Aquathermolysis: A Synopsis of Work on the Chemical Reactions between Water and Heavy Oil Sands during Stimulated Steam Stimulation, AOSTRA Synopsis Report No. 50; 1986. (4) Clark, P. D.; Hyne, J. B. Studies on the Chemical Reactions of Heavy Oils under Steam Stimulation Condition. AOSTRA J. Res. 1990, 29, 2939. (5) Clark, P. D.; Hyne, J. B.; Tyrer, J. D. Chemistry of Organosulphur Compound Types Occurring in Heavy Oil Sands: 1. High Temperature Hydrolysis and Thermolysis of Tetrahydrothiophene in Relation to Steam Stimulation Processes. Fuel 1983, 62, 959962. (6) Clark, P. D.; Hyne, J. B.; Tyrer, J. D. Some Chemistry of Organosulphur Compound Types Occurring in Heavy Oil Sands: 2. Influence of pH on the High Temperature Hydrolysis of Tetrahydrothiophene and Thiophene. Fuel 1984, 63, 125128. (7) Clark, P. D.; Hyne, J. B.; Tyrer, J. D. Chemistry of Organosulfur Compound Type Occurring in Heavy oil Sands. 3. Reaction of Thiophene and Tetrahydrothiophene with Vanadyl and Nickel Salts. Fuel 1984, 63, 16491645. (8) Clark, P. D.; Dowling, N. I.; Hyne, J. B.; Lesage, K. L. The Chemistry of Organosulphur Compound Types Occurring in Heavy Oils: 4. The High-Temperature Reaction of Thiophene and Tetrahydrothiophene with Aqueous Solutions of Aluminium and FirstRow Transition-Metal Cations. Fuel 1987, 66, 13531357. (9) Clark, P. D.; Dowling, N. I.; Lesage, K. L.; Hyne, J. B. Chemistry of Organosulphur Compound Types Occurring in Heavy Oil Sands: 5. Reaction of Thiophene and Tetrahydrothiophene with Aqueous Group VIIIB Metal Species at High Temperature. Fuel 1987, 66, 16991702.

1. Introduction With increasing demands for energy resources and a serious shortage of conventional hydrocarbon resources, heavy oil, which is a type of unconventional hydrocarbon resource with great potential, has attracted worldwide interest. However, its high viscosity and solidification often cause difficulties in exploitation. Therefore, reducing its viscosity to enhance oil recovery has become a point of focus recently. Presently, catalytic aquathermolysis recovery has been a new exploitation technology of heavy oil with great potential. It is a complex recovery system of steam stimulation and chemical recovery. In this technology, the catalyst is added into the oil floor at an interval when the high-temperature steam is injected. At the oil floor, three types of actions occur: thermolysis, the action of high-temperature steam, and catalysis. The first two actions can be described together as aquathermolysis, which provides the energy and power for the entire process. Under the action of aquathermolysis, the large molecules of heavy oil are heated by the high-temperature steam and pyrolyzed into smaller ones. The catalysis can improve the pyrolysis of heavy oil, reduce its viscosity to a greater degree, and, finally, enhance the oil recovery. This action promotes the entire process and determines its rate and course. Hyne et al. began the study on this field in the 1980s; they researched the details of the chemical reactions between steam, heavy oil, and minerals, and they described all of these reactions collectively as aquathermolysis.1 They found that the injection steam not only can reduce the viscosity of heavy oil, but also react with some components of the heavy oil, thereby leading to changes in the properties and compositions
*Author to whom correspondence should be addressed. Tel.: 8613886113362. Fax: 86-027-87801763. E-mail: ylchen@cug.edu.cn. (1) Hyne, J. B.; Greidanus, J. W. Aquathermolysis of Heavy Oil. In Proceedings of the 2nd International Conference on Heavy Crude and Tar Sands, Caracas, Venezuela, 1982; pp 25-30.
r 2010 American Chemical Society

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that the groups that contain heteroatoms (N, O, and S) in the heavy oil could cause polymerization or form hydrogen bonds, eventually leading to high viscosity. Therefore, breaking the heteroatom-containing groups would be an efficient way to reduce the viscosity. To date, almost all studies support the mechanism that the role of catalysts is mainly to catalyze the hydrodesulfurization, which is the main reason of viscosity reduction in heavy oil. They also discussed the role of water in catalytic aquathermolysis. The results show that, in this process, water participates as a solvent, catalyst, and reactant. High-temperature water under autogenic pressure provides a significant favorable reaction medium for heavy oil molecules. At high temperature, water exhibits density and polarity properties that are similar to those of acetone at room temperature. As the water temperature is increased, the solubility of nonpolar organic compounds increases much more than expected for the natural effect of temperature. Meanwhile, the negative logarithmic ionic product of water [pKw] at 250 C is 11, compared to a value of pKw = 14 at 20 C. This means that, as the temperature increases, water becomes both a stronger acid and a stronger base. Therefore, in addition to the natural increase in kinetic rate with temperature, both acid and base catalysis by water are enhanced
(10) McFarlane, R. A.; Cyr, T.; Hawkins, R. W. T. Process for Dispersing Transition Metal Catalytic Particles in Heavy Oil, U.S. Patent 5,916,432, 1999. (11) Pelrine, B. P.; Comolli, A. G.; Lee, L. K. Iron-based Ionic Liquid Catalysts for Hydroprocessing Carbonaceous Feeds, U.S. Patent 6,139,723, 2000. (12) Soled, S. L.; Riley, K. L.; Schleicher, G. P. Hydroprocessing Using Bulk Group VIII Catalysts, U.S. Patent 6,162,350, 2000. (13) Cordova, J.; Pereira, P.; Guition, J. Andriollo A, Cirilo A, Granadillo F, Production of Oil Soluble Catalytic Precursors, U.S. Patent 6,043,182, March 28, 2000. (14) Babcock, L. M.; Morrell, D. G. Flourinated Solid Acid as Catalysts for the Preparation of Hydrocarbon Resins, U.S. Patent 6,281,309 B1, Aug. 28, 2001. (15) Fan, H. F.; Liu, Y. J.; Zhao, X. F. Studies on Effect of Metal Ions on Aquathermolysis Reaction of Liaohe Heavy Oil under Steam Treatment. J. Fuel Chem. Technol. 2001, 29, 430433. (16) Rivas, O. R.; Campos, R. E.; Borges, L. G. Experimental Evaluation of Transition Metals Salt Solutions as Additives in Steam Recovery Processes. Presented at the SPE Annual Technical Conference and Exhibition, Houston, TX, October 2-5, 1988; Paper No. 18076. (17) Clark, P. D.; Kirk, M. J. Studies on the Upgrading of Bituminous Oils with Water and Transition Metal Catalysts. Energy Fuels 1994, 8, 380387. (18) Fan, Z. X.; Zhao, F. L.; Wang, J. Upgrading and Viscosity Reduction of Extra Heavy Oil by Aquathermolysis with Hydrogen Donor. J. Fuel Chem. Technol. 2006, 34, 315318. (19) Wen, S. B.; Liu, Y. J.; Song, Y. W. Effect of Silicotungstic Acid on Catalytic Visbreaking of Extra Heavy Oil from Shengli Oilfield. J. Daqing Pet. Inst. 2004, 28, 2527. (20) Liu, Y. J.; Chen, E. Y.; Wen, S. B. The Preparation and Evaluation of Oil-soluble Catalyst for Aquathermolysis of Heavy Oil. Chem. Eng. Oil Gas 2005, 34, 511512. (21) Chen, E. Y.; Liu, Y. J.; Ge, H. J. A Study on the Degradation of the Asphaltene in Liaohe Heavy Oil during Catalytic Aquathermolysis Reaction. J. Daqing Pet. Inst. 2005, 29, 911. (22) Chen, E. Y.; Liu, Y. J.; Wen, S. B. A Study on the Degradation of the Resin in Liaohe Heavy Oil during Catalytic Aquathermolysis Reaction. Chem. Eng. Oil Gas 2005, 35, 4950. (23) Fan, H. F.; Liang, T. Function of Catalysts in Hydrothermal Cracking of Heavy Oil. Ind. Catal. 2006, 14, 14. (24) Zou, C. J.; Huang, Z. Y.; Luo, P. Y. Oxidative Degradation of Macromolecular Constituents of Heavy Oil in [(MoO2)(acac)2]/tBuOOH/H3PO4 Catalyzed Oxidative Degradation System. J. Chem. Ind. Eng. (China) 2005, 56, 853856. (25) Zou, C. J.; Liu, C.; Huang, Z. Y. Catalyst Degradation of Macromolecular Constituents of Asphaltic Sands in Ionic Liquids. J. Chem. Ind. Eng. (China) 2004, 55, 20952098. (26) He, S. Z.; Fan, H. F. Viscosity and Molecular Weight Change of Heavy Oil under Steam and Metal Salts Coexistence. Chem. Eng. 2006, 8 (1-2), 9.

at higher temperatures. Furthermore, during the reaction, water, as a hydrogen donor, provides hydrogen for hydrogenation and hydrodesulfurization. Their studies provided a good research method for us; later, our research group researched the aquathermolysis catalyzed by five catalysts: iron naphthenate,27 aromatic sulfonic iron,28 aromatic sulfonic molybdenum,29 shiff base,30 and HPAS.31 We approved the above viewpoints about the role of water in catalytic aquathermolysis, but also found some different and more comprehensive contributions of catalyst to viscosity reduction. It is found that, besides the cleavage of a few C-S bonds, catalysts also may cause changes in oxygen-containing groups (e.g., cleavage of C-O bonds in phenolic, ethereal molecules, etc. from the heavy oil). It is well-known that the heteroatoms (N, O, and S) are contained in the heavy oil in small amounts. Could such small changes result in such a large reduction in viscosity? Do any other changes happen during the catalytic aquathermolysis? For these reasons, choosing the typical catalysts to conduct comprehensive research on the mechanism of catalytic aquathermolysis is necessary and important, which can provide some instruction for synthesizing or choosing the suitable catalysts for field application. In our previous research, we found that the aromatic sulfonic iron and aromatic sulfonic molybdenum could show good effects on viscosity reduction in the laboratory, and the former has obtained great achievement with regard to enhanced oil recovery (EOR) in field tests. In addition, we also conducted experiments on the aquathermolysis with and without catalysts, and we have discussed the role of the catalyst in the catalytic aquathermolysis. The results show that catalysts can enhance the changes of heavy oil molecules only in the presence of water, terminate their regression, and cause many new changes.27-31 Therefore, this study emphasizes evaluation of the same and different influences on heavy oil during the aquathermolysis catalyzed by these two typical catalysts, which contain two different types of efficient catalytic ions: Fe3 and Mo6. In this work, changes in the heavy oil, reaction water, and pyrolytic gas after catalytic aquathermolysis were first analyzed systemically. 2. Experimental Section
2.1. Aquathermolysis Catalyzed by Aromatic Sulfonic Iron and Aromatic Sulfonic Molybdenum. Aromatic sulfonic iron and aromatic sulfonic molybdenum were synthesized according to refs 28 and 29, and then they were used in the aquathermolysis of the extra-heavy oil DF32005 with a viscosity of 91 000 mPa s. The experiments were conducted by placing 100 g of oil sample, 43 g of water (oil/water = 7:3), and 0.3 g
(27) Chen, Y.; Chen, Y. L.; Zhu, M. Catalytic Effect of Organic Acid Transitional Metallic Salt on Aquathermolysis Reaction of Heavy Oil. Geol. Sci. Technol. Inf. 2005, 24, 7579. (28) Chen, Y. L.; Wang, Y. Q.; Wu, C.; Xia, F. Laboratorial Experiments and Field Tests of an Amphiphilic Metallic Chelate for Catalytic Aquathermolysis of Heavy Oil. Energy Fuels 2008, 22, 15021508. (29) Wu, C.; Chen, Y. L.; Wang, Y. Q.; Yang, C. Upgrading and Visbreaking of Shengli Ultra-Heavy Oil by Aquathermolysis with Catalyst. Oilfield Chem. 2009, 26, 121127. (30) Xia, F.; Chen, Y. L.; Wu, C. Indoor Study of Aryl Bisschiff Base Used for Aquthermolytic Reaction at Lower Temperature. Geol. Sci. Technol. Inf. 2007, 26, 9194. (31) Chen, Y. L.; Wang, Y. Q.; Lu, J. Y.; Wu, C. The Viscosity Reduction of Nano-Keggin-K3PMo12O40 in catalytic aquathermolysis of heavy oil. Fuel 2009, 88, 14261434.

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Table 1. Group Composition of Heavy Oil DF32005 before and after Reaction
asphaltene (%) 12.6 6.3 4.3 resin (%) 35.4 19.7 21.6 aromatic HC (%) 21.5 26.5 30.3

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oil sample oil before aquathermolysis oil after aquathermolysis with aromatic sulfonic iron oil after aquathermolysis with aromatic sulfonic molybdenum

saturated HC (%) 30.5 47.5 43.8

Table 2. Elemental Content of Resins and Asphaltenes of DF32005 Extra-Heavy Oil before and after Reaction
Composition (%) group asphaltenes before aquathermolysis asphaltenes after aquathermolysis catalyzed by aromatic sulfonic iron asphaltenes after aquathermolysis catalyzed by aromatic sulfonic molybdenum resins before aquathermolysis resins after aquathermolysis catalyzed by aromatic sulfonic iron resins after aquathermolysis catalyzed by aromatic sulfonic molybdenum C 76.83 79.78 79.84 78.33 81.82 79.86 H 10.00 11.16 11.43 8.46 11.78 11.47 N 2.209 2.049 1.723 1.697 1.547 1.255 S 2.693 2.361 0.775 2.476 1.821 0.762 O 8.268 4.650 6.235 9.037 3.032 6.653

Table 3. Changes in the NH/NC Ratio and Concentrations of N, S, and O of Resins and Asphaltenes of DF32005 Extra-Heavy Oil before and after Reaction
Composition group asphaltenes after aquathermolysis catalyzed by aromatic sulfonic iron resins after aquathermolysis catalyzed by aromatic sulfonic iron asphaltenes after aquathermolysis catalyzed by aromatic sulfonic molybdenum resins after aquathermolysis catalyzed by aromatic sulfonic molybdenum (NH/NC) 0.118 0.459 0.156 0.454 N -0.160 -0.150 -0.486 -0.442 S -0.332 -0.655 -1.918 -1.714 O -3.618 -6.005 -2.033 -2.420

of catalyst into a high-pressure reactor (Model FYX-0.5). The reaction continued for 24 h at a temperature of 200 C. The original pressure was maintained at 3 MPa by aeration with N2. 2.2. Characterization of the Changes of Heavy Oil, Reaction Water, and Pyrolytic Gas. The viscosity of the resulting heavy oil was recorded by a Brookfield Model DV-II programmable viscometer at 50 C before and after the reaction. The rate of viscosity reduction (4) was calculated as follows: % 0 - 100 0

Table 4. Assignment of Protons in the 1H NMR Spectrum

parameter HA HR H H type of protons chemical shift (ppm) 6.0-9.0 2.0-4.0 1.0-2.0 0.5-1.0

aromatic hydrogen aliphatic hydrogen on CR to aromatic rings aliphatic hydrogen on C and the CH2, CH beyond the C to aromatic rings aliphatic hydrogen on C and the CH3 beyond the C to aromatic rings

where is the rate of viscosity reduction, 0 the viscosity of the oil before the reaction (expressed in units of Pa s), and the viscosity of the oil after the reaction (also expressed in units of Pa s). The group compositions of the extra-heavy oil were analyzed before and after reaction on a Iatroscan uewMK-5 thin-layer chromatography-flame ionization detection (TLCFID) system, following the Industrial Specification of China Petroleum standard SY/T 6338.32 Furthermore, DF32005 extra-heavy oil was further analyzed for structural changes and group compositions. Four compound groups;namely, asphaltenes, resins, saturated hydrocarbons, and aromatic hydrocarbons;were separated from DF32005 using the column chromatography-based SARA method (saturates, aromatics, resins, and asphaltenes), according to the Industrial Specification of China Petroleum standard SY/T 5119.33 The organic compounds in reaction water after catalytic aquathermolysis were extracted using CCl4. The pyrolytic gas was collected using a 1-L bag that was composed of aluminum foil. Elemental analyses of the resins and asphaltenes before and after reaction were performed on a Model EL-2 elemental analyzer. 1 H NMR spectra of the resin and asphaltene fractions were
(32) Analysis of Family Composition of Rock Extract and Crude Oil by TLC-FID, China Petroleum Standard SY/T 6338-1997; China National Petroleum Corporation. Dec. 31, 1997. (33) Analysis of Family Composition of Rock Extract and Crude Oil by Column Chromatography, China Petroleum Standard SY/T 51191995; China National Petroleum Corporation, Dec. 25, 1995.

recorded before and after reaction on a Bruker Model ARX300 NMR spectrometer, using CDCl3 as a solvent. The concentration of the samples with 10 mg in CDCl3 (containing trimethylsilane (TMS) as an internal reference) was maintained constant. The gas chromatography/mass spectroscopy (GC/ MS) analyses of the saturated hydrocarbons, aromatic hydrocarbons, and organic compounds in reaction water before and after catalytic aquathermolysis were performed on an Agilent Technologies Model 7890 gas chromatograph and a Leco Model Pegasus 4D TOFMS mass spectroscope. The concentration of the saturated and aromatic hydrocarbon samples, with 5 wt % in n-hexane, and that of the organic compounds in reaction water with 3 wt % in CCl4 were maintained constant. The pyrolytic gases were detected on a Saturn Model 2200 GC/MS system.

3. Results and Discussion 3.1. Results of Laboratory Study of Catalytic Aquathermolysis. The results show a viscosity reduction by 95.6% for DF32005 extra-heavy oil with aromatic sulfonic iron, and by 99.3% for DF32005 extra-heavy oil with aromatic sulfonic molybdenum. Table 1 lists the group compositions of DF32005 extra-heavy oil before and after reaction, which were determined by TLC-FID, according to the Industrial Specification of China Petroleum standard SY/T 6338. It can be seen that, after the aquathermolysis that was catalyzed by aromatic sulfonic iron, the resins content decreased by 15.7% and the asphaltenes content decreased by 6.3%, while the saturated and aromatic hydrocar1504

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Composition (%) group HA 0.71 6.04 5.48 1.40 5.94 6.40 HR 4.34 8.02 10.31 12.94 9.09 8.24 H 59.42 51.80 48.05 60.65 56.46 58.23

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Table 5. 1H NMR of Resins and Asphaltenes of DF32005 Extra-Heavy Oil before and after Reaction

H 35.53 34.14 36.16 25.01 28.51 27.13

asphaltenes before aquathermolysis asphaltenes after aquathermolysis catalyzed by aromatic sulfonic iron asphaltenes after aquathermolysis catalyzed by aromatic sulfonic molybdenum resins before aquathermolysis resins after aquathermolysis catalyzed by aromatic sulfonic iron resins after aquathermolysis catalyzed by aromatic sulfonic molybdenum

Figure 1. 1H NMR spectra of resins and asphaltenes before and after catalytic aquathermolysis: (a) 1H NMR spectrum of asphaltenes before aquathermolysis (panel (a1) shows the 1H NMR spectrum of asphaltenes after aquathermolysis catalyzed by aromatic sulfonic iron, and panel (a2) shows the 1H NMR spectrum of asphaltenes after aquathermolysis catalyzed by aromatic sulfonic molybdenum); (b) 1H NMR spectrum of resins before aquathermolysis (panel (b1) shows the 1H NMR spectrum of resins after aquathermolysis catalyzed by aromatic sulfonic iron; panel (b2) shows the 1H NMR spectrum of resins after aquathermolysis catalyzed by aromatic sulfonic molybdenum).

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Table 6. Changes in the Aromaticity (fA), Aromaticity Condensation (HAU/CA), and Branchiness Index (BI) of Resins and Asphaltenes of DF32005 Extra-Heavy Oil before and after Reaction
Composition group asphaltene before aquathermolysis asphaltene after aquathermolysis catalyzed by aromatic sulfonic iron asphaltene after aquathermolysis catalyzed by aromatic sulfonic molybdenum resin before aquathermolysis resin after aquathermolysis catalyzed by aromatic sulfonic iron resin after aquathermolysis catalyzed by aromatic sulfonic molybdenum fA 0.225 0.193 0.188 0.361 0.189 0.193 HAU/CA 0.200 0.895 0.971 0.282 0.954 0.938 BI 0.371 0.413 0.413 0.227 0.289 0.272

Figure 2. Spectra of n-alkane fragments in saturated hydrocarbon before (spectrum c) and after aquathermolysis catalyzed by aromatic sulfonic iron (spectrum a) and aromatic sulfonic molybdenum (spectrum b).

Figure 4. Spectra of steroid and higher-olefin fragments in saturated hydrocarbon before (spectrum c) and after aquathermolysis catalyzed by aromatic sulfonic iron (spectrum a) and aromatic sulfonic molybdenum (spectrum b).

Figure 3. Spectra of terpenoid and higher-olefin fragments in saturated hydrocarbon before (spectrum c) and after aquathermolysis catalyzed by aromatic sulfonic iron (spectrum a) and aromatic sulfonic molybdenum (spectrum b).

Figure 5. Spectra of methylbenzene-containing fragments in aromatic hydrocarbon before (spectrum c) and after aquathermolysis catalyzed by aromatic sulfonic iron (spectrum b) and aromatic sulfonic molybdenum (spectrum a).

bons contents increased by 17% and 5%, respectively; after the aquathermolysis that was catalyzed by aromatic sulfonic molybdenum, the resins content decreased by 13.8% and the asphaltenes content decreased by 8.3%, while the saturated and aromatic hydrocarbons increased by 13.3% and 8.8%, respectively. The comparison results verify that aromatic sulfonic iron is likely to act on the resins and saturated hydrocarbons, while the aromatic sulfonic molyb1506

denum is likely to act on the asphaltenes and aromatic hydrocarbons. 3.2. Elemental Analysis of Resins and Asphaltenes before and after Catalytic Aquathermolysis. The results for elemental (EL) analysis are listed in Table 2. After calculation, the changes of NH/NC (the ratio of hydrogen to carbon) and concentrations of N, S, and O are listed in Table 3. The results show that, for the resins and asphaltenes,

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Figure 6. Spectra of methylnaphthalene-containing fragments in aromatic hydrocarbon before (spectrum c) and after aquathermolysis catalyzed by aromatic sulfonic iron (spectrum b) and aromatic sulfonic molybdenum (spectrum a).

Figure 8. Spectra of the organic compounds in reaction water after aquathermolysis catalyzed by aromatic sulfonic iron (spectrum a) and aromatic sulfonic molybdenum (spectrum b). Table 7. Organic Compounds in Reaction Water after Aquathermolysis Catalyzed by Aromatic Sulfonic Iron
peak 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 formula C10H22O4 C10H22O2 C6H11N3O4 C16H34 C17H28 C10H18O4 C17H36 C18H30 C19H32 C12H14O4 C16H22O4 C20H42 C21H44 C17H16 C18H38 C22H44 name dimethyl phthalate propane, 1,10 -[ethylidenebis(oxy)]bis[2-methyl-] Gly-Gly-Gly hexadecane benzene, (1-butylheptyl)hexanedioic acid, bis(2-methylpropyl) ester heptadecane benzene, (1-propylnonyl)benzene, (1-pentyloctyl)1,2-benzenedicarboxylic acid, bis(2-methylpropyl) ester dibutyl phthalate eicosane eicosane, 2-methylphenanthrene, 2,3,5-trimethylheptadecane, 2-methyl1-docosene

Figure 7. Spectra of methylphenanthrene-containing fragments in aromatic hydrocarbon before (spectrum c) and after aquathermolysis catalyzed by aromatic sulfonic iron (spectrum b) and aromatic sulfonic molybdenum (spectrum a).

the saturation increased, while the aromaticity and the concentrations of N, S, and O decreased. These changes demonstrate that the catalyst promoted the hydrogenation during the reaction and acted on the groups that contained the heteroatoms (N, O, and S), and they made them undergo cleavage from the resins and asphaltenes, resulting in the pyrolytic gas and the reaction water. Furthermore, these changes also show that the aromatic sulfonic iron causes more changes of resins and groups containing O atoms, whereas the aromatic sulfonic molybdenum causes more changes of the asphaltenes and groups containing S atoms. 3.3. 1H NMR of Resins and Asphaltenes before and after Catalytic Aquathermolysis. The 1H NMR result of resins and asphaltenes before and after catalytic aquathermolysis can be observed in Table 4, Table 5, and Figure 1. Parameters such as aromaticity (fA), aromaticity condensation (HAU/ CA), and branchiness index (BI) were obtained using eqs 1, 2,
(34) Liang, W. Heavy Oil Chemistry; China University of Petroleum: Shandong, Dongying, PRC, 2003.

Table 8. Organic Compounds in Reaction Water after Aquathermolysis Catalyzed by Aromatic Sulfonic Molybdenum
peak 10 20 30 40 50 60 70 80 90 formula C6H12N2O C5H7NO2 C13H13NO2 C10H10O4 C10H22O2 C6H9NO2 C6H11N3O4 C10H18O4 C16H22O4 name (3R)-()-3-acetamidopyrrolidine proline, 3,4-didehydro1-(2,5-dihydropyrrol-1-yl)3-phenylpropane-1,3-dione dimethyl phthalate propane, 1,10 -[ethylidenebis(oxy)]bis[2-methyl-] D,L-3,4-dehydroproline methyl ester Gly-Gly-Gly hexanedioic acid, dipropyl ester 1,2-benzenedicarboxylic acid, mono(2-ethylhexyl) ester

and 3, respectively:34 fA CT =HT - HR H H =2HT CT =HT 1

HAU HA =HT HR =2HT CT =HT - HR H H =2HT CA

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Wang et al. Table 10. Compositions of the Pyrolytic Gas after Aquathermolysis Catalyzed by Aromatic Sulfonic Molybdenum
peak 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 formula C8H16 C9H18 C7H14O2S C11H22O2S C16H34O2 C10H20 C15H26 C17H34O C18H34O C19H36 C10H18 C13H26 C10H16O C12H20O C14H26O2 C13H22O C14H24O C17H32O C15H24O C16H28O C15H28 C18H32O C19H36O C20H28O C20H40O2 C21H28O2 C21H36O2 C28H48O name 3,4-dimethyl-1-hexene 1-methylpentyl cyclopropane trans-2,4-dimethylthiane, S,S-dioxide trans-2-methyl-4-n-pentylthiane, S,S-dioxide 1,10-hexadecane cyclohexane, 1-ethyl-1,4-dimethyl-, cis1,3-dicyclohexylpropene (R)-(-)-(Z)-14-methyl-8-hexadecen-1-ol (Z)-13-octadecenal 2-methyl-7-octadecyne bicyclo[3.1.1] heptanes, 2,6,6- trimethyl-, [1S(1.alpha., 2.beta., 5.alpha.)] 5-butyl-4-nonene trans-2-methyl-5-(1-methyllethenyl-)2-cyclohexen-1-ol trans-decahydro-9a-methyl-2Hbenzocyclohepten-2-one (Z)-isobutyrate-3,7-dimethyl-2-octen-1-ol trans-decahydro-10a-methyl-2(1H)benzocyclooctenone 2(1H)-naphthalenone, octahydro-4a-methyl-, 7-(1-methylethyl)-, (4a.alpha., 7.beta., 8a.alpha.) (R)-(-)-14-methyl-8-hexadecyn-1-ol cis-Z-.alpha.-bisabolene epoxide 11-hexadecynal naphthalene, decahydro-1,4a-dimethyl-7-, (1-methylethyl)-, [1S-(1.alpha., 4a.alpha., 7.alpha., 8a.beta.)] (Z)-9,17-octadecadienal 2-methyl-Z,Z-3,13-octadecadienol vitamin A aldehyde (Z)-2-(9-octadecenyloxy)-ethanol 2-[5-(2,2-dimethyl-6-methylene-cyclohexyl)3-methyl-pent-2-enyl]-[1,4] benzoquinone 7,10,13-eicosatrienoic acid, methyl ester cholestan-3-ol, 2-methylene, (3.beta., 5.alpha.)

Figure 9. Spectra of compositions of the pyrolytic gas after aquathermolysis catalyzed by aromatic sulfonic molybdenum (spectrum a) and aromatic sulfonic iron (spectrum b).

17 18 19 20 21 22 23 24 25 26 27 28

Table 9. Compositions of the Pyrolytic Gas after Aquathermolysis Catalyzed by Aromatic Sulfonic Iron
peak 10 20 3
0 0

formula C9H16O C7H14O2S C10H18O C9H18O C9H16 C15H26O C17H34O C10H20 C18H34O C10H18 C19H36 C18H36O C12H20O C13H22O C14H24O C13H24 C19H36O C15H28 C15H24O C16H28O C20H28O C28H48O

name 2-(1-methylpropyl)cyclopentanone trans-2,4-dimethylthiane, S,S-dioxide (1-bicyclo[3.1.1]heptan-3-one, 2,6,6-trimethyl-, alpha., 2.beta., 3.alpha.) 1,1,4-trimethylcyclohexane 3,4,4-trimethylcyclohexene 2-butyl-3-methyl-5-(2-methylprop2-enyl) cyclohexanone (R)-(-)-(Z)-14-methyl-8-hexadecen-1-ol 1,1,2,3-tetramethyl-cyclohexane (Z)-13-octadecenal 2,3,4,5-tetramethyl-1,4-hexadiene 2-methyl-7-octadecyne E-2-octadecadecen-1-ol trans-decahydro-9a-methyl-2Hbenzocyclohepten-2-one trans-decahydro-10a-methyl-2(1H)benzocyclooctenone 2(1H)-naphthalenone, octahydro-4a-methyl-, 7-(1-methylethyl)-, (4a.alpha., 7.beta., 8a.alpha.) 1,1,6,6,-tetramethylspiro[4.4]nonane 2-methyl-Z,Z-3,13-octadecadienol naphthalene, decahydro-1,4a-dimethyl-7-, (1-methylethyl)-, [1S-(1.alpha., 4a.alpha., 7.alpha., 8a.beta.)] cis-Z-.alpha.-bisabolene epoxide 7,11-hexadecadienal vitamin A aldehyde cholestan-3-ol, 2- methylene, (3.beta., 5.alpha.)

4 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220

BI

1 H 3 1 HR H 2

In eqs 1, 2, and 3, CT and HT represent the total amounts of carbon and hydrogen, respectively (HT = HA HR H H);
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CT/HT is the ratio of carbon to hydrogen (the value of CT/HT for the saturated composition is assumed to be equal to 2. In eq 2, the larger the HAU/CA value, the lower the aromaticity condensation. In eq 3, the larger the BI value, the shorter the branch chain and the higher the isomerization. The results, after calculation, are shown in Table 6. It is not difficult to see that, for the asphaltenes and resins after catalytic aquathermolysis, the aromaticity and aromaticity condensation decreased, the isomerization of the side chains became higher, and the side chains became shorter. The decrease in aromaticity could be attributed to the hydrogenation of unsaturated groups; the decrease of the aromaticity condensation likely is caused by the ring opening and depolymerization of the closed aromatic system, as well as isomerization of the side chains; the shorter side chains could be caused by the pyrolysis of side chains. These changes make the resin and asphaltene molecules smaller and become loosened. It is also not difficult to see that the aromatic sulfonic iron causes greater changes in the resins, whereas the aromatic sulfonic molybdenum led to greater changes in the asphaltenes. 3.4. GC/MS Analysis of Heavy Oil, Pyrolytic Gas, and Reaction Water before and after Catalytic Aquathermolysis. 3.4.1. Changes of the Saturated and Aromatic Hydrocarbons of Heavy Oil. Figures 2-7 show GC/MS analyses of the saturated and aromatic hydrocarbons of the heavy oil

Energy Fuels 2010, 24, 15021510

: DOI:10.1021/ef901339k

Wang et al.

before and after aquathermolysis catalyzed by these two catalysts. Figures 2, 3, and 4 show the changes regarding saturated hydrocarbons. It is easy to see that, after reaction, the amount of N-alkanes with small molecules increased while that of the terpenoids, steroids, and higher olefins with large molecules decreased in the saturated hydrocarbons. Some of the increased small alkanes are pyrolytic fragments of the resins and asphaltenes, and the others are attributed to the probable pyrolysis, isomerization, and reconstruction of large alkanes, the ring opening of cycloalkanes, and hydrogenation of the olefins during the reaction. Figures 5, and 7 show the changes regarding the aromatic hydrocarbons. Obviously, during the reaction, the number of molecules that contain methylbenzene, methylnaphthalene, and methylphenanthrene increased after reaction. The increased number of small aromatic molecules probably came from the fragments after pyrolysis and depolymerization of the resins and asphaltenes. Figures 2-7 also show that the aromatic sulfonic iron causes more changes regarding the saturated hydrocarbons and the aromatic sulfonic molybdenum causes more changes with regard to the aromatic hydrocarbons. 3.4.2. Changes of Compounds in Reaction Water. Figure 8, Table 7, and Table 8 show the appearance of the organic compounds in reaction water after catalytic aquathermolysis. The results illustrate that, after the aquathermolysis catalyzed by aromatic sulfonic iron, the abundant oxygencontaining compounds such as alcohols, ethers, esters, etc., and few types of small saturated and aromatic hydrocarbons appear in the reaction water. In addition, after catalytic aquathermolysis catalyzed via aromatic sulfonic molybdenum, several forms of nitrogen-containing compounds appear in the reaction water, in addition to a few types of oxygen-containing compounds. 3.4.3. Changes of Compounds in Pyrolytic Gas. Figure 9, Table 9, and Table 10 show the compounds of the pyrolytic gas after catalytic aquathermolysis. The results show that, under catalysis with aromatic sulfonic iron and aromatic sulfonic molybdenum, the pyrolytic gas contains several types of small oxygen- and sulfur-containing organic compounds (such as alcohols, ethers, esters, thioesters, thiols, etc.) and some types of cycloalkanes, olefins, and aromatic hydrocarbons. In addition, the former leads to the appearance of more oxygen-containing compounds in pyrolytic gas, while the latter causes an increase in the amount of sulfur-containing compounds. From above results and discussion, all the four compound groups of heavy oil have changed during the catalytic aquathermolysis. Generally speaking, in the resins and asphaltenes, the side chains with aromatic structure were branched and pyrolyzed to alkane or olefin fragments, and the closed aggregation of polycyclic aromatic hydrocarbons were depolymerized to relative smaller aromatic fragments. Parts of these fragments were dissolved into the saturated and aromatic hydrocarbons, reaction water, and pyrolytic gas, and the remainding depolymeric aromatic fragments with high branchiness side-chains were reconstructed to looser molecules of resins and asphaltenes. The decrease and looseness of the heavy contents (resins and asphaltenes), as well as the increase and the dissolution of the light contents (saturated and aromatic hydrocabons), caused
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the viscosity reduction. Specifically, the catalyst acted on C-R (where R = N, S, O), conjugated -bonds, and the relative weaker C-C and CdC bonds, causing the following seven actions during the entire catalytic aquathermolysis: pyrolysis; depolymerization; hydrogenation; isomerization; ring opening; oxygenation, alcoholization, and esterification; and reconstruction. (1) Pyrolysis:

This action mainly happened on the side chains of aromatic rings in the resins and asphaltenes and of the cycloalkane in saturated hydrocarbons. (2) Depolymerization:

This action mainly happened on the aggregated polycyclic aromatic hydrocarbons. In the previously given reaction scheme, Mn is the metal ion in the catalysts. (3) Hydrogenation:

This action mainly happened on the unsaturated hydrocarbons and the heteroatom-containing groups.

Energy Fuels 2010, 24, 15021510

: DOI:10.1021/ef901339k
(7) Reconstruction:

Wang et al.

(4) Isomerization:

This action mainly happened on parts of n-alkanes, the side chains of aromatic rings, and cycloalkane in the four compound groups of the heavy oil. (5) Ring opening:

This action mainly happened on the cycloalkane in the saturated hydrocarbons and the heterocyclic aromatic groups. (6) Oxygenation, alcoholization, and esterification:

This action mainly happened in the resins and asphaltenes. Parts of the relative smaller pyrolytic and depolymeric fragments were dissolved into the saturated and aromatic hydrocarbons, and the remaining fragments were reconstructed to form a large complex structure. Furthermore, the use of aromatic sulfonic iron enhanced actions 1, 5, and 6, causing more changes regarding the resins and saturated hydrocarbons; use of the aromatic sulfonic molybdenum promoted actions 2, 3, 4, and 5, leading to more changes regarding the asphaltenes and aromatic hydrocarbons. Therefore, the former is suitable for application to catalyze the aquathermolysis of the heavy oil with high resins and oxygen contents, and the latter is suitable to catalyze the aquathermolysis of the heavy oil with high asphaltenes and sulfur contents. 4. Conclusion In summary, through comprehensive analysis of the changes in the heavy oil, reaction water, and pyrolytic gas in the entire catalytic aquathermolysis, we have described the same and different influences on heavy oil during aquathermolysis catalyzed by the aromatic sulfonic iron and the aromatic sulfonic molybdenum, which contained two types of efficient catalytic ions: Fe3 and Mo6. The results showed that there were seven types of actions during the catalytic aquathermolysis of heavy oil: pyrolysis; depolymerization; hydrogenation; isomerization; ring opening; oxygenation, alcoholization, and esterification; and reconstruction. The comparison analysis showed that the aromatic sulfonic iron caused more changes with regard to the resins, saturated hydrocarbons, and oxygen-containing groups, while the use of the aromatic sulfonic molybdenum led to more changes with regard to the asphaltenes, aromatic hydrocarbons, and sulfur-containing groups.
Acknowledgment. The authors would like to thank the financial support from the National Natural Science Foundation and from Hubei Key Lab of Petroleum Exploration and Development Theory and Technology.

This action mainly happened on the oxygen-containing and sulfur-containing groups in the resins and asphaltenes and parts of alkanes, olefins, and cycloalkanes in the saturated hydrocarbons.

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