The Effect of Carbon-Supported Nickel Nanoparticles in the Reduction

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The effect of carbon supported nickel nanoparticles in the reduction of carboxylic acids for in-situ upgrading of heavy crude oil Kun Guo, Yahe Zhang, Quan Shi, and Zhixin Yu Energy Fuels, Just Accepted Manuscript • Publication Date (Web): 05 May 2017 Downloaded from http://pubs.acs.org on May 6, 2017

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The effect of carbon supported nickel nanoparticles in the reduction of carboxylic acids for in-situ upgrading of heavy crude oil Kun Guoa,b, Yahe Zhangc, Quan Shic* and Zhixin Yua,b* a

Department of Petroleum Engineering, University of Stavanger, 4036 Stavanger, Norway

b

The National IOR Centre of Norway, University of Stavanger, 4036 Stavanger, Norway

c

State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249,

China

*Corresponding authors: Quan Shi: Tel.: +86 10 897 33 738; E-mail: [email protected] Zhixin Yu: Tel.: +47 518 32 238; Fax: +47 518 32 050; E-mail: [email protected]

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Abstract Nickel (Ni) nanoparticles (NPs) supported on different supports, including three carbon nanomaterials, i.e., ketjenblack (KB) carbon, carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs), and zeolite, are prepared and studied as catalysts in the upgrading of heavy crude oil. X-ray diffraction and transmission electron microscopy measurements confirm the formation of dispersed Ni NPs with similar crystal size of approximately 10 nm in all the supported catalysts. In the upgrading tests, the reaction temperature and time as important reaction parameters are optimized to 300 °C and 2 h, respectively. The importance of external hydrogen source is also verified as the upgrading effect is further enhanced in hydrogen than that in nitrogen. When pristine supports are employed as the catalysts, KB exhibits slightly better viscosity reduction compared with CNT, GNP and zeolite. More importantly, in the case of supported catalysts, Ni/KB displays the highest viscosity reduction ratio of 75% relative to Ni/CNT, Ni/GNP and Ni/zeolite catalysts, indicating possible synergistic effect between the Ni NPs and support. All the viscosity reduction results are in good agreement with the hightemperature simulated distillation analysis, demonstrating the effective upgrading of heavy crude oil. Furthermore, from the molecular structural information obtained from Fourier transform ion cyclotron resonance mass spectrometry, the viscosity reduction and catalytic upgrading is attributed to the conversion of large molecule carboxylic acid compounds to derivatives with smaller carbon numbers and higher saturation. This result is further confirmed by the significant oxygen reduction by the elemental analysis. Therefore, it is concluded that the decomposition of carboxylic acid compounds contributes greatly to the viscosity reduction and Ni/KB can catalyze the decomposition process as an effective catalyst. This work highlights the potential application of carbon-based nanocatalysts for the in-situ upgrading and recovery of heavy crude oil, especially crude oils with high oxygen content.


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Keywords: Nickel; nanoparticle; carbon material; heavy crude oil; upgrading; oxygen removal


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1. Introduction Heavy crude oil, which constitutes approximately 70% of the total oil reserve, holds great promise to supplement the conventional oil resources and to meet the ever-increasing energy demand, but its recovery is challenging due to the inherent high viscosity and high contents of asphaltenes and resins.1 Traditionally, heat-induced viscosity reduction has been utilized as the major mechanism to recover these unconventional oil resources. However, industrially applied methods, e.g., steam assisted gravity drainage, cyclic steam stimulation, and steam flooding, are normally accompanied with the generation of high-temperature and high-pressure steam and considerable amount of greenhouse gases, resulting in large capital investment, potential environmental damage and low efficiency.2-4 Furthermore, the extracted heavy oil entails higher requirements for the transportation and refinery upgrading processes than conventional oil, which brings additional complexity for the production and marketing of heavy crude oil. In-situ catalytic upgrading and recovery of heavy crude oil, one technology that integrates both the upgrading and recovery processes inside the reservoir, is a promising method to exploit the heavy crude oil in a cost-effective and environmentally friendly way.5 Nevertheless, the development of this technology largely remains at the research stage in laboratories and is far from field applications. Among the facing challenges, the development of cost-effective, active and robust catalysts that are operative under the harsh reservoir conditions is of paramount importance. Several types of catalysts, including oil-soluble6-7, water-soluble8 and amphiphilic9-10 catalysts, minerals11, zeolites12-13, solid acids14-15, and metal nanocatalysts16-18, have shown remarkable performance in the upgrading reactions with viscosity reduction ratios of > 90%, sulfur removal of > 50%, and asphaltene conversion of > 40% under typical temperatures of 200-


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400 °C and pressures of < 10 MPa. However, issues related to the cost, efficiency and recycling of the catalysts need to be addressed prior to the implementation of this technology. The key roles of high-performance catalysts in the upgrading of heavy crude oil have been recognized as to facilitate the hydrocracking (HCK) and hydrodesulfurization (HDS) reactions, which account for the decomposition of heavy hydrocarbon molecules with reduced viscosity and enhanced mobility.4-5 Inspired by the prevailing application of alumina, silica or zeolite supported nickel (Ni), cobalt (Co), iron (Fe), copper (Cu), molybdenum (Mo) and their alloys for the industrial HCK and HDS processes, researchers are paying increasing attention to the metalbased catalysts.19-22 Li et al.23 showed that nano-Ni microemulsion can effectively catalyze the visbreaking, sulfur removal and asphaltene conversion, presenting a high viscosity reduction of 98.9%. The influence of metal type, size and concentration of NP on the catalytic upgraiding is studied by Babadagli’s24 and Ovalles’s25 groups. They concluded that these parameters are important for developing high-performance catalysts for the upgrading of heavy crude oil. Several papers have comprehensively reviewed the application of metallic nanoparticles (NPs) as catalysts for in-situ upgrading and recovery of heavy crude oil.4-5, 26-27 A proposed prototype is to prepare stable suspension containing monodispersed metal NPs and this suspension can be injected to the reservoirs and deliver the metal NPs to reach the water-oil phases. This idea, undoubtedly, brings high requirements on the stability of metal NPs because the high surface energy of NPs can cause them to aggregate or get attached to the rock surface, leading to poor stability and activity. Even though successful transport of metal NPs through the rock cores in the core flooding tests has been testified by previous studies28-30, considerable NP retention in the core is also observed and should be minimized. This therefore highlights the importance of further research on the rational structure design and morphology control of the metal catalysts.


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Benefiting from their availability, high specific surface area and controllable surface chemistry, carbon-based materials have found wide applications in many different fields, in particular as metal-free catalysts.31-33 Recently, Li at al.34 reported the study of carbon nanocatalysts in the microwave-assisted upgrading of heavy crude oil. The crude oil is effectively upgraded by carbon NPs with viscosity reduction ratio over 96% at reaction temperature of about 150 °C in short reaction time. It is indicated the carbon NPs help activate and break the C−S bonds. It should be mentioned that among the chemical bonds existing in heavy hydrocarbons, C−S bonds have the smallest bond dissociation energy. Therefore, carbon materials can serve as effective catalysts in the upgrading of heavy crude oil. A study by our group35 demonstrated that carbon black with ultrahigh specific surface area and graphene nanoplatelets with high graphitization degree exhibited superior activity compared with the carbon nanotube catalysts in the HDS of thiophene. Furthermore, carbon-based catalysts would bring minimal impacts to the environment. These advantages endow carbon nanomaterials as promising candidates as high-performance catalysts for the in-situ upgrading of heavy crude oil. Supported catalyst, composed of metallic NPs and support, is important in heterogeneous catalysis. By anchoring the active NPs onto the surface of support material, a good dispersion and thus efficient utilization of NPs is maintained. Possible synergistic effect between the active NPs and support can also enhance the catalytic activity or selectivity.36 In this contribution, three carbon materials, i.e., ketjenblack (KB) carbon, graphene nanoplatelets (GNPs), and carbon nanotubes (CNTs), and the industrially used zeolite supported Ni NPs (denoted as Ni/KB, Ni/GNP, Ni/CNT and Ni/zeolite, respectively) are prepared and employed as catalysts. The potential synergistic effect of the support and Ni NPs is explored in the upgrading of heavy crude oil. Different characterization techniques are used to obtain the structural information of the


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synthesized catalysts. Upgrading of heavy crude oil (API 9.3° at 30 °C) are conducted in a batch reactor under different reaction conditions to investigate the effect of temperature, reaction time and hydrogen donor on the catalytic performance. The upgrading activities of the pristine supports and supported catalysts are also comparatively investigated. Advanced oil sample analysis before and after the upgrading reactions serves to understand the underlying reaction mechanism. This work aims to gain insights into the potential implementation of carbonsupported catalysts in the in-situ upgrading and recovery of heavy crude oil. 2. Experimental Section 2.1 Chemicals All chemicals are used as received without further treatment. Multi-walled CNTs are supplied by Shenzhen Nanotech Port Co., Ltd. Ketjenblack® EC-600JD is ordered from AkzoNobel. GNPs are bought from American Elements. Zeolite (Y, hydrogen) is purchased from Alfa Aesar with a Si:Al mole ratio of 5.1:1. Other chemicals, including ethylene glycol (EG, anhydrous, 99.8%), sodium

borohydride

(NaBH4,

powder,

≥98.0%),

and

nickel(II)

nitrate

hexahydrate

(Ni(NO3)2·6H2O, ≥98.5%) are received from Sigma-Aldrich. Ethanol (96%) is obtained from VWR Norway. Heavy crude oil samples are from Venezuela and provided by Statoil ASA, Norway. The measured density is 1.005 kg/L at 15 °C. The corresponding API gravity of the crude oil is 9.3° at 30 °C. The heavy crude oil is very viscous at room temperature and is pre-heated within a beaker that is placed inside an oven at 80 °C to ease its transfer prior to the upgrading reaction.


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2.2 Synthesis of supported Ni catalysts Supported Ni catalysts are prepared via the modified polyol method. For the preparation of Ni/KB catalyst, typically, a 250 mL three-neck round-bottom flask is added with 50 mL EG, 0.2908 g Ni(NO3)2·6H2O and 0.2348 g KB. The nominal loading of Ni metal is set to be 20 wt %. After dispersing the mixture by ultrasound for 15 min, the flask is sealed, stirred and purged with nitrogen for another 30 min. Afterwards, the flask is placed inside an oil bath and heated to 200 °C. When the temperature stabilizes at 200 °C, 0.2 g NaBH4 is rapidly added to the flask. The reaction system is kept for another 2 h and then the flask is removed from the oil bath to cool down to room temperature. The resulted products are separated by centrifugation, washed with ethanol and distilled water (18 MΩ), and dried in N2 flow at room temperature. The other supported Ni catalysts are synthesized in the same way but replacing the KB with the same amount of CNT, GNP and zeolite, respectively. 2.3 Catalyst characterization X-ray powder diffraction (XRD) is performed to characterize the crystal phase of the samples. The diffraction patterns are recorded on a Bruker-AXS Microdiffractometer (D8 ADVANCE) using Cu Kα radiation source (λ=1.54 Å). Scanning angles for all samples are set in the 2θ range of 10~90° with a step interval of 2.25 °/min. Peaks are indexed according to the database established by Joint Committee on Powder Diffraction Standards (JCPDS). The morphology and structure of the NP catalysts are also characterized by transmission electron microscopy (TEM, JEOL JEM-2100F) with an accelerating voltage of 200 kV. For specimen preparation, one droplet of the suspension is dropped onto a copper grid coated with carbon film


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(400 mesh, TAAB). The grid is dried at room temperature protected under nitrogen flow to avoid oxidation. Nitrogen adsorption–desorption measurements are conducted at liquid nitrogen temperature of 77 K on a Micromeritics TriStar II surface area and porosity analyzer. Specific surface area (SSA) is calculated using the Brunauer–Emmett–Teller (BET) method, whereas single point total pore volume (PVtotal) is measured by using the quantity of gas adsorbed at P/P0 of 0.99. Total mesopore volume (PVmeso) is determined by the desorption branch of the isotherms using the Barrett–Joyner–Halendar (BJH) method, while total micropore volume (PVmicro) is obtained using the Horvath–Kawazoe method. 2.4 Upgrading of heavy crude oil The upgrading reactions are carried out in a 4564 Parr Mini Reactor with a volume capacity of 160 mL. Typically, 30 g heavy crude oil and 0.1 g catalyst are loaded to the reactor. After being sealed tightly, the reactor is purged with hydrogen or nitrogen for 30 min and then pressurized to 11 bar with the corresponding gas. The reactor is then heated up from room temperature to the designated reaction temperatures. A final pressure in the range of 20-40 bar is reached. The reaction system is held for different reaction periods and cooled down naturally after the reaction. During the whole reaction period, the stirring torque is maintained at half of the full power. Finally, the oil samples are taken out and stored in glass bottles for further analysis. 2.5 Analysis of oil samples The rheological properties of heavy oil samples are measured on the Anton Paar MCR 302 Rheometer at 30 °C and atmospheric pressure. In the viscosity-shear rate curves, 25 measuring


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points are taken with the shear rate in the range of 1-100 s−1. Viscosity data at the shear rate of 30 s−1 is taken to calculate the ratio of viscosity reduction, which is based on the equation

Δߟ =

(ߟ଴ − ߟଵ )ൗ ߟ଴ × 100%

where Δߟ is the ratio of viscosity reduction; ߟ଴ and ߟଵ are the viscosities of the original and upgraded oil, respectively. True boiling point (TBP) distribution is determined on an AC Analytical Controls hightemperature simulated distillation (HT-SimDis) instrument modified with an Agilent 6890N gas chromatograph (GC) in accordance with the ASTM D7169 standard test method. An AC capillary GC column (5 m × 0.53 mm × 0.17 µm) is equipped on the GC. Cumulative mass as a function of the boiling point up to 750 °C of the feedstock is measured. Carbon disulfide is used as the solvent to dissolve the oil sample with concentration in the range of 1-2 wt %. The original and upgraded crude oil samples were analyzed by negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS, Bruker). Typically, 10 mg oil sample was thoroughly dissolved in 1 mL toluene, and 20 µL of this solution was taken out and diluted with 1 mL toluene/methanol (1:3, v/v) mixture. Subsequently, 20 µL ammonium hydroxide (28 %) solution was added to the 1 mL oil sample solution and mixed for further analysis. The MS analysis was carried out on a Bruker Apex-ultra FT-ICR mass spectrometer with a 9.4 T superconducting magnet. Sample solutions were infused via an Apollo II electrospray source at 180 µL/h with a syringe pump. The main operating conditions with regard to the negative-ion formation were: emitter voltage, 3.3 kV; capillary column introduce voltage, 3.8 kV; and capillary column end voltage, -320 V. Ions were


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accumulated for 0.1 s in an hexapole with 2.4 V direct current voltage and 400 Vp-p of radiofrequency (RF) amplitude. The optimized mass for Q1 was 200 Da. An argon-filled hexapole collision pool were operated at 5 MHz and 450 Vp-p of RF amplitude, in which ions were accumulated for 1.0 s. The extraction period for ions from the hexapole to the ICR cell was set to 1.1 ms. The RF excitation was attenuated at 12.5 dB and used to excite ions over the range of 150–800 Da. Spectra consisting of 4 M data set were acquired. A number of 32 scan FT-ICR data sets were co-added to improve the signal-to-noise ratio. Mass spectra were internally calibrated using an extended homologous alkylation series (molecular ions of aromatic hydrocarbons and thiophenes) of high relative abundance in a mixed heavy oil within the mass range of 200–800 Da. Data analysis was performed using custom software and the procedure has been described in detail elsewhere.37 The compounds were characterized by class (numbers of N, O, and S heteroatoms), type (rings plus double bond equivalence, or DBE), and carbon number. Each class species and their isotopes with different DBE and carbon number values were searched within a set ±0.001 Kendrick mass defect tolerance. Contents of C, H, O, N and S in the oil samples were measured on different instruments. C and H contents were determined on the Elementar (Germany) VARIO EL cube instrument. O content was examined on the Elementar (Germany) rapid OXY cube oxygen analyzer. N and S contents were analyzed on the Analytik Jena (Germany) Multi EA 3100 Micro-Elemental Analyzer. 3. Results and Discussion 3.1 Catalyst Characterization The crystal phase structure of four supported catalysts and their corresponding supports is characterized by XRD. Figure 1 compares the XRD patterns of supported Ni samples with the


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pristine supports. In all the four samples, apart from the diffraction peaks of supports, newly appeared peaks at 2θ of 44.5°, 51.8° and 76.4° of the supported samples match well with the cubic Ni phase (JCPDS No. 04-0850) and can be indexed as (111), (200) and (220) lattices, respectively. This confirms that the Ni(NO3)2 precursor has been reduced by NaBH4 to form metallic Ni phase, and the metallic Ni phase is well preserved from being oxidized as no NiO phase is detected. Additionally, the broad peaks of Ni phase in all supported samples imply a relatively small crystal size and the similar peak intensities suggest that the Ni NPs in four samples have close crystal sizes. Based on the Scherrer equation, the mean crystal size of four supported samples is calculated to be around 12 nm using the diffraction peaks at 2θ of 44.5° and 51.8°. Table S1 in the Supporting Information shows the detailed crystal sizes for all the supported samples.


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Figure 1. XRD patterns of the (a) KB and Ni/KB, (b) CNT and Ni/CNT, (c) GNP and Ni/GNP, and (d) zeolite and Ni/zeolite samples. TEM characterization is performed to observe the morphology and dispersion of the supported catalysts. Our previous work35 and Figure S1 in the Supporting Information illustrate typical TEM images of KB, CNT, GNP and zeolite. KB carbon (Figure S1a) presents the amorphous appearance of aggregated nanopellets with sizes of tens of nanometers, and CNTs (Figure S1b) display multiwalled tubular structure with outer diameter in the range of 10-20 nm. The stacked platelet morphology of GNPs (Figure S1c) on the micron scale is also observed. Zeolite in Figure S1d shows porous aggregates in micron size. After Ni NPs are deposited on these supports, their TEM images are shown in Figure 2. Note that the Ni NPs and carbon or zeolite have different contrast in the TEM image, where the more dark particles are the Ni particles. Accordingly, it is clear that the Ni NPs are well dispersed on the KB carbon (Figure 2a) with small and uniform particle size; while for the Ni/CNT (Figure 2b), Ni/GNP (Figure 2c) and Ni/zeolite (Figure 2d) catalysts, the Ni NPs are anchored on the surface and to certain extent aggregated relative to the Ni/KB sample. The good dispersion and small size of Ni/KB can provide this catalyst with improved active sites and accessibility compared to the other supported catalysts.


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Figure 2. TEM images of the (a) Ni/KB, (b) Ni/CNT, (c) Ni/GNP, and (d) Ni/zeolite samples. Furthermore, N2 adsorption–desorption measurements are carried out to determine the SSA and PV of the supported catalysts and pristine supports. Figure 3 shows the N2 adsorption–desorption isotherms of four supported samples and their corresponding supports. In Figure 3a, 3b and 3c, all the isotherms of KB, Ni/KB, CNT, Ni/CNT, GNP and Ni/GNP exhibit type-IV isotherms according to the IUPAC classification. The hysteresis loops in the medium P/P0 range represent


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mesoporous characteristics for all the samples. The isotherms also experience a sharp rise at high relative pressure (P/P0) region, suggesting the presence of macropores in these carbon supports and supported catalysts. Differently, the isotherms of zeolite and Ni/zeolite in Figure 3d display the characteristics of type-I isotherms. The sharp rise of isotherms at low P/P0 range indicates the presence of large amounts of micropores (Ni/CNT>Ni/GNP>Ni/zeolite. Synergistic effect is demonstrated by the further enhanced upgrading activity of Ni/KB relative to KB. Fourier transform ion cyclotron resonance mass spectrometry and elemental analysis confirm that the viscosity reduction of heavy crude oil is attributed to the decomposition of carboxylic acids, and the Ni/KB catalyst can effectively catalyze this decomposition process. Therefore, the carbon-supported Ni catalysts can be potentially applied in the in-situ upgrading and recovery of heavy crude oil, especially for oils with high oxygen content. Acknowledgement The authors thank Dr. Anne Hoff, Statoil ASA, for supplying the heavy crude oils used in this study. We also thank State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing for accessing the facilities, in particular Prof. Yongmei Liang for the HTSimDis analysis and Prof. Xuxia Liu for the elemental analysis. We are also grateful to Prof. Vidar Folke Hansen, University of Stavanger, for the TEM characterization. The authors acknowledge the Research Council of Norway and the industrial partners; ConocoPhillips Skandinavia AS, BP Norge AS, Det Norske Oljeselskap AS, Eni Norge AS, Maersk Oil Norway AS, DONG Energy A/S, Denmark, Statoil Petroleum AS, ENGIE E&P


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NORGE AS, Lundin Norway AS, Halliburton AS, Schlumberger Norge AS, Wintershall Norge AS of The National IOR Centre of Norway for financial support. Supporting Information. Calculated average crystal sizes of four supported Ni (Table S1), TEM images of the four supports (Figure S1), TBP distribution curves of oil samples upgraded for different reaction time (Figure S2), upgraded in H2 and in N2 (Figure S3), and upgraded with four support catalysts (Figure S4), viscosity reduction ratios with different supported catalysts (Figure S5), broadband mass spectra of different oil samples (Figure S6), DBE versus carbon number distribution of N1 (Figure S7), N1O1 (Figure S8), N1S1 (Figure S9), O1 (Figure S10), O1S1 (Figure S11), O2 (Figure S12), and O2S1 (Figure S13) class species in different oil samples References 1. Shah, A.; Fishwick, R.; Wood, J.; Leeke, G.; Rigby, S.; Greaves, M., A review of novel techniques for heavy oil and bitumen extraction and upgrading. Energy Environ. Sci. 2010, 3 (6), 700−714. 2. Zhao, D. W.; Wang, J.; Gates, I. D., Thermal recovery strategies for thin heavy oil reservoirs. Fuel 2014, 117, 431−441. 3. Guo, K.; Li, H.; Yu, Z., Metallic nanoparticles for enhanced heavy oil recovery: Promises and challenges. Energy Procedia 2015, 75, 2068−2073. 4. Guo, K.; Li, H.; Yu, Z., In-situ heavy and extra-heavy oil recovery: A review. Fuel 2016, 185, 886−902. 5. Hashemi, R.; Nassar, N. N.; Almao, P. P., Nanoparticle technology for heavy oil in-situ upgrading and recovery enhancement: Opportunities and challenges. Appl. Energy 2014, 133, 374−387.


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6. Yusuf, A.; Al-Hajri, R. S.; Al-Waheibi, Y. M.; Jibril, B. Y., In-situ upgrading of Omani heavy oil with catalyst and hydrogen donor. J. Anal. Appl. Pyrol. 2016, 121, 102−112. 7. Ren, R. L.; Liu, H. C.; Chen, Y.; Li, J.; Chen, Y. L., Improving the aquathermolysis efficiency of aromatics in extra-heavy oil by introducing hydrogen-donating ligands to catalysts. Energy Fuels 2015, 29 (12), 7793−7799. 8. Li, J.; Chen, Y.; Liu, H.; Wang, P.; Liu, F., Influences on the aquathermolysis of heavy oil catalyzed by two different catalytic ions: Cu2+ and Fe3+. Energy Fuels 2013, 27 (5), 2555−2562. 9. Cao, Y. B.; Zhang, L. L.; Xia, D. H., Catalytic aquathermolysis of Shengli heavy crude oil with an amphiphilic cobalt catalyst. Pet. Sci. 2016, 13 (3), 463−475. 10. Wang, J.; Liu, L.; Zhang, L.; Li, Z., Aquathermolysis of heavy crude oil with amphiphilic nickel and iron catalysts. Energy Fuels 2014, 28 (12), 7440−7447. 11. Abdrafikova, I. M.; Kayukova, G. P.; Petrov, S. M.; Ramazanova, A. I.; Musin, R. Z.; Morozov, V. I., Conversion of extra-heavy Ashal’chinskoe oil in hydrothermal catalytic system. Petrol. Chem. 2015, 55 (2), 104−111. 12. Junaid, A. S. M.; Rahman, M. M.; Rocha, G.; Wang, W.; Kuznicki, T.; McCaffrey, W. C.; Kuznicki, S. M., On the role of water in natural-zeolite-catalyzed cracking of Athabasca oilsands bitumen. Energy Fuels 2014, 28 (5), 3367−3376. 13. Junaid, A. S. M.; Street, C.; Wang, W.; Rahman, M. M.; An, W.; McCaffrey, W. C.; Kuznicki, S. M., Integrated extraction and low severity upgrading of oilsands bitumen by activated natural zeolite catalysts. Fuel 2012, 94 (1), 457−464.


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Graphical Abstract 339x211mm (96 x 96 DPI)


The Effect of Carbon-Supported Nickel Nanoparticles in the Reduction

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