Improving the Aquathermolysis Efficiency of Aromatics in Extra-Heavy

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Improving the Aquathermolysis Efficiency of Aromatics in Extraheavy Oil By Introducing Hydrogen-donor Ligands to Catalysts Ruilin Ren, Huachao Liu, Yu Chen, Jian Li, and YanLing Chen Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.5b01256 • Publication Date (Web): 02 Nov 2015 Downloaded from http://pubs.acs.org on November 2, 2015

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Energy & Fuels

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Improving the Aquathermolysis Efficiency of Aromatics in

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Extra-heavy Oil By Introducing Hydrogen-donor Ligands to

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Catalysts

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Ruilin Rena, Huachao Liua, Yu Chena, Jian Lib ,Yanling Chena,b*

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a

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Resources of Ministry of Education, China University of Geosciences, Wuhan 430074, PR China

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*Corresponding author: Tel: +86-13886113362; Fax: +86-027-87801763.

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E-mail address: [email protected] (Y. Chen).

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Postal address: Faculty of Materials Science and Chemistry, China University of Geosciences,

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Faculty of Materials Science and Chemistry, bthe Key Laboratory of Tectonics and Petroleum

Wuhan 430074, PR China

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ACS Paragon Plus Environment

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Abstract

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We develop a new type of catalyst, dimethylbenzene sulfonic copper, which composed by

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hydrogen-donative ligands and a Cu2+ center for catalytic aquathermolysis viscosity reduction of

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extra-heavy oil. The component variations of extra-heavy oil before and after aquathermolysis

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are designedly analyzed via elemental analysis (EL), 1H nuclear magnetic resonance (1H-NMR)

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and gas chromatography-mass spectrometry (GC-MS). An optimal viscosity reduction value of

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81.47% can be achieved using 0.3 wt% catalyst at 240℃for 24h, where 8.28 wt% of the heavy

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components, namely as resins and asphaltenes, are converted to light saturates and aromatics.

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The improved viscosity reduction efficiency can be ascribed to the hydrogen donating role from

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the dimethylbenzene sulfonic ligands. The active hydrogens, not only generated from these

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ligands but originated from the dehydrogenation of naphthene aromatics during the

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aquathermolysis, are capable of tackling the heavy components or participating in the

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hydrogenation of heavy components for heavy-light conversion, leading to enhanced visbreaking

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effect and improved oil quality. The results enrich the catalytic mechanism of aquathermolysis

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which can guide the design and development of new efficient catalysts.

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Keywords: Dimethylbenzene sulfonic copper; Catalytic aquathermolysis; Hydrogen-donating

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effect; Heavy-light conversion; Viscosity reduction.

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1. Introduction

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Catalytic aquathermolysis is a promising technology for chemically mining extra-heavy oil.

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Developing low cost, efficient and universal catalysts as well as understanding their catalytic

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mechanisms are of essential importance for reducing the viscosity of extra-heavy oil to facilitate

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field mining. Since the first concept of aquathermolysis proposed by Hyne et al.1 in 1982,

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numerous efforts have been attempted to develop appropriate catalysts, majorly transition metal

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ion coordinates, and to explore the possible catalytic viscosity-reduced mechanisms in

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aquathermolysis2-13. Many new type of catalysts have been reported for reducing the viscosity of


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extra-heavy oil, including mineral, water-soluble catalyst, oil-soluble catalyst, dispersed catalyst 2.

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Although the reported catalysts exhibit improved viscosity reduction value comparing with bare

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aquathermolysis, however, most of them failed to meet the industrial requirements for field

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mining of extra-heavy oil.

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The viscosity reduction of heavy or extra-heavy oils in a typical aquathermolysis process is due to

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the cleavage of the C-R (R =S, N, O, etc.) bonds14, which will generate large amounts of free

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radicals. However, these free radicals may repolymerize and lead to the viscosity regress after

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reaction. It has been recognized that, introducing hydrogen donors, such as tetralin15, can inhibit

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the generated free radicals in coal liquefaction and residuum hydrocrackings. This concept has

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been naturally employed to deal with the catalytic aquathermolysis of heavy or extra-heavy oil.

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Many types of hydrogen donors, involving formic acid16,17, methylbenzene18,19, tetralin20-23, and

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methane24-30, have been utilized to couple with different types of catalysts for aquathermolysis of

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heavy oils. Chen et al.18 has proven that, using 0.8 wt% of toluene as additive and 0.2 wt% of

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ammonium molybdate as catalyst, the viscosity reduction value could achieve 85%. Ovalles et

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al.26 demonstrated that methane, as the hydrogen donor (4.8 MPa), in conjugation with a dispersed

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molybdenum catalyst(250 ppm) at 410 °C, leading to an increase of 7 degrees in the API gravity,

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16% of reduction in sulfur content, and 55% conversion of the >500°C fraction with respect to the

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original crude oil, which was also testified by Li et al.25. The hydrogen donating mechanisms of

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these hydrogen donors were sequentially discussed.18,22,29,31-32 In general, a hydrogen donor not

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only serves as solvent to dilute the macromolecular radicals but mitigates the collision of free

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radicals and the condensation of heavy components, which is beneficial for decreasing the

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viscosity of heavy oils to a large extent. However, adding excessive hydrogen donors, either in


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fine or large amount, would of course result in technical complexity in field oil exploration, and

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may cause health, environmental or safety issues (HSE).

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To simultaneously take account of both the catalytic function of the transition metal center and the

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hydrogen-donating function of the hydrogen donors, it is not hard to speculate that if we can

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synergistically couple these two functions in one catalyst molecule. Inspired by this, here we

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designed a new type of catalyst (dimethylbenzene sulfonic copper). Through the elemental

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analysis (EL), 1H nuclear magnetic resonance (1H-NMR) and gas chromatography-mass

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spectrometry (GC-MS) characterizations, we emphatically analyzes the changes of aromatic

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hydrocarbons which contain the structure parameters and the compositions before and after

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reaction. The results show that the naphthene aromatics which have the potential

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hydrogen-donating capability could be generated in the catalytic aquathemolysis process. While in

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the presence of the new catalyst, the naphthene aromatics could donate hydrogen by aromatization.

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Thus, the hydrogen-donating effect achieved the goal to upgrade the heavy oil and to reduce the

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viscosity. The current study enriches the mechanism of catalytic aquathermolysis which can be

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used to guide screening more efficient catalyst.

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2. Experimental

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2.1. Preparation of catalysts

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Preparation of catalyst: 0.025mol copper (II) sulfate was dissolved in distilled water and an

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aqueous solution of sodium hydroxide was dropwisely added into the water until a pale blue

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slurry was completely formed under stirring condition. When the pH of the mixture was equal to

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7 approximately, 0.10 mol dimethylbenzene sulfonic acid was placed into a beaker in 100°C

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oil-bath for 20 minutes. Then the prepared slurry was added into the beaker under the condition


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of stirring and heated for 2h. The product was cooled to room temperature. Upon concentrating

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and drying in vacuum at 60°C for 24 h, dimethylbenzene sulfonic copper was obtained.

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2.2. Experiment of catalytic aquathermolysis

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The extra-heavy oil with the viscosity of 178,000 mPa·s at 70°C and the density of 0.9915 kg/m3

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at 20℃ extracted from Shengli Oilfield of China was selected in the experiment of catalytic

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aquathermolysis. All experiments were conducted with 180g oil samples with the ratio of

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oil/water of 8:2, and the water pH value of approximately 7~8. The quality of the catalyst is 0.3

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percent of the crude oil quality (the optimized conditions were confirmed after a series of tests).

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The aquathermolysis was carried out in a 500 mL FYX-0.5 high pressure reactor, and the initial

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pressure was kept at about 3 MPa by aerating N2. Then the reaction proceeded at 240°C for 24h.

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The viscosity of oil samples I (crude heavy oil prior to reaction), oil sample II (crude heavy oil

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after aquathermolysis without catalyst), oil sample III (the post-reacted crude heavy oil sample

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with the as-prepared catalyst) were tested using the BROOKFIELD DV-2+ programmable

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Viscometer at 70°C. The viscosity reduction values (Table1) obtained were calculated by ∆ η =

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((η0 – η)/ η0) × 100%, where η0 (mPa·s) is the viscosity of extra-heavy oil, and η (mPa·s) is the

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viscosity of the oil samples after reaction9.

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2.3. Separation of four group compositions

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Four group compositions including the saturate hydrocarbons, aromatic hydrocarbons, resins, and

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asphaltenes of the oil samples were separated by a chromatography column according to the

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Industrial Specification of China Petroleum Standard (SY/T5119)33. Firstly, about 1g oil sample

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was dissolved into 100ml n-hexane through ultrasonic, and stood for 12h to precipitate asphaltene.

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After filtering out asphaltene, the filtrate was separated by chromatography column(1.5cm in the


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diameter, 40cm in the length) filled with the active alumina (activated at 450℃ for 6h, with 1

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wt% water). Saturated hydrocarbons, aromatics and resins were eluted out respectively by 120ml

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n-hexane solution, 120ml n-hexane mixed with dichloromethane in the volume ratio of 1:1, and

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100ml dichloromethane mixed with methanol in the volume ratio of 1:1. (Fig. S1. Support

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information). The water in oil samples was already removed before and after reaction. Firstly, the

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sample oil was stirred and allowed to separate into layers after reaction, then the free water was

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decanted. The oil sample was dehydrated by ultrasonic crude rapid dehydration instrument

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(BT-350, Hubei Broad Electronics Co., Ltd., China). The water contents of the dehydrated

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samples were determined via the Karl Fischer (Coulomb) SF101 Tester (Precision Instrument Co.,

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Ltd., Taizhou, Jiangsu province, China) following the GB/T1146-2009 standard of People's

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Republic of China. The measured water contents of the samples, either before or after the catalytic

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aquathermolysis, are all below 0.002%. The content of four group compositions was obtained by

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weight (Table1). Then, saturate hydrocarbons and aromatic hydrocarbons were prepared in a

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solution of n-hexane, ready for the GC-MS analysis.

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2.4. Measurement and Characterization

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2.4.1. Elemental analysis

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Organic elements (C, H, N, S) of the aromatics, resins and asphaltenes before and after reaction

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were detected by an elemental analyzer (EL, VARIO EL-2).

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2.4.2. 1H-NMR analysis

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The aromatics in three oil samples before and after reaction were measured by 1H nuclear

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magnetic resonance spectroscopy (1H−NMR, Bruker ARX300), using CDCl3 as solvent,

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containing TMS as internal reference.


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2.4.3. GC-MS analysis

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Saturates and aromatics in three oil samples before and after reaction were analyzed by using gas

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chromatography-mass spectrometer (GC-MS, Agilent 7890A/5975C). Saturates was injected in

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the GC injection port (300°C) and operated with the splitless mode. GC oven was kept at the

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temperature of 80°C for 3 minutes and then kept the incremental rate of 3°C /min until the

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temperature became as high as 230°C. After that, the temperature increment was maintained at

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2°C /min until it rose to 310°C, at which the reaction was kept for 15 minutes. The MS was

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operated by using electron impact ionization with the default setting. While aromatic

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hydrocarbons were injected into the GC injection port (290°C) and operated with the splitless

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mode. The GC oven was programmed to retain the temperature at 60°C for 3 minutes and then

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kept the incremental rate of 3°C /min until the temperature was up to 310°C. After that, the

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reaction was maintained for 15 minutes sequentially. The MS was operated by using electron

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impact ionization with the default setting.

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3. Results and discussion

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3.1. Aquathermolysis experiments

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Table 1 shows the the changes of four components, viscosity, viscosity reduction value and

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density and in extra-heavy oil. The results are the average of three parallel experiments. The

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viscosity reduction value of oil sample Ⅱ was only 32.93%, compared with the oil sampleⅠ.

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But in the participation of catalyst, the viscosity reduction value reached 81.47%. Obviously,

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only a small part of heavy components cracked in aquathermolysis for the oil sample Ⅱ. For the

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oil sample Ⅲ, the intensive conversion reaction occurred in the heavy component in the catalytic

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aquathermolysis. This may indicate that light components have been generated through this


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cleavage reaction.

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3.2. Elemental analysis before and after reaction

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Organic elements (C, H, N, S) of aromatics, resins and asphaltenes in the three types of oil

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samples were measured by EL as shown in Table 2. Table 2 also shows the molar H/C ratio of

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each component before and after the reaction to compare with the crude oil after the catalytic

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aquathermolysis reaction.

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The mass balance of N and S were calculated according to the equation Nt= Wc∗Mc, where Wc is

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the group composition mass fraction and Mc is the N, S elemental content in the group

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compositions. Thus we obtained the total content (Nt) per 10000g oil samples. Table S1 and Table

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S2 (Supporting Information) show the results of N and S elemental content (weight ratio) in

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aromatics, resins, and asphaltenes of oil samples before and after the reaction. The saturates were

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ignored, because the separation of the four group compositions depends on the polar property.

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The decreased content of asphaltenes in oil sample Ⅱ indicates that a water-gas reaction may

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have taken place and a part of asphaltenes may have been cracked into the light component (the

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increased molar H/C ratio of aromatic hydrocarbon) based on the analysis of the data shown in

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Table 1 and Table 2. The remarkable content decrease of resins and asphaltenes in oil sample Ⅲ

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indicates that the catalyst has the ability to accelerate resins and asphaltenes to split into light

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components, leading to an increase of molar H/C ratio of aromatic hydrocarbon and a decrease of

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molar H/C ratio of asphaltenes and resins. It suggests that the catalyst is capable of accelerating

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the catalytic dehydrogenation of aromatics to generate more free radicals, and to impede the

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condensation polymerization of resins and asphaltenes.

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The variation tendency of mass balance of element N and S is similar to the data discussed above.


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This result further proves that the catalyst can catalyze the dehydrogenation reaction of aromatic

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species and thereby promote the heavy components into light components34,35.

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3.3. 1H-NMR analysis of the aromatic hydrocarbons before and after reaction

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The distributions of different hydrogen (HA(9.0-6.0), Hα(4.0-2.0ppm), Hβ(2.0-1.0ppm), and

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Hγ(1.0-0.5ppm)) (Table 3) were obtained based on different chemical shifts and integral area36.

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Using the improved Brown-Ladner methods with the Equations (1), (2), (3) and (4),37 the

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structure parameters of aromatic hydrocarbons such as aromaticity (fA), aromaticity condensation

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(HAU/CA), branching index (BI) and substitution rate of aromatic ring (σ) (Table 3) were

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calculated by the formula as shown in Supporting Information. 1H-NMR spectra of aromatic

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compositions are in Fig.S2.(Support information).

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Table 3 also shows the changes of fA , HAU/CA , BI and σ of all the samples before and after the

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reaction. It demonstrates that the decreased fA value of aromatic hydrocarbon is attributed to the

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aquathermolysis of the heavy components in the oil samples II. The aquathemolysis produced

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small molecules with a high molar H/C ratio that enter into the light components. The increased fA

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of aromatic hydrocarbon found only in the oil sample Ⅲ indicates that an aromatication reaction

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occurred. This reaction may be viewed as a hydrogen-donating reaction. However, this

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aromatication reaction takes place only in the presence of the prepared catalyst. The increment of

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the HAU/CA ratio indicates that no aromatic hydrocarbon condensation reaction occurred. The

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decrease of BI demonstrates that the branch of the side-chain of the aromatics may have fractured.

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The increase of σ shows that a substitution reaction occurred in the aromatic ring. This substitution

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reaction may be an effective way to terminate the active alkyl chains.

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The above analyses lead to the conclusion that the aromatic hydrocarbons not only quench the


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alkyl chain radicals via the substitution reaction on the aromatic ring but also function as a

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hydrogen donor via the aromatization reaction in the presence of the catalyst.

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3.4. GC-MS analysis of aromatic hydrocarbons before and after reaction

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Aromatization reaction of aromatic hydrocarbon provides an hydrogen source for the heavy

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components in the catalytic aquathermolysis, while the naphthene aromatic hydrocarbon is one of

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the ideal substances for hydrogen-donating . In order to find the source of the naphthene aromatics,

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biomarked compounds monoaromatic sterane and triaromatic sterane were selected for a

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comparative analysis using GC-MS because of their stable structures and their relationship to

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hydrogenationship and dehydrogenation in content change.38

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The biomarker monoaromatic steranes (m/z=253) (Fig.1) and triaromatic steranes (m/z =231)

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(Fig. 2) were extracted from the total ion chromatorgraphy of the aromatic hydrocarbons in the

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oil samples before and after the reaction. The compound identification of monoaromatic steranes

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and triaromatic steranes are shown in Table 439-42.

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As shown in Fig. 1 and Fig. 2, the content of monoaromatic sterane and triaromatic sterane in the

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oil sample II is increased, compared with the oil sample I. They were produced through the

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cracking and hydrogenation of heavy components in the extra-heavy oil. There was little

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monoaromatic sterane left in the oil sample III, and the content of triaromatic sterane was increased.

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This is attributed to the dehydrogenation reaction of monoaromatic sterane in the presence of the

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catalyst, which provides active hydrogen for the cracking reaction of heavy components, leading to

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the increase of triaromatic sterane.

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These results indicate that the aromatic side chains of aromatic hydrocarbon in the oil sample II

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were fractured during the catalyst aquathermolysis. For the oil sample III, the aromatic


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hydrocarbon with unsaturated side chains and tetralin was disappeared. This indicates that the

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catalyst not only catalyzed the cyclization but also promoted dehydrogenation aromatization

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reaction, leading to the increase of fA of aromatics in the oil sample III. This is consistent with the

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result shown in section 3.3.

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A detail assessment of the aromatic hydrocarbons was made to better understand the

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hydrogen-donating mechanism of aromatic hydrocarbon. The selected ion mass chromatogram

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(m/z=132) of aromatic compositions in three oil samples was investigated. As shown in Fig. 3, the

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aromatic substances with longer unsaturated side chains, such as 1-phenyl-1-nonyne,

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octynyl-benzene ethanol, (3, 7-dimethyl-octa-2, 6-dienyl)-benzene, etc. (Fig. 3a and Table 5)

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mainly exist in crude oil. The substances, such as 2-butenylbenzene and 1-methyl-1-propenyl-

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benzene, etc. (Fig.3.b & Table 5), contain shorter unsaturated side chains detected in the oil sample

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II. However, the above substances such as aromatics with unsaturated side-chain and tetralin were

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disappeared in the oil sample III (Fig. 3c and Table 5). The results of the ion mass chromatograms

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of naphthalenes (Fig. 4 and Table 6) obviously agree with the results above (Fig. 3). Furthermore,

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the abundance of n-alkane was increased, which indicates that a dealkylation reaction took place in

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the aromatic cycles. The iron mass chromatograms of n-alkane(m/z=85)

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support the conclusions.

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From the above analysis, it is clear that the naphthenic aromatic hydrocarbons come from three

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sources: the crude oil, the thermolysis of heavy components and the hydrogenation of polycyclic

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aromatic hydrocarbons. The naphthene aromatics donate hydrogen through aromatization in the

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catalytic aquathermolysis.


43,44

(Fig. 5) could also

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In order to avoid the impact of the product derived from the catalysts after aquathermolysis,

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experiments were performed in the absence of heavy oil. In the experiments, the hydrothermal

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reactions of the as-prepared catalyst was carried out at 240°C for 24h. Subsequently, the products

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were detected with GC-MS (Fig. S3, Supporting Information). The results (Table S3 which

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referred to Fig. S3, Supporting Information) show that the hydrocarbons discussed in the paper

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were not derived from these catalysts. This, in turn, proves that the hydrocarbons are derived from

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the heavy oil. We also added the thermal stability characterization of the as-prepared catalyst in

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the supporting information (Fig. S4). The TG-DSC curve shows that the catalyst is very stable at

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the aquathermolysis temperature (240°C), which suggest that under our experimental condition,

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the catalyst could maintain its structure and function. It can completely eliminate the influence of

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the catalyst on the composition and structure changes of components in extra-heavy oil.

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3.5 The transformation of various components and the hydrogen-donating mechanism in

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extra-heavy oil

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The above results show that, as the designed catalyst with hydrogen-donative ligands participating

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in the catalytic aquathermolysis of heavy oil, a satisfactory viscosity reducing rate can be achieved,

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which accompanies with the simultaneous dehydrogenation aromatization of naphthenic aromatics.

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Interestingly, although the addition amount of hydrogen donors are relatively higher than the

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introduced hydrogen-donative ligands in our experiments, the dehydrogenation aromatization

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could not even be observed. This motivate us to speculate realistic role that the hydrogen-donative

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ligands play during the aquathermolysis process. Considering the very few adding amount of the

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designed catalyst (0.3 wt%), we can only expect the active hydrogen split from the ligand should

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facilitate the initial stage of the catalytic viscosity reduction where partial of resins and


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asphaltenes can be dissociated to saturates and aromatics with lower C/H ratio. In particular, under

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our catalytic condition, the naphthenic aromatics such as polyaromatic steranes can successively

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undergo dehydrogenation aromatization process which could generate more active hydrogens for

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further attacking the intact heavy components in conjugation with the catalytic activity of the Cu2+

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centers. Fig.6 shows the dehydrogenation aromatization reaction45,46 of naphthenic aromatics

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occurred in catalytic aquathermolysis. Firstly, Cyclization reactions of aromatic hydrocarbons with

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the unsaturated side chains occurred and generated into naphthenic aromatic hydrocarbons. Then

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through further catalytic reaction, the naphthenic aromatics ’aromatization reaction happened and

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produced active hydrogen. This dehydrogenation aromatization reaction provides a more active

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hydrogen source for the resins and asphaltenes. At last, those active hydrogen entered into the

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heavy components. On one hand, they can participate in the hydrogenation reaction of the heavy

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components, on the other hand can inhibit the condensation of heavy components, such a

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self-assistant process promising a continuous viscosity reduction efficiency of heavy oil.

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4. Conclusion

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Extra-heavy oil, one of the great potential hydrocarbon resources, contains many kinds of

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substances with potential hydrogen-donating ability. Stimulated by the new catalyst, the quality

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of the extra-heavy oil can be significantly improved and the viscosity can be remarkably reduced

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by making full use of the abundant potential hydrogen donating source of the extra-heavy oil

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itself. It is of tremendous practical significance to further study the aquathermolysis viscosity

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reduction of extra-heavy oil through catalytic thermal cracking of autonomous hydrogen.

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Acknowledgements

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This work was supported by the National Natural Science Foundation of People’s Republic of

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China(No.51174179)and the Key Laboratory of Tectonics and Petroleum Resources of Ministry

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of Education(China University of Geosciences).

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

406 407 408 409 410

Page 18 of 30

Tables

Table 1 Four group compositions, viscosity, viscosity reduction value and density in different oil samples before and after reaction Oil samples Group compositions (wt %)

Oil sample Ⅲ

Saturates

18.82±0.05

20.48±0.03

22.53±0.03

25.77±0.06

26.97±0.05

30.34±0.05

resins

31.27±0.05

31.83±0.07

27.89±0.07

24.14±0.01

20.72±0.01

19.24±0.01

178,000

119,384

32900

0.9915

0.9558

0.9017

—

32.93%

81.47%

Asphaltane Viscosity(at 70 C) mPa·s ∆η

Oil sample Ⅱ

Aromatics

0

Density (at 200C)

Oil sample Ⅰ

Kg/m3

411

412 413


Page 19 of 30

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

414 415 416

Table 2 Percentage of hydrogen，carbon，nitrogen , sulfur elements and molar H/C ratio of aromatics, resins and asphaltenes in different oil samples Group

compositions

Aromatics

Resins

Asphaltenes

85.591

82.163

82.013

10.843

9.459

8.268

0.739

1.877

2.094

S

2.557

1.898

2.596

NH/NC

1.52

1.381

1.21

C

85.527

83.968

83.71

H

11.237

9.858

8.379

0.753

1.887

2.125

S

2.606

2.053

2.528

NH/NC

1.577

1.409

1.201

C

86.652

82.959

83.573

10.885

10.057

8.458

C H Oil sample Ⅰ

Oil sample Ⅱ

N

N

H Oil sample Ⅲ

N

(%)

(%)

(%)

0.814

1.841

2.187

S

2.720

2.039

2.496

NH/NC

1.507

1.455

1.215

417 418 419 420 421 422


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

423 424 425

Page 20 of 30

Table3 1H-NMR analysis of aromatic compositions and aromatic structure parameters of the aromatic compositions in different oil samples Aromatics of Oil sample Ⅰ

Aromatics of oil sample Ⅱ

Aromatics of oil sample Ⅲ

13.89

16.07

16.79

54.85

53.89

53.64

22.92

21.56

20.44

HA

8.34

8.47

9.13

fA

0.303

0.279

0.315

HAU/CA

0.766

0.934

0.838

BI

0.222

0.205

0.193

σ

0.454

0.487

0.479

Aromatic hydrocarbons Hα composition

Hβ Hγ

(%)

426


Page 21 of 30

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

427 428 429

Table 4 The identification of monoaromatic sterance (m/z=253) and triaromatic sterance (m/z= 231) m/z

Peak

Chemical formula

Compounds

253

1

C22H32

C22 monoaromatic sterane (MAS)

2

C20H14

1,1-binaphthyl

3

C27H42

20R,5β C27 + 20R C27 dia MAS

4

C28H44

20S,5β C28 MAS

5

C29H46

20S,5β C29 + 20R,5β C29 MAS

6

C28H44

20S,5α C28 MAS

7

C29H46

20R,5β C29 + 20R,5α C29 MAS

8

C29H46

20R,5α C29 MAS

1

C20H20

C20 triaromatic sterane (TAS)

2

C21H22

C21 TAS

3

C26H32

20S,C26 TAS

4

C26H32 + C27H34

20R,C26 + 20S,C27 TAS

5

C28H36

20S,C28 TAS

6

C27H34

20R,C27 TAS

7

C28H36

20R,C28 TAS

231

430 431


Energy & Fuels

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432 433 434

Table 5 The identification of ion mass chromatogram (m/z=132) of the aromatic hydrocarbons before and after reaction Peak

Chemical formula

Compounds

1

C10H12

2-butenylbenzene

2

C10H12

1-butenylbenzene

3

C10H12

o-isopropenyltoluene

4

C10H12

2-methylallylbenzene

5

C10H12

2-methyl-1-propenylbenzene

6

C10H12

2-butenylbenzene

7

C10H12

1-methyl-1-propenylbenzene

8

C10H12

1,2,3,4-tetrahydronaphthalene

9

C11H14

1,2,3,4-tetrahydro-1-methylnaphthalene

10

C11H14

2,3,-dihydro-4.7-dimethyl-1H-indene

11

C11H14

2-methyl-1-butenyl-benzene

12

C12H16

1,2,3,4-tetrahydro-1,4-dimethylnaphthalene

13

C12H12

1,4-cyclohexadien-1-ylbenzene

14

C13H16O

2-benzyllidenecyclohexanol

15

C12H15N

1,2,3,4-tetrahydro-2-naphthyl-1-aziridine

16

C14H20

1,4-dimethyl-2-cyclohexylbenzene

17

C13H14

2,3,6-trimethylnaphthalene

18

C15H24O

butylated hydroxytoluene

19

C15H20

1-phenyl-1-nonyne

20

C14H16O

1,2-bis(1-buten-3-yl)-benzene

21

C16H22O

octynyl-benzeneethanol

22

C14H20

1,2,3,4-tetrahydro-5,6,7,8-tetramethyl-naphthalene

23

C16H22

(3,7-dimethyl-octa-2,6-dienyl)-benzene

24

C15H18O

3a,9b-dimethyl-1,2,3a,4,5,9b-hexahydrocyclopenta-naphthalen-3-one

25

C15H20

9-methyl-S-octahydroanthrancene

435 436


Page 22 of 30

Page 23 of 30

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Energy & Fuels

437 438

Table 6 The identification of naphthalene and its homologous series (m/z=128+142+156) m/z

peak

Chemical formula

Compounds

128

1

C10H8

naphthalene

142

2

C11H10

1-methyl-naphthalene + 2-methyl-naphthalene

156

3

C12H12

1-ethyl-naphthalene + 2-ethyl-naphthalene

4

C12H12

2,3-dimethyl-naphthalene + 1,4-dimethyl-naphthalene

5

C12H12

2,3-dimethyl-naphthalene + 1,3-dimethyl-naphthalene

6

C12H12

2,6-dimethyl-naphthalene

7

C12H12

1,2-dimethyl-naphthalene

439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466 467


Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

468 469 470 471 472 473 474 475 476 477 478 479 480 481 482 483 484 485 486 487 488 489 490

Figure captions Fig.1 Monoaromatic steranes ion mass chromatogram (m/z=253) of aromatic hydrocarbons (a. Aromatic hydrocarbons of crude oil sampleⅠ b. Aromatic hydrocarbons of oil sampleⅡ c. Aromatic hydrocarbons of oil sample Ⅲ) Fig.2 Triaromatic steranes ion mass chromatogram (m/z=231) of aromatic hydrocarbons (a. Aromatic hydrocarbons of crude oil sampleⅠ b. Aromatic hydrocarbons of oil sampleⅡ c. Aromatic hydrocarbons of oil sampleⅢ) Fig.3 The selected ion mass chromatogram (m/z=132) of aromatic compositions (a. Aromatic hydrocarbons of crude oil sampleⅠ b. Aromatic hydrocarbons of oil sampleⅡ c. Aromatic hydrocarbons of oil sampleⅢ) Fig.4 Naphthalene and its homologous series ion mass chromatograms (m/z=128+142+156) of aromatic compositions (a. Aromatic hydrocarbons of crude oil sampleⅠ b. Aromatic hydrocarbons of oil sampleⅡ c. Aromatic hydrocarbons of oil sampleⅢ) Fig.5 The ion mass chromatograms of alkanes (a. Saturate hydrocarbons of crude oil sampleⅠ b. Saturate hydrocarbons of oil sampleⅡ c. Saturate hydrocarbons of oil sampleⅢ) Fig.6 The dehydrogenation aromatization of aromatic hydrocarbons with the unsaturated side chains in catalytic aquathermolysis of super-heavy oil with viscosity reducer

491 492 493 494 495 496 497 498 499 500 501 502 503 504 505 506 507


Page 24 of 30

Page 25 of 30

508 509

Fig. 1

20000

c

2 8 7 6 5 43

Abundance

15000

1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

b

10000

5000

a

0 40

50

60

70

Time(min)

510


80

Energy & Fuels

511 512 513

Fig. 2

260000 240000 220000

5 4 7

200000

Abundance

1

6

160000

3

180000

2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 30

c

140000 120000 100000

b

80000 60000 40000

a

20000 0 60

70

Time(min)

514 515


80

Page 27 of 30

516 517 518

Fig. 3

6000 18

5000

7

4000

Abundance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

16

c

16 18

b

7

3000

6

8

12

9

10 11

13 14 15 17 20

2000

24

18 19 23 21

1000

a 25

34

5

16 15

12

8

0 10

15

20

25

30

Time(min)

519 520


35

40

Energy & Fuels

521 522 523

Fig. 4

200000

2

300000

7 6 5 4 3

150000

1

250000

100000 50000

Abundance

200000 0

2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 30

23

24

25

26

27

28

29

30

31

150000

100000

c

50000

b a

0 10

20

30

40

50

60

Time(min)

524


70

80

Page 29 of 30

525 526 527

Fig. 5

C 25

80000 C 21

C 17

60000

Abundance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

ph Pr

c

40000

b 20000

a 0

20

40

60

80

Time(min)

528 529 530 531 532 533 534 535 536 537 538 539 540 541 542 543 544 545 546 547 548 549 550 551


100

Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

552 553

Fig. 6

554 555 556


Page 30 of 30

Improving the Aquathermolysis Efficiency of Aromatics in Extra-Heavy

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