Journal Information
China Petroleum Processing and Petrochemical Technology
Included in the Science Citation Index(SCI)
Sponsor: Research Institute of Petroleum Processing, SINOPEC
Publisher: Editorial Office of China Petroleum Processing and Petrochemical Technology
Editor: Editorial Office of China Petroleum Processing and Petrochemical Technology
Editor in Chief: Member of Chinese Academy of Engineering, Wang Xieqing
Deputy Editor in Chief: Liu Hongzhou
ISSN 1008-6234
CN 11-4012/TE
Current Issue
30 September 2023 Volume 25 Issue 3
2023, 25(3):  0. 
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Contents of This Issue
Adsorption and Adsorption-Photocatalytic Degradation of VOCs Based on Carbon Materials
Li Ying, Zhang Hongxing, Tao Bin, Zhang Jianzhong, Li Jianzhe
2023, 25(3):  1-11. 
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Adsorption and the combination of adsorption and photocatalysis are prospective strategies for treating lowconcentration volatile organic compounds (VOCs). Behind the adsorption technology of VOC treatments are carbon-based materials with large surface areas and high VOC uptake. This review summarizes the research progress in carbon-based adsorbents and adsorbent-photocatalysts for VOC removal. Firstly, the VOC adsorption performances of various carbon materials, including activated carbon, activated carbon fiber, biochar, graphene and its derivatives, and carbon nanotubes, are summarized, and the adsorption mechanism of VOCs on carbon materials is analyzed. Then, the VOC adsorptionphotocatalytic properties of composites comprised of different carbon materials and photocatalysts are presented. Finally, perspectives on the adsorption and adsorption-photocatalysis of VOCs via carbon materials are proposed. This review provides an optimal reference for the research and development of adsorbents and adsorption-photocatalysts of VOCs.
Scientific Research
Spectral and Morphological Analysis of Graphene-Based Two-Dimensional Carbon Materials
Diao Yuxia, Xiang Yanjuan, Xin Mudi, He Wenhui, Xu Guangtong, Qiu Limei
2023, 25(3):  12-21. 
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This paper describes the spectral and morphological analysis of graphene, N-doped graphene, and graphene modified with functional groups. The similarities and differences in the surface and microstructure are characterized by infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. Compared with high-purity graphene, the introduction of functional groups leads to more defects in the two-dimensional structure. The quality of graphene, reflected by the intensity ratio of peak D and G modes in the Raman spectroscopy, is consistent with that observed by scanning electron microscopy and transmission  electron microscopy. The infrared spectra of graphene-based two-dimensional carbon materials are different from that of high-purity graphene, and the absorption peaks of the functional groups are obvious. The X-ray photoelectron spectroscopy results illustrate the diverse chemical states of carbon, and the atomic ratio of carbon to oxygen directly reflects the quality of the graphene-based materials. The results of electron microscopy and spectroscopic characterization of graphene samples provide an excellent basis for a wide range of applications in graphene production and quality control.
Properties of Durable Magnetorheological Elastomers
Wang Jing, Wei Yintao
2023, 25(3):  22-28. 
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Magnetorheological elastomers (MREs) are a type of intelligent material that can be actively controlled. However, the  ferromagnetic particles in MREs are large, meaning that MREs contain many holes, which degrade the mechanical properties and fatigue resistance of MREs. In this work, liquid nitrile butadiene rubber-phenolic resin microcapsules were added as a self-healing agent to an MRE. The microcapsules reduced the number of holes caused by ferromagnetic particles and improved the mechanical properties and fatigue resistance of MREs. The magnetorheological effect of the MRE was not affected and was similar to that of the MRE without the self-healing agent. Under 100% strain and with the same number of cycles, the crack growth rate of the MRE without the self- healing agent was approximately 236% faster than that of the corresponding MRE with the self-healing agent and the crack length was approximately 136% longer.
Engine Performance and Emission Characteristics of Cellulosic Jet Biofuel Blends
Liu Ziyu, Yang Xiaoyi
2023, 25(3):  29-36. 
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Aviation biofuels have the potential to reduce greenhouse gas emissions and improve engine performance. The aim of this study was to assess the suitability of various jet biofuel blends for use in a ZF850 jet engine. The effects of the blends on engine performance were assessed under various thrust output settings with respect to the thrust, thrust-specific fuel consumption, emission characteristics, exhaust gas temperature, acceleration and deceleration performance. Blending with catalytic hydrothermolysis jet (CHJ) fuel improved the combustion efficiency by reducing carbon monoxide and unburned hydrocarbon emissions and markedly reducing PM2.5 emissions. However, a slight reduction in thrust output was observed. Throughout the entire range of thrust output settings, the 10% CHJ fuel blend provided higher thrust, lower thrustspecific fuel consumption, and lower exhaust gas temperature. The CHJ fuel blends exhibited no significant effects on the deceleration performance, while the 5% and 15% blends caused a 0.4 s delay in the time required for complete acceleration. Global sensitivity analysis was conducted to better understand the effects of the fuel blends on engine performance and emission characteristics. This analysis identified the critical parameters of engine performance as engine-influence and fuel influence parameters and engine-influence and fuel-less influence parameters. The overall engine efficiency benefit was nonlinearly related to the blend ratio and thrust output. The results indicate that the use of CHJ fuel blends can improve engine efficiency if they comply with the engine design and control regulations.
Contact Angle Prediction Model for Underwater Oleophobic Surfaces Based on Multifractal Theory
Jiang Huayi, You Yanzhen, Hu Juan, Tian Dongmei, Qi Hongyuan, Sun Nana, Liu Mei
2023, 25(3):  37-48. 
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Traditional microstructure scale parameters have difficulty describing the structure and distribution of a rough material’s surface morphology comprehensively and quantitatively. This study constructs hydrophilic and underwater oleophobic surfaces based on polyvinylidene fluoride (PVDF) using a chemical modification method, and the fractal dimension and multifractal spectrum are used to quantitatively characterize the microscopic morphology. A new contact angle prediction model for underwater oleophobic surfaces is established. The results show that the fractal dimension of the PVDF surface first increases and then decreases with the reaction time. The uniformity characterized by the multifractal spectrum was generally consistent with scanning electron microscope observations. The contact angle of water droplets on the PVDF surface is negatively correlated with the fractal dimension, and oil droplets in water are positively correlated. When the fractal dimension is 2.0975, the new contact angle prediction model has higher prediction accuracy. The maximum and minimum relative deviations of the contact angle between the theoretical and measured data are 18.20% and 0.72%, respectively. For water ring transportation, the larger the fractal dimension and spectral width of the material surface, the smaller the absolute value of the spectral difference, the stronger the hydrophilic and oleophobic properties, and the better the water ring transportation stability.

Process Research
Oxidation of Fe-Cr-Ni Alloys in a Low Oxygen Partial Pressure Atmosphere to Mitigate Coke Formation
Wang Hongxia, Wang Guoqing, Zhang Lijun, Wang Shenxiang, Jia Jingsheng, Cui Lishan
2023, 25(3):  49-59. 
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Anti-coking oxide films were prepared on a 25Cr35Ni and 35Cr45Ni alloy surface under the low oxygen partial pressure atmosphere of a H2-H2O mixture. The composition and phase structure of the oxide films were analyzed by energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The anti-coking performance of a mini tube made of a HP40 (25Cr35Ni) alloy was evaluated on a bench scale pyrolysis and coking test unit. The results showed that the surface Fe and Ni content decreased after the oxidation of the two alloys in a low oxygen partial pressure atmosphere. The oxide films were mainly composed of MnCr2O4 and Cr2O3. The average mass of coke in the mini tube with oxide film decreased by 87% relative to that of a tube without an oxide film when the cracking temperature was 900 °C. The ethylene, propylene, and butadiene yields in the pyrolysis tests were almost the same for the mini tubes with and without an oxide film. The oxide film on the alloy surface effectively inhibited catalytic filamentous coke formation. An industrial test showed that the run length of the cracking furnace with the in-situ coating technology was significantly extended.

Synthesis of Sustainable Sulfur-Rich Copolymers as Mercury Sorbents at 130 °C Using Tung Oil as an Activator#br#
Lyu Ya, Zhang Sai
2023, 25(3):  60-70. 
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Sulfur-rich copolymers made through inverse vulcanization exhibit a wide range of potentially valuable applications, for example as adsorbents to capture mercury pollution. Among the diverse second monomers of the copolymers, vegetable oil is a renewable resource, and recycled cooking oils have an important role in saving natural products. However, they need relatively high temperatures (160–180 °C) to react with sulfur. To develop a low-temperature (130 °C) reaction process for non-conjugated vegetable oil, we incorporate a small amount of tung oil, which contains conjugated trienes that can produce highly active free radicals during reactions. A variety of analytical techniques (proton nuclear magnetic resonance and Fourier-transform infrared spectroscopy, differential scanning calorimetry thermogravimetric analysis, X-ray diffraction, and dynamic mechanical analysis) are used to characterize the chemical structures and physical properties of the copolymers. The addition of tung oil is found to significantly improve the thermal stability and mechanical properties of the copolymers. We also investigate the effect of different ratios of raw materials on the gel time, free sulfur content, glass transition temperature Tg, and degradation temperature of the copolymers. We find that increasing the amount of tung oil in the raw material mixture decreases the gel time and free sulfur content, but increases Tg and the degradation temperature. The copolymers exhibit a high adsorption capacity for mercury ions up to 33 mg Hg2+ per gram of adsorbent. These results demonstrate the feasibility of using sulfur-rich copolymers as effective mercury removal adsorbents, with the potential for further improvement by foaming the copolymers into porous materials.
Application and Regeneration of a Non-Aqueous System of Cu/HCl and DMF for the Oxidation of Hydrogen Sulfide in Natural Gas#br#
Wang Yingjie, Liu Siyuan, Wang Xuening, Liu Zhihao, Chen Hongyuan, Qiu Kui
2023, 25(3):  71-82. 
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A copper-based non-aqueous-phase desulfurization agent is prepared by adding CuCl2 to the solvent N,Ndimethylformamide (DMF). Static desulfurization experiments show that the agent has high efficiency. However, the desulfurization reaction leads to the formation of a copper sulfide precipitate. It is found that the addition of chloride ions in the form of hydrochloric acid or potassium chloride prevents the formation of copper sulfide, and elemental sulfur is precipitated instead. The efficient absorption of H2S by the Cu/HCl–DMF agent relies on the rapid coordination of Cu2+ with DMF, Cl−, and H2S molecules to form a [Cu(DMF)n−p(HS−)p(Cl−)m](2−p−m)+ complex. The desulfurization agent has a sulfur capacity of up to 9.81 g/L when used in static bubble desulfurization at atmospheric pressure. The system has low viscosity and good chemical and thermal stability. It can be rapidly regenerated through continuous oxidation. After five repetitions of the regeneration procedure, the sulfur capacity reaches more than 91% of the initial capacity, indicating the potential of the system for commercial applications.

Effect of Mixed Dispersants on Suppression of the Gel Effect during Aqueous Adiabatic Terpolymerization of AM, NaAA, and DMC
Yang Junfeng, Zhou Manli, Wang Meng
2023, 25(3):  83-91. 
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Gelation adversely affects the aqueous adiabatic terpolymerization of acrylamide (AM), sodium acrylate (NaAA), and 2-methacryloyloxyethyl trimethylammonium chloride (DMC). Here, the mixed dispersants sorbitan monooleate (Span 80) and polyoxyethylene sorbitan monooleate (Tween 80) were introduced to the terpolymerization system in an attempt to mitigate the gel effect. This enabled the preparation of high-performance amphoteric polyacrylamides, which were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. The influences of the dispersant type and content as well as the hydrophilic-lipophilic balance (HLB) on the gel effect were examined, and the mechanism underlying the suppression of the gel effect was considered. The obtained results indicated that the gel effect can be effectively mitigated using an aqueous adiabatic terpolymerization system containing mixed Span 80/Tween 80 dispersants at various contents. In particular, mixed dispersant contents of 0.6%–0.8% with HLB values of 5.06.0 afforded the optimal performance (e.g., high viscosity, fast aqueous dissolution time, and the like).

Catalyst Research
A Metal-free Polyimide Photocatalyst for the Oxidation of Amines to Imines
Zhou Yafen, Cheng Hong, Song Yu, Wang Qing, Zhao Wenjie, Chen Qilin, Zhou Limei, Xu Bin
2023, 25(3):  92-103. 
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Polyimide (PI) is an organic polymer material with good stability and diverse sources that has attracted widespread attention in the field of photocatalysis. In this study, a series of PI photocatalysts were synthesized by a thermal polymerization approach using pyromellitic dianhydride (PMDA) and various diamine monomers (melamine (MA), 4,4′-oxydianiline, and melem) as the precursors as well as different heating rates. The effects of the diamine precursor and heating rate on the structure, composition, morphology, and optical properties of the as-prepared PI materials were systematically investigated by various characterization techniques. The selective photo-oxidation of benzylamine was used as a model reaction to evaluate the photocatalytic activities of the resulting PI samples for the oxidation of amines to imines. The results revealed that the PI sample prepared using MA and PMDA as the precursors and a heating rate of 7 °C/min (MA-PI-7) exhibited the best catalytic performance, with 98% benzylamine conversion and 98% selectivity for N-benzylidene benzylamine after 4 h of irradiation. Several benzylamine derivatives and heterocyclic amines also underwent the photo-oxidation reaction over the MA-PI-7 catalyst to afford the corresponding imines with good activity. In addition, MA-PI-7 exhibited good stability over four successive photocatalytic cycles.

Effect of CeO2 on Activity of Catalysts CuO/ZnO/Al2O3/CeO2 for Synthesis of Methanol
Zhou Songhua, Li Wenbo, Wu Zongjin, Chen Zhongyang, Huang Chen, Zhang Chuanwei, Wang Bo, Pan Hongyan, Lin Qian
2023, 25(3):  104-114. 
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The size of the nanoparticles and the number of oxygen vacancies have a significant effect on the catalytic activity of copper-based catalysts used for the synthesis of methanol from syngas. In this study, the authors prepared a series of catalysts CuO/ZnO/Al2O3/CeO2 (CZAC) with CuO particles of different sizes and varying number of oxygen vacancies on the surface by changing the added volume of CeO2 by using the co-precipitation method. The properties of the catalysts were characterized and their activity was evaluated by using high-pressure fixed-bed reaction equipment. The results showed that the addition of CeO2 to CuO/ZnO/Al2O3 not only influenced the size of the CuO particles and metal-metal interactions, but also had an effect on the concentrations of oxygen vacancies and strongly basic sites. The presence of CuO particles of small sizes and a large numbers of oxygen vacancies on the surface of the catalyst were beneficial to its activity for the synthesis of methanol. The catalyst CZAC, when modified by 5% of CeO2, recorded CuO particles of the smallest size (8.9 nm), strong intermetallic interactions, and the highest concentrations of oxygen vacancies and strongly basic sites. It also exhibited the highest catalytic activity, with a space-time yield of methanol of 0.315 g/(h·g) that was higher than that of the enterprise RK-5 catalyst [0.215 g/(h·g)].

C9H10O2:0.5ZnCl2/SG as a High-Efficiency Catalyst for Desulfurization of Model Oil
Li Xiuping, Wei Yuanyuan, Liu Xiaoyi, Zhao Rongxiang
2023, 25(3):  115-126. 
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A C9H10O2:0.5ZnCl2/SG catalyst was synthesized using a one-step sol-gel method with silica gel (SG) as the carrier and C9H10O2:0.5ZnCl2 deep eutectic solvent (DES) as active component. The structure of the supported catalyst was characterized by FT-IR, XRD, SEM, and N2 adsorption-desorption, and the DES was found to have successfully permeated the SG through its pores. The removal of dibenzothiophene (DBT) in model diesel was studied using C9H10O2:0.5ZnCl2/SG as a catalyst and H2O2 as an oxidant. The influence of loading dose of DES, reaction temperature, catalyst dosage, O/S molar ratio, and sulfide type on the desulfurization rate was investigated. The removal rates of DBT, 4,6-dimethyldibenzothiophene (4, 6-DMDBT), and benzothiophene (BT) under optimal reaction conditions were 99.4%, 96%, and 78.2%, respectively. C9H10O2:0.5ZnCl2/SG catalyst could be recycled five times with a little decrease of oxidative desulfurization activity, and the adsorption-oxidation desulfurization mechanism was examined.

Simulation and Optimization
Ultra-deep Removal of Metal Ions from Coal Tar by Complexation: Experimental Studies and Density Functional Theory Simulations#br#
Wu Hao, Wei Hongyuan, Li Wangliang
2023, 25(3):  127-135. 
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As one of the important aspects of upgrading coal tar, the ultra-deep removal of metal ions via the complexation method was investigated by screening four complexing agents and performing density functional theory (DFT) simulations. Analysis of the compositions and contents of the metallic compounds in the coal tar revealed that the main components were iron and calcium naphthenates. Direct filtration reduced the mechanical impurity content from 0.24% to 0.0752%, indicating that most of the large particles could be easily removed. Among the four complexing agents, namely, acetic acid, oxalic acid, citric acid, and ethylene diamine tetraacetic acid, oxalic acid exhibited the best demetallization performance. The DFT simulations suggested that the high performance of oxalic acid originated from its 1:1 coordination mode, rigid dicarboxyl structure, and greater binding energy.
Pyrolysis Mechanism of a Cyclotriphosphazene-Based Flame- Retardant Epoxy Resin by ReaxFF Molecular Dynamics
Jiang Shuaijun, Meng Weifeng, Wan Yongqing, Qin Weihua, Liu Xiaoqing, Lan Yanhua
2023, 25(3):  136-152. 
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Cyclotriphosphazene derivatives can effectively improve the flame retardancy and fire safety of epoxy resins (EPs) via their influence on the pyrolysis process. In this work, the effects of hexa(5-methyl-2-pyridinoxyl)cyclotriphosphazene (HMPOP) incorporation on the initial pyrolysis of an EP at 500–3500 K were studied using the ReaxFF method. The pyrolysis fragments, initial reaction pathways, and main products were identified for the EP and EP/HMPOP composites. The activation energies were derived by fitting the weight percentage curves for solid species during the pyrolysis reactions and the obtained values were in good agreement with experimental data. The initial EP pyrolysis reactions included four major decomposition modes, which primarily involved the cleavage of C–O and C–N bonds. The main pyrolysis products were H2O, CO, C2H4, and CH2O. HMPOP bonded with the oxygen-containing fragments to form larger molecular fragments and reduced the amounts of C0–C4 products, especially that of the harmful gas CH2O. Thus, HMPOP promoted the formation of carbon clusters and reduced the generation of combustible gases, ultimately decreasing the capacity for fire propagation.
Simulation of Solvent Extraction for Naphthenic Lubricating Base Oils
Xu Xiaoling, Wang Tianqi, Tian Qingmei, Liu Yansheng
2023, 25(3):  153-164. 
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Solvent extraction is the process of separating aromatics from vacuum distillates for the production of lubricating base oils. In this study, the authors use dimethyl sulfoxide (DMSO) instead of furfural as solvent, in light of its higher selectivity, to obtain extracts with a high aromatic content for naphthenic lubricating base oils. We systematically investigated effects of the solvent-to-oil (S/O) ratio and extraction temperature on the yield of the extract, efficiency of aromatic removal, and composition of the extracts and raffinates. The results showed that the aromatic content of extracts for naphthenic oils could reach a high value of about 80%. The solvent maintained a high selectivity for aromatics for naphthenic oils even under a high S/O ratio and a high extraction temperature. Moreover, the efficiency of aromatic removal for naphthenic lubricating base oils could be enhanced by increasing either the S/O ratio or the extraction temperature, although these measures had limited effects in practice. Following this, we used the non-random two-liquid (NRTL) model based on the pseudo-component approach to simulate the liquid-liquid equilibrium of the system of DMSO + naphthenic lubricating base oils, and determined the parameters of binary interaction through regression based on the data on phase equilibrium. The modeling results showed that the predicted yield, content of the solvent, and composition of the raffinates and extracts were in good agreement with those obtained in the experiments. This validates the reliability of the model used to represent the DMSO + naphthenic lubricating base oil system. Both the experimental data and the method of simulation reported here can help optimize the extraction of naphthenic lubricating base oils, and provide a better understanding of the corresponding process.