Table of Content

    30 December 2023, Volume 25 Issue 4
    2023, 25(4):  1. 
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    Content of this issue
    Scientific Research
    Experimental Investigation on Macro Spray Characteristics of Octanol-Biodiesel-Diesel Ternary Fuel Blend
    Tian Junjian, Qiu Zhicong, Zhao Lifei, Li Fengyu, Hu Peng, Lin Qizhao
    2023, 25(4):  1-15. 
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    This study investigates the spray characteristics of ternary blends composed of octanol, biodiesel, and diesel fuel. Experiments are conducted using six materials to examine the variation in spray characteristic and to verify and compare a previously established spray tip penetration model with a modified model. The results show that the addition of OB100 (30% of octanol, 70% of biodiesel) improves the spray characteristics of the fuel. Specifically, the addition of 10% or 20% of OB100 leads to a slight increase in the spray tip penetration, average spray cone angle, maximum spray width, and the spray area of the fuel blend; however, further addition of OB100 causes a corresponding decrease in these parameters. Based on previous research, this study uses kinematic viscosity instead of dynamic viscosity and density to modify the prediction model of spray tip penetration. The modified model exhibits a better fit quality and agreement with the experimental data, making it more suitable for predicting the spray tip penetration of fuel blends compared to the Hiroyasu-Arai model.
    Apparent Kinetics of 1-Decene Polymerization Catalyzed Using the Ionic Liquid [Bmim]x[C2H5NH3]1-x[Al2Cl7]
    Chen Yingze, He Jinxue, Wang Ben, Pan Shiguang, Zhang Di, Bai Zhongxiang, An Liangcheng, Liu Dan, Ma Aijing, Li Hu, Gui Jianzhou
    2023, 25(4):  16-22. 
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    Poly-α-olefin (PAO) synthetic oil, a regular long-chain alkane produced from the catalytic polymerization of α-olefin, is a high-quality lubricating base oil with huge market potential. In this study, PAO synthesis based on the catalytic polymerization of 1-decene using the ionic liquid (IL) [Bmim]x[C2H5NH3]1−x[Al2Cl7] as the catalyst was studied. Compared with the conventional catalyst [Bmim] [Al2Cl7], the obtained PAO product incorporates more trimers and tetramers of 1-decene and contains few double-bond end groups, demonstrating a better catalytic system for PAO-10 production. The apparent polymerization kinetics of 1-decene in this catalytic system were studied based on the 1-decene concentration, catalyst concentration, and reaction temperature. An apparent kinetic equation for PAO formation was determined, providing a promising strategy for PAO production using 1-decene polymerization.
    Chemical Properties, Low-Temperature Performance, and Burning Performance of Bio-Jet Fuel
    Zhang Zongwei, Wang Zihan, Yang Ze, Li Junqi, Liu Haonan
    2023, 25(4):  23-30. 
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    The effects of composition of bio-jet fuels on freezing point, smoke point, distillation range, and flash point are investigated. Performance tests using petroleum-based jet fuel with different compositions are conducted in line with standard test specifications. The results show that alkylbenzenes reduce the freezing point, with the amount of  reduction becoming greater with increasing alkylbenzene content. For a 25% content of the C8 aromatic xylene, the freezing point is in the range from −55.5 °C to −60.1 °C. The presence of monocyclic aromatic hydrocarbons leads to an increase in carbon deposition performance, especially when alkyl side chains are present. With cycloalkanes, carbon deposition is reduced, although alkyl side chains weaken this beneficial effect. Isomeric hydrocarbons are beneficial in reducing carbon deposition. The ASTM D7566 specifications for the distillation range are based on the average properties of petroleum-based aviation fuel, and if all the parameters governing the distillation range of an alternative jet fuel are at their lower limits, it is necessary to check whether other performance standards are met. Light components affect the flash point greatly, with 5% of benzene reducing the flash point by 17 °C, whereas intermediate components (e.g., xylene and ethylbenzene) and heavier components have less impact. Although alcohols provide better combustion performance, their content must be strictly limited owing to their effects in reducing the flash point.
    Kinetics of Selective Hydrogenation of PAHs from FCC Slurry Extract over Ni-W/γ-Al2O3 Catalyst
    Cui Wenlong, Wu Fubu, Chen Yulong, Qian Junfeng, Luo Hui, Liu Yingjie, Yang Jihe
    2023, 25(4):  31-40. 
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    The selective hydrogenation of polycyclic aromatic hydrocarbons (PAHs) from fluid catalytic cracking (FCC) slurry extract was conducted in a batch reactor over a γ-Al2O3-supported bimetallic Ni-W catalyst. For the Ni-W/γ-Al2O3 catalyst, the experiment run was divided into three processes according to the reaction conditions used: (1) the absence of hydrogenation as both temperature and pressure increased; (2) the desulfurization of FCC slurry extract under a fixed pressure as the temperature increased; and (3) the selective hydrogenation of PAHs when both pressure and temperature remained constant. The hydrogen consumption could be accurately calculated from the Redlich–Kwong equation of state. The results for the removal of PAHs with hydrogenation displayed an excellent fit to the first-order kinetics. The apparent activation energy was determined to be 20.80 kJ/mol.
    Catalyst Research
    Core-shell-structured Composite ZSM-5@MCM-41 Catalysts: Fabrication, Characterization, and Enhanced Performance in Hexane Catalytic Cracking
    Zhu Jiale, Zhu Xuedong, Yang Fan
    2023, 25(4):  41-51. 
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    A series of core-shell zeolites with a ZSM-5 zeolite core and a MCM-41 shell with varying shell thicknesses were successfully fabricated via a cetyltrimethylammonium bromide (CTAB)-directed sol-gel coating method in an ultradilute solution. Extensive characterization techniques, including XRD, TEM, N2 adsorption-desorption, NH3-TPD, and IR measurements, confirmed the successful coating of a microporous ZSM-5 core with a mesoporous MCM-41 shell layer and were further employed to explore the textural properties and acidic properties of the samples. The hexane cracking results revealed a significant enhancement in olefin yields after introducing the MCM-41 shell to ZSM-5. Interestingly, a volcanic trend in olefin yields was observed with the increase in the shell thickness. In particular, the highest olefin yield of 51.5%, exceeding that of the core catalyst by 17.1%, was achieved when the shell thickness was controlled at 40 nm. Moreover, the catalyst lifetime investigation revealed that the core-shell composite catalyst exhibited a minimal reduction in hexane conversion of merely 3.8% over a 120 h reaction period, significantly outperforming the 11.3% reduction exhibited by the core catalyst. This remarkable catalytic performance was attributed to the passivation of external acid sites and the introduction of more developed pore channels by the shell, which effectively mitigated unwanted side reactions. The successful synthesis of these core-shell structured catalysts presents a novel strategy for improving catalytic performance in hexane cracking, in addition to serving as a solid foundation for the design of industrial catalysts for light naphtha cracking.
    Study on the Catalytic Reforming Law of Solid-Phase Carbon and Nitrogen Sources Loaded with MnO2 at Low Temperatures in Tahe Heavy Oil#br#
    Tan Dichen, Ma Zhaofei, Peng Gaoyao, Xiong Pan, Yan Xuemin
    2023, 25(4):  52-60. 
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    MnO2/Melem composites were synthesized with MnO2 nanoparticles loaded onto the Melem using the hydrothermal method. As raw materials for C and N carriers, Melem was prepared from melamine roasted at 354 ℃, and KMnO4 as a raw material for Mn, MnO2 nanoparticles were prepared using the hydrothermal synthesis of KMnO4. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and a laser particle size analyzer were used for structural characterization, and the catalytic oxidation performance of the heavy oil was investigated at different reaction temperatures (100 ℃ to 180 ℃) using MnO2/Melem with an oxidant and donor protonic acid. The results showed that the synthesized β-MnO2 nanoparticles were successfully loaded onto the Melem surface; the oil samples before and after the reaction at different temperatures were subjected to SARA analysis using Fourier transform infrared (FT-IR), elemental analysis, gas chromatography-mass spectrometry (GC-MS) and viscosity tests, respectively. It was determined that the hydrocarbons in the crude oil were converted to heavy mass by oxidation reactions with the oxidant mainly through a low-temperature oxidation process below 140 ℃ in the heavy oil when the temperature exceeds 140 ℃, in addition to the oxidation reaction with the oxidant, a cleavage reaction in the carbon chain occurs to form hydrocarbon substances with lower molecular weights.
    Seed-solution-induced Synthesis of FER Zeolite and Its Catalytic Application in the Skeletal Isomerization of n-Butene
    Fan Jinlong, Yang Fan, Zhu Xuedong, Xu Yarong, Chen Lantian
    2023, 25(4):  61-73. 
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    A series of Ferrierite (FER) zeolites were prepared via hydrothermal synthesis in the absence of organic templates with the aid of sodium-type FER zeolite (NaFER) or NaFER suspensions (NaFERsus) acquired by NaOH solution treatment as seeds. The differences in the structures and acid sites of the obtained FER zeolite catalysts arising from the choice of seed were investigated, and the catalytic performances of the obtained FER zeolites were evaluated in the skeletal isomerization of n-butene. The results indicate that the samples synthesized using NaFERsus feature more Brønsted acid sites (BAS) in the 10-membered-ring (10-MR) at the expense of strong acid and Lewis acid sites (LAS), compared with samples derived from NaFER. Therefore, the FER samples synthesized using NaFERsus outperformed the NaFER counterparts as the BAS in 10-MR and LAS were the main active sites, while BAS in 8-MR and LAS were responsible for side reactions, such as polymerization, cracking, and carbon deposition in n-butene isomerization. The optimized FER catalyst was continuously used for 720 h at 350 °C at 0.1 MPa under an n-butene space velocity of 2.0 h−1, during which the n-butene conversion remained at >40%, and the isobutylene yield was >37.5%.
    Process Research
    New Method for the Deep Dehydration and Desalination of Crude Oil
    Lu Yuejia, Jiang Peng, Song Yueqin, Zhou Xiaolong
    2023, 25(4):  74-85. 
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    The present work focused on the environmentally friendly deep desalination of crude oil using ethylene glycol as the extraction solvent and quartz sand as the demulsifier. The effect of droplet size distribution in the emulsion on the dehydration results and desalination efficiency was investigated. Experimental results showed that the desalination efficiencies of Sarir and Basra crude oils were 93.3% and 90.0%, respectively. Furthermore, the desalination efficiency of Basra crude oil using ethylene glycol could be enhanced up to 96.7% by adding 30 g/L quartz sand with a particle size of 15 μm. Finally, 94% of the ethylene glycol and 86% of the quartz sand could be recovered from the emulsion. This process offers an alternative method to the deep desalination of crude oil.
    Oxidation of Partially Hydrolyzed Polyacrylamide from Polymer Flooding Processes Using Fenton Reagents
    Li Jinlian, Wang Jia, Liu Hongyan, Wu HongJun, Zhang Yongjun
    2023, 25(4):  86-92. 
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    The degradation of partially hydrolyzed polyacrylamide (HPAM) found in alkaline/surfactant/polymer flooding sewage was investigated using Fenton-type reagents. Different Fenton reagent treatments for HPAM degradation were compared. The effects of pH, hydrogen peroxide (H2O2), ferrous ion (Fe2+), and tartaric ion (C4H4O62−)  concentrations were studied. The degradation reaction occurred within a wide range of pH (3–9). The HPAM degradation performance of photo-Fenton processes using solar light and UV were compared with that of the Fenton process. The degradation rate was found to be strongly dependent on the H2O2/Fe2+/ C4H4O62− molar ratio. The HPAM degradation efficiency was 90%, and the chemical oxygen demand removal efficiency was 85%. HPAM could be degraded into a compound with a lower molecular weight, but it was difficult to achieve complete mineralization to CO2. The presence of intermediate products hindered further oxidation in the Fenton process.
    Orientational Separation of Sulfur in Petroleum Coke by Alkali Calcining and Reflux Washing
    Su Song, Li Minting, Ye Fu, Wei Chang, Li Xingbin, Deng Zhigan
    2023, 25(4):  93-105. 
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    The application of high-sulfur petroleum coke after desulfurization in aluminum electrolysis anodes is an important development trend. However, removing sulfur from high-sulfur petroleum coke is still a significant challenge. This study proposes alkali calcining and reflux washing to examine the impacts of temperature, particle size, the mass ratio of Na2CO3 to NaOH, and total sodium addition on the desulfurization efficiency and mechanism. The results show that the desulfurization rate increases with increasing temperature, increasing total sodium content, and decreasing particle size. The addition of alkali can significantly reduce the opening-ring reaction temperature of thiophene and convert organic sulfur into inorganic sulfur (Na2S). Three washing methods were compared, and reflux washing was selected to separate inorganic sulfur (Na2S) from calcined petroleum coke. The sulfur content in petroleum coke decreased from 7.29% to 1.90%, with a desulfurization rate of 80.13% under optimal conditions. The petroleum coke was analyzed before and after desulfurization using X-Ray diffraction(XRD), Scanning Electron Microscopy(SEM), Infrared Spectroscopy(IR), Thermogravimetric Analysis and Differential Scanning Calorimetry(TG-DSC), Gaschromatography-mass Spectrometry(GC-MS). The results show that thiophene and benzothiophene in petroleum coke are decomposed and converted into octane and ethyl cyclohexane. These new observations are expected to provide further understanding and guidance for the utilization of highsulfur petroleum coke.
    Simulation and Optimization
    Identification of a Reliable DFT Calculation Method to Predict the Ground- and Excited-State Properties of Nickel(II) Complexes with Porphyrin in Crude Oil
    Pu Ning, Ren Qiang, Hu Dawei, Fang Wei, Yang Qinghe, Wang Zhen, Hu Anpeng, Xu Lei, Ge Xin
    2023, 25(4):  106-116. 
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    Metalloporphyrins have devastating effects on the deep processing and efficient utilization of petroleum resources. Various porphyrins are derived from porphin by substitution at the β, meso, or both positions. Herein, we focus on the interaction between nickel(II) and the porphyrin skeleton. Five different density functionals were selected for determining a reliable approach to simulate porphyrin-nickel(II) complexes. At D4h symmetry, the 10b1g, 15a1g, 4e1g and 9b2g were dominated by the 3d character of nickel. Compared with pure density functional, the hybrid functional gave larger highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) gap, and the higher HOMO-LUMO gap also corresponded to a higher excitation energy. The characteristic Soret and Q bands modeled by timedependent density functional theory (TDDFT) calculations matched well with experimental results, and the absorption was discussed in detail with natural transition orbitals (NTO) analysis. Furthermore, the binding character of nickel(II) with various substituted porphyrins were calculated at perdew-burke-ernzerhof (PBE) level, showed that the geometry and complexation behavior of porphyrin-nickel(II) complexes could be significantly tuned by different substituents. The symmetry of the complex was reduced and the skeleton ring get distortion when introducing different substituents. Compared with ETIO porphyrin, the introduction of phenyl on the β position can expand the conjugated system and promote the covalent character of Ni-N bond.
    Study of Macro-Mixing in a Microreactor
    Cao Huili, Tang Xiaojin, Bao Di, Hou Shuandi
    2023, 25(4):  117-126. 
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    The transfer rate between fluids in a microreactor is directly influenced by the mixing within the reactor, which subsequently impacts the reaction rate. This paper investigates the flow behavior and macro-mixing performance in a microreactor. First, the flow performance of the Ehrfeld Miprowa microreactor is studied. Cold experiments are conducted to examine fundamental flow laws and verify the accuracy of the chosen computational fluid dynamics simulation model. Subsequently, macro-mixing performance in the microreactor, both with and without internal components, is investigated through both experiment and simulation. A bromocresol violet–NaOH–H2SO4 system is utilized in the macro-mixing experiments, which explore the effects of flow rate and internal components on macro-mixing. The Navier–Stokes equation is adopted as the computational model for macro-mixing simulations, which also consider the mass transfer and diffusion of tracer. The simulation results are in good agreement with the experimental results. Both experimental and simulation results demonstrate that the presence of internal components in the microreactor enhance its macro-mixing performance. 
    Synthesis and Design of Distillation Columns for Wide-Boiling Binary Mixtures with Vapor Recompression Heat Pumps
    Shi Li
    2023, 25(4):  127-138. 
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    The vapor recompression heat pump (VRHP) distillation technology offers significant improvements in energy efficiency for distillation systems with small temperature differences between the top and bottom of the column. However, the separation of wide-boiling binary mixtures leads to substantial temperature differences between the top and bottom of the column. This limits the applicability of conventional VRHP due to high capital costs and strict performance requirements of the compressor. To overcome these challenges and to accommodate compressor operating conditions, a novel synthesis and design method is introduced to integrate VRHPs with wide-boiling binary mixture distillation columns (WBMDCs). This method enables quick determination of an initial configuration for the integrated WBMDC-VRHP system and helps identify the optimum configuration with the minimum total annual cost. Two examples, namely the separation of benzene/toluene and isopropanol/chlorobenzene, are employed to derive optimum configurations of the WBMDC-VRHP and compare them with the WBMDC. A systematic comparison between the WBMDC-VRHP and WBMDC demonstrates the superior steady-state performance and economic efficiency of the WBMDC-VRHP.
    Integrity-Management Characteristics and Efficiency Evaluation of Oil and Gas Pipelines
    Zhang Xiaodong, Sun Jiazheng, Fu Yong, Lei Shaojuan
    2023, 25(4):  139-150. 
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    Pipeline integrity is a cornerstone of the operation of many industrial systems, and maintaining pipeline integrity is essential for preventing economic losses and ecological damage caused by oil and gas leaks. Based on integritymanagement data published by the US Pipeline and Hazardous Materials Safety Administration, this study applied the k-means clustering and data envelopment analysis (DEA) methods to both explore the characteristics of pipeline-integrity management and evaluate its efficiency. The k-means clustering algorithm was found to be scientifically valid for classifying pipeline companies as either low-, medium-, or high-difficulty companies according to their integrity-management requirements. Regardless of a pipeline company’s classification, equipment failure was found to be the main cause of pipeline failure. In-line inspection corrosion and dent tools were the two most-used tools for pipeline inspection. Among the types of repair, 180-day condition repairs were a key concern for pipeline companies. The results of the DEA analysis indicate that only three out of 34 companies were deemed to be DEA-effective. To improve the effectiveness of pipeline integrity management, we propose targeted directions and scales of improvement for non-DEA-effective companies.
    Lubrication Research
    Effect of Synthetic Conditions and Thickener Formulation on the Rheological and Tribological Properties of Polypropylene Grease
    Zhao Xinrui, Hao Lei, Wu Yiling, Xu Hong, Dong Jinxiang
    2023, 25(4):  151-163. 
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    Polypropylene (PP) grease holds great potential for special industrial applications. In this study, synthetic conditions, thickener content, and the ratio of two different molecular weight PPs were investigated systematically using a rheometer, scanning electron microscope, X-ray diffraction, Fourier transform infrared spectrometer, oscillating tribometer, and 3D surface profiler measurements. The results showed that suitable synthetic conditions are two quenching cycles, and the synthetic temperature and time is 240 ℃ for 12 h. The rheological analysis showed that thickener content and different proportions of the two PP molecular weights have a significant influence on the rheological properties of PP grease. High molecular weight PP (H-PP) has a stronger thickening ability than low molecular weight PP (L-PP). The higher the amount of H-PP in the fixed thickener content or the higher the thickener content with a specific proportion, the higher the viscoelasticity of PP grease. The tribological performance is related to the rheological properties. The proportion of two different molecular weight PPs in the thickener content should be appropriate; excessive H-PP content leads to lubrication failure.
    Effect of Photovoltaic Power Generation on Carbon Dioxide Emission Reduction under Double Carbon Background
    He Boyang
    2023, 25(4):  164-174. 
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    Increasing the efficiency and proportion of photovoltaic power generation installations is one of the best ways to reduce both CO2 emissions and reliance on fossil-fuel-based power supplies. Solar energy is a clean and renewable power source with excellent potential for further development and utilization. In 2021, the global solar installed capacity was about 749.7 GW. Establishing correlations between solar power generation, standard coal equivalent, carbon sinks, and green sinks is crucial. However, there have been few reports about correlations between the efficiency of tracking solar photovoltaic panels and the above parameters. This paper calculates the increased power generation achievable through the use of tracking photovoltaic panels compared with traditional fixed panels and establishes relationships between power generation, standard coal equivalent, and carbon sinks, providing a basis for attempts to reduce reliance on carbon-based fuels. The calculations show that power generation efficiency can be improved by about 26.12% by enabling solar panels to track the sun’s rays during the day and from season to season. Through the use of this improved technology, global CO2 emissions can be reduced by 183.63 Mt, and the standard coal equivalent can be reduced by 73.67 Mt yearly. Carbon capture is worth approximately EUR 15.48 billion, and carbon accounting analysis plays a vital role in carbon trading.