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2023年 第25卷 第2期    刊出日期:2023-06-30
Catalyst Research
Catalyst for Increasing Ethylene and Propylene Production and Its Industrial Application in a Catalytic Pyrolysis Unit#br#
Sha Yuchen, Wang Peng, Ouyang Ying, Zhu Genquan, Lu Lijun, Song Haitao, Lin Wei, Luo Yibin
2023, 25(2):  1-9. 
摘要 ( 143 )   PDF (627KB) ( 283 )  
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Light olefins, particularly ethylene and propylene, are the most important building blocks for the petrochemical industry, and demand for their production has been increasing. The catalytic pyrolysis process (CPP) and the corresponding catalyst, developed by SINOPEC Research Institute of Petroleum Processing Co., Ltd., are designed to maximize the light olefin yield from catalytic cracking of heavy feedstocks. However, owing to the continuing degradation of feedstocks, the original catalyst can no longer maintain its activity. Herein, we describe the rational design of the new catalyst, Epylene, from a new metal-modified hierarchical ZSM-5 zeolite and matrix. Epylene was tested in the CPP unit of Shaanxi Yanchang Coal Yulin Energy and Chemical Company. A test run and base run were conducted to demonstrate the better performance of Epylene compared with the original catalyst. The properties of the feedstocks and the operating conditions in both runs were similar. The light olefin yield was increased from 33.95% to 36.50% and the coke yield was only 9.58% in the test run, which was lower than that in the base run.
Synthesis of AgCl/Ti3C2@TiO2 Ternary Composite Photocatalysts for Photocatalytic Oxidation of 1,4-Dihydropyridine and Tetracycline Hydrochloride#br#
Wu Hanliu, Quan Yan, Liu Meiling, Tian Xuemei, Ren Chunguang, Wang Zhonghua
2023, 25(2):  10-23. 
摘要 ( 66 )   PDF (4235KB) ( 126 )  
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AgCl/Ti3C2@TiO2 ternary composites were prepared to form a heterojunction structure between AgCl and TiO2 and introduce Ti3C2 as a cocatalyst. The as-prepared AgCl/Ti3C2@TiO2 composites showed higher photocatalytic activity than pure AgCl and Ti3C2@TiO2 for photooxidation of a 1,4-dihydropyridine derivative (1,4-DHP) and tetracycline hydrochloride (TCH) under visible light irradiation (λ > 400 nm). The photocatalytic activity of AgCl/Ti3C2@TiO2 composites depended on Ti3C2@TiO2 content, and the catalytic activity of the optimized samples were 6.9 times higher than that of pure AgCl for 1,4-DHP photodehydrogenation and 7.3 times higher than that of Ti3C2@TiO2 for TCH photooxidation. The increased photocatalytic activity was due to the formation of a heterojunction structure between AgCl and TiO2 and the introduction of Ti3C2 as a cocatalyst, which lowered the internal resistance, sped up the charge transfer, and increased the separation efficiency of photogenerated carries. Photogenerated holes and superoxide radical anions were the major active species in the photocatalytic process.
Removal of Organochlorine from Model Oil Using Mg-Modified ZSM-5 Zeolite: Dechlorination Performance, Regeneration, and Thermodynamics
Cheng Xingyuan, Gu Jie, Huang Bingtian, Bing Liancheng, Han Dezhi, Wang Guangjian, Wang Fang
2023, 25(2):  24-32. 
摘要 ( 80 )   PDF (1389KB) ( 104 )  
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Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha. The adsorption performance and regeneration stability were investigated by static adsorption experiments. The morphologies, structural features, and physicochemical properties of the adsorbents were characterized by X-ray diffraction, Brunauer-Emmett-Teller analysis, NH3 temperature-programmed desorption, scanning electron microscopy, transmission electron microscopy, and pyridine adsorption infrared spectroscopy. The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance. The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface. A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite. Furthermore, the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions. The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic, spontaneous, disordered, and primarily involved physical adsorption.
Design and Development of Highly Efficient Ni/ZnO Catalysts Based on Semiconductor Metal Oxide Catalysis Theory#br#
Bian Yankun, Kang Lei, Wu Feng, Wang Haiyan, Bai Yingzhi, Sun Na
2023, 25(2):  33-40. 
摘要 ( 46 )   PDF (2313KB) ( 86 )  
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In the context of reactive adsorption desulfurization, the development of an efficient Ni/ZnO desulfurizer has attracted increasing attention. In the work reported here, a novel Ni/Mn-ZnO composite nanowire desulfurizer is designed on the basis of the catalytic theory of semiconductor metal oxides and the characteristics of one-dimensional nanomaterials. X-ray diffraction, scanning electron microscopy, N2 adsorption-desorption, and X-ray photoemission spectroscopy demonstrate that Mn doping changes the crystal structure and morphology of the Ni/ZnO desulfurizer, increases the number of quasi-free electrons in the ZnO, and promotes H2S adsorption. The Ni/Mn-ZnO composite nanowire desulfurizer exhibits good desulfurization performance when used with gasoline as the raw material.
Process Research
Effects of Ethylene Tar-Based Pitch Coatings on the Electrochemical Properties of Graphite Anode Materials
Xing Yicheng, Dai Chang, Wu Qiang, Wang Taoxiang, Li Zhi, Lei Jie, Han Haibo, Li Kang, Wang Youhe
2023, 25(2):  41-50. 
摘要 ( 46 )   PDF (1935KB) ( 64 )  
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To improve the electrochemical performance of graphite anode materials, pitches with various softening points (150 °C, 180 °C, 200 °C, and 250 °C) were prepared from ethylene tar and used to coat graphite through a liquid coating process. The effects of the softening point of the pitch and the coating amount on the microstructure and electrochemical properties of graphite were studied by methods including thermogravimetric analysis, X-ray diffraction, Raman spectroscopy, surface area analysis, scanning electron microscopy, transmission electron microscopy, and electrochemical testing. The graphite particles were coated uniformly by the pyrolytic carbon in the pitch. The coating changed the degree of graphitization, decreased the average specific surface area, and improved the electrochemical performance significantly. The best battery anode performance was obtained when the mass ratio of pitch to graphite was 10%, the heat treatment temperature was 1100 °C, and the softening point of the pitch was 250 °C. Under the optimum conditions, the irreversible capacity loss in the first cycle at 0.1 C was only 23 mAh/g, and the first Coulombic efficiency reached 94.2%. The capacity retention rate was 98.3% after 100 charge-discharge cycles at 0.1 C.
Residual Stresses and Forming Quality of Metal Bipolar Plates for PEMFC During the Stamping Process
Zhang Jie, Wang Ruichuan, Wu Ningpan
2023, 25(2):  51-64. 
摘要 ( 42 )   PDF (6670KB) ( 65 )  
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Stamping is a critical step in the manufacture of metallic bipolar plates. Typically, residual stress and a spring back effect appear on the bipolar plate after the stamping process, which impacts on the performance and lifetime of the proton exchange membrane fuel cell (PEMFC). The residual stress and spring back behavior which occur as a result of stamping a bipolar plate are investigated in this study. The effects of the punch radius, the die radius, the channel depth, and the clearance between the punch and the die on the residual stress and forming quality of the bipolar plate are examined. The stamping process can be divided into three stages. The high stress area and the middle section residual stress area were selected to study the formation process and to obtain the composition of the residual stress regions. Spring back was mainly related to the position of the fixed end of the sheet and the degree of plastic deformation, and the sheet thickness have increased by 2 μm after spring back. Based on the results of finite element analysis, as described by the distribution of residual stress, the formation, the thickness of the middle cross section and the equivalent plastic strain, it was found that all the tool parameters affected the distribution of the residual stress. This research can provide a design reference for the manufacture of metallic bipolar plates based on the stamping process.
Catalytic Elimination of Oxygenated Byproducts in the Toluene Methylation Process
Hou Min, Qi Xiaolan, Zheng Junlin
2023, 25(2):  65-73. 
摘要 ( 33 )   PDF (739KB) ( 60 )  
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Catalytic methylation of toluene with methanol is an important alternative pathway for xylene production. Previous studies have indicated that methanol always undergoes several side reactions on acidic zeolites, resulting in oxygen containing byproducts such as dimethyl ethers, ketones, and carboxylic acids. Herein, the presence and distribution of the oxygenated compounds formed during toluene methylation were firstly examined by systematic chromatographic analysis. Plausible formation mechanisms for the various oxygenates are discussed. The most problematic byproduct is found to be acetic acid, which can lead to inferior product quality and damage downstream units. A feasible solution is presented for oxygenate removal after toluene methylation, in which acetic acid is eliminated by catalytic decomposition into low-boiling point acetone over a MgO catalyst. This process allows for all of the low-boiling-point oxygenates, including methanol, dimethyl ether, acetone, and butanone, to be removed from the aromatics phase, taking advantage of the temperature of the reaction effluent and standard distillation equipment. X-ray diffraction was used to characterize the crystal phase of the fresh and used MgO decarbonylation catalysts, while thermogravimetry/mass spectrometry and Fourier-transform infrared spectroscopy were applied to investigate the transformation mechanism of acetic acid over the decarbonylation catalyst.
CO insertion and ketonization of acetic acid accounted for the formation and elimination of acetic acid, respectively. The
combined methylation/decarbonylation process should enable the production of high-quality xylenes, an important industrial
feedstock, by overcoming the main technical obstacles associated with the toluene methylation process.
Scientific Research
Mechanism Study of BF3/n-Butanol-catalyzed 1-Decene Oligomerization Reaction#br#
He Leilei, Su Shuo, Zhao Yi, Xu Bing, Long Jun
2023, 25(2):  74-80. 
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The active catalysts of the BF3/n-C4H9OH-catalyzed 1-decene oligomerization reaction, as well as the distribution of the reaction products, was investigated by molecular simulation. The calculation results show that (BF3)2·n-C4H9OH catalyzes the 1-decene oligomerization reaction with higher activity compared to BF3·n-C4H9OH, which is the most catalytically active substance in the BF3/n-C4H9OH catalyst system. The reaction energy barriers and heats of reaction of chain initiation, chain growth, and chain termination in BF3/n-C4H9OH-catalyzed 1-decene oligomerization are calculated to reveal the product distribution. The calculation results show that the contents of the oligomerization reaction products in descending order are trimer, tetramer, pentamer, and dimer. The calculated results were consistent with the experimentally obtained product distribution.
Molecular Characterization of C9+ Aromatics in Gasoline by Gas Chromatography-Mass Spectrometry
Han Xu, Song Chunxia, Qian Qin, Li Changxiu, Sun Xinyuan
2023, 25(2):  81-91. 
摘要 ( 29 )   PDF (1042KB) ( 59 )  
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The comprehensive characterization of heavy aromatic hydrocarbons in gasoline is important to optimize the blending process and understand the correlation between aromatics content and engine particulate emissions. However, most current analysis methods can only provide the composition of C8/C8- aromatics. In this study, a simple and fast gas chromatography-mass spectrometry (GC-MS) method to identify and quantify C9+ aromatics in gasoline was developed. A selected ion monitoring model was employed to eliminate interference from non-aromatic compounds in the detection of target compounds, as well as that between target compounds with different molecular formulas. The identification of C9+ aromatics was based on the retention time of model compounds, combined with characteristic mass fragment ions, boiling points, and retention indexes. Seventy-nine C9–C12 aromatic compounds were quantified based on the calibration of representative model compounds, and the method demonstrated good linearity, and high accuracy and precision.  Furthermore, the developed methodology was successfully applied to the analysis of gasoline fractions from the reforming, pyrolysis, straight-run, delayed coking, and catalytic cracking processes, as well as commercial gasolines. The results showed that C9 aromatics were the predominant aromatics in all gasoline samples, followed by C10 aromatics. Alkylbenzenes such as C9H12 and C10H14 were the main components in the reforming, straight-run, delayed coking, and catalytic cracking gasoline fractions, as well as in the commercial gasolines, in which 1,2,4-trimethylbenzene and 3-ethyltoluene were dominant; in contrast, aromatics with higher degrees of unsaturation such as indene were the most abundant aromatics in the pyrolysis gasoline fraction.
Selective Hydrogenation of Polycyclic Aromatics to Monocyclic Aromatics over NiMoC/Hβ Catalysts in a Methane and Hydrogen Environment
Shen Zhibing, Fu Rao, Zhang Shangli, Wang Shunmei, Zhang Wu, Tang Ruiyuan, Liang Shengrong, Zhang Juntao, Yuan Shibao, Jiang Haiyan
2023, 25(2):  92-100. 
摘要 ( 39 )   PDF (588KB) ( 79 )  
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To obtain higher yields of monocyclic aromatic hydrocarbons with methyl side chains, such as toluene and xylene, methane(CH4) can be introduced into the hydrocracking of polycyclic aromatic hydrocarbons. CH4 can participate in the reaction, supply methyl side chains to the product, and improve product distribution. In this study, the hydrogenation reaction of polycyclic aromatic hydrocarbons over a carbonized NiMo/Hβ catalyst in a CH4 and hydrogen (H2) environment was investigated to study the promotional effect of CH4 on the hydrocracking of polycyclic aromatics.Under conditions of 3.5 MPa, 380 ℃, volume air velocity of 4 h-1, gas-oil volume ratio of 800, and H2:CH4 ratio of 1:1, the conversion rate of naphthalene was 99.97%, the liquid phase yield was 93.62%, and the selectivity’s of BTX were 17.76%, 25.17%, and 20.47%, respectively. In comparison to the use of a H2 atmosphere, the selectivity of benzene was significantly decreased, whereas the selectivity’s of toluene and xylene were increased. It was shown that CH4 can participate in the hydrocracking of naphthalene and improve the selectivity of toluene and xylene in the liquid product. The carbonized NiMo/Hβ catalyst was characterized by a range of analytical methods (such as X-ray diffraction (XRD), ammonia-temperatureprogrammed desorption (NH3-TPD), hydrogen-temperature-programmed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS)). The results indicated that Ni and Mo carbides were the major species in the carbonized NiMo/Hβ catalyst and were considered to be active sites for the activation of CH4 and H2. After loading the metal components, the catalyst displayed prominent weak acidic sites, which may be suitable locations for cracking, alkylation, and other related reactions. Therefore, the carbonized NiMo/Hβ catalyst displayed multiple functions during the hydrocracking of polycyclic aromatic hydrocarbons in a CH4 and H2 environment. These results could be used to develop a new way to efficiently utilize polycyclic aromatic hydrocarbons and natural gas resources.
Preparation of Poly-α-Olefin Microcapsule Particles Coated with Polyurethane as a Drag Reducer Based on Interface Polymerization#br#
Li Chenhao, Lu Yong, Li Hao, Chen Yue, Meng Yeqiao, Zhou Pengfei, Xu Dan, Wang Yiran, Zhang Xiaolai
2023, 25(2):  101-112. 
摘要 ( 35 )   PDF (3119KB) ( 62 )  
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The molecular behavior of polyurethane (PU) coating materials during the surface adsorption of poly-α-olefin as a drag reducing polymer was explored by a molecular dynamics simulation. Three different PU capsule wall materials were synthesized using two reaction monomers, and a poly-α-olefin/PU drag reducer microcapsule was prepared based on interface polymerization. The structure, morphology, thermal stability, compressive strength, and drag reduction performance of the microcapsules were characterized and compared. The results showed that a non-bonding interaction induced the adsorption of the PU coating material, poly-α-olefin and PU then fused at the interface, and the PU coating material was embedded into the inner grooves of poly-α-olefin in the form of a local mosaic, thereby forming a stable core–shell structure. The morphological characterization indicated that PU and poly-α-olefin could form microcapsule structures. The thermal decomposition temperature of the microcapsule was dependent on the type of capsule wall material. The microcapsule structure had a slight effect on poly-α-olefin drag reduction. The system enabled poly-α-olefin to exist in powdered particles through microcapsulation, and had a good dispersion effect that facilitated storage and transport processes. The method effectively inhibited the accumulation and bonding of poly-α-olefin at room temperature.
Mechanism, Kinetics, and Thermodynamic Characteristics for the Demetallization of Used Lubricating Oil via Pyrolysis
Yang Haiyu, Jiang Zhenxin, Chu Qingyan, Jiang Peng, Wang Ming
2023, 25(2):  113-127. 
摘要 ( 38 )   PDF (3106KB) ( 72 )  
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This study analyzed the pyrolysis mechanism, developed a pyrolysis kinetic model, and determined the corresponding thermodynamic parameters for the removal of calcium from used lubricating oil using sulfurized calcium alkyl phenolate (T-115B) as a model compound. The pyrolysis process and products were evaluated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Visual inspection indicated that the removal of calcium from T-115B depended primarily on the destruction of micelles caused by the pyrolysis of compounds at high temperatures. The pyrolysis characteristics of T-115B at different heating rates were investigated by thermogravimetry and differential thermal analysis, which revealed two distinct pyrolysis phases. Thus, the pyrolysis mechanism can be described by a twostep model. The activation energy and thermodynamic parameters (ΔH, ΔG, and ΔS) were determined by applying the Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, Friedman, and Starink methods; the average activation energies for T-115B pyrolysis obtained using these methods were 115.80, 119.84, 124.96, and 116.14 kJ/mol, respectively. Further, both stages of the pyrolysis reaction followed Fn mechanisms with n = 1.39 in the first stage and n = 0.86 in the second stage. This study provides reliable and effective pyrolysis models along with kinetic and thermodynamic parameters to facilitate the largescale industrial application of used lubricating oil.
Simulation and Optimization
Continuous Process Optimization and Computational Fluid Dynamics Simulation of a Methyl Anthranilate Jet Reactor#br#
Chen Zhuohang, Xu Lin, Wang Xiaoping, Song Jianhua, Long Haoyu, Li Xinping, Liu Dianhua, Xu Yongjing, Chen Hebing, Liu Hui, Zhang Ying, Lei Wei
2023, 25(2):  129-141. 
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Methyl anthranilate (MA) is an important material for the synthesis of sodium saccharin, but the yield and quality of MA are not stable due to the batch operation conditions. In this study, the optimum conditions obtained by an orthogonal test in a batch reactor were a volume ratio of methanol to amide solution of 5:4, volume ratio of sodium hypochlorite to amide solution of 7:4, Hoffmann degradation reaction duration of 10 min, Hoffmann degradation reaction temperature of 10 ℃, esterification reaction duration of 10 min, and esterification reaction temperature of 40 ℃. The working flow velocity and allowable working viscosity range of a Venturi ejector inlet were both determined by a computational fluid dynamics (CFD) simulation. Based on the above experimental data, the continuous operation of the process was tested in a three-stage continuous reactor, which improved the product yield and quality of the process.
Simulation of Gas Oil Hydrotreater Heat Exchange Tube and Crystallization Prediction of NH4Cl by Thermodynamic Equilibrium#br#
Jin Haozhe, Liu Xinyu, Liu Xiaofei, Gu Youjie, Li Xiaojun, Fu Dexiao
2023, 25(2):  142-154. 
摘要 ( 52 )   PDF (4565KB) ( 78 )  
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The hydrotreater system heat exchanger is one of the main pieces of heat exchange equipment in petrochemical enterprises. In recent years, oil resources have shown a deterioration trend of high sulfur and high acid content, with corrosion risk being prominent in oil processing. Taking the multi-medium flow corrosion risk of the hydrotreater heat exchanger pipeline in a petrochemical enterprise as the research object, based on the parameter characteristics of corrosive NH3 and HCl media under a high-temperature and high-pressure environment, the ammonium salt crystallization and deposition mechanism under multi-phase flow is revealed. The thermodynamic equilibrium curve is modified based on the thermodynamic principle and fugacity coefficient variation, and the prediction model of ammonium chloride crystallization in hydrotreater heat exchanger under high temperature and high pressure is constructed according to the modification. This study uses the mixture model, the flow-thermal coupling method, and the discrete phase model method to carry out the numerical simulation of multiphase flow and the numerical prediction of particle distribution characteristics in the heat exchanger pipeline of the hydrotreater heat exchange equipment, so as to realize the quantitative prediction of the particle crystallization deposition distribution in the pipeline. The results show that with the decrease of temperature, the crystallization occurs first on both sides of the center of the tube bundle, and more crystallization occurs in the lower half of the U-shaped tube, which may seriously lead to problems such as pipe blockage and under-deposit corrosion.
PEMFC Identification Based on a Fractional-Order Hammerstein State-Space Model with ADE-BH Optimization#br#
Qin Hao, Qi Zhidong, Ye Weiqin, Sun Chengshuo
2023, 25(2):  155-164. 
摘要 ( 42 )   PDF (3497KB) ( 62 )  
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Considering the fractional-order and nonlinear characteristics of proton exchange membrane fuel cells (PEMFC), a fractional-order subspace identification method based on the ADE-BH optimization algorithm is proposed to establish a fractional-order Hammerstein state-space model of PEMFCs. Herein, a Hammerstein model is constructed by connecting a linear module and a nonlinear module in series to precisely depict the nonlinear property of the PEMFC. During the modeling process, fractional-order theory is combined with subspace identification, and a Poisson filter is adopted to enable multi-order derivability of the data. A variable memory method is introduced to reduce computation time without losing precision. Additionally, to improve the optimization accuracy and avoid obtaining locally optimum solutions, a novel ADEBH algorithm is employed to optimize the unknown parameters in the identification method. In this algorithm, the Euclidean distance serves as the theoretical basis for updating the target vector in the absorption-generation operation of the black hole (BH) algorithm. Finally, simulations demonstrate that the proposed model has small output error and high accuracy, indicating that the model can accurately describe the electrical characteristics of the PEMFC process.
Recent Advances in the Rapid Detection and Performance Evaluation Methods of Detergent Additives for Gasoline#br#
Zhi Wanwan, Li Na, Zhu Zhongpeng, Li Yan, Guo Xin
2023, 25(2):  165-176. 
摘要 ( 54 )   PDF (1578KB) ( 87 )  
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Although detergent additives for gasoline have been widely commercialized, their formulas are often kept confidential and there is still no standardized method for quickly detecting the main active ingredients and evaluating their effectiveness, which makes their regulation difficult. An overview of the current state of the development and application of detergent additives for gasoline in China and other regions, as well as a review of the rapid detection and performance evaluation methods available for analyzing detergent additives are given herein. The review focuses on the convenience, cost, efficiency, and feasibility of on-site detection and the evaluation of various methods, and also looks into future research directions, such as detecting and evaluating detergent additives in ethanol gasoline and with advanced engine technologies.
2023, 25(2):  0. 
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