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    A chemical kinetic perspective on the high-temperature oxidation of methane/propane through experiments and kinetic analysis
    Ma Shoutao, Yang Zhe, Zhu Yunfeng, Sun Bing, Jiang Jie, Xu Wei, Meng Ruiji
    China Petroleum Processing & Petrochemical Technology    2022, 24 (4): 1-11.  
    Abstract151)      PDF(pc) (1822KB)(265)       Save
    In the conversion of methane and propane under high temperature and pressure, the ignition delay time is a key parameter to consider for the inherent safer design of process. In this manuscript, the ignition delay time characteristics of methane and propane (700k~1000K, 10 and 20bar) were studied by means of experiments and kinetic modeling tools in the stoichiometric ratio of fuel to oxygen. All the experimental data are designed by isentropic compression and adiabatic core to meet the reliable experimental data which can be used to generate and verify the detailed chemical kinetic model. The ignition delay time of methane and propane was recorded by rapid compression machine (RCM) and compared to the predicted data obtained by NUIGMech 3.0 mechanism. To test the applicability of NUIGMech 3.0 mechanism under different reaction conditions, the influence of temperature over the range of 700K to 1000K (and the influence of pressure over the range of 10bar to 20bar) on ignition delay time was studied. The results show that NUIGMech 3.0 mechanism can reasonably reproduce the ignition delay time of the experiment under a wide range of conditions studied. The constant volume model of chemical kinetic mechanism was used to reveal the effect of temperature on the elementary reaction, and the negative temperature coefficient (NTC) behavior of propane was also found at the pressure of 20 bar. The experimental data can provide a reference for the correction and application of kinetic data, and also provide a theoretical basis for the safe conversion of low-carbon hydrocarbon chemicals.
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    Catalyst for Increasing Ethylene and Propylene Production and Its Industrial Application in a Catalytic  Pyrolysis Unit
    Sha Yuchen, Wang Peng, Ouyang Ying, Zhu Genquan, Lu Lijun, Song Haitao, Lin Wei, Luo Yibin
    China Petroleum Processing & Petrochemical Technology    2023, 25 (2): 1-9.  
    Abstract143)      PDF(pc) (627KB)(283)       Save
    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.
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    Morphology, nanostructure and oxidation reactivity of particulate matter emitted by diesel blending with various aromatics
    Yang He, Li Bo, Liu Shuntao, Wang Yajun, Zhang Ran, Guo Lingyan
    China Petroleum Processing & Petrochemical Technology    2023, 25 (1): 1-9.  
    Abstract118)      PDF(pc) (1576KB)(193)       Save
    This study aims to analyze the influence of the polycyclic aromatic hydrocarbon (PAH) content in diesel on  the physical and chemical properties of diesel soot particles. Four diesel fuels with different PAH content were tested on  a 11.6 L direct- injection diesel engine. The raw particulate matter (PM) before the after-treatment devices was collected  using the thermophoresis sampling system and the filter sampling system. A transmission electron microscope and Raman  spectrometer are used to analyze the physical properties of the soot particles, including morphology, primary particle size  distribution, and graphitization degree. A Fourier transform infrared spectrometer and thermogravimetric analyzer are
    used to characterize the surface chemical composition and oxidation reactivity of soot particles, respectively. The results  show that as the PAH content in the fuel decreases, the size of the primary soot particles decreases from 29.58 to 26.70  nm. The graphitization degree of soot particles first increases and then decreases, and the relative content of the aliphatic  hydrocarbon functional groups of soot particles first decreases and then increases. The T10, T50, and T90 of soot from high- PAH fuel are 505.3, 589.3, and 623.5 °C, while those from low-PAH fuel are 480.1, 557.5, and 599.2 °C, respectively. This  indicates that exhaust PM generated by the low-PAH fuel has poor oxidation reactivity. However, as the PAH content in fuel  is further decreased, the excessively high cetane number may cause uneven mixing and incomplete combustion, leading to  enhanced oxidation reactivity.
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    Demulsification Behavior, Characteristics, and Performance of Surfactant Stabilized Oil-in-Water Emulsion  under Bidirectional Pulsed Electric Field
    Ren Boping, Kang Yong, Zhang Xianming, Gong Haifeng, Chen Ling, Liu Yunqi
    China Petroleum Processing & Petrochemical Technology    2023, 25 (1): 10-22.  
    Abstract110)      PDF(pc) (2444KB)(178)       Save
    As a novel electric demulsification method, bidirectional pulsed electric field (BPEF) was employed to demulsify  the surfactant stabilized oil-in-water (SSO/W) emulsion for oil/water separation in this work. The demulsification behavior,  characteristics, and stages under BPEF were explored. It was discovered that BPEF drove SSO/W emulsion to move and  form vortexes, during which the oil droplets aggregated and accumulated to generate an oil droplet layer (ODL). ODL  subsequently transformed into a continuous oil layer (COL) leading to the demulsification and separation of SSO/W  emulsion. The conversion rate of ODL to COL was defined and used to evaluate the demulsification process and reflect  the coalescence ability and transformation efficiency of dispersed oil droplets into COL. Furthermore, the effects of  BPEF voltage, frequency, duty cycle, ratio of pulse output time, and surfactant type and content on the demulsification  performance were examined. The optimal values of BPEF parameters for demulsification operation were 400 V, 25 Hz,  50%, and 4:1. O/W emulsion containing anionic surfactant was apt to be demulsified by BPEF, nonionic surfactant took  the second place and cationic surfactant was the most difficult. A high surfactant content was not conducive to the BPEF  demulsification. This work is anticipated to provide useful guidance for oil/water separation and oil recovery from actual  emulsified oily wastewater by BPEF.
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    Optimized Process and Design: Incomplete Combustion in FCC Regenerators to Produce CO
    Yi Cai, Li Shiyu, Liu Zhiqiang
    China Petroleum Processing & Petrochemical Technology    2022, 24 (4): 64-75.  
    Abstract95)      PDF(pc) (2641KB)(142)       Save
    The catalyst regeneration process running under the partial oxidation mode in traditional fluid catalytic cracking (FCC) units needs a carbon monoxide (CO) boiler to burn the flue gas, resulting in a large volume of CO2 emissions. In this study, the performance of a set of industrial serial-type FCC regenerators and the changes in flue gas composition were analyzed by establishing a model of the regenerators and the flue gas energy recovery section. Considering the value of utilizing CO, based on the simulation, this paper proposes two schemes for maximizing CO content in the flue gas of regenerators. The two sets of optimal process operating parameters were obtained using a genetic algorithm. Compared with the original process, the CO contents of flue gas in the two optimized processes increased to 6.6% and 12.5%, CO2 emissions were reduced by 48.4% and 96.7%, and the costs of CO production were 0.57 $/Nm3 and 0.84 $/Nm3, respectively.
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    Mechanistic Insights into the Catalytic Cracking of Cyclohexane
    Chen Hui, Yan Jiasong, Su Youyou, Wei Xueer, Li Rui, Wang Peng, Yu Shanqing, Dai Zhenyu
    China Petroleum Processing & Petrochemical Technology    2022, 24 (4): 12-20.  
    Abstract94)      PDF(pc) (1328KB)(112)       Save
    Although naphthenes have long been identified as important feedstock components for the production of light olefins and aromatics in fluid catalytic cracking units, their cacking mechanism and microscopic reaction networks, such as activation modes, ring-opening paths, and aromatization production, remain debated. In this context, we reported experimental and computational work aimed at elucidating the reaction network of naphthenes in fluid catalytic cracking using cyclohexane as the model naphthene. First, the main reactions for the formation of highly selective and value-added products such as light olefins and aromatics were discussed. Then, the proportions of cyclohexane activation via (i) the non-classical carbonium mechanism and (ii) the classical carbenium mechanism were analyzed by data fitting methods, which revealed that around 32.6% of cyclohexane was initiated by path (i), and the remaining naphthene was activated by path (ii). Moreover, our DFT results showed that the ring opening of cyclohexane through pathway (i) was more difficult than that through path (ii), and ring opening followed by the ring contraction of cyclohexane carbenium ions was the most energetically favorable route among the different ring-opening ways.
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    Effect of Different Loadings on the Performance of Ni2P/Al2O3 Catalysts for Low-Temperature Thioethering  and Selective Hydrogenation of Diolefins in Liquefied Petroleum Gas
    Xiao Han, Sun Jinru, Song Guoliang, Xie Xianna, Ke Ming, Tong Yanbing, Zhao Zhiping, Wang Zijian, Li Jiahan
    China Petroleum Processing & Petrochemical Technology    2023, 25 (1): 79-90.  
    Abstract91)      PDF(pc) (1305KB)(74)       Save
    In this study, different loadings of x%Ni2P/γ-Al2O3 (x = 6%, 9%, 12%, 15%, 18%) catalysts with aluminum  oxide (Al2O3) as the carrier, nickel chloride (NiCl2) as the nickel (Ni) source, and ammonium hypophosphite (NH4H2PO2)  as the phosphorus (P) source were prepared by the equal volume impregnation method to investigate the effects of different  loadings on the performance of the selective hydrogenation of diolefins and thiol etherification in LPG. The physicochemical  properties of the catalysts were characterized by XRD, BET, SEM, TEM, H2-TPR, and XPS, and the catalytic activity of  the catalysts was evaluated in a fixed-bed microreactor. The results showed that a change in the loading affected the catalyst  crystalline phase structure and size, specific surface area, P coverage, active phase dispersion, and catalytic activity. At  6%, 9%, and 12% loadings the catalysts had an Ni phase but there was no obvious Ni2P phase in the nickel phosphide; at  15% loading a single Ni2P phase was obtained, and at 18% loading both Ni2P and Ni12P5 phases appeared. There was a P  enrichment on the catalyst surface, and the higher the loading the more P species were enriched on the surface, but some  of the P was lost during the catalyst reduction process due to the production of phosphine (PH3) gas. The 15%Ni2P/γ-Al2O3  catalyst had the largest Ni/Al ratio and the best dispersion. The Ni2P active phase size was small at about 4.25 nm and Ni2P  was uniformly dispersed on the catalyst surface without agglomeration. The 15%Ni2P/γ-Al2O3 catalyst had the best catalytic  activity at a pressure of 2.0 MPa, a liquid hourly space velocity (LHSV) of 3.0 h-1, and a hydrogen to hydrocarbon ratio of  12. The 1,3-butadiene conversion was 97.45% and the methanethiol removal was 100% at a temperature of 140°C.
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    Synthesis and Performance of an Associative Anti-shear Drag Reducer Based on Hydrogen Bond Association of Dodecyl Methacrylate#br#
    Lu Yong, Li Chenhao, Li Hao, Chen Yue, Xu Dan, Wang Yiran, Meng Yeqiao, Zhang Xiaolai
    China Petroleum Processing & Petrochemical Technology    2023, 25 (1): 23-33.  
    Abstract90)      PDF(pc) (1110KB)(92)       Save
    Using K2S2O8-Na2SO3 as the redox initiation system, a hydrogen-bond-association-based dodecyl methacrylate  system associative anti-shear drag reducer was synthesised by standard emulsion polymerisation. The reaction process  was simple and gentle as well as safe and stable. Molecular design was carried out using molecular dynamics simulation  methods. The results of infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, gel  chromatography, and laser light scattering showed that the reaction polymerisation was relatively complete, the product was  uniform, the molecular weight distribution was controllable, and the synthesised polymer had good flexibility. The donor  lauryl methacrylate-styrene-methacrylic acid (LMA-St-MAA) and acceptor lauryl methacrylate-styrene-dimethylaminoethyl  methacrylate (LMA-St-DMA) polymers had an associative intermolecular interaction force, which increased the molecular  cluster size of the associative system complex. The complex had good shear resistance, and the test results of the tube pump  shear test showed that the synthesised associative oil-soluble polymer drag reduction system exhibited better drag reduction  rate performance than poly-α-olefins over repeated cycles. The research results provide a reference plan for minimising the  number of station-to-station inputs, thereby ensuring the stability of oil pipelines and reducing transportation costs.
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    Diffusion Characteristics and Removal of Cyclohexane in Polyolefin Elastomer Melt
    Qi Jibing, Yang Tong, Liu Yandong, Yuan Zhiguo, Zhang Qiaoling, Liu Youzhi, Yi Jianjun
    China Petroleum Processing & Petrochemical Technology    2022, 24 (4): 76-85.  
    Abstract86)      PDF(pc) (1377KB)(132)       Save
    Diffusion coefficient of volatiles in polymer solutions is a crucial parameter to describe the mass transfer efficiency and ability of volatiles. In this research, polyolefin elastomer (POE) was used as polymer, and cyclohexane was used as volatiles, the gravimetric analysis was applied to measure the diffusion coefficient of cyclohexane in POE. The devolatilization rate of POE-cyclohexane system under different conditions was measured. The effects of temperature, film sample thickness and initial concentration of volatiles on the devolatilization rate were discussed. Based on the devolatilization rate data, the average diffusion coefficient of cyclohexane in POE was obtained by fitting with the mathematical model. Experimental results indicate that the devolatilization rate increased with increasing temperature and initial concentration of volatiles, but decreased with increasing thickness of sample. With the thickness increases, the overall diffusion resistance increases. With the temperature increases, the molecular movement increases, resulting in the increase of average diffusion coefficient. The diffusion coefficient of POE-cyclohexane system with temperature follows the Arrhenius law. The diffusion activation energy E=6201.73 J·mol-1, and the pre-exponential factor of the diffusion coefficient D0=2.64×10-10 m2/s. This work can provide basic data for exploring the devolatilization of POE polymer, and provide a useful reference for enhancing the effect of devolatilization.
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    Determination of the Henry’s Law Constant of Hexane in  High-Viscosity Polymer Systems
    Qi Jibing, Li Yuliang, Liu Youzhi, Yang Tong, Liu Yandong, Yuan Zhiguo, Yi Jianjun
    China Petroleum Processing & Petrochemical Technology    2023, 25 (1): 34-43.  
    Abstract85)      PDF(pc) (1037KB)(93)       Save
    Henry's coefficient of volatiles in the polymer system is a crucial parameter reflecting the gas-liquid equilibrium, which is very important for the devolatilization process. In this research, POE-cyclohexane and PDMS-hexane systems were taken as examples, using the gas-liquid equilibrium method, Henry's coefficient was obtained by measuring the gas phase equilibrium partial pressure when polymer solution containing different mass fractions of volatiles reached a saturated state. The effects of temperature, kinds of volatiles and polymer viscosity on the gas phase equilibrium partial pressure and Henry's coefficient of volatiles were investigated. Experimental results indicate that, with the increase of temperature and polymer viscosity, the gas phase equilibrium partial pressure and Henry's coefficient of volatile cyclohexane increase. As temperature increases, the solubility of gas in liquid decreases. In POE-cyclohexane system, the relationship between Henry's coefficient of cyclohexane and temperature can be expressed by lnH=389.39-244402.54×(1/T)+3.86×10^7×(1/T)^(2 ). While in the PDMS-cyclohexane, it can be expressed by lnH=106.57-60139.08×(1/T)+8.69×10^6×(1/T)^2 . In PDMS-hexane system, the gas phase equilibrium partial pressure and Henry's coefficient of n-hexane with straight chain structure are higher than those of cyclohexane with cyclic structure. Henry's coefficient obtained in this study can provide a reference for perfecting the devolatilization process and improving the devolatilization effect.
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    Attenuation of Chlorinated Contamination in Three  Different Depths of Aquifers at Remediation Site
    Sun Shaodong, Li Weisi, Huang Yongjun, Jiang Qing, Bai Yu, Wang Kunhua, Xue Jianliang, Wang Bo, Yan Dongdong, Xu Conghai
    China Petroleum Processing & Petrochemical Technology    2023, 25 (1): 162-178.  
    Abstract84)      PDF(pc) (5008KB)(106)       Save
    The cleanup of carbon tetrachloride (CCl4) in groundwater is challenging due to its high volatility and tendency to  form a dense nonaqueous liquid phase. From the engineering applications perspective, the pump-and-treat (PAT) technology  has substantial advantages owing to its large-scale implementation ability to solve groundwater contamination. However,  few studies focused on the variation in chloride contaminants in remediation sites after the contaminated groundwater was  pumped and treated. Herein, we monitored the changes in chlorinated contamination in groundwater from 12 aquifers at the  field level for 6 months. Considering that the natural attenuation of chlorinated contamination is inseparable from the action  of microorganisms, the major environmental factors influencing biodegradation were also evaluated. A redundancy analysis  (RDA) showed that inorganic salts (DS, DN, and DF) were the most important factor (>60%) affecting the concentration  of chloride contaminants, including the negative correlation between DN and the degradation of contaminants in shallow  aquifers. In deep aquifers, DS, DF, and pH explained most of the degradation of chloride contaminants. For bedrock layers,  DCl was positively relevant to the chloride contaminants in wells PTJ2 and PTJ10. In addition, EC and DS accounted for  73.2% and 92.4% of the contaminant’s variance in wells PTJ4 and PTJ8, respectively. Moreover, the concentrations of  the corresponding contaminations and physicochemical variation in three different depths of aquifers were compared; the  shallower aquifers showed a higher biodegradation. The in situ monitoring and analysis of contaminated groundwater in  remediation sites under PAT will promote practical wastewater treatment technologies in engineering applications. 
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    Preparation of a TiO 2 @o-Vanillin@TEOS-APTES Nanocontainer and Its Anti-Corrosion Performance on  Steel
    Wu Yaqi, Xing Jinjuan, Qian Jianhua, Liu Lin
    China Petroleum Processing & Petrochemical Technology    2022, 24 (4): 36-50.  
    Abstract81)      PDF(pc) (3137KB)(130)       Save
    A TiO2@o-vanillin@TEOS-APTES nanocontainer was prepared by an experimental process in which, first, 2-hydroxy-3-methoxybenzaldehyde (o-vanillin) was loaded in a TiO2 container to obtain TiO2@o-vanillin. Then, TiO2@o-vanillin was encapsulated by tetraethyl orthosilicate (TEOS). Finally, 3-aminopropyl triethoxysilane (APTES) was used to modify the obtained sample. The morphology, structural phase and thermal stability of the TiO2@o-vanillin@TEOS-APTES nanocontainer were analyzed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD) and thermal gravimetric analysis (TG). The release rate of o-vanillin was investigated using an ultraviolet-visible (UV-vis) spectrometer. The anti-corrosion performances of the epoxy, epoxy@o-vanillin and epoxy@TiO2@o-vanillin@TEOS-APTES coatings on steel sheets were evaluated using an electrochemical method and scarification experiments. The results showed that the impedance value of the epoxy@TiO2@o-vanillin@TEOS-APTES coating was two orders of magnitude higher than that of the blank epoxy coating, and one order of magnitude higher than that of the epoxy@o-vanillin coating. The maximum inhibition rate of the epoxy@TiO2@o-vanillin@TEOS-APTES coating on the steel can reach 97.3%. The scarification experiments confirmed that the epoxy@TiO2@o-vanillin@TEOS-APTES coating had the best anti-corrosion performance.
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    Experimental and Numerical Investigation on Erosion Corrosion of the Air Cooler Tube Bundle in a Residue  Hydrotreating Unit
    Jin Haozhe, Yu Chenyang, Gu Youjie, Qian Guangwei, Liu Xiaofei, Ou Guofu, Jia Yongna
    China Petroleum Processing & Petrochemical Technology    2022, 24 (4): 151-162.  
    Abstract80)      PDF(pc) (2879KB)(121)       Save
    Corrosion leakage occurred in the 14th tube bundle of the first row in residual oil hydrotreating air cooler after operating for two years. The failure location was 0.5m away from the outlet header box. In this paper, the erosion-corrosion of the air cooler tube bundle was investigated by experimental and numerical method. Visual inspection, SEM and XRD test were performed, and the failure morphology and material composition proved the damage was caused by erosion-corrosion. SST k-w turbulence model was used to investigate the flow and erosion-corrosion characteristic combined with mass transfer, corrosion rate and ionization equilibrium model. Numerical simulation results show that the increase of water phase volume fraction result in the mass flow rate and concentration of hydrogen sulfide in the process of flow and heat transfer. The mass transfer coefficient and corrosion rate is an important parameter to characterize, and the local concentration of wall shear stress rises the risk of erosion-corrosion. The predicted high-risk area is consistent with the actual failure area, which proved that this failure incident is attributed to the erosion-corrosion in the water phase.
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    Removal of Organochlorine from Model Oil Using Mg-Modified ZSM-5 Zeolite: Dechlorination Performance, Regeneration, and Thermodynamics#br#
    Cheng Xingyuan, Gu Jie, Huang Bingtian, Bing Liancheng, Han Dezhi, Wang Guangjian, Wang Fang
    China Petroleum Processing & Petrochemical Technology    2023, 25 (2): 24-32.  
    Abstract80)      PDF(pc) (1389KB)(104)       Save
    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.
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    The Preparation of B2O3/SBA-15 and Its Application in Nickel-Tolerated FCC Catalyst as Matrix Component
    Yuan Chengyuan, Ju Guannan, Chen Qiang, Yan Tao, Li Zhongfu
    China Petroleum Processing & Petrochemical Technology    2023, 25 (1): 144-150.  
    Abstract78)      PDF(pc) (553KB)(90)       Save
    Fluid catalytic cracking (FCC) is still a key process in the modern refining area, in which nickel-contamination for FCC catalyst could obviously increase the dry gas and coke yields and thus seriously affect the stability of FCC unit. Therefore, in this paper, B2O3-modified SBA-15 molecular sieves (B2O3/SBA-15) with different B2O3 contents were prepared, characterized and further used in preparation of Ni-tolerated FCC catalyst as matrix component. Characterization results suggested that, B2O3/SBA-15 samples possessed excellent Ni-passivation ability and structure properties of SBA-15 parent such as high-ordered mesopores, big surface area and high pore volume, which made B2O3/SBA-15 sample could greatly improve the Ni-tolerance performance of FCC catalyst by promoting the Structure properties and Ni-passivation ability of the prepared FCC catalyst. The evaluation results of heavy oil catalytic cracking indicated that, at the same Ni-contamination condition, the dry gas, coke and heavy oil yields for the FCC catalyst containing B2O3/SBA-15 could obviously decrease by 0.92, 1.65 and 1.26 percentage points respectively with total liquids yield increasing by 3.83 percentage points in compared with conventional FCC catalyst.
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    Effect of Particle Shape on Catalyst Deactivation during 2-Butene and Isobutane Alkylation of Liquid Phase  in Fixed-Bed Reactor Using Particle-Resolved CFD Simulation
    Zhang Sizhen, Zhu Zhenxing, Xin Feng, Chu Menghan
    China Petroleum Processing & Petrochemical Technology    2022, 24 (4): 139-150.  
    Abstract77)      PDF(pc) (3182KB)(108)       Save
    How catalyst shape affects its deactivation is a crucial issue for quickly decaying catalysts such as zeolite in 2-butene  and isobutane alkylation. In this work, steady simulations are used to determine the temperature and species distribution in  fixed beds filled with particles of four shapes. Subsequently, unsteady simulations are used to study the deactivation behavior  of the catalysts based on the steady simulation results. We describe the deactivation rate and type of catalyst deactivation by  defining a local internal diffusivity, which is affected by catalytic activity. The results reveal that the internal diffusion distance  of the catalyst determines the deactivation rate, whereas the local internal diffusivity determines its deactivation type.
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    Preparation of Ionic Liquids Immobilized on FMIL-101 Catalysts for Conversion of CO2 to Propylene  Carbonate
    Sun Wenjie, Ran Weiting, Guo Liying, Song Xiaohui, Lü Donghao
    China Petroleum Processing & Petrochemical Technology    2023, 25 (1): 54-65.  
    Abstract75)      PDF(pc) (1223KB)(95)       Save
    The FMOFs-[HeMIM]Cl/(ZnBr2)2, FMOFs-[CeMIM]Cl/(ZnBr2)2, and FMOFs-[AeMIM]Cl/(ZnBr2)2 were, respectively, immobilized in functional metal -organic framework materials (FMOFs). They were used to catalyze the cycloaddition reaction of carbon dioxide (CO2) and epoxides. The results from the investigation showed that the three metal-based ionic liquid catalysts were the target products. Under the conditions of reaction temperature 110 oC, reaction pressure 2.0 MPa, and catalyst dosage accounting for 2.0% of the mass of epoxide, the conversion of epoxide was 96.63% and the selectivity of propylene carbonate was 98.64%, thus forming the optimal catalyst FMOFs-[CeMIM]Cl/(ZnBr2)2. Moreover, the catalyst has no obvious change in catalytic performance after being recycled four times.
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    Hydrogenation Behavior of Hydrogen Peroxide in a Microreactor
    Zhu Hongwei, Sun Bing, Jin Yan, Feng Junjie, Zhao Chenyang, Yan Junjie, Jiang Jie, Xu Wei
    China Petroleum Processing & Petrochemical Technology    2022, 24 (4): 29-35.  
    Abstract73)      PDF(pc) (879KB)(117)       Save
    The hydrogenation of hydrogen peroxide is an unwanted side reaction in the direct synthesis of hydrogen peroxide and remains a problem to solve. The mechanism of this reaction has been studied with batch reactors but the slow heat and mass transfer in batch reactors hindered the understanding of its intrinsic kinetics. In this study, a microreactor is employed to investigate the parameters that influence the hydrogenation reaction, including flow rate, channel length, hydrogen pressure, solvent composition, and initial hydrogen peroxide concentration. The activity of different catalysts was compared and the hydrogenation law was confirmed, providing guiding information to better control the hydrogenation process.
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    Preparation of Cu/N-TiO2 nano photocatalyst using high gravity technology for photodegradation of phenol wastewater
    Ren Xueqing, Zhang Qiaoling, Zhang Yanfen, Qi Guisheng, Guo Jing, Gao Jing
    China Petroleum Processing & Petrochemical Technology    2023, 25 (1): 151-161.  
    Abstract71)      PDF(pc) (1983KB)(95)       Save
    TiO2 is a promising photocatalyst, but the limited contact area of liquid-liquid interface and low catalytic efficiency caused by catalysts with large particle size and uneven distribution restrict the practical application. As an effective process intensification equipment, the impinging stream-rotating packed bed (IS-RPB) overcomes the mixing limitation of traditional stirred tank reactor, and provides a micro-mixing environment at the molecular scale for liquid-liquid two phase, which could reduce the particle size and distribution range. Cu/N-TiO2 nanoparticles were successfully prepared by one-step precipitation method using urea as the nitrogen source, titanyl sulfate as the titanium source, copper chloride as the copper source and ammonium hydroxide as the precipitant in an IS-RPB. The particle size of obtained photocatalyst was about 11.40 nm with narrow size-distribution via SEM and TEM. According to XPS, N replaced part of O, and was uniformly dispersed in the TiO2 lattice in the form of interstitial N and substitutional N. Cu replaced part of Ti and existed in the form of Cu2+. The synergistic effect of these two elements forms a new impurity energy level and reduces band gap energy of TiO2 nanoparticles. The specific surface areas of Cu/N-TiO2 are 152.97 m2/g. The influence of the main factors on the degradation rate was studied, the results showed that the removal efficiency could reach 100% under the optimal operating conditions after 2 hours UV light irradiation. The EPR measurement showed that the superoxide radical (O2-·) played a leading role in the degradation process, while the effect of photogenerated holes (h+) and hydroxyl radicals (OH·) were relatively weak.
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    Synthesis of Hierarchical Porous Fe 2 O 3 /Al 2 O 3  Materials and Study on Catalytic Viscosity Reduction of  Heavy Oil
    Wu Peiyue, Ma Zhaofei, Yang Haiyang, Xiong Pan, Tan Dichen, Yan Xuemin
    China Petroleum Processing & Petrochemical Technology    2022, 24 (4): 98-107.  
    Abstract69)      PDF(pc) (2782KB)(86)       Save
    Fe2O3 nanoparticles were dispersed in the sol solution containing the aluminum component by the prophase doping method, then the composite catalyst hierarchical porous Fe2O3/Al2O3 materials (HPFA) were synthesized through a sol-gel method and phase separation via phase separation method. The performance of HPFA were compared with that of Fe2O3 nanoparticle catalyst. The structure of the composite catalyst was characterized by SEM, XRD and N2 adsorption and desorption. The results show that Fe2O3 nanoparticles could be loaded on porous skeletons to achieve uniform dispersion, avoid agglomeration, and improve the mechanical strength of porous materials significantly. The HPFA were then used as a hydrothermal cracking catalyst in the viscosity reduction process of Tuha thick oil, and the viscosity reduction was investigated. The viscosity reduction rate of HPFA was 81%, which was better than that of Fe2O3 nanoparticles (56%) and hierarchical porous Al2O3 materials (47%).
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