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    A novel MIL-101(Cr) acidified by silicotungstic acid and its catalytic performance for isomerization of n-heptane
    China Petroleum Processing & Petrochemical Technology    2022, 24 (1): 68-80.  
    Abstract412)      PDF(pc) (1596KB)(34)       Save
    0.4%Pt/xSTA-MIL-101(Cr) metal-acid bifunctional catalysts were prepared by impregnation using STA-MIL-101(Cr) as the support. The synthesized samples were verified to exhibit a typical octahedral structure of MIL-101(Cr) and the pore structure were arranged orderly. The specific surface area of the samples was extremely high and the samples were micro-mesoporous composite materials. Silicotungstic acid could retain its Keggin structure in the 0.4%Pt/xSTA-MIL-101(Cr) samples and the catalyst possessed moderately strong Br?nsted acid sites. Besides, the dispersion of Pt particles in MIL-101(Cr) was relatively high. n-Heptane isomerization was first used as a probe to test the novel 0.4%Pt/xSTA-MIL-10(Cr) catalyst. Compared with the conventional silicate catalysts, the catalytic performance of 0.4%Pt/30wt%STA-MIL-101(Cr) was significantly improved with n-heptane conversion of 58.93% and iso-heptane selectivity of 95.68%, respectively, when the reaction time was 2 h at the reaction temperature of 260 oC. The catalyst could still maintain a relatively high catalytic performance during the reaction time of 5 h. Compared with the non-noble metal catalysts, the catalytic efficiency is relatively high. The mechanism model of n-heptane isomerization over 0.4%Pt/xSTA-MIL-101(Cr) catalyst was established.
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    Insights into the Reaction Network and Mechanism of Green Aerobic Oxidative Esterification of Methacrolein over Different Heterogeneous Catalysts
    Li Chenhao, Xia Changjiu, Liu Yujia, Huang Kaimeng, Peng Xinxin, Liu Jinsheng, Lin Min, Zhu Bin, Luo Yibin, Shu Xingtian
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 1-11.  
    Abstract233)      PDF(pc) (848KB)(251)       Save
    The oxidative esterification of methacrolein (MAL) is an important way to prepare high-valued methyl methacrylate (MMA), but this process is ultra-complex, due to the highly reactivity of both C=O and C=C bonds within MAL. In order to further improve the selectivity of MMA selectivity, the reaction network and mechanisms over different catalysts have been profoundly investigated in this paper. Five kinds of reactions are involved in this process, including (a) hemiacetal/acetal reaction; (b) aerobic oxidation of aldehyde/alcohol; (c) alkoxylation of C=C double bond; (d) Diels-Alder reaction; (e) hydrogenation reaction of double bond/ carbonyl. Among them, Diels-Alder reaction of MAL is noncatalyzed, and Br?nsted acid sites favor promoting hemiacetal/acetal reaction of MAL with methanol, while alkaline sites enhance the alkoxylation of C=C bond with methanol. In particular, by using Pd-based catalysts, several kinds of hydrogenated products are formed, hence with lower MMA selectivity than those of Au-based catalysts. Notably, it is of necessary to match the hemiacetal reaction of MAL with methanol to and aerobic oxidation of hemiacetal, which is relevant with the amount of Br?nsted acid and redox sites. Consequently, this work provides a good guidance for the further design of both catalysts and processes in future.
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    Recent Progresses on Optimal Design of Heat integrated water allocation network
    Zhang Chijin, Ren Congjing, Liao Zuwei, Sun Jingyuan, Wang Jingdai, Yang Yongrong
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 69-75.  
    Abstract188)      PDF(pc) (577KB)(166)       Save
    It is well known that the process industry is an energy-intense and water-consuming industry and is the main source of industrial water consumption and energy in China. Energy integration and mass integration are important approaches to achieve energy saving and emission reduction in the process industry. Generally, the methods can be classified into two groups: conceptual design methods and mathematical programming methods. The former includes mainly graphical methods based on pinch technology that is operated easily. A feasible solution can be quickly obtained. Conceptual design methods are sequential in nature including targeting and design two steps. The latter is based on superstructure optimization and corresponding algorithm is adopted to solve the model. The trade-offs and connections among the entire network can be established and explored. Multiple factors can be considered and optimized simultaneously by mathematical programming methods. This paper describes the synthesis of heat integrated water allocation networks (HIWAN) based on both conceptual design methods and mathematical programming methods systematically. In addition, the characteristics and shortcomings of the existing research methods are summarized, and the future research direction is prospected.
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    Carbon Encapsulated Nickel Nanocomposites for the Cathode in Advanced Lithium Sulfur Batteries
    Yang Yuxiang, Xie Jingxin, Wu Genghuang, Zhu Na, Li Huan, Rong Junfeng
    China Petroleum Processing & Petrochemical Technology    2021, 23 (4): 1-6.  
    Abstract165)      PDF(pc) (882KB)(179)       Save
    Lithium sulfur (Li-S) batteries are poised to be the next generation of high-density energy storage devices. In recent years, the concept of “electrocatalysis” has been introduced into the field of Li-S batteries, and some transition metals have been proved to catalyze the electrochemical conversion reaction of sulfur species. In this study, carbon encapsulated nickel nanoparticles (Ni@C) with a specific surface area of 146 m2/g are shown to play a definitive electrocatalytic role for the sulfur cathode. With Ni@C incorporated, the Ni@C/G-S electrode achieved a better electrochemical performance than the G-S electrode. Moreover, the reversible capacity and cycle stability were further improved through chemical modifications of the carbon shell. The influence of doping with different elements on the Li-S battery performance was also investigated in detail. Higher specific capacities of 1229 mAh/g, 927 mAh/g, and 830 mAh/g were achieved at 0.2 C, 0.5 C, and 1.0 C for the N-Ni@C-G/S electrode. Besides, the B-Ni@C-G/S electrode possessed a best cycle stability.
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    Study on the effect of the position of the particle electrode on the electrocatalytic reaction efficiency in three dimensional electrocatalytic system
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 30-39.  
    Abstract152)      PDF(pc) (1621KB)(134)       Save
    In order to explore the effect of particle position on the electrocatalytic reaction rate in three-dimensional electrocatalytic reactor,methylene blue was used as the simulated organic wastewater, and spherical graphite particles were used as the electron electrode, COMSOL Multiphysics software were used to simulate potential distribution in three dimensional electrocatalytic reactor. The logarithmic regression model was established with the particle size, potential and position as independent variables and the first-order kinetic constant as dependent variable. Combined with the model, the degradation efficiency of the particle electrodes at different positions in the reactor was predicted, the simulation results show that the reaction efficiency of particle electrode for pollutant degradation is uneven in the three-dimensional electro catalytic oxidation reactor, the increasement of the electric field intensity can change the distribution of electrocatalytic efficiency of particle electrode, the closer the particle electrode is to the anode position, the higher the ability of degradation of pollutants. The difference of electrocatalytic reaction rate between different positions in the particle is large. According to the degree of difference, it can be roughly divided into three regions, and the distribution of electrocatalytic reaction efficiency at different positions in the particle electrode is simulated.
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    Controlling the Pore Structure and Photocatalytic Performance of the Flexible FeⅢ Metal-Organic Framework MIL-53(Fe) by Using Surfactants
    Zhang Dan Yang Ping Zhang Youhua Duan Linhai Meng Xiuhong
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 23-29.  
    Abstract129)      PDF(pc) (829KB)(134)       Save
    An approach for dominating the channel form of the flexible MIL-53(Fe) was developed by using a surfactantassisted modified method. The surfactant tetraethylammonium hydroxide (TEAOH) can control the channel form of MIL- 53(Fe) to be a “closed-pore” form, whereas the surfactant polyoxyethylene polyoxypropylene polyoxyethylene (P123) or polyvinyl alcohol (PVA) can dominate the channel form of MIL-53(Fe) for a “large-pore” form. The photocatalytic performance of MIL-53(Fe) with different channel forms was investigated through the degradation of rhodamine B (Rh B) in water under violet light irradiation. The results showed that MIL-53(Fe) with a “large-pore” form exhibited higher photocatalytic activity than that of MIL-53(Fe) with a “closed-pore” form. MIL-53(Fe) modified with PVA exhibit the best photocatalytic activity degraded almost 100% Rh B in 90 minutes.
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    Xia Xiaoqi, Li Hongming, Li Chunman, Miao Qing, Li Jing, Zhu Feng, Huang Qigu, Yi Jianjun, Zhao Zhong
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 12-22.  
    Abstract126)      PDF(pc) (948KB)(130)       Save
    Due to the development of the new energy industry, polypropylene with ultra-high molecular weight plays a crucial role for battery isolation membrane. This work investigated the effect of internal electron donor of Ziegler-Natta catalyst system on the molecular weight of the obtained polypropylene. The scanning electron microscope (SEM) and Canon camera were used to characterize the surface morphologies of catalyst particles and polymer particles, respectively. Compared with the polypropylene particles featuring a spherical shape, these study results confirmed that the morphology duplication theory from the catalyst particle to the morphology of polymer particle was exhibited. The gel permeation chromatography (GPC) results revealed that the obtained polypropylene has a much higher average molecular weight than those prepared by conventional method. The Fourier transform infrared spectrometry (FT-IR) and X-ray photoelectron spectroscopy (XPS) revealed that the carbonyl oxygen atom on ester group was preferentially bound to Mg and Ti, as compared to the ether oxygen atom. The XPS results showed that the ratio of Ti3+/Ti4+ could be changed by internal electron donors. When Ti3+content was nearly 99% in the Ziegler-Natta catalyst system, isotactic polypropylene with an ultra-high molecular weight of up to 1.42×106 g/mol was obtained by Cat. 3. This result  implied that internal electron donor ID3 could reduce the β-hydride elimination reaction to further increase the molecular weight of the obtained polymer.
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    Chemoselective catalytic hydrogenation of nitroarenes using MOF-derived graphitic carbon layers encapsulated Ni catalysts
    Wu Genghuang, Rong Junfeng
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 40-49.  
    Abstract121)      PDF(pc) (1352KB)(114)       Save
    Replacement of precious noble metal catalysts with cost-effective, non-noble heterogeneous catalysts for chemoselective hydrogenation of nitroarenes holds tremendous promise for the clean synthesis of nitrogen-containing chemicals. Graphitic carbon layers encapsulated Ni catalysts (Ni@CN) are generated by a facile, scalable and straightforward strategy via the pyrolysis of 2,5-pyridinedicarboxylic acid coordinated Ni-MOF acting as the precursor. Physicochemical properties of the Ni@CN catalysts have been investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, elemental analysis and N2 adsorption-desorption analysis. The Ni@CN catalysts were found to be highly efficient in the chemoselective hydrogenation of various nitroarenes with other functional groups towards corresponding anilines under mild reaction conditions (85 °C, 1.0 MPa of H2 pressure). Based on the results of controlled tests, the catalytic activity can be attributed to the Ni NPs, while the presence of graphitic carbon layers favors the preferential adsorption of the nitro groups. The recyclability and anti-sulfur poisoning capability of Ni@CN were also investigated.
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    Heteroatom-doped carbon Spheres from Fluidized Catalytic Cracking Slurry Oil as anode material for lithium-ion battery
    China Petroleum Processing & Petrochemical Technology    2022, 24 (1): 1-10.  
    Abstract118)      PDF(pc) (1988KB)(103)       Save
    A facile injected pyrolysis strategy to synthesize heteroatom-doped carbon spheres (CSs) with good conductivity is proposed by only using fluidized catalytic cracking slurry oil (FCCSO) as carbon source through a pyrolysis reaction process at 700-1000°C. The structures of CSs are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The influence of preparation conditions on the morphology of CSs and its electrochemical properties as anode material for Lithium-ion battery (LIBs) are investigated. The XPS measurement results show that the CSs mainly contain C, N, O and S elements. With the increase of pyrolysis temperature, the particle size of CSs decreases but the graphitization degree of CSs increases. As the anode material for lithium-ion batteries (LIBs), CSs shows excellent electrochemical performance with a high maximum reversible capacity of 365 mAh·g-1 and an initial coulombic efficiency of 73.8% at a low current density of 50 mA·g-1. CSs exhibits excellent cycling stability in the current range of 50 mA·g-1 to 2 A·g-1 and still maintains a stable reversible capacity of 347 mAh·g-1 when the current is cycled back to 50 mA·g-1. This is mainly due to the existence of suitable heteroatom content and unique spherical structure of CSs. The heteroatom-doped CSs provides a new choice for the preparation of high efficiency anode materials for LIBs.
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    Synthesis of Bimodal Mesoporous TiO2 -PTA/BMMS and its Enhanced Performance in the Photocatalytic Oxidative Desulfurization
    Yang Lina, Zhang Xi, Cui Licheng, Xu Meizhen, Li Jian
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 58-68.  
    Abstract116)      PDF(pc) (1371KB)(86)       Save
    Abstract: With the bimodal mesoporous silica (BMMS) acting as the support and the composite of TiO2 with phosphotungstic acid (PTA) functioning as the active constituent, TiO2-PTA/BMMS was synthesized by the two-step impregnation route. This catalyst was applied in the photocatalytic oxidative desulfurization (PODS) process, with the dibenzothiophene serving as the model sulfur compound. PODS proceeds in one pot, in which H2O2 acts as the oxidant and methanol plays the role of the solvent. TiO2-PTA/BMMS was characterized by XRD, N2 adsorption and desorption, XRF, FTIR, UV-vis, SEM, EDS and TEM techniques. It showed that the introduction of PTA contributes higher order, higher surface area and pore volume to the bimodal mesoporous support. With TiO2-PTA/BMMS used as the catalyst under the UV irradiation, the desulfurization rate can reach 99.6%. This result is obviously higher than that achieved by TiO2/BMMS. The catalyst also has no significant drop in catalytic activity after eight runs of reusing. In such catalytic system, the synergistic effects of this photocatalytic oxidation and the extraction with the methanol serving as the solvent played an indispensable role.
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    Acidity evaluation of industrially dealuminated Y zeolite via methylcyclohexane transformation
    Hou Kaige, Qin Bo, Han Junjie, Du Yanze, Ma Jinghong, Li Ruifeng
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 50-57.  
    Abstract109)      PDF(pc) (512KB)(99)       Save
    The catalytic transformation of methylcyclohexane as an accepted probe reaction to evaluate zeolitic acidity (concentration, strength, and accessibility) is employed to study the acidity and the reactivity of three commercial dealuminated Y zeolites (DAY) with different Si/Al ratios and meso/microporosities, accompanied by N2 adsorption/desorption, pyridine-IR, hydroxyl-IR spectroscopy technologies. The global activity (conversion) is largely dependent on the concentration of the acid sites, and the activity of the protonic sites in terms of turnover frequency (TOF) reflects the accessibility of acid sites. The products of aromatics and isomers, and the yield of cracking products increase with the increase of concentration of strong protonic sites in zeolite micropores. Moreover, the decrease of aromatics with the reduction of the concentration of acid sites and the diffusion length within DAY zeolites are observed due to the decrease of the secondary reaction. For the same reason, it results in the increasing of C7 products and alkenes/alkanes ratios in the cracking products. The high i-C4 product selectivity is a unique reflection of the high percentage of very strong acid sites, which is characterized by the hydroxyl-IR band at 3600 cm-1.
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    Dechlorination of Crude Oil by Phase Transfer Catalyst in Nucleophilic Substitution Reaction
    Gu Jin, Han Xin†, Liu Jichang, Huang Zihao, Xing Biao
    China Petroleum Processing & Petrochemical Technology    2021, 23 (4): 18-28.  
    Abstract108)      PDF(pc) (836KB)(119)       Save
    Dechlorination of crude oil is an effective way to alleviate corrosion in refinery units, and the critical process is the removal of organochlorine which can be efficiently removed through nucleophilic substitution reaction catalyzed by phase transfer. Herein, seven typical chlorinated alkanes were selected as model compounds to study the mechanism of dechlorination of crude oil by phase transfer catalyst in the nucleophilic substitution method, and a new dechlorination reagent using hexamethyl quaternary ammonium hydroxide with two quaternary ammonium groups as phase transfer catalyst, ethylenediamine as nucleophile and ethanol as solvent was developed. The results show that the dechlorinating performances of the dechlorination reagent on the model compounds are as follows: epichlorohydrin > 1,2-dichlorobutane > 1,2-dichloroethane > 1,3-dichloropropane > 2-chloropropane > 1-chlorobutane > chloroisobutane, and the results of the reaction kinetics show that epichlorohydrin with epoxy structure has the lowest activation energy in the process of nucleophilic substitution reaction by the phase transfer catalyst which makes it easier to be removed by the dechlorination reagent. The removal rate of epichlorohydrin can reach up to 99.4%. The optimal dechlorination reagent used ethylenediamine as nucleophile, ethanol as solvent and hexamethyl quaternary ammonium hydroxide as phase transfer catalyst. The dechlorinating rate of the Iranian crude oil reached 71.6 % at the reaction temperature of 95°C, the reaction time of 90 minutes, the dechlorination reagent dosage of 1000 mg/kg and the 6:1 molar ratio of phase transfer reagent and nucleophile. In addition, the mechanism of phase transfer in nucleophilic substitution reaction of chloroalkanes is investigated in the paper.
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    Effects of Hydrotreating Severity on hydrocarbon Compositions and Deep Catalytic Cracking Product Yields
    Deng Zhonghuo, Dai Lishun, Niu Chuanfeng, Jia Yanzi, Wei Xiaoli, Cai Xinheng
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 112-118.  
    Abstract107)      PDF(pc) (868KB)(113)       Save
    Residue deep hydrotreating (RDHT) process was developed by the Research Institute of Petroleum Processing  (RIPP) to provide high quality feedstock for deep catalytic cracking (DCC) process. In this research work, the effects  of RDHT process and reaction severity on heteroatom removal, hydrogen content increase, hydrocarbon composition  improvement, and DCC product yields were studied. It was showed that the RDHT process can effectively reduce  heteroatoms, increase hydrogen content and improve the hydrocarbon compositions, which can contribute to an increase of  light olefins yield in DCC unit.
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    Adsorption and regeneration of Volatile Organic Compounds(VOCs) on coal-based activated carbon by ferric nitrate modification
    Jin Chunjiang Wang Luyuan
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 137-150.  
    Abstract102)      PDF(pc) (1963KB)(72)       Save
    In this work, heishan coal was used to prepare a series of activated carbon samples (ACs) l via a vapor depositition method. The effects of the weight ratio (Fe(NO3)3:coal ) on the physicochemical properties of the activated carbon were systematically investigated, and the ACS samples were detected by N2 adsorption-desorption, SEM, XRD, Raman and FTIR. Furthermore, the adsorption properties for ethyl acetate were tested. The results indicated that as the ratio increasing from 1:8 to 1:2, the specific surface area, total pore volume and micropore volume first increase and then decrease,the specific surface area increased from 560.86 m2/g to 685.90 m2/g and then decreased to 299.56m2/g. The total pore volume and micropore volume increased from 0.29cm3/g, 0.17cm3/g to 0.30cm3/g, 0.22cm3/g, and then decreased to 0.16cm3/g and 0.10cm3/g, respectively. The optimized ratio is ~. in the activation process, The iron ions would be infiltrated into the activated carbon could significantly promote the development of pore structure, especially the pores with pore size between 2.5-3nm, which enhance the adsorption capacity of ethyl acetate. It is worth noting thatthe ACs had the largest specific surface area and total pore volume of 685.90 m2/g and 0.30 cm3/g under the optimized activation (950oC, 20 vol.% CO2 ,the ratio is 1:5), the maximum adsorption capacity of ethyl acetate was 962.62mg/g, and after 7 times of repeated thermal regeneration experiments, the saturated adsorption capacity was still above 90%.
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    The preparation of modified enteromorpha-immobilized microbial agent and the research on diesel removal performance
    Yang Yuping, Li Nana, Duan Weichao, An Chenye, Xue Jianliang, Jiang Qing, Cheng Dongle, Shen Chanchan
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 151-160.  
    Abstract102)      PDF(pc) (1248KB)(89)       Save
    In order to improve the application effect of immobilization technology in the treatment of marine oil spills, we used sodium dodecylbenzene sulfonate (SDBS) as the modifier to modify enteromorpha by dipping method. Enteromorpha modified by SDBS (SDBS-E) served as an adsorption carrier material for immobilization. At the same time, a marine degrading bacteria Sp8 (Shewanella algae) was selected as the research object. Sodium alginate was used as the embedding carrier, and anhydrous calcium chloride was used as the cross-linking agent to prepare the SDBS-E immobilized microbial agent by embedding method. Compared with the degradation rate of free bacteria (78.87%), the removal rate of diesel by SDBS-E immobilized microbial agent increased to 90.39%. The removal pathway of diesel by SDBS-E immobilized microbial agent was studied, and the results showed that the pathway mainly included surface adsorption, internal uptake and biodegradation. The early stage relied on surface adsorption, and the later relied on biodegradation. The removal of diesel by SDBS-E immobilized microbial agent conformed to the quasi-first-order degradation kinetic model.
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    Real-Time Optimization Model for Continuous Reforming Regenerator
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 90-103.  
    Abstract100)      PDF(pc) (3090KB)(278)       Save
    An approach for the simulation and optimization of continuous catalyst-regenerative process of reforming is proposed in this paper. Compared to traditional method such as finite difference method, orthogonal collocation method is less time-consuming and more accurate, which can meet the requirement of real-time optimization (RTO). In this paper, the equation-oriented method combined with the orthogonal collocation method and the finite difference method is adopted to build the RTO model for catalytic reforming regenerator. The orthogonal collocation method was adopted to discrete the differential equations and sequential quadratic programming (SQP) algorithm was used to solve the algebraic equations. The rate constants, active energy and reaction order were estimated, with the sum of relative errors between actual value and simulate value as optimization objective function. The model can quickly predict the fields of component concentration, temperature and pressure inside the regenerator under different conditions, as well as real-time optimized conditions for industrial reforming regenerator.
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    MnxCo3-xO4 microtubules with enhanced catalytic activity towards toluene combustion:effects of redox property and oxygen species
    Zhang Hanyu Hu yue Zhang Xiaohan Sun Mengyao Liu Rui Jin Quan Qi Jian
    China Petroleum Processing & Petrochemical Technology    2021, 23 (4): 7-17.  
    Abstract100)      PDF(pc) (1344KB)(102)       Save
    Redox property and oxygen species play important role in the catalytic oxidation of volatile organic compounds (VOCs). In this paper, a series of MnxCo3-xO4 catalysts with tubular structure were synthesized and applied for the catalytic combustion of toluene. Various characterization technologies were employed to reveal the relationship between the catalytic performance of the MnxCo3-xO4 catalysts and Mn doping. The results of XRD, SEM and N2 adsorption-desorption showed that the Mn doping had significant effects on the structure and morphology of the MnxCo3-xO4 catalysts. The H2-TPR, O2-TPD and XPS results proved that the strong interaction between Co and Mn resulted in the enhanced Olatt mobility, richer active oxygen species, and enhanced redox property in comparison with the pure Co3O4 sample, which were crucial to the improvement of the catalytic activity of Co-Mn catalysts. The best catalyst, Co5-Mn5 sample, exhibited a good and stable activity to catalytically oxidize toluene at low temperatures even in the presence of water vapor, indicating that it is a potential material for the practically catalytic industrialization for the abatement of toluene.
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    Effect of Diesel Soot on the Distribution, Composition and Mechanical Properties of ZDDP Tribofilm
    Feng Weimin Song Hui Bingxun Yang Hu Xianguo
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 119-126.  
    Abstract86)      PDF(pc) (1425KB)(98)       Save
    To investigate the effect of diesel soot on the distribution, composition and mechanical properties of ZDDP tribofilm. The HFRR tribometer was adopted to study the tribological performance. Worn surfaces lubricated with ZDDP and soot were analyzed by laser microscope, SEM/EDS, Raman spectroscopy, XPS and nano-indentation equipment. Results show that soot scrapes off ZDDP tribofilm and embeds into the worn surface, leading to the reduction of film thickness and non-uniform distribution of tribofim. The phosphate structure in ZDDP tribofilm changes from short chain pyrophosphate to long chain metaphosphate due to the increased contact stress caused by the soot abrasive wear promotes the cross-linking of ZDDP. The hardness (H) and elastic modulus (E) of the worn surfaces increase while the ratio of hardness to elastic modulus, H/E, decreases, which indicates the reduction of wear resistance caused by soot.
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    Biochar Supported Nanoscale Zero-valent Iron Composites for The Removal of Petroleum
    Qin Feifei, Xu Wenfei, Hao Boyu, Yin Linghao, Song Jiayu, Zhang Xiuxia
    China Petroleum Processing & Petrochemical Technology    2021, 23 (4): 47-57.  
    Abstract83)      PDF(pc) (873KB)(64)       Save
    In the process of oilfield exploitation, the extensive use of chemical agents leads to serious crude oil emulsification, which makes the produced liquid contain a large amount of crude oil that is difficult to remove. In order to treat oily wastewater efficiently, quickly and without secondary pollution, nanoscale zero-valent iron (nZVI) was supported on biochar prepared from spent mushroom substrate (SMS) to prepare a novel iron-carbon composite (SMS-nZVI), and its ability to treat high concentration of oily wastewater was comprehensively evaluated. The results of the indoor simulated removal of petroleum experiment show that, compared with SMS and nZVI, SMS-nZVI can remove petroleum quickly and effectively. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) nitrogen-adsorption and Fourier transform infrared (FTIR) were used to characterize the morphology, structure and properties of the composite. The results showed that SMS biochar can effectively prevent the agglomeration of nZVI, increase the overall specific surface area and enhance the adsorption capacity of the composite. Comparing with other biochar substrates, it was found that the iron-carbon composits prepared by spent mushroom substrate has a better petroleum removal effect than the traditional wheat straw biochar. By optimizing the experimental conditions, an operation process with the best petroleum removal effect was obtained: when the mass ratio of nZVI to biochar was 1:5, pH was 4, and the initial concentration of petroleum was 1000mg·L-1, the petroleum removal rate could reach 95% at 5h. After exposing SMS-nZVI to air for 30 days for natural aging treatment, SMS-nZVI can still maintain an oil removal rate of more than 62%, which indicates that the composite has good stability.
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    Process Optimization of RTS Technology for Ultra-Low Sulfur Diesel
    Ge Panzhu, Ding Shi, Xi Yuanbing, Zhang Le, Nie Hong, Li Dadong
    China Petroleum Processing & Petrochemical Technology    2021, 23 (3): 104-111.  
    Abstract82)      PDF(pc) (438KB)(96)       Save
    The RTS technology can produce ultra-low sulfur diesel at lower costs using available hydrogenation catalyst and device. However, with the increase of the mixing proportion of secondary processed diesel fuel in the feed, the content of nitrogen compounds and polycyclic aromatic hydrocarbons in the feed increased, leading to the acceleration of the deactivation rate of the primary catalyst and the shortening of the service cycle. In order to fully understand the reason of catalyst deactivation, the effect of mixing secondary processed diesel fuel oil on the operating stability of the catalyst in the first reactor was investigated in a medium-sized fixed-bed hydrogenation unit. The results showed that the nitrogen compounds mainly affected the initial activity of the catalyst, but had little effect on the stability of the catalyst. The PAHs had little effect on the initial activity of the catalyst, but could significantly accelerate the deactivation of the catalyst. Combined with the analysis of the reason of catalyst deactivation and the study of RTS technology, the direction of RTS technology process optimization was put forward, and the stability of catalyst was improved obviously after process optimization.
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