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Table of Content

    28 July 2021, Volume 21 Issue 7
    Contents
    Cover and Contents
    The Chinese Journal of Process Engineering. 2021, 21(7):  0. 
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    Review
    Research progress on synergistic extraction of typical organophosphorus extractant in solvent extraction
    Hao ZHANG, Guohua YE, Ziyang CHEN, Yu XIE, Qi ZUO
    The Chinese Journal of Process Engineering. 2021, 21(7):  741-751.  DOI: 10.12034/j.issn.1009-606X.220179
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    As a branch of solvent extraction, synergistic extraction has been widely studied. In order to explore the mechanism of synergistic extraction, it is necessary to clarify the internal reasons of the extraction system and give the relationship between the micro and macro properties. Therefore, it is important to understand the synergistic extraction system and the influencing factors from the microscopic structure and internal movement of molecules. In this owrk, the mechanism of synergistic action between extractant, extractant and metal ions and the influencing factors were reviewed. It pointed out that the essence of synergistic extraction was the formation of hydrogen bonds, which led to the change of the structure and energy of extractant, thus improving the extraction effect. Synergistic extraction mainly includes two aspects: one is easier to generate stable extraction complex to improve the extraction efficiency; the other is to improve the separation performance by using the difference between extractant. The pH of the extraction system, the combination and proportion of different extractant, the concentration of extractant and the addition of neutral phosphorus extractant significantly affect the synergistic extraction process, and there are interactions among various factors. It will be one of the effective methods in the field of chemical research in the future to carry out theoretical prediction by simulation calculation, verify by experimental means, and characterize with modern analytical chemistry method. The theory is popularized to practice, so as to better guide the production.
    Research progress on kinetic models of ethane pyrolysis
    Juan WANG, Haohan XU, Kai XIE, Haiyan YU
    The Chinese Journal of Process Engineering. 2021, 21(7):  752-761.  DOI: 10.12034/j.issn.1009-606X.220208
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    As the basic raw material for the production of various petrochemical products, ethylene plays an important role in the petrochemical field. With the global energy structure adjustment brought about by the shale gas revolution, ethane has gradually become the preferred raw material for ethylene production. Ethane pyrolysis technology has the advantages of high yield, low cost and low energy consumption. As the core content of cracking furnace mathematical model, the establishment of reaction kinetics model is the basis of simulation, control and optimization of cracking process. Therefore, under the current energy environment, it is of great significance for the development of domestic ethylene industry to study and summarize the kinetic model of ethane pyrolysis. In this work, the research status of ethane cracking process, pyrolysis reaction kinetic model and coking reaction kinetic model are summarized. The kinetic models of pyrolysis reaction are divided into empirical model, mechanism model and molecular reaction dynamics model. The kinetic models of coking reaction are divided into catalytic coking and free radical coking. This work not only introduces the basic models, but also compares and summarizes the process of gradual optimization of the models. In addition, this work puts forward new prospects for the future research direction. In the future, the combinations of the empirical model with the automatic control technology of cracking furnace and the reaction kinetics model with CFD technology are of great necessity. The co-cracking process of ethane and propane and optimization the product distribution needs to be further researched. The establishment of reaction kinetics model which can accurately predict the coking process need to be explored. In conclusion, ethane pyrolysis not only brings opportunities for industrial production, but also provides a new direction for researchers.
    Recent advances in catalysts for direct synthesis of cyclic carbonates from olefins and CO2
    Qilu HU, Guoying ZHAO, Caihong YU
    The Chinese Journal of Process Engineering. 2021, 21(7):  762-773.  DOI: 10.12034/j.issn.1009-606X.220195
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    The valorization of CO2 into value-added chemical compounds via economically viable process could be one of effective strategies to reduce CO2 emission and therefore the climate change impact. The cyclic carbonates are industrially produced by cycloadditions between CO2 and epoxides. However, there are safety risks in this technology due to the need to handle the flammable and explosive epoxides. Direct synthesis of cyclic carbonates from olefins and CO2 could provide a safer, more economic and environment-friendly alternative technology. Herein, the latest research progress in catalysts for synthesis of cyclic carbonates via one-step oxidative carboxylation, sequential oxidative carboxylation and hydroxyl bromide carboxylation of olefins is summarized. The reported catalysts for oxidative carboxylation approach are mainly multi-component composite catalysts, of which include at least both catalytic components for epoxidation of olefins and carboxylation with CO2. Single component catalysts with catalytic active function or site for both epoxidation of olefins and carboxylation with CO2, have been rarely reported in the literature and are also described here. The catalysts for hydroxyl bromide carboxylation of olefins typically consist of a halogenating reagent and an inorganic/organic base deprotonating reagent. The effects of reaction approach, catalyst structure/components, catalytic mechanism and reaction conditions on the yields and selectivity of CC are also systematically summarized and explored. In the view of green chemistry, oxidation carboxylation of olefin is of higher atom-economy and environmental benefits while hydroxyl bromide carboxylation is always accompanied by the formation of a large number of side-products. An efficient heterogeneous single component catalyst with integrated cooperative catalytic active sites for epoxidation, carboxylation, CO2 adsorption concentration, etc., which simplity the separation and recovery of catalysts and products, will be the future research trend of catalyst development for oxidative carboxylation of olefin with CO2 to produce cyclic carbonates.
    Flow & Transfer
    Numerical simulation of hollow catalyst with pores in gas-solid reaction system
    Qiuying WU, Lingkai KONG, Ji XU, Wei GE, Shaojun YUAN
    The Chinese Journal of Process Engineering. 2021, 21(7):  774-785.  DOI: 10.12034/j.issn.1009-606X.220229
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    In the gas-solid flow, fluid and particle usually aggregate to form dense-phase and dilute-phase respectively, resulting in unbalanced mass transfer and reaction rates between the dense- and dilute-phase. The unbalance of dilute- and dense-phase reduces the overall efficiency of the reactor. To solve this problem, a hollow catalyst particle with pores structure is designed. It is aimed to enhance the overall efficiency of fluidized reactors by improving the mass transfer rate between the dense- and dilute-phase. Dense- and dilute-phase are widely distributed during fluidization processes, which can be respectively described by the cluster system and single particle system. In these two phases, the flow, reaction process and mass transfer process of hollow porous particles are studied by numerical simulation, and compared with the solid spherical particle system at the same fluidization condition. Then, the frequency of particle clusters formation and breakage is studied under various fluidization conditions. The time scale is analyzed to measure the possibility of gas transport in the fluidization process. It is found that the time-scales of the mass transfer, the reaction, and the movements of particles between the dilute- and dense-phase could be at the same order for some fluidization conditions. Thus, hollow porous catalyst particle can store the reacting material in the dilute-phase efficiently. When moving to the dense phase, the particle would release the reacting material to provide additional material for the dense-phase reaction. When the reaction is faster than the mass transfer, the overall reaction rate of the hollow porous catalyst system is 26.92%~29.55% higher than that of the solid spherical catalyst system at the studied conditions. It could be predicted that this hollow porous catalyst would be capable to improve the overall reaction efficiency of large gas-solid fluidized bed reactors due to wider distributions of the dilute- and dense-phase.

    Research on internal structure optimization and energy storage characteristics of electric water heater
    Li WU, Jie HE, Jinli LU, Yafang HAN, Ze HONG
    The Chinese Journal of Process Engineering. 2021, 21(7):  786-793.  DOI: 10.12034/j.issn.1009-606X.220206
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    The energy consumption of electric water heater in China has a large proportion of total energy consumption. Therefore, it is of great significance to optimize the energy consumption process of electric water heater. The phase change materials (PCM) have the characteristics of high energy storage density and approximately constant temperature in the process of phase transition. In addition, the thermal conductivity of phase change materials can be enhanced by adding nanometer materials such as graphite. Therefore, it has obvious advantages in heat energy storage and utilization of phase change materials. So, the phase change energy storage technology can be applied to electric water heater to adjust the energy storage process and the goal of "peak shifting" also can be achieved. In this work, the energy storage characteristic of energy storage water heater with phase change material were researched employing numerical simulation method. Four different structural models were established and the influent of inlet and outlet piping construction, electric heating tube arrangement, insulation structure on flow and heat transfer characteristics of water in water heater were discussed. And the influence of energy storage layer thickness on energy storage of electric water heater were researched. The results showed that, compared with the vertical heating tube, the water temperature distribution of horizontal heating tube was more uniform during heating process, and the heating efficiency was improved by about 2.2%. When the inlet tube diameter increased to 1.5 times, the output status of hot water can be excellent improved, and the hot water output efficiency can be increased 17.9%. The addition of phase change materials can increase the water temperature by 10.6% under the condition of same heat preservation time (36 h). The results of this study can provide data support for structural optimization of electric water heater and application of phase change energy storage technology.

    Reaction & Separation
    Optimization of preparation of cassava alcohol sludge-based activated carbon by response surface methodology and its adsorption properties for gallic acid
    Zhilin ZHANG, Lei DING, Qiang ZHOU, Jian YU, Changjin GUO, Dewei ZHANG
    The Chinese Journal of Process Engineering. 2021, 21(7):  794-806.  DOI: 10.12034/j.issn.1009-606X.220204
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    The dewatered sludge from the production process of cassava alcohol plant was used as raw material. Response surface methodology was applied to optimize the preparation of cassava alcohol sludge activated carbon. At the same time, a series of characterization analysis was carried out for the optimal product, which was applied to the treatment of gallic acid wastewater. The results showed that the optimal preparation conditions were: activation temperature of 489℃, impregnation time of 14 h, activation time of 51 min, zinc chloride concentration of 21.53%, the adsorption iodine value under this condition was 521.64 mg/g. The results of characterization to CASAC suggested that the BET surface was found as 441.86 m2/g and the average pore diameter as 2.50 nm. It was full of different sizes of small pores on the carbon surface. The activated carbon owned a low metal content but more oxygen-containing functional group after activation process. The effects of carbon dosage, pH, contact time and solution temperature on the removal of gallic acid from water were investigated. It is suggested that the sample carbon could remove gallic acid efficiently, and the removal rate of gallic acid increased with the increase of carbon dosage and the decrease of pH value. The adsorption of gallic acid by cassava alcohol sludgy-based activated carbon was in line with pseudo second-order kinetics model as well as Freundlich isothermal model. The maximum adsorption capacity was 126.72 mg/g. The diffusion mechanism showed that the adsorption process was influenced by the diffusion of liquid film in addition to the diffusion within particles. Thermodynamic analysis indicated that the adsorption of gallic acid was a spontaneous process of heat absorption and entropy increase. This study provided a theoretical basis for the preparation of high-performance activated sludge and the application of high concentration of natural organic wastewater treatment.

    Effects of hydrophilicity/hydrophobicity of humic acid components on the removal of bromide adsorbed on magnetic ion exchange resin
    LI Ling, Lei DING, Gang XUE, Yunhan JIA, Meiying ZHONG, Dewei ZHANG
    The Chinese Journal of Process Engineering. 2021, 21(7):  807-816.  DOI: 10.12034/j.issn.1009-606X.220217
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    The effect of different hydrophilic/hydrophobic humic acid on the removal of bromide adsorbed on magnetic ion exchange resin was studied. When the pH value of the solution was 7.0, the presence of four humic acid components (very hydrophobicity, slightly hydrophobicity, polar hydrophilicity, neutral hydrophilicity) reduced the removal efficiency of bromide. In contrast, the hydrophobic components of humic acid had the most significant adverse effect on the removal efficiency of bromide. Humic acid weakened the pH dependence of the adsorption process of bromide on resin. The fractions of humic acid can accelerate the adsorption rate of bromide. The adsorption equilibrium was attained quickly. With or without the fractions of humic acid, the kinetic processes of bromide adsorbed on resin agreed with the pseudo-second-order model. Because of the competitive adsorption, the humic acid fractions reduced significantly the equilibrium adsorption capacity of resin for bromide. The adsorption equilibrium can be simulated by Langmuir and Freundlich isotherm model. The existence of HA components can reduce the spontaneity of adsorption system, and the very hydrophobicity component had more significant effect. The results of this investigation were of great significance for the effective control of bromide in water sources.

    Process & Technology
    Study on uniaxial/triaxial impact dynamic properties of structurally heterogeneous coal
    Weimin LIANG, Heng LIU, Minmin LI, Gaowei YUE
    The Chinese Journal of Process Engineering. 2021, 21(7):  817-826.  DOI: 10.12034/j.issn.1009-606X.220178
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    As a heterogeneous, anisotropic and porous porous brittle material, the coal body has a large number of micro-scales such as bedding, joints, cracks, etc. so that the blasting and cracking effects in different directions will be significantly different. Based on this, a split Hopkinson pressure bar (SHPB) experimental device was used to perform impact loads of 0.1, 0.15, 0.2, 0.3, 0.5 MPa on the coal samples taken from the vertical and parallel bedding directions. The uniaxial/triaxial SHPB impact test was used to compare the uniaxial/triaxial impact dynamics performance of the anisotropic coal body stress-strain, peak stress, average strain rate, etc. after the impact. The results showed that under the action, the uniaxial and triaxial stress-strain curves had the same trend, and the peak stress and average strain rate increased with the impact load, and the growth trend was also the same. When the uniaxial impact, the stress of the coal sample followed the strain which can reach the peak stress quickly and dropped down quickly to complete the unloading. During triaxial impact, this stage was relatively smooth and had a longer elastoplastic deformation, so its dynamic mechanical properties were also improved well. Due to the relatively weak bonding surface between coal layers, the dynamic compressive strength was relatively smaller than the dynamic compressive strength in the vertical bedding direction; the triaxial SHPB impact had the peak stress and average strain rate under the constraint of the axial and confining pressures on the coal sample compared to the uniaxial improved, and the peak stress increased the most when the impact load was 0.15~0.2 MPa, increasing by about 50%. The dynamic performance improvement in the vertical bedding direction was slightly better than that in the parallel bedding direction. The effect of pressure had certain limitations, that was a certain confining pressure had a certain limit to improve the mechanical properties of coal samples.

    Effect of V content on microstructure and mechanical properties of Ti-V complex microalloyed steel
    Zihao CHEN, Ke ZHANG, Xibin FU, Zhaodong LI, Xi ZHANG, Xiaofeng ZHANG, Xinjun SUN, Jianqing QIAN
    The Chinese Journal of Process Engineering. 2021, 21(7):  827-835.  DOI: 10.12034/j.issn.1009-606X.221107
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    Using the combination of microalloying technology and controlled rolling and controlled cooling technology, the development of microalloyed high-strength steels with well-matched strength and toughness and low cost has gradually become a research hotspot, which mainly improve the properties of microalloyed steel by the soft toughness of ferrite and the precipitation strengthening of nano microalloyed carbonitride. At present, there are few reports about the effect of V content on the strength and plasticity of hot-rolled Ti-V complex microalloyed steel sheet at domestic and abroad. Therefore, the research on the microstructure and mechanical properties of hot-rolled Ti-V complex microalloyed steel sheet can provide theoretical basis and process guidance for the development and microstructure and properties control of Ti-V complex microalloyed high strength steel. Two kinds of Ti-V complex microalloyed steels with different V contents were obtained by adding Ti and V microalloying elements. Meanwhile, the effect of V content on the microstructure and mechanical properties of Ti-V microalloyed steels at different coiling temperatures were discussed by optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron backscatter diffraction (EBSD) and physicochemical phase analysis. The results showed that when the two Ti-V microalloyed steels were coiled at 500~650℃, the microstructure was composed of polygonal ferrite and pearlite, and the formation of pearlite was inhibited by increasing the V content. When coiled at 500~650℃, with the increase of V content, the uniform elongation and total elongation decreased to a certain extent, while the tensile strength and yield strength increased significantly. The coiling temperature had little effect on the uniform elongation and total elongation and the comprehensive mechanical properties of the two experimental steels were up to best when coiled at 600℃. With the increase of V content significantly increased the number of (Ti, V)C particles smaller than 10 nm in size when coiled at 600℃. The precipitation strengthening increment σP of high vanadium steel was about 183 MPa, and the strengthening mechanisms were mainly precipitation strengthening and fine grain strengthening. V content was the main factor affecting precipitation strengthening increment and yield strength of Ti-V complex microalloyed steel.

    First-principles calculation of adsorption mechanism of hydrochloric acid on chalcopyrite surface
    Xiaoliang LI, Guocai TIAN
    The Chinese Journal of Process Engineering. 2021, 21(7):  836-846.  DOI: 10.12034/j.issn.1009-606X.220175
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    The leaching of chalcopyrite has always been the core of copper sulfide hydrometallurgy, but chalcopyrite is a sulfide mineral that is difficult to be oxidized and decomposed. At present, a large number of macroscopic phenomena are obtained by focusing on experimental research, and the mechanism is mostly inferred. However, the lack of information on atomic or molecular level hinders the clear and effective explanation to these macroscopic phenomena. Therefore, it is necessary to study the surface interaction between liquid medium and chalcopyrite and the influence of medium on the formation of surface products by means of atomic or molecular level calculation and analysis, which are of great significance to reveal the reaction mechanism of leaching process and improve or develop a green hydrometallurgical technology of chalcopyrite. As a common leaching agent, hydrochloric acid can be used in the leaching of chalcopyrite, and it has been widely studied because of its advantages of recyclable leaching agent, high solubility of metal ions, good oxidation reduction performance and fast leaching rate. In this work, the adsorption and reaction mechanism of hydrochloric acid on different sites of chalcopyrite surface were studied with first-principles calculation. It was shown that the reconstructed sulfur terminated chalcopyrite (001) surface [labeled as (001)-S surface] led to the formation of disulphide S22-. Hydrochloric acid was adsorbed on the sulfur terminated surface (001)-S of chalcopyrite in the form of dissociation. In the process of leaching, the adsorption of H+ on sulfur terminated surface (001)-S of chalcopyrite destroyed the S22- formed on the surface. The surface structure of chalcopyrite (001)-S was destroyed by adsorption of chloride ion Cl-. During the adsorption process, the chemical reactions between H+ and Cl- with the surface of chalcopyrite produce the FeCl2 and H2S, which were both beneficial to the leaching of chalcopyrite. The results can provide a theoretical basis and guidance for future research.

    Environment & Energy
    Molecular dynamics simulations of short-chain lithium polysulfides clustering in ionic liquids
    Tianyuan HU, Yanlei WANG, Feng HUO, Hongyan HE
    The Chinese Journal of Process Engineering. 2021, 21(7):  847-856.  DOI: 10.12034/j.issn.1009-606X.220221
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    Ionic liquids have been widely used in lithium-sulfur battery electrolytes in recent years due to their excellent physicochemical properties and the ability to inhibit the dissolution of lithium polysulfides intermediates. Among those products during the battery cycling processes, insoluble Li2S and Li2S2 are inclined to aggregate and deposit on the electrode surface, affecting the battery performance. However, there are few studies on the microscopic mechanism of their clustering behaviors and electrolyte properties. In this work, the microstructure of Li2S/Li2S2 in ionic liquids and the formation of clusters were studied by DFT calculations and molecular dynamics simulations. From the optimized configurations using DFT methods, it can be seen that ionic liquids and Li2S/Li2S2 always tended to form a "cation-short chain polysulfide-anion" sandwich-like structures. By analyzing the microstructures of the molecular dynamics simulation systems, it can be found that the methyl group in side chain of cation mainly interacted with S in Li2S/Li2S2, and the Li-S interaction between short-chain polysulfides was much stronger than Li-O interaction in anions. The results of cluster size distribution showed that short-chain polysulfides were more likely to form large clusters in the [TFSI]-based ionic liquid, while the proportion of large clusters in Li2S2 system was higher than Li2S systems. Moreover, the tendency of forming large clusters increased with the concentration of Li2S/Li2S2. Additionally, stronger coordination ability of anions brought smaller proportion of large Li2S clusters. However, the configuration characteristics and interaction forms of anions-Li2S will also affected the sizes and structures of clusters. These understandings could provide theoretical guidance for future systematic studies on screening and designing ionic liquids electrolytes for lithium-sulfur batteries.

    Study on the catalytic degradation of dibutyl phthalate by ferric cerium bimetal in electric-Fenton system
    Yingjun ZHENG, Hailing MENG, Zailiang LIU, Han ZHOU, Junjie ZHU
    The Chinese Journal of Process Engineering. 2021, 21(7):  857-864.  DOI: 10.12034/j.issn.1009-606X.220135
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    Dibutyl phthalate as a plasticizer is widely used in all walks of life. As an endocrine interferon, the pollution caused by it cannot be ignored, and it will harm the health of biology and human body. Because it is difficult to degrade effectively in common wastewater treatment processes, it is urgent to find effective treatment methods. As one of the advanced oxidation technologies, electro-Fenton has great advantages in treating refractory wastewater and has made many achievements. But the difficulty of electro-Fenton technology is to find an efficient and reusable catalyst. In this work, an efficient bimetal catalyst for the treatment of dibutyl phthalate in electro-Fenton system was studied. Aluminum modified bimetallic catalyst Fe-Ce/Al-MCM-41, was prepared by hydrothermal-calcination method using MCM-41 as template and characterized by XRD, BET and FT-IR. Taking dibutyl phthalate simulated wastewater as the treatment object, the effects of four different conditions, such as initial pH, catalyst dosage, current intensity and oxygen flux, on the degradation efficiency of Perth-carbon felt electro-Fenton system were discussed, and the best operation conditions were found. The characterization results showed that the loading of metal ions did not change the mesoporous structure of MCM-41, which provided sufficient active sites for the follow-up reaction. Under the best experimental conditions, the removal rate of 10 mg/L DBP was 97.1%, the removal rate under acidic and neutral conditions was more than 92.1%, and the removal rate of DBP was reduced under alkaline conditions. Through the comparative experimental analysis of the degradation mechanism, it was found that the iron and cerium bimetallic catalyst had good catalytic activity for the degradation of dibutyl phthalate in electric-Fenton system. Among them, iron ion and cerium ion participated in the catalytic reaction and had synergistic effect, while aluminum ion did not directly participate in the catalytic reaction, but the addition of aluminum ion can improve the catalytic performance of the catalyst. In addition, carbon felt as a cathode had a certain adsorption effect. The main active substance in the electro-Fenton system for the degradation of DBP was ·OH, degrades the target pollutants by the oxidation of ·OH.