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中国化学工程学报（英文版）
中国化学工程学报（英文版）

廖叶华

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1004-9541

64980783@126.com

010-64980783

100011

北京东城区青年湖南街13号

中国化学工程学报（英文版）/Journal Chinese Journal of Chemical EngineeringCSCDCSTPCD北大核心EISCI
查看更多>>The Chinese Journal of Chemical Engineering (Bimonthly, started in 1982) is the official journal of the Chemical Industry and Engineering Society of China and published by the Chemical Industry Press. The aim of the journal is to develop the international exchange of scientific and technical information in the field of chemical engineering. It publishes original research papers that cover the major advancements and achievements in chemical engineering in China as well as some articles from overseas contributors. The topics of journal include chemical engineering, chemical technology, biochemical engineering, energy and environmental engineering and other relevant fields. Papers are published on the basis of their relevance to theoretical research, practical application or potential uses in the industry as Research Papers, Research Notes, Chemical Engineering Data and Reviews. Prominent domestic and overseas chemical experts and scholars have been invited to form an International Advisory Board and the Editorial Committee. It enjoys recognition among Chinese academia and industry as a reliable source of information of what is going on in chemical engineering research, both domestic and abroad.
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    B-COPNA resin formation from ethylene tar light fractions: Process development and mechanical exploration by molecular simulation

    Hongyan ShenLingrui CuiXingguo WeiYuanqin Zhang...
    118-129页
    查看更多>>摘要：An efficient utilization strategy of ethylene tar (ET), the main by-product of the ethylene cracking unit, is urgently required to meet demands for modern petrochemical industry. On the other hand, condensed polynuclear aromatic resin of moderate condensation degree (B-COPNA) is a widely used carbon material due to its superb processability, the production of which is, however, seriously limited by the high cost of raw materials. Under such context, an interesting strategy was proposed in this study for producing B-COPNA resin using crosslinked light fractions of ethylene tar (ETLF, boiling point<260 °C) facilitated by molecular simulation. 1,4-Benzenedimethanol (PXG) was first selected as the crosslinking agent ac-cording to the findings of molecular simulation. The effects of operating conditions, including reactions temperature, crosslinking agent, and catalyst content on the softening point and yield of B-COPNA resin products were then investigated to optimize the process. The reaction mechanism of resin production was studied by analyzing the molecular structure and transition state of ETLF and crosslinking agents. It was shown that PXG exhibited a superior capacity of withdrawing electrons and a higher electrophilic reactivity than other crosslinking agents. In addition to the highest yield and greatest heat properties, PXG-prepared resin contained the most condensed aromatics. The corresponding optimized conditions of resin preparation were 180 °C, 1:1.9 (PXG:ETLF), and 3％(mass) of catalyst content with a resin yield of 78.57％. It was the electrophilic substitution reaction that occurred between the ETLF and crosslinking agent molecules that were responsible for the resin formation, according to the experimental charac-terization and molecular simulation. Hence, it was confirmed that the proposed strategy and demon-strated process can achieve a clean and high value-added utilization of ETLF via B-COPNA resin preparation, bringing huge economic value to the current petrochemical industry.
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    Synthesis of NaY zeolite from a submolten depolymerized perlite:Alkalinity effect and crystallization kinetics

    Yanli QuPeng DongLi YangYuanyuan Yue...
    130-138页
    查看更多>>摘要：NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer. Effects of alkalinity ranging from 0.38 to 0.55 (n(Na2O)/n(SiO2)) on the relative crystallinity, textural properties and crystallization kinetics were investigated. The results show that alkalinity exerts a nonmonotonic influence on the relative crystal-linity and textural properties, which exhibit a maximum at the alkalinity of 0.43. The nucleation kinetics are studied by fitting the experimental data of relative crystallinity with the Gualtieri model. It is shown that the nucleation rate constant increases with increasing alkalinity, while the duration period of nucleation decreases with increasing alkalinity. For n(Na2O)/n(SiO2) ratios ranging from 0.38 to 0.55, the as-synthesized NaY zeolites exhibit narrower crystal size distributions with the increase in alkalinity. The growth rates determined from the variations of average crystal size with time are 51.09, 157.50, 46.17 and 24.75 nm·h-1, respectively. It is found that the larger average crystal sizes at the alkalinity of 0.38 and 0.43 are attributed to the dominant role of crystal growth over nucleation. Furthermore, the combined action of prominent crystal growth and the longer duration periods of nucleation at the alkalinity of 0.38 and 0.43 results in broader crystal size distributions. The findings demonstrate that control of the properties of NaY zeolite and the crystallization kinetics can be achieved by conducting the crystalli-zation process in an appropriate range of alkalinity of the reaction mixture.
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    Cation-doped LiNi0.8Co0.1Mn0.1O2 cathode with high rate performance

    Long ZhangShengming XuDongsheng YangLilei Miao...
    139-148页
    查看更多>>摘要：The nickel-rich layered cathode material LiNi0.8Co0.1Mn0.1O2 (NCM811) has high energy density, lower cost and is a promising cathode material currently under development. However, its electrochemical and structural stability is poor during cycling. Among the many modification methods, cation doping has been consistently proven to be an effective strategy for enhancing electrochemical performance. Herein, the NCM811 cathode material was modified by solid-phase reactions with Mg and Al doped. In addition, the corresponding mechanism of NCM811 cathode material-doped modification is explored by density functional theory (DFT) calculations, and we have extended this approach to other ternary cathode materials with different ratios and obtained universal laws. Combined with DFT calculations, the results show that Mg2+occupies the Li+site and reduces the degree of Li+/Ni2+mixture;Al3+acts as a structural support during charging and discharging to prevent structural collapse. The electrochemical properties were tested by an electrochemical workstation and the LAND system, and the results showed that the capacity retention rate increased to varying degrees from 63.66％to 69.87％and 89.05％for NCM811-Mg and NCM811-Al at room temperature after 300 cycles, respectively. This study provides a theoretical basis and design strategy for commercializing cationic-doped modification of nickel-rich cathode materials.
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    Rheological study of methane gas hydrates in the presence of micron-sized sand particles

    Bohui ShiShangfei SongYuchuan ChenShunkang Fu...
    149-161页
    查看更多>>摘要：Natural gas hydrates, intricate crystalline structures formed by water molecules and small gas molecules, have emerged as a significant and globally impactful clean energy resource. However, their commercial exploitation faces challenges, particularly operational disruptions caused by sand-related blockages. Understanding the rheological properties of hydrate slurry, especially in the presence of micron-sized sand particles, is imperative for ensuring the flow assurance of subsea hydrate exploitation. This study extensively investigates the rheological properties of sand-containing hydrate slurries. The findings reveal that these slurries exhibit non-Newtonian fluid characteristics, including yield stress, thixotropy, and shear-thinning behavior. Solid-like elastic features are observed in sand-containing hydrate slurries before yielding, transitioning to viscous behavior after yielding. Even with a minimal amount of sand, both static yield stress and yield strain experience substantial changes, correlating with the increase in sand concentration. The research conclusively establishes the thixotropic nature of sand-hydrate slur-ries, where the viscosity decay rate is directly influenced by the shear rate. These insights aim to contribute comprehensively to the development of effective flow assurance strategies, ensuring the safe and stable operation of subsea hydrate exploitation.
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    Optimizing hemicelluloses pre-extraction in eucalyptus kraft pulping:A pathway towards enhancing pulp mill biorefineries

    Yuhan WangDanqi XueJingjing ZhuoZhouyang Xiang...
    162-172页
    查看更多>>摘要：A critical pathway towards enhancing pulp mill biorefineries is to integrate the extraction and utilization of hemicelluloses into the pulping processes. Hence, an industrial pre-extraction strategy for hemi-celluloses targeting eucalyptus kraft pulping process was developed. Alkaline solution or pulping white liquor was used to pre-extract hemicelluloses before the actual pulping process. The response surface methodology (RSM) technique was applied to investigate the most suitable conditions to maximize the yield of these hemicelluloses while simultaneously minimizing the damage to pulp yields and properties. Temperature (105 to 155 °C), alkali concentration (3％to 8％), sulfidity (20％to 30％) and retention time (19 to 221 min) were combined to evaluate their effects on hemicellulose yields and chemical structures. The optimal pre-extraction conditions identified in this work (5.75％ NaOH concentration, 25％ sulfidity at 135°C for 60 min) successfully allowed recovering 4.8％of hemicelluloses (based on the wood dry mass) and limited damages to pulp yields and properties. The cellulose content in pulp can even be increased by about 10％. Hemicellulose emulsification properties were also evaluated, which were comparable to synthetic emulsifiers. This study provides an industrial pathway to effectively separate and utilize wood hemicelluloses from the pulping process, which has the potential to improve the economy and material utilization of pulp and paper mills.
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    CFD-PBM coupled modeling of the liquid-liquid dispersion characteristics and structure optimization for Kenics static mixer

    Junhai DengShilin LanJuchang WuShenghua Du...
    173-188页
    查看更多>>摘要：Kenics static mixers (KSM) are extensively used in industrial mixing-reaction processes by virtue of high mixing efficiency, low power homogenization and easy continuous production. Resolving liquid droplet size and its distribution and thus revealing the dispersion characteristics are of great significance for structural optimization and process intensification in the KSM. In this work, a computational fluid dynamics-population balance model (CFD-PBM) coupled method is employed to systematically inves-tigate the effects of operating conditions and structural parameters of KSM on droplet size and its dis-tribution, to further reveal the liquid-liquid dispersion characteristics. Results indicate that higher Reynolds numbers or higher dispersed phase volume fractions increase energy dissipation, reducing Sauter mean diameter (SMD) of dispersed phase droplets and with a shift in droplet size distribution (DSD) towards smaller size. Smaller aspect ratios, greater blade twist and assembly angles amplify shear rate, leading to smaller droplet size and a narrower DSD in the smaller range. The degree of impact exerted by the aspect ratio is notably greater. Notably, mixing elements with different spin enhance shear and stretching efficiency. Compared to the same spin, SMD becomes 3.7-5.8 times smaller in the smaller size range with a significantly narrower distribution. Taking into account the pressure drop and efficiency in a comprehensive manner, optimized structural parameters for the mixing element encompass an aspect ratio of 1-1.5, a blade twist angle of 180°, an assembly angle of 90°, and interlaced assembly of adjacent elements with different spin. This work provides vital theoretical underpinning and future reference for enhancing KSM performance.
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    Silica-modified Pt/TiO2 catalysts with tunable suppression of strong metal-support interaction for cinnamaldehyde hydrogenation

    Zhengjian HouYuanyuan ZhuHua ChiLi Zhao...
    189-198页
    查看更多>>摘要：Tuning Strong Metal-support Interactions (SMSI) is a key strategy to obtain highly active catalysts, but conventional methods usually enable TiOx encapsulation of noble metal components to minimize the exposure of noble metals. This study demonstrates a catalyst preparation method to modulate a weak encapsulation of Pt metal nanoparticles (NPs) with the supported TiO2, achieving the moderate sup-pression of SMSI effects. The introduction of silica inhibits this encapsulation, as reflected in the char-acterization results such as XPS and HRTEM, while the Ti4+ to Ti3+ conversion due to SMSI can still be found on the support surface. Furthermore, the hydrogenation of cinnamaldehyde (CAL) as a probe re-action revealed that once this encapsulation behavior was suppressed, the adsorption capacity of the catalyst for small molecules like H2 and CO was enhanced, which thereby improved the catalytic activity and facilitated the hydrogenation of CAL. Meanwhile, the introduction of SiO2 also changed the surface structure of the catalyst, which inhibited the occurrence of the acetal reaction and improved the con-version efficiency of C=O and C=C hydrogenation. Systematic manipulation of SMSI formation and its consequence on the performance in catalytic hydrogenation reactions are discussed.
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    Phosphotungstic acid immobilized on amino-functionalized TS-1 zeolite as a solid acid catalyst for the synthesis of tributyl citrate

    Pei LiBianfang ShiJunyao ShenRan Cui...
    199-210页
    查看更多>>摘要：The amino-functionalization of TS-1 zeolite followed by immobilization of phosphotungstic acid (HPW) was presented to prepare a strong solid acid catalyst for the synthesis of bio-based tributyl citrate from the esterification of citric acid and n-butanol.γ-Aminopropyltriethoxysilane (APTES) was first grafted on the TS-1 zeolite via the condensation reactions with surface hydroxyl groups, and subsequently the HPW was immobilized via the reaction between the amino groups and the protons from HPW-forming strong ionic bonding. The Keggin structure of HPW and MFI topology of TS-1 zeolite were well maintained after the modifications. The amino-functionalization generated abundant uniformly distributed active sites on TS-1 for HPW immobilization, which promoted the dispersity, abundance, as well as the stability of the acid sites. The tetrahedrally coordinated framework titanium and non-framework titania behaved as weak Lewis acid sites, and the protons from the immobilized HPW acted as the moderate or strong Brønsted acid sites. An optimized TBC yield of 96.2％ (mol) with a conversion of -COOH of 98.1％ (mol) was achieved at 150 °C for 6 h over the HPW immobilized on amino-functionalized TS-1. The catalyst exhibited good stability after four consecutive reaction runs, where the activity leveled off at still a relatively high level after somewhat deactivation possibly caused by the leaching of a small portion of weakly anchored APTES or HPW.
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    Complete kinetic model for esterification reaction of lauric acid with glycerol to synthesize glycerol monolaurate

    Han-Qiao HuYue ZhangMing FanYong Cai...
    211-221页
    查看更多>>摘要：Glycerol monolaurate (GML) is a widely used industrial chemical with excellent emulsification and antibacterial effect. The direct esterification of glycerol with lauric acid is the main method to synthesize GML. In this work, the kinetic process of direct esterification was systematically studied using p-tolue-nesulfonic acid as catalyst. A complete kinetic model of consecutive esterification reaction has been established, and the kinetic equation of acid catalysis was deduced. The isomerization reactions of GML and glycerol dilaurate were investigated. It was found that the reaction was an equilibrium reaction and the reaction rate was faster than the esterification reaction. The kinetic equations of the consecutive esterification reaction were obtained by experiments as k1 =(276+92261Xcat)exp(-37720/RT) and k2 =(80+4413Xcat)exp(-32240/RT). The kinetic results are beneficial to the optimization of operating conditions and reactor design in GML production process.
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    Porous silica nano-flowers stabilized Pt-Pd bimetallic nanoparticles as heterogeneous catalyst for efficiently synthesizing guaiacol from 2-methoxycyclohexanol

    Junbo FengJunyan WuDongdong YanYadong Zhang...
    222-233页
    查看更多>>摘要：Porous silica nano-flowers (KCC-1) immobilized Pt-Pd alloy NPs (Pt-Pd/KCC-1) with different mass ratios of Pd and Pt were successfully prepared by a facile in situ one-step reduction, using hydrazinium hydroxide as a reducing agent. The as-synthesized silica nanospheres possess radial fibers with a dis-tance of 15 nm, exhibiting a high specific surface area (443.56 m2·g-1). Meanwhile, the obtained Pt-Pd alloy NPs are uniformly dispersed on the silica surface with a metallic particle size of 4-6 nm, which exist as metallic Pd and Pt on the surface of monodisperse KCC-1, showing the transfer of electrons from Pd to Pt. The as-synthesized 2.5％Pt-2.5％Pd/KCC-1 exhibited excellent catalytic activity and stability for the continuous dehydrogenation of 2-methoxycyclohexanol to prepare guaiacol. Compared with Pt or Pd single metal supported catalysts, the obtained 2.5％Pt-2.5％Pd/KCC-1 shows 97.2％ conversion rate of 2-methoxycyclohexanol and 76.8％ selectivity for guaiacol, which attributed to the significant synergistic effect of bimetallic Pt-Pd alloy NPs. Furthermore, turn over frequency value of the obtained 2.5％Pt-2.5％Pd/KCC-1 NPs achieved 4.36 s-1, showing higher catalytic efficiency than other two monometallic cat-alysts. Reaction pathways of dehydro-aromatization of 2-methoxycyclohexanol over the obtained cata-lyst are proposed. Consequently, the obtained 2.5％Pt-2.5％Pd/KCC-1 NPs prove their potential in the dehydrogenation of 2-methoxycyclohexanol, while the kinetics and mechanistic study of the dehydro-genation reaction over the catalyst in a continuous fixed-bed reactor may provide valuable information for the development of green, outstanding and powerful synthetic pathway of guaiacol.
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