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2021年 第23卷 第3期    刊出日期:2021-09-30
Scientific Research
Insights into the Reaction Network and Mechanism of Green Aerobic Oxidative Esterification of Methacrolein over Different Heterogeneous Catalysts
厉晨豪 夏长久 刘聿嘉 黄开盟 彭欣欣 刘金胜 林民 朱斌 罗一斌 舒兴田
2021, 23(3):  1-11. 
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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.
The Synthesis of Ultra-High Molecular Weight Polypropylene Using Supported Ziegler-Natta Catalyst via Combining Internal Electron Donor and Cocatalyst Loaded on
夏晓琪 李红明 李春漫 苗青 李静 朱峰 黄启谷 义建军 赵众
2021, 23(3):  12-22. 
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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.
表面活性剂对柔性金属有机骨架材料MIL-53(Fe)的孔结构及光催化性能的控制
张丹 杨萍 张尤华 段林海 孟秀红
2021, 23(3):  23-29. 
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提出了一种利用表面活性剂控制柔性金属有机骨架材料MIL-53(Fe)孔道结构的方法。表面活性剂四乙基氢氧化铵(TEAOH)控制MIL-53(Fe)的孔道形式为“闭孔”的形式,而表面活性剂聚环氧乙烷-聚环氧丙烷-聚环氧乙烷(P123)或者聚乙烯醇(PVA)控制MIL-53(Fe)的孔道形式为“开孔”的形式。通过紫外光辐射降解罗丹明B水溶液的方式来考察不同孔道形式的MIL-53(Fe)的光催化性能。结果表明“开孔”的MIL-53(Fe)比“闭孔”的MIL-53(Fe)呈现出更高的光催化活性。由表面活性剂PVA改良的MIL-53(Fe)具有最好的光催化活性,90分钟内讲解了100%的罗丹明B水溶液。
研究三维电催化体系中粒子电极位置对电催化反应效能的影响
陆楷天 张永刚
2021, 23(3):  30-39. 
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为了探究三维电催化反应器填充粒子的放置位置对电催化反应速率的影响,本文以亚甲基蓝为模拟有机废水,球状石墨颗粒为研究粒子电极,利用COMSOL Multiphysics软件模拟三维电催化反应器内的电势分布。以粒径大小、电势和位置为自变量,以一级反应动力学常数为因变量建立对数回归模型。结合模型预测了反应器不同位置的粒子电极降解有机污染物的效能。模拟结果表明,在三维电催化氧化反应器内粒子电极对污染物降解的反应效能是不均匀的,增加电场强度可以改变粒子电极电催化反应效能的分布,其中越靠近阳极端位置的粒子电极其降解污染物的能力越高。粒子颗粒内部不同位置之间的电催化反应速率的差异较大,按照差异程度可大致分为三个区域并模拟了粒子电极内部不同位置的电催化反应效能分布。
Catalyst Research
MOF衍生的高选择性加氢芳香硝基化合物的石墨碳包覆镍催化剂
吴耿煌 荣峻峰
2021, 23(3):  40-49. 
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针对芳香硝基化合物的催化选择性加氢反应,开发可替代贵金属催化剂的低成本、高效非贵金属催化剂,对于芳香胺类化合物的绿色生产具有重要意义。利用简易、可规模化的制备方法,以镍—2,5-吡啶二羧酸金属有机框架为前驱体,热解制备了氮掺杂石墨碳包覆镍纳米催化材料(Ni@CN)。采用X射线衍射、扫描电镜、透射电镜、元素分析、N2吸脱附等检测手段对Ni@CN的物化性质进行了表征,并对其催化性能进行了评价。结果表明,Ni@CN可在温和条件下(85℃,1.0 MPa H2)高效加氢含取代官能团的芳香硝基化合物生成对应的芳香胺类化合物。对比试验表明,镍纳米颗粒是Ni@CN的加氢活性中心,而石墨碳壳的存在有利于优先吸附硝基官能团。此外,进一步考察了Ni@CN的循环使用性能以及抗硫化物中毒的特性。
甲基环己烷催化转化反应对改性工业Y沸石酸性的表征
侯凯歌 秦波 韩俊杰 杜艳泽 马静红 李瑞丰
2021, 23(3):  50-57. 
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以甲基环己烷(MCH)的催化转化反应为模型反应,并结合吡啶吸附红外光谱和羟基红外光谱技术对三种具有不同硅铝比和介孔孔隙的改性工业脱铝Y沸石的酸性(酸量、酸强和酸性点的可接近性)进行了表征研究。通过MCH催化转化反应的反应结果分析,可以得出,MCH的反应活性(总转化率)依赖于Y沸石催化剂表面的酸量, 而TOF值可反映沸石内质子位酸性点的可接近性。MCH催化转化的产品由裂解、芳香烃和异构三类产品构成,其中裂解产物的产率随着沸石微孔中强质子酸位点的浓度的增加而增加;随着Y沸石脱铝程度的增加,沸石内酸量减少,分子的扩散距离缩短从而导致二次反应的几率降低,从而使芳香烃的产率随之降低;同时,裂解产物中C7产物和烯烃/烷烃比率增加。研究结果还显示出,i-C4产物的选择性随脱铝Y沸石在其羟基红外光谱中3600cm-1处的吸收峰强度的增加而增加,即i-C4产物的选择性可反映沸石内强质子酸位点的数目。
双介孔TiO2-PTA/BMMS的合成及其光催化氧化脱硫性能研究
杨丽娜 张熙 崔莉程 徐美珍 李剑
2021, 23(3):  58-68. 
摘要 ( 116 )   PDF (1371KB) ( 86 )  
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为了提高TiO2的光催化氧化脱硫(PODS)活性,利用负载和复合的协同作用,将TiO2与磷钨酸 (PTA)复合,通过两步浸渍法合成制备了TiO2-PTA/BMMS。采用XRD、N2 吸附脱附、XRF、FTIR、UV-vis、SEM、EDS 和 TEM 对催化剂进行了表征;以含二苯并噻吩(DBT)的十二烷溶液为模拟油,评价了催化剂的催化性能。表征结果表明,PTA 的引入为双介孔载体提供更高的表面积和孔体积。在紫外光照射下,TiO2-PTA/BMMS在模拟反应体系中脱硫率可达到 99.6%,脱硫率远高于 TiO2/BMMS 脱硫率。同时对催化剂进行重复使用实验,重复八次后催化活性没有显着下降。
Simulation and Optimization
热集成水网络优化设计的最新进展
张池金 任聪静 廖祖维 孙婧元 王靖岱 阳永荣
2021, 23(3):  69-75. 
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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.
潮汐作用下的混合连续时间原油调度MILP模型
周智菊 周祥 周涵
2021, 23(3):  76-89. 
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为了防止搁浅事故的发生,油轮,特别是巨型油轮(VLCC)和超巨型油轮(ULCC)经常只能在涨潮期靠泊和离港。但是当前所报道的原油调度模型并未考虑这一现状,很容易编制出不可行的调度方案。为此,首次考虑油轮潮汐靠泊,搭建了新的连续时间混合整数线性规划(MILP)模型。该模型创建了一种混合时间表示模式,整合了全局时间和具体装置时间表示方法。原油多次调合操作容易引起生产波动。为了避免这一操作,保证装置平稳加工,制定了码头罐只能储存单一原油、厂区罐只能在放空后才能重新接收原油等合理假设。基于这些假设,可以构建MILP模型且不会发生组分不一致现象。通过2个案例对模型的优化性能进行验证。实验表明,方案实现蒸馏装置(CDUs)的进料切换次数和油轮滞期费用最小化,能够助力企业平稳生产和降低企业运营成本。
Real-Time Optimization Model for Continuous Reforming Regenerator
江树宝 江洪波 厉镇铭 田健辉
2021, 23(3):  90-103. 
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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.
Process Research
生产超低硫柴油RTS技术的工艺优化
葛泮珠 丁石 习远兵 张乐 聂红 李大东
2021, 23(3):  104-111. 
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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.
加氢苛刻度对烃类组成和催化裂解产品分布的影响
邓中活 戴立顺 牛传峰 贾燕子 魏晓丽 蔡新恒
2021, 23(3):  112-118. 
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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.
Lubrication Research
柴油碳烟对ZDDP摩擦反应膜的分布、成分及力学性能的影响
凤维民 宋晖 宋汝鸿 杨炳训 胡献国
2021, 23(3):  119-126. 
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为研究柴油碳烟对ZDDP摩擦反应膜的分布、成分和力学性能的影响。采用HFRR摩擦磨损试验机进行了摩擦磨损试验。采用激光显微镜、SEM/EDS、拉曼光谱、XPS和纳米压痕仪对由ZDDP和碳烟摩擦磨损后的表面进行了分析。结果表明,碳烟会刮离ZDDP摩擦反应膜并嵌入磨损表面,导致膜厚减小和摩膜的不均匀分布。ZDDP摩擦膜中的磷酸盐结构由短链焦磷酸盐向长链偏磷酸盐转变,归于碳烟磨粒磨损引起的接触应力增加,促进了ZDDP的交联。磨损表面的硬度(H)和弹性模量(E)增加,而硬度与弹性模量的比值(H/E)降低,这表明碳烟导致耐磨性降低。
Prediction of Density and Refractive Index of Lubricating Oils during Secondary Solvent Extraction Process by Furfural
许孝玲 刘艳升
2021, 23(3):  127-136. 
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To meet the requirements of high aromatic content and low polycyclic aromatic (PCA) concentration, eco-friendly aromatic-rich rubber extender oils are usually produced by two-stage solvent extraction processes with furfural. Among the different properties of rubber processing oils, density and refractive index are some of the most important properties related to their final quality. Two types of methods, including a pseudo-component approach by using mixing rules and several correlations, were used for calculation of density and refractive index at 20 ℃ of paraffinic furfural-extract oils and their secondary raffinates. Results indicated that both the pseudo-component approach and the quadratic correlation predicted density and refractive index of furfural + furfural-extract paraffinic oil systems with similar accuracy. However, the quadratic correlation presents its advantage over the pseudo-component approach when composition of oils is not available. Moreover, the quadratic correlation was also used for naphthenic lubricating oils during two-stage solvent extraction processes. The predictions showed much larger discrepancies with respect to experimental values than those of paraffinic lubricating oils, which indicated that the quadratic correlation was more suitable for paraffinic oils with CN value below 37%.
Environmental Protection
Adsorption and regeneration of Volatile Organic Compounds(VOCs) on coal-based activated carbon by ferric nitrate modification
金春江 王鲁元
2021, 23(3):  137-150. 
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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%.
改性浒苔固定化微生物制剂的制备及其对柴油的降解性能研究
薛建良 杨玉萍 李娜娜 安晨烨 蒋晴 成东乐
2021, 23(3):  151-160. 
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为了提高固定化技术在海洋溢油处理中的应用效果,采用十二烷基苯磺酸钠(SDBS)为改性剂,采用浸渍法对浒苔进行改性。SDBS改性的浒苔(SDBS-E)作为固定化的吸附载体材料。同时,以海洋降解菌Sp8(Shewanella属)为研究对象。以海藻酸钠为包埋载体,无水氯化钙为交联剂,采用包埋法制备了SDBS-E固定化微生物制剂。与游离菌的降解率(78.87%)相比,SDBS-E固定化微生物对柴油的去除率提高到90.39%。研究了SDBS-E固定化微生物去除柴油的途径,主要包括表面吸附、内吸附和生物降解。早期依靠表面吸附,后期依靠生物降解。SDBS-E固定化微生物对柴油的降解符合准一级降解动力学模型。
Contents
2021, 23(3):  0. 
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