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Frontiers of Chemical Science and Engineering 2024年第8期18卷 25-35页

作者： Kai Bian Sirui Liu Huahua Fan Guanghui Zhang Xinwei Zhang Gideon Abaidoo Ocran Mingrui Wang Quanjie Liu Xiaowa Nie shuandi hou Xinwen Guo Sinopec Dalian Research Institute of Petroleum and Petrochemicals Dalian 116045China State Key Laboratory of Fine Chemicals Frontier Science Center for Smart MaterialsPSU-DUT Joint Center for Energy ResearchSchool of Chemical EngineeringDalian University of TechnologyDalian 116024China

Unraveling the structure-activity relationship and improving the catalytic performance is paramount in propane dehydro-aromatization reactions. Herein, a tandem catalyst with high propane dehydro-aromatization reaction performance was prepared via coupling the PtFe@S-1 with Zn/ZSM-5 zeolites (PtFe@S-1&1.0Zn/ZSM-5), which exhibits high dehydrogenation activity, aromatics selectivity (~60% at ~78% propane conversion), and stability. The addition of zinc inhibits the cleavage of C_(6)^(=) intermediates on ZSM-5 and promotes the aromatization pathway by weakening zeolite acid strength, significantly improving the selectivity to aromatics. This understanding of the structure-activity relationship in propane dehydro-aromatization reaction helps develop future high-performance catalysts.

关键词： propane dehydro-aromatization reaction tandem catalysts the structure-activity relationship of zinc species

中美石化行业源空气污染物控制标准对比分析与展望和建议

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化工进展 2024年第7期43卷 4089-4101页

作者：刘世达侯栓弟刘忠生中石化(大连)石油化工研究院有限公司辽宁大连116045

在新能源快速发展和“双碳”目标背景下,长期来看我国化石能源空气污染物排放将大幅度减少,但2030年之前,我国需要治理的煤炭、石油等传统化石能源空气污染物排放量仍会增加,我国可能升级与石化烟气和挥发性有机物(VOCs)排放相关的空气... 详细信息

在新能源快速发展和“双碳”目标背景下,长期来看我国化石能源空气污染物排放将大幅度减少,但2030年之前,我国需要治理的煤炭、石油等传统化石能源空气污染物排放量仍会增加,我国可能升级与石化烟气和挥发性有机物(VOCs)排放相关的空气质量标准和污染物排放标准政策。本文指出:美国环保标准政策对我国今后制修订标准政策仍有参考意义,建议我国针对各种烟气和VOCs排放源,进一步建立或完善污染物排放量大小判据,抓大放小;在制定严于美国标准的控制指标时应依托成熟可靠技术,高度重视标准政策的时效性、相对稳定性和地域性;建议研究论证在生态环境部《重污染天气重点行业应急减排技术指南》中增加燃煤电厂等烟气中可凝结颗粒物排放控制指标的可行性;如果要进一步提高石化VOCs排放标准政策,建议将有机液体储罐列为优先管控对象;建议将油气田作为石化行业甲烷排放管控重点,研究在重污染天气通过干涉大气阴阳离子组成来减轻或尽快结束重污染天气过程。在对GB 31570—2015(石油炼制工业污染物排放标准)、GB 31571—2015(石油化学工业污染物排放标准)、GB 31572—2015(合成树脂工业污染物排放标准)这3项污染物排放标准修订时,建议:①原则上修订内容应使污染物排放总量减少;②参考美国标准中术语定义和分析方法,将我国标准中的非甲烷总烃修改为总有机化合物(TOC),TOC不包括甲烷、乙烷;③将GB 31570—2015表4、GB 31571—2015表5中废水处理有机废气处理装置污染物项目非甲烷总烃修改为TOC,TOC≤60mg/m^(3);④将GB 31570—2015表4、GB 31571—2015表5中有机废气排放口的非甲烷总烃去除率≥97%修改为TOC去除率≥99%,或者TOC浓度≤60mg/m^(3);GB 31570—2015表4中增加苯≤4mg/m^(3)、甲苯≤15mg/m^(3)、二甲苯≤20mg/m^(3)控制指标;⑤取消有机废气排放口大气污染物排放浓度的氧浓度折算。

关键词：石化污染排放标准空气质量标准烟道气挥发性有机物可凝结颗粒物

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我国石化储罐VOCs安全高效深度减排、回收和热氧化技术进展

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化工进展 2024年第4期43卷 2063-2076页

作者：刘世达王海燕侯栓弟刘忠生廖昌建王宽岭中石化(大连)石油化工研究院有限公司辽宁大连116045 大连理工大学化工海洋与生命学院辽宁大连116081

全面总结了石化储罐VOCs产排机理、排放特征以及VOCs减排、回收和热氧化技术进展,并提出了意见和建议,希望对我国石化储罐VOCs深度减排有所裨益。石化储罐除大小呼吸产气外,还有高温重油储存热裂解等产气现象。在计算储罐排气中可燃物... 详细信息

全面总结了石化储罐VOCs产排机理、排放特征以及VOCs减排、回收和热氧化技术进展,并提出了意见和建议,希望对我国石化储罐VOCs深度减排有所裨益。石化储罐除大小呼吸产气外,还有高温重油储存热裂解等产气现象。在计算储罐排气中可燃物浓度时不应忽视硫化氢、甲烷、氢气、氨等组分。目前,中美储罐VOCs管控都以选择浮顶罐等源头减排为主,以储罐使用过程控制和排放气末端治理为辅,我国应适时修订现行标准,以适应越来越严的环保要求。核算得出2019年我国有机液体储罐VOCs排放量为(39.2~90.4)×10^(4)t,主要来自石化企业,建议将粗柴油、粗汽油、粗航煤、蜡油、燃料油、渣油等中间产品罐或重油罐与苯、甲苯、二甲苯、甲醇等储罐一起列为优先管控对象。建议我国开展石化储罐VOCs深度减排,包括源头减排、过程控制和末端治理,内浮顶罐内置气袋有可能成为继浮盘之后又一重要的源头减排技术;低温柴油吸收与吸附、冷凝相比,在处理含硫量较高的粗汽油、粗柴油、高温重油等储罐废气上具有优势。总体上,我国石化储罐外排VOCs治理正在从回收向回收+热氧化(催化氧化、蓄热氧化、焚烧炉、工艺加热炉、锅炉)转变,控制热氧化单元出口非甲烷总烃小于20mg/m^(3)。

关键词：石化储罐挥发性有机物产气机理减排回收氧化安全

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加氢裂化理论创新与实践

石油炼制与化工 2024年第1期55卷 164-170页

作者：范思强张通王继峰方向晨侯栓弟中石化(大连)石油化工研究院有限公司辽宁大连116000

中石化(大连)石油化工研究院有限公司通过深入研究烃类分子多相催化反应过程,发现烃分子的诱导偶极矩和反应中间体碳正离子的稳定性是影响烃类分子吸附和反应的关键因素,并在此基础上提出渐次反应理论,用于指导加氢裂化工艺与催化材料... 详细信息

中石化(大连)石油化工研究院有限公司通过深入研究烃类分子多相催化反应过程,发现烃分子的诱导偶极矩和反应中间体碳正离子的稳定性是影响烃类分子吸附和反应的关键因素,并在此基础上提出渐次反应理论,用于指导加氢裂化工艺与催化材料的开发与升级。渐次反应理论的应用避免了低效无秩序反应的发生,使得加氢裂化反应过程科学有序,从而在低能耗、低氢耗的反应环境下提升了加氢裂化过程的产品选择性与产品质量,有效推进中国炼油结构调整,实现科学有序的“油转化”、“油转特”转型发展。

关键词：加氢裂化渐次反应吸附催化反应转型升级

Pt-Pd/MnCo_(2)O_(4)复合型催化剂的制备及其对低碳烃等有机物的催化燃烧性能

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石油炼制与化工 2024年第10期55卷 94-101页

作者：刘世达侯栓弟刘淑鹤赵磊刘忠生中石化(大连)石油化工研究院有限公司辽宁大连116045

在涂覆氧化铝的陶瓷蜂窝载体上,通过化学还原法原位构建MnCo_(2)O_(4)纳米小球颗粒使其生长于氧化铝涂层,制备出两种Pt-Pd/MnCo_(2)O_(4)复合型催化燃烧催化剂MnCo-2、MnCo-3。MnCo-2的贵金属含量比国外参比剂少约44%、比国产参比剂少约... 详细信息

在涂覆氧化铝的陶瓷蜂窝载体上,通过化学还原法原位构建MnCo_(2)O_(4)纳米小球颗粒使其生长于氧化铝涂层,制备出两种Pt-Pd/MnCo_(2)O_(4)复合型催化燃烧催化剂MnCo-2、MnCo-3。MnCo-2的贵金属含量比国外参比剂少约44%、比国产参比剂少约16%,乙烷等低碳烃氧化活性与国外参比剂相当,其乙烷转化率为99%时的氧化转化温度(T_(99))、丙烷T_(99)、甲烷转化率为90%时的氧化转化温度(T_(90))分别为440,380,460℃,比国产参比剂低60℃,且在累积800 h的测试中性能稳定。MnCo-3的贵金属含量比国外参比剂少约61%、比国产参比剂少约41%,其试剂总成本约比国产参比剂低38%,其乙烷T 99为475℃,比国产参比剂低25℃。

关键词：低碳烃催化燃烧贵金属非贵金属氧化物复合型催化剂

Microchannel reactors for Fischer-Tropsch synthesis:Experimental investigation and mathematical modeling

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Chinese Journal of Chemical Engineering 2023年第12期64卷 224-240页

作者： Huili Cao Run Xu Xiaojin Tang Tao Yang shuandi hou Chaopeng hou SINOPEC Research Institute of Petroleum Processing Co. Ltd.Beijing 100083China

The Fischer-Tropsch synthesis is a significant technology for converting coal,natural gas,and biomass into synthetic *** recent years,the use of microchannel reactors for the Fischer-Tropsch synthesis has attracted significant ***-Tropsch synthesis experiments were carried out in a microchannel reactor and the influences of reaction conditions on the experimental results were investigated in this *** on the experimental data,a dynamic multi-component pseudo-homogeneous variable-volume flow model of microchannel reactors for the Fischer-Tropsch synthesis was built to determine the pressure-,velocity-,conversion-and(component-wise)concentration-distributions in reaction *** model takes into account the combined effects of gas volume expansion caused by the frictional pressure drop and gas volume contraction caused by reaction consumption.A novel effective method for calculating the pressure and superficial gas velocity values in microchannel reactors was proposed in the *** that,two sets of experimental data were selected from references to evaluate the validity and accuracy of the *** reaction performances in the microchannels were analyzed carefully based on the calculated results.

关键词： Fischer-Tropsch synthesis Microchannel reactors Modeling Variable-volume flow

Influence of Gas Density on Hydrodynamics in a Bubble Column

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China Petroleum Processing & Petrochemical Technology 2014年第1期16卷 66-70页

作者： Tang Xiaojin hou shuandi Zhang Zhanzhu Research Institute of Petroleum Processing SINOPEC

Two kinds of gases were used to investigate the influence of gas density on the hydrodynamic characteristics in a bubble column. It can be found out that higher gas density leads to smaller bubble diameter and the flow patterns are different for the both gases. Energy balance mechanisms are analyzed by considering the gas density difference. Models were developed to predict the average bubble diameter with good accuracy.

关键词： bubble column hydrodynamics,gas density

Study of Macro-Mixing in a Microreactor

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China Petroleum Processing & Petrochemical Technology 2023年第4期25卷 117-126页

作者： Cao Huili Tang Xiaojin Bao Di hou shuandi SINOPEC Research Institute of Petroleum Processing Co. Ltd.Beijing 100083 SINOPEC(Dalian)Research Institute of Petroleum and Petrochemicals Co. Ltd.Dalian 116045

The transfer rate between fluids in a microreactor is directly influenced by the mixing within the reactor, which subsequently impacts the reaction rate. This paper investigates the flow behavior and macro-mixing performance in a microreactor. First, the flow performance of the Ehrfeld Miprowa microreactor is studied. Cold experiments are conducted to examine fundamental flow laws and verify the accuracy of the chosen computational fluid dynamics simulation ***, macro-mixing performance in the microreactor, both with and without internal components, is investigated through both experiment and simulation. A bromocresol violet–NaOH–H2SO4 system is utilized in the macro-mixing experiments, which explore the effects of flow rate and internal components on macro-mixing. The Navier–Stokes equation is adopted as the computational model for macro-mixing simulations, which also consider the mass transfer and diffusion of tracer. The simulation results are in good agreement with the experimental results. Both experimental and simulation results demonstrate that the presence of internal components in the microreactor enhance its macro-mixing performance.

关键词： microreactor flow model macro-mixing

Study on Separation of Water and Alumina Fine Particles by Cross-Flow Microfiltration

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China Petroleum Processing & Petrochemical Technology 2017年第2期19卷 96-103页

作者： Zheng Bo Tang Xiaojin hou shuandi Zong Baoning SINOPEC Research Institute of Petroleum Processing Beijing 100083

A cross-flow microfiltration process had been developed to separate alumina fine particles from the suspension using a stainless steel membrane tube with a pore size of 10 μm. The influence of cross-flow velocity and trans-membrane pressure on the permeate flux and the solid holdup in permeate had been investigated. It was found that both the permeate flux and the solid holdup in permeate decreased with time. Moreover, the permeate flux increased with an increasing transmembrane pressure but the influence of cross-flow velocity on the permeate flux was quite complex. Both the permeate flux and the solid holdup in permeate in long term filtration had been studied. The operation of cross-flow microfiltration could be carried out stably for 10 hours with the permeate flux values ranging from 520.5 to 936 L/(m^2·h) at rs=1%, while it could continue in 10 hours with the permeate flux values ranging from 226 to 432 L/(m^2·h) at rs=5%. The solid holdup in permeate had been less than 10 mg/L during the whole operating cycle.

关键词： cross-flow microfiltration permeate flux rejection rate alumina fine particles

Modeling of Isobutane/Butene Alkylation Using Solid Acid Catalysts in a Fixed Bed Reactor

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China Petroleum Processing & Petrochemical Technology 2016年第2期18卷 63-69页

作者： Liu Zheng Tang Xiaojin Hu Lifeng hou shuandi Research Institute of Petroleum Processing SINOPEC

A dynamic mass transfer model of isobutane/butene alkylation over solid acid catalysts in a fixed bed reactor was established. In the model, a modified equation for the relationship between point activity and effective diffusion coefficient was proposed. It is found that the simulation results fit the experimental data well and the breakthrough time of the bed layer is predicted accurately. By modeling the alkylation process, the time-space distribution of butene and point activity profiles of catalysts can be obtained. Furthermore, the reasons for the deactivation of solid acid catalysts were investigated. It indicates that the main reason for the deactivation of catalysts is the site coverage near the inlet of the reactor, while it is ascribed to the steric effect in the region far away from the inlet.

关键词： mass transfer model isobutane/butene alkylation fixed bed reactor deactivation internal diffusion