正庚烷催化裂解生产低碳烯烃的影响因素探索

The influence of zeolite structure and process parameters (including reaction temperature and catalyst/oil ratio) on rules for formation of ethylene and propylene in the course of catalytic pyrolysis of n-heptane was studied in a small- scale fixed fluid catalytic cracking unit. Test results have revealed that compared to the USY zeolite and Beta zeolite, the catalytic pyrolysis of n-heptane in the presence of the ZRP zeolite catalyst can result in higher yield and selectivity of ethyl- ene and propylene, while a higher reaction temperature and a higher catalyst/oil ratio can promote the formation of ethylene and propylene during catalytic pyrolysis of n-heptane. The ethylene formation reaction is more sensitive to the changes in reaction temperature, whereas the changes in catalyst/oil ratio are more influential to the propylene formation reaction. This paper has made a preliminary exploration into the different reaction pathways for formation of ethylene and propylene on zeolites with different structures.     

Kinetics of the ethylene trimerization reaction on a homogeneous chromium-pyrrole catalyst

The results of studying the kinetics of the reaction of ethylene trimerization under the action of a homogeneous chromium-pyrrole catalyst have been presented. It has been shown that the reaction order with respect to ethylene decreases from 1.4 to a value close to 1 within 15 min after the start of the reaction, which is explained by the presence of two types of catalytic centers that catalyze the reactions of the first and second order with respect to ethylene. A model that includes the degradation of the second type of the catalyst during the reaction and inhibition of the activity of the first-type catalyst by the products has been proposed.     

乙烷与CO_2反应制乙烯催化剂研究

以CO2 与乙烷的主要反应热力学为基础 ,研制出Cr/Si 2和Fe Mn/Si 2两种催化反应性能较好的催化剂 ,得到乙烷转化率 69%、乙烯选择性 93%、乙烯单程收率 57%的好结果 ,并显示出很好的催化反应稳定性。将所研制的催化剂进行放大制备 ,可直接应用于催化裂化尾气中乙烷与CO2 反应制乙烯 ,取得好的结果。     

合成乙二醇醚类高活性催化剂NKC-1A的研究

NKC-1A固体酸催化剂于室温或低于室温的条件下,在合成乙二醇醚类的反应中具有催化活性,可使合成乙二醇乙醚的反应温度下降50—80℃,反应的活化能仅是NKC-01催化剂的1/3。NKC-1A催化剂用于在乙醇沸点(78℃)合成乙二醇乙醚非常有效,故该催化剂可适用于常压下合成乙二醇乙醚的催化精馏工艺,从而大大简化催化精馏的操作。     

Commercial Application of CPP for Producing Ethylene and Propylene from Heavy Oil Feed

A new process named CPP (Catalytic Pyrolysis Process) for producing ethylene and propylene from heavy oil feedstock has been developed. The catalyst CEP was specially designed for this process, which has bi-functional catalytic activities for both carbonium ion reaction and free radical reaction, so as to maximize the yields of ethylene and propylene. The commercial trial showed that the yield of ethylene and propylene was 20.37% and 18.23% respectively in maximum ethylene operation with Daqing AR as feedstock, and the yield of ethylene and propylene was 9.77% and 24.60% respectively in maximum propylene operation by using the same feedstock.Compared with steam cracker, the feed cost of CPP is much lower for producing ethylene and propylene.     

气相法聚乙烯催化剂QCP-02的反应行为及反应动力学

采用微机控制的气相搅拌床反应器对实验室自制的还原型铬催化剂ＱＣＰ－０２进行了聚合反应行为和动力学研究。讨论了还原剂种类以及聚合反应的温度和压力对催化剂的活性和所生成产品性能的影响。当反应压力为０９～１６ＭＰａ时,最大聚合反应速率与乙烯压力呈一级动力学关系,并据此求出反应温度为８０～９５℃时ＱＣＰ－０２催化剂上乙烯均聚反应的表观活化能。     

二氧化硅负载磷钨钼酸催化合成环己酮乙二醇缩酮

采用溶胶-凝胶法制备了二氧化硅负载磷钨钼酸H3PW6Mo6O40/SiO2催化剂,以环己酮和乙二醇为原料,合成了环己酮乙二醇缩酮.探讨了H3 PW6 Mo6 O40/SiO2对缩酮反应的催化活性,考察了酮醇物质的量比、催化剂用量、带水剂用量、反应时间对产物收率的影响.结果表明,H3 PW6 Mo6O40/SiO2是合成...     

乙醇脱水制烯烃过程分析

针对乙醇脱水制乙烯的反应,计算了不同温度、压力下的反应热、化学平衡常数和系统中各组分的平衡转化率和收率。在此平衡体系中,乙醇和乙醚的含量几乎接近于零,而乙烯和C4烯烃的含量取决于乙烯叠合反应的平衡。随之,讨论了温度、压力和水醇比对平衡转化率和收率的影响。并将上述平衡数据与以自主研发的γ-Al2O3为催化剂的实验数据相比较,得出现有催化剂已具有良好的抑制生成C4烯烃作用。因此,如何提高催化剂的活性,降低反应温度和进程能耗将成为进一步的研究重点。     

稀乙烷与CO_2反应制乙烯及催化裂化干气的综合利用

将研制的Fe/Si-2和Cr/Si-2系列催化剂用于催化裂化干气中的稀乙烷与CO2 反应制乙烯 ,考察了催化剂的反应性能、放大效应、单程反应寿命和再生性能。试验结果表明 ,干气中乙烷转化率达到 67 6%、乙烯选择性达到93 4 %。在 1 0 0ml规模的试验装置上 ,进行了 90 0h寿命试验和催化剂再生试验 ,为中试放大提供数据。并考察了Ni/Si-2系列催化剂用于催化裂化干气中甲烷和乙烷同时与CO2 转化制合成气的反应性能。在此基础上 ,提出催化裂化干气综合利用新流程。     

A STUDY ON ACIDITY AND CATALYTIC PROPERTY OF [B] ZSM-5 CATALYST MODIFIED WITH SILICON COMPOUND BY CHEMICAL SURFACE DEPOSITION OF LIQUID-PHASE TECHNIQUE

ABSTRACT

The boron heteroatom zeolite catalyst has been modified with silicon compound by Chemical Surface Deposition of Liquid-phase (CLD) technique and the catalytic property of the modified catalyst is studied. Meanwhile, the acidity of the modified zeolite catalysts is characterized through TPD and IR technique, and the fluid adsorption method is used to determine its pore structure. The relationship between the catalytic property of the zeolite catalyst and its pore structure, its acidity has been found. The results of toluene–ethylene alkylation reaction indicate that the selectivity of p-ethyltoluene on the modified zeolite catalyst is higher than that on the zeolite catalyst before silanizated, reaching 94.14%.     

Influence of the preparation procedure on the properties of supported molybdenum catalysts for ethylene and trans-butene-2 metathesis to propylene

The influence of the preparation method on the properties of a supported catalyst for the metathesis of ethylene and trans-butene-2 to propylene has been studied. A catalyst composed of molybdenum oxide supported on an alumina-carbon sorbent (manufactured by SKTB Katalizator, Novosibirsk, Russia) has been examined. It has been shown that the addition of nitric acid to an ammonium paramolybdate solution for impregnation during the preparation of the catalyst has an effect on the morphology and phase composition of the active component formed on the support surface, thereby improving the catalytic properties of the resulting systems in the metathesis of ethylene and trans-butene-2 to propylene.     

PNSiP/Cr(III)/MMAO催化乙烯选择性齐聚连续化反应性能及其动力学研究

设计了乙烯选择性齐聚连续化反应装置,将硅胺基桥联双膦型配体铬配合物(PNSiP/CrCl₃(THF)₃)、改性甲基铝氧烷(MMAO)组成催化体系,考察了其催化乙烯选择性齐聚连续化反应性能,并对该反应动力学进行研究。结果表明：当反应温度为60 ℃、乙烯压力为5.0 MPa、氢气分压为0.2 MPa、连续化反应20 h时,该催化体系的催化活性可达46.13×106 g/(mol Cr·h);产物中1-己烯和1-辛烯的总选择性最高达到88.52%,固体产物聚乙烯（PE）质量分数为0.09%。PNSiP/Cr(Ⅲ)/MMAO催化体系在乙烯选择性齐聚连续化反应中具有催化活性高、副产物(甲基环戊烷+亚甲基环戊烷)少、固体低聚物少、可实现长周期运行的优点。对PNSiP/Cr(Ⅲ)/MMAO催化乙烯选择性齐聚连续化反应动力学方程进行拟合计算,得到该反应对主催化剂浓度的反应级数为1.32、对乙烯压力的反应级数为1.92;当主催化剂摩尔浓度为7.09 μmol/L、反应温度为40～60 ℃、压力为5.0 MPa时,该反应的表观活化能为109.7 kJ/mol。     

Sb_2O_3在对苯二甲酸与乙二醇的缩聚反应中的催化活性

根据对苯二甲酸与乙二醇缩聚反应中所需高真空条件下的反应时间、产物聚对苯二甲酸乙二醇酯的内在质量以及Ｓｂ２Ｏ３催化剂的各项物理指标等三方面因素提出了综合评价Ｓｂ２Ｏ３催化活性的方法，并依据该方法对数种国产和进口的Ｓｂ２Ｏ３在对苯二甲酸与乙二醇缩聚反应中的催化活性进行了评定。试验表明，该方法能较全面地评价Ｓｂ２Ｏ３，其结果与实际生产中所反映的使用情况基本一致。     

基于BP神经网络的重油催化裂解模型

基于BP神经网络,利用重油催化裂解反应过程的试验数据,以涉及原料性质、催化剂活性、操作条件等的11个参数作为输入变量,以乙烯、丙烯和轻芳烃 BTX（苯、甲苯、二甲苯）的产率作为输出变量,构建了结构为11-12-3、以贝叶斯算法为学习算法的BP神经网络重油催化裂解模型,并进行了验证。结果表明,该模型对乙烯、丙烯和BTX产率的预测平均相对误差分别为4.59%,3.92%,2.28%,说明所建模型对重油催化裂解反应产物产率的预测效果较好。     

负载磷钨酸催化苯与乙烯液相烷基化

以负载磷钨酸为催化剂 ,考察催化剂预处理温度、反应温度、原料苯中溶解水量、苯烯摩尔比和苯进料质量空速对苯与乙烯液相烷基化反应的影响。实验表明 ,负载磷钨酸的催化活性和预处理温度密切相关 ,在 2 10℃预处理时 ,催化活性最高 ;负载磷钨酸在 14 0℃以上 ,具有很高的催化活性和很好的乙苯选择性。在优化的反应条件下 ,乙烯的转化率为 10 0 % ,乙苯的选择性大于 90 % ,乙基化的选择性大于 98%。     

单质碘催化合成苹果酯

以单质碘为催化剂,通过乙酰乙酸乙酯和乙二醇反应合成了苹果酯,考察了乙酰乙酸乙酯与乙二醇摩尔比、碘催化剂用量、反应时间对产品收率的影响,并用单质碘催化剂与其他催化剂进行催化活性比较。结果表明,在乙酰乙酸乙酯与乙二醇摩尔比1：1．8,单质碘催化剂用量占反应物总量0．3％,环己烷为带水剂,反应时间1．0h条件下,苹果酯产品收率可达73．2％;单质碘催化剂与其他催化剂相比较,具有反应时间短、催化剂用量少、产品收率高等优点。     

Hydroalkoxycarbonylation of isobutylene with polyhydric alcohols in the presence of catalytic systems based on palladium compounds and tertiary phosphines

The reaction of isobutylene hydroalkoxycarbonylation at low carbon monoxide pressures (??2.0 MPa) with ethylene glycol and glycerol in the presence of catalytic systems based on Pd and mono- and bidentate organic phosphines has been studied. The effect of different conditions of the reaction in the presence of the Pd(Acac)₂-PPh₃-TsOH catalyst system on the ratio of the products, mono- and diglycolides (mono-, di-and triglycerides) of isovaleric acid has been investigated. The relative catalytic activity of a number of binary and ternary systems based on synthesized Pd(Acac)₂, Pd(PPh₃)₄, and PdCl₂(PPH₃)₂ complexes has been determined.     

硅胶表面积碳催化作用的研究

研究了硅胶表面积碳经化学改性后在环氧乙烷水合制备乙二醇反应系统中的催化作用 ,探讨了硫酸处理时间、硫酸处理温度、反应温度、空速对环氧乙烷转化率和乙二醇选择性的影响。实验表明 ,硅胶表面积碳经化学改性后作为环氧乙烷水合制备乙二醇反应的催化剂 ,具有很好的催化活性     

纳米Pd/TiO_2加氢催化剂的制备及其催化性能研究

以沉淀法制备纳米Pd/TiO2催化剂,并采用XRD、TEM检测分析手段对Pd/TiO2催化剂进行了表征,以乙炔选择催化加氢制备乙烯为反应模型考察了制备方法、反应温度、钯含量对催化剂性能的影响。实验结果表明,用沉淀法制备的催化剂,经过500℃焙烧,TiO2呈锐钛型,平均粒径为16nm,乙炔的转化率达到100%,乙烯选择性最高达到86%左右,稳定性好。比浸渍法制备的催化剂的选择性提高了约43%。     

CpTi(dbm)Cl_2催化烯烃聚合及其聚合物性质

开发了一种新型非茂聚烯烃催化剂———CpTi(dbm)Cl2,考察了催化剂在均相及负载条件下对乙烯及乙烯-1-己烯共聚的催化行为。催化剂在均相条件下对乙烯聚合的催化活性较低,但用MgCl2和MgCl2/SiO2复合双载体对催化剂进行负载后,催化乙烯聚合具有非常好的催化活性。催化剂还具有良好的共聚能力及良好的氢调敏感性。