Highly selective ethylbenzene production through alkylation of dilute ethylene with gas phase-liquid phase benzene and transalkylation feed

A novel industrial process was designed for the highly selective production of ethylbenzene.It comprised of a reactor vessel,vapor phase ethylene feed stream,benzene and transalkylation feed stream.Especially the product stream containing ethylbenzene was used to heat the reactor vessel,which consisted of an alkylation section,an upper heat exchange section,and a bottom heat exchange section.In such a novel reactor,vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between the upper heat exchange section and the bottom heat exchange section.The process was demonstrated by the thermodynamic analysis and experimental results.In fact,during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction,the ethene conversion was above 95%,and the ethylbenzene selectivity was above 83% (only benzene feed) and even higher than 99% (benzene plus transalkylation feed).At the same time,the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried out under the reaction conditions of 140-185℃ of temperature,1.6-2.1 MPa of pressure,3.0-5.5 of benzene/ethylene mole ratio,4-6 v% of transalkylation feed/(benzene+transalkylation feed),0.19-0.27 h-1 of ethene space velocity,and 1000 g of 3998 catalyst loaded.Thus,compared with the conventional ethylbenzene synthesis route,the transalkylation reactor could be omitted in this novel Industrial process.     

Kinetics and mechanisms of transalkylation and disproportionation of meta‐diethylbenzene by triflic acid catalyst

The kinetics of transalkylation and isomerization of meta‐diethylbenzene in the presence of benzene using triflic acid as a catalyst has been investigated. High catalytic activity of the triflic acid catalyst was observed in homogeneous liquid‐phase reactions. On the basis of the product distribution obtained, transalkylation, disproportionation, and isomerization reactions have been considered and the main product of the reaction was ethylbenzene. These reactions are conducted in a closed liquid batch reactor with continuous stirring under dry nitrogen and atmospheric pressure over the temperature range of 288–308 K. The main transalkylation, disproportionation, and isomerization reactions occurred simultaneously and were considered as elementary reactions. The apparent activation energy of the transalkylation reaction was found to be 35.5 kJ/mol, while that of disproportionation reaction was 42.3 kJ/mol. The reproducibility of the experimental product distribution occurred with an average relative error of ±2%. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 555–563, 2003     

晶化时间对ZSM-5分子筛物化性质及催化性能的影响

 考察了ZSM－5分子筛在晶化过程中的变化规律及其在苯与乙烯气相烷基化制乙苯反应中的催化性能．结果表明,当晶化时间为70h时,分子筛晶体开始出现;晶化90h时无定形物相基本消失．晶化时间从90h再延长至150h,ZSM－5分子筛晶粒的大小、形貌和体相硅铝比都基本不变,但分子筛表面的硅铝比逐渐降低．以晶化时间为90h的ZSM－5分子筛原粉为活性组元制备的催化剂,对苯与乙烯气相烷基化制乙苯反应表现出最佳的催化性能．     

DFT方法研究酸性沸石上苯与乙烯烷基化反应的机理

采用B3LYP/6-31G*水平计算来研究酸性沸石上苯与乙烯的烷基化反应历程,从生成能和反应活化能角度分析并讨论了苯与乙烯的反应机理.选取4T簇模型模拟分子筛的酸性位,使用密度泛函理论对烷基化反应三种不同的反应机理(两个联合反应机理和一个分步反应机理)进行计算分析.结果表明,在联合反应机理中,乙烯的质子化和苯与乙烯间C-C键的形成同时发生;分步反应机理中,首先形成一个稳定的乙醇盐中间物种,然后与苯分子反应形成乙苯.联合机理速控步骤的活化能约为160kJ/mol,分步机理速控步骤的活化能为190.24kJ/mol,因此,酸性沸石上苯与乙烯烷基化反应机理主要以联合机理为主,但分步机理与其有一定程度的竞争。     

苯与乙烯在ZSM－5上的烷基化反应──Ⅰ．动力学规律及反应机理

用无梯度反应器在１．１ＭＰａ，６２８Ｋ到７１３Ｋ范围内研究了低浓度乙烯和苯在ＺＳＭ－５催化剂上烷基化反应的动力学规律．实验发现，乙烯的转化速率与苯分压无关；苯生成乙苯的选择性随苯分压增加而增高，但与乙烯分压无关．实验结果清楚地表明；乙烯在活性位上的吸附是反应的控制步骤；苯的吸附属弱吸附，吸附粒子既不成为活性分子，也不影响乙烯的吸附，但有效地阻止了乙烯的双分子聚合反应，使烷基化反应顺利进行．     

Untersuchungen an oxidischen Katalysatoren. XXVIII. Einfluß der Vorbehandlungsbedingungen auf Die katalytischen Eigenschaften von NiNaY- und NiCoNaY-Zeolithen

Studies on Oxide Catalysts. XXVIII. Influence of Pretreatment on Catalytic Properties of Zeolites NiNaY and NiCoNaY The influence of the pretreatment conditions on the acidic properties, the reduction degree of nickel, and the catalytic activity and selectivity of zeolites NiNaY and NiCoNaY in the alkylation of benzene with ethylene has been investigated. From the experimental results can be concluded that sec. buthylbenzene from benzene and ethylene is only formed on zeolite samples which contain both together BRÖNSTED acidic centres and Ni²⁺ cations or NiO. Catalysts which contain only metallic nickel are inactive for this reaction. Catalysts with nickel in different forms are active in the formation of ethylbenzene, diethylbenzene, butane and sec. buthylbenzene, the yields depending on the relation of Ni°, Ni²⁺, and NiO. Changing this relation makes possible to regulate the selectivity in the alkylation of benzene with ethylene.     

Unsteady state behavior of CO oxidation over a supported Pt catalyst in the millibar range

The alkylation of naphthalene with isopropanol was investigated over a HY (Si/Al=4) zeolite under the following conditions: flow reactor, liquid phase with decalin as solvent, 623 K, 40 bar. Despite complete filling of the zeolite pores by coke during the first hour of reaction, the rate of formation of isopropylnaphthalene remained very high. This is due to the development of a new reaction process involving transalkylation between the polyisopropyl naphthalenes entrapped in the pores and naphthalene followed by the realkylation of the former compounds with isopropanol.     

The Carbon Depositing Behavior and its Kinetic Research in Benzene Alkylation Process Over High Silicate ZSM-5 Zeolite

In our invention, FCC (fluid catalytic cracking) dry gas could be used to react with benzene without any special purification, and more than 90% ethylene was converted to ethylbenzene. The phenomenon of carbon deposition over catalyst surface was obvious and leads to a deactivation of catalyst, so it is important to study the behavior of carbon deposition of catalyst during alkylation of benzene. The influence of several factors such as temperature, reaction time, reactant concentration of the amount and the kinetics of carbon deposition were investigated, during which carbon depositing rate equations were obtained for different reactant.This revised version was published online in November 2005 with corrections to the Cover Date.     

Investigation of coupling dehydrogenation and hydrogenation reactions in a fixed bed catalytic reactor with well-mixed catalyst pattern

The enhancement of ethylbenzene conversion by further displacement of the thermodynamic equilibrium via the influence of the dual-functionality of a well-mixed catalyst pattern has been investigated. A rigorous steady state mathematical model based on the dusty gas model is implemented for the simulation. The simulation results reveal that the introduction of the concept of the reaction coupling has significant effect on the displacement of the thermodynamic equilibrium and considerable enhancement of simultaneous production of styrene and cyclohexane. Almost 100% conversion of the ethylbenzene and benzene is achieved through the application of this approach. It is also found that considerable decrease in the reactor length is achieved by employing a reactor catalyst bed with different bed compositions. Effective operating regions with optimal conditions are observed. An effective reactor length criterion is used to evaluate the performance of the reactor under these optimal conditions. The effective reactor length is found to be sensitive and favored by high feed temperature and pressure. The sensitivity analysis shows that the key parameters of feed temperature, pressure, and the bed composition play an important role on the reactor performance. The results also show that almost 100% conversion of ethylbenzene and benzene at low temperature and shorter reactor length can be achieved by maintaining the reactor beds at different temperatures. This temperature switching policy may result in appreciable energy saving. Moreover, operating the reactor at low temperature protect the catalyst from the excessive temperatures which have destructive effects on the catalysts and the mechanical stability of the reactors. Also, the low temperature operation has significant contribution to the reduction of the operating cost.     

Studies on the Mechanism of the Direct Synthesis of Styrene form Benzene and Ethylene

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Vapor-Phase Alkylation of Phenol with Tert-butyl Alcohol Catalyzed by H3PO4/MCM-41

 The catalytic performance of Al-MCM-41 containing 5?5 wt% H3PO4 was studied for the vapor phase alkylation of phenol with tert-butyl alcohol (TBA) from 383 to 493 K. 4-Tert-butyl phenol was produced as the main product with moderate selectivity. The product distribution depends on the reaction temperature, number of acid sites, and the Br鰊sted to Lewis sites ratios. A lower molar ratio of reactants (TBA/phenol = 2) and a higher space velocity facilitated the production of 4-tert-butyl phenol. The influence of various parameters such as temperature, reactant feed molar ratio, feed rate, and time on stream were investigated for conversion yield and product selectivity.     

Thermally Responsive Selenide-containing Materials Based on Transalkylation of Selenonium Salts

Covalent adaptable networks (CANs) possess unique properties as a result of their internal dynamic bonds, such as self-healing and reprocessing abilities. In this study, we report a thermally responsive C−Se dynamic covalent chemistry (DCC) that relies on the transalkylation exchange between selenonium salts and selenides, which undergo a fast transalkylation reaction in the absence of any catalyst. Additionally, we demonstrate the presence of a dissociative mechanism in the absence of selenide groups. After incorporation of this DCC into selenide-containing polymer materials, it was observed that the cross-linked networks display varying dynamic exchange rates when using different alkylation reagents, suggesting that the reprocessing capacity of selenide-containing materials can be regulated. Also, by incorporating selenonium salts into polymer materials, we observed that the materials exhibited good healing ability at elevated temperatures as well as excellent solvent resistance at ambient temperature. This novel dynamic covalent chemistry thus provides a straightforward method for the healing and reprocessing of selenide-containing materials.     

大孔沸石催化剂上苯与丙烯液相烷基化反应行为的研究

围绕具有工业实用价值的苯与丙烯液相烷基化制取异丙苯这一课题,对比考察了不同硅铝组成的ＨＹ型和Ｈβ型沸石的催化性能,利用烧炭试验、结炭前驱物萃取方法及色－质谱表征手段探索了沸石催化剂在烷基化反应中的结炭行为。烷基化试验结果表明,β沸石对异丙苯的选择性和催化剂稳定性都明显优于Ｙ型,其异丙苯选择性可达９６ｍｏｌ％以上。同时,提高原料苯烯比、降低反应温度或保持适当高的进料空速能够提高异丙苯的选择性。结炭催化剂的烧炭结果显示,在烷基化反应中Ｈβ比ＨＹ具有较强的抗结炭能力。结炭催化剂的溶剂萃取结果表明,反应中的液相苯能够有效地使催化剂孔道中的结炭前驱物种脱离催化剂表面,从而抑制结炭,提高催化剂的稳定性     

Alkylation of Ethylbenzene with Methanol on HY,HM and HZSM-5 Zeolite

The alkylation of ethylbenzene with methanol on various zeolites has been studied at atmospheric pressure, 300–500 °C and with ethylbenzene/methanol = 3 mol/mol in a fixed-bed, integral-flow reactor. The catalytic activity decreased in the order HZSM-5 > HY > HM. The optimum conditions for the formation of ethyltoluene were HY zeolite, 400 °C and W/F = 4.1 g-cat h/g-feed. The catalyst decay rate increased in the order HZSM-5 << HY < HM; coking of the zeolite increased the fraction of para-isomer in the ethyltoluenes. On HZSM-5 modified with alkaline earth metal, the conversion of ethylbenzene decreased with concomitantly increased selectivity of para-ethyltoluene especially evident in cases of magnesium and calcium (> 93% para-selectivity). These results are interpreted in terms of diminution of both the strong acid sites and the pore size of zeolites. For the reaction on HY at 400 °C, the reaction paths were determined; the ethylbenzene reacted via alkylation, disproportionation and dealkylation with initial selectivities 84.7%, 13.1% and 2.2%, respectively.     

乙醇直接气相羰基化新催化剂

醇的羰基化合成是极有工业价值的过程 ,也是绿色化学中提倡的原子经济性反应 [1] .甲醇均相羰基化合成醋酸是 Monsanto公司成功开发应用的典范 [2 ] ,而乙醇羰基化合成丙酸或丙酸乙酯的研究尤其重要 .前文对一种性能优良的负载型 Ni系催化剂用于乙醇常压气相羰基化合成丙酸及其酯作了报道 [3,4] ,与均相羰基化相比 ,该反应具有条件温和 ,不使用贵金属铑 ,催化剂与产物不存在分离上的困难等优点 ,但反应体系仍需使用卤化物作促进剂 .由于碘乙烷的存在 ,反应系统设备腐蚀严重 (有 HI生成 ) ,产物分离精制复杂 .目前 ,醇的均相羰基化及多相羰…     

Fractionation step in the technological process on reaction-rectification column of ethylene glycol manufacturing

Features of fractionation of reaction mixture in the synthesis of ethylene glycol by hydration of ethylene oxide in a reaction-rectification column are studied. Adequacy of the mathematical model applied to the process is evidenced. The ethylene glycol purity is shown depending on the process chemistry mainly. Side reaction of polyglycols formation restrict obtaining of high purity ethylene glycol: it can be isolated only as sideway stream in the bottom section of the reaction-rectification column.     

Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction

In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m⁻³, ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages.     

Preparation of metallosilicates with zeolite structure by atom-planting method

Atom-planting, a useful method to prepare some metallosilicates having zeolitic structure, was proposed. By treatment of highly siliceous zeolite with metal chloride vapor at selected temperature, metal cation could be introduced into the defect sites (hydroxyl nests) of zeolite framework. By the atom-planting method, some metallosilicates which are difficult to be synthesized by hydrothermal synthesis could be prepared. The vapor phase shape-selective alkylation of ethylbenzene with ethanol, and the liquid phase selective oxidation with hydrogen peroxide on the metallosilicates prepared by atom-planting method were reviewed.     

H-ZSM-5分子筛上苯与乙醇和乙烯烷基化反应的理论研究

采用ONIOM2(B3LYP/6-31G(d):UFF)计算方法研究了H-ZSM-5分子筛上苯与乙醇和乙烯烷基化反应历程.选取40T簇模型模拟了H-ZSM-5分子筛位于孔道交叉点的酸性位.从生成能和反应活化能角度分析并比较了苯与乙醇和乙烯烷基化反应机理.结果表明,苯与乙醇的烷基化按照分步机理进行,速控步骤的活化能为170.34 kJ/mol.而乙烯作为烷基化剂与苯反应时同时存在联合机理和分步机理,且二者之间存在一定程度的竞争,其中联合机理的活化能为167.24 kJ/mol,分步机理速控步骤的活化能为155.20 kJ/mol.比较苯与乙醇和乙烯发生烷基化反应的机理可以看出,二者作为烷基化试剂对烷基化反应性能影响不大.     

Solid-phase microextraction and chromatography of water samples containing aromatic compounds

A concentrator was designed for solid-phase microextraction of aromatic compounds (benzene, toluene, ethylbenzene, o-xylene) from water samples. The concentrator was used as an attachment to a water vapor mobile phase chromatograph with a detection limit (compounds <1 μg/l).