甘油氯化合成二氯丙醇的研究

对甘油制环氧氯丙烷中间体二氯丙醇的催化剂进行了研究;考察了催化剂A、己二酸、丙酸、丙二酸、正己酸、正辛酸、醋酸锌、氯化亚锡e、γ-丁内酯等多种催化剂对目的产物二氯丙醇的收率、组成以及反应速率的影响。研究结果表明,以催化剂A为催化剂,用量为甘油质量的6.0%,反应温度为110℃,反应时间为5 h左右时达到平衡,二氯丙醇收率可达到84%,1,3-二氯丙醇选择性可达96%。并且,所用催化剂A可重复使用次数不少于5次,该工艺单位催化剂用量少,形成的工艺技术符合工业化生产的要求。     

A molecular kinetic model incorporating catalyst acidity for hydrocarbon catalytic cracking

This work built a molecular-level kinetic model for hydrocarbon catalytic cracking, incorporating the catalyst acidity as the parameter to estimate reaction rates. The n-decane and 1-hexene co-conversion catalytic cracking process was chosen as the studying case. The molecular reaction network was automatically generated using a computer-aided algorithm. A modified linear free energy relationship was proposed to estimate the activation energy in a complex reaction system. The kinetic parameters were initially regressed from the experimental data under several reaction conditions. On this basis, the product composition was evaluated for three catalytic cracking catalysts with different Si/Al. The Bronsted acid and Lewis acid as the key catalyst properties were correlated with kinetic parameters. The built model can calculate the product distribution, gasoline composition, and molecular distribution at different reaction conditions for different catalysts. This sensitive study shows that it will facilitate the model-based optimization of catalysts and reaction conditions according to product demands.     

Experiment and a catalyst acid property-included global reaction modeling for catalytic pyrolysis of 1-pentene

The acid property of the catalyst is usually one of the most important parameters for the selection and design of catalysts for catalytic pyrolysis of 1-pentene. Here, seven catalysts with similar pore properties and different acid properties were evaluated and characterized in terms of three key properties: Total acid amount (TA), Brønsted to Lewis acid ratio (B/L), and strong to weak acid ratio (S/W). A database of the stoichiometric coefficients of 26 pyrolysis products was constructed. Then, a novel catalyst acid property-included global reaction modeling method was developed, which was used to predict the yields of the 26 pyrolysis products. Besides, a suitable range of TA, B/L, and S/W was obtained for enhancing ethylene and propylene. The model thus can predict the product composition, and be used for the design and selection of the acid properties of catalysts. This simulation method can also be extended to other hydrocarbon systems.     

Characterization of Ni-Mo/Al2O3 catalysts prepared by simltaneous impregnation of the active components

Three Ni-Mo/Al₂O₃, catalysts were prepared, containing similar amounts of NiO (2.8%) and MoO₃ (13.5%), by simultaneous impregnation of the active components, varying the nature of the solubilizing agent (ammonia, citric acid and phosphoric acid). The catalysts were characterized with respect to texture (surface area and pore volume), presence of crystalline phases (XRD), distribution of active components (EPMA) and nature of the active phases (DRS). Catalytic activity was measured using thiophene hydrogenolysis as a model reaction. A commercial Ni-Mo catalyst of similar composition was characterized by the same methods.

The catalyst prepared in the phosphoric acid medium (catalyst P) had a significantly lower surface area. In phosphorus-containing catalysts there was a marked tendency of this element to be deposited on the external region of the catalyst extrudates. The DRS spectra showed that Mo was present predominantly as polymolybdate species in all cases. In the industrial catalyst (catalyst I) the presence of nickel spinel was clearly observed. Catalyst P had an absorption minimum in the visible region displaced to higher wavelength compared to the catalysts prepared in ammonia (catalyst A) and citric acid (catalyst C) media. The observed order of activity was P > C > A > I.     

PtAu/ZrO_2催化甘油选择性制备乳酸

采用溶胶-沉积法制备了Pt Au/ZrO_2系列催化剂,在惰性气体气氛下用于催化甘油选择性制备乳酸。研究不同反应温度下,不同单金属负载和不同比例Pt Au双金属负载催化剂的催化活性以及不同气氛下催化剂重复使用性能,对催化剂进行BET、AAS和TEM等表征。结果表明,在浓度1.1 mol·L-1甘油水溶液10 m L、(1∶1)Pt Au/ZrO_2催化剂用量0.132 g、反应温度160℃、氮气压力1.4 MPa和反应时间6 h条件下,甘油转化率90%,乳酸选择性93.7%。催化剂重复使用性能实验验证了氧气气氛下催化剂活性保持良好。     

助剂对莫西沙星侧链合成用钯炭催化剂性能的影响

采用浸渍法制备不同助剂的钯炭催化剂,考察不同金属硝酸盐、酸根离子和甲酸镍用量对莫西沙星侧链合成用钯炭催化剂的影响。结果表明,助剂镍能够提高催化剂催化活性,助剂甲酸镍用量为钯物质的量的15%时,产物收率达96%。不同酸根离子对催化剂催化活性产生一定影响。     

Catalytic performance of sulfate-grafted graphene oxide for esterification of acetic acid with methanol

Graphene oxide possesses tremendous mechanical and electronic properties in combination with large surface area and accessible active sites leading to the development of novel innovative heterogeneous catalysts. The present study elaborates the catalytic activity of graphene oxide, enhanced by grafting active sulfate groups on its surface to result as a superior catalyst. The catalyst was evaluated in the model acetic acid esterification reaction with methanol in terms of acid conversion. Catalysts consisting of varied sulfate concentrations and calcination time were synthesized and optimized for its best catalytic activity. The prepared catalysts (GO-SO₄) were characterized using XRD, FT-IR, SEM-EDS, XPS, and BET. A 44% enhancement in catalyst activity was observed using sulfate-grafted graphene oxide (GO-SO₄) catalyst over bare GO due to the synergistic effect of sulfate ions. The catalyst can be separated out by simple filtration. Further, the influence of operating process parameters including catalyst loading, and the reaction temperature was evaluated toward the maximum acid conversion. In addition, the detailed kinetic study was also done in this system using Pseudo-homogeneous model.     

低温烟气脱硝催化剂制备工艺及性能探究

为了满足低温脱硝催化剂工业化的需求,对以相同组成的氧化物粉末、工业偏钛酸、水热偏钛酸为前驱体制备的脱硝催化剂的催化性能进行了考察,并利用X射线衍射、N2吸附-脱附、热重分析、机械强度等手段对催化剂的表面结构及性质进行表征分析。结果表明,随焙烧温度升高,各催化剂的活性先升高后降低,催化剂以水热偏钛酸为原料制备的催化剂(催化剂C)更适宜于工业应用,其拥有较好的低温活性、抗压强度及成型率;经过550℃焙烧10 h后催化剂的纵向抗压强度为1.06MPa,在250℃时NO转化率为97.79%。此外,对该催化剂进行脱硝活性评价及宏观动力学分析并考察了1～3 m/s气速下催化剂活性在不同烟气温度下的脱硝性能,结果表明,随气速增加催化剂的脱硝性能逐渐降低;根据Eley-Rideal机理,建立动力学方程,推算出该催化剂的反应速率常数k,并根据Arrhenius公式求得催化剂C的SCR脱硝反应活化能为32.15 kJ/mol,指前因子A为15.37×10³L/(g·min),为实际工业烟气SCR脱硝系统设计提供参考。     

稀土固体催化剂在生物柴油合成中的应用研究进展

由于稀土元素具有独特的价电子构型,因而含有稀土元素的固体酸碱催化剂通常都具有独特的空间结构和催化性能。本文对稀土固体酸碱催化剂的种类及特点进行了综述,并对其在分别及同时催化酯化和酯交换反应合成生物柴油中的研究进展进行了详细论述;对各类稀土固体酸碱催化剂的优缺点进行了综合比较分析;对各类稀土固体酸碱催化剂具有不同催化活性和稳定性的内在影响原因进行了分析;着重介绍了稀土氧化物的催化反应机理;指出固体酸催化剂已成为经化学催化法合成生物柴油的新发展趋势,如何通过稀土元素掺杂来获得高活性和稳定性的固体酸催化剂,将是今后的一个重要研究方向。     

Rheokinetics in curing process of polyfurfuryl alcohol: effect of homologous acid catalysts

Curing reaction of polyfurfuryl alcohol (PFA) resin was investigated using rheological measurements in the presence of different acid catalysts. A homologous series of dicarboxylic acid catalysts with even number of carbons of 2, 4 and 6 were chosen, i.e., oxalic acid (OX, 2 carbon), succinic acid (SU, 4 carbon) and adipic acid (AD, 6 carbon). Acidity of these catalysts in terms of pK _a was in the range of 1.25–4.43. Firstly, non-isothermal curing kinetics were investigated, and then, isothermal studies were performed at three different temperatures using 3 and 5 wt% of each acid catalyst. Isothermal cure behavior was best described by an empirical Arrhenius model of viscosity. An isoconversional method was applied to compute the changes in the effective activation energy as a function of degree of conversion. The change in activation energy at 50–10 kJ mol^?1 was observed for PFA/3 wt% OX system due to the vitrification and diffusion-controlled processes. Gel time, t _gel, was determined as a function of curing temperature, acid catalyst type and its concentration. The gelation time was consistent for all the formulations with an extent of conversion of about 0.7. Significant differences were observed in the curing behavior of resins in the presence of different acid catalysts. Increasing of the curing temperature significantly accelerated the curing process and increased curing rate constant of the PFA resin.     

Mo/REHY催化剂的加氢脱硫性能

将钼酸按溶液与REHY等体积浸渍和焙烧,制备了Mo/REHY催化剂,采用XRD和NH3-TPD对其进行表征.以质量分数0.6%的二苯并噻吩/正癸烷溶液为模型反应物评价其加氢脱硫性能.结果表明,不同焙烧温度制备的Mo/REHY催化剂,归属于REHY的晶相峰保持完好,金属活性组分Mo进入REHY体相超笼,引起REHY分子筛...     

甘油催化氧化合成二羟基丙酮研究进展

对甘油选择性催化氧化转化为二羟基丙酮的研究进行综述,介绍了负载型催化剂在不同条件下对产物选择性和反应物转化率的影响,以及催化剂的作用机理。阐述了甘油催化氧化存在的问题以及发展前景。从均相到非均相催化,从单金属到双金属负载催化,从金属到非金属催化,甘油氧化反应的研究不断在完善。研究发现用Bi改性的Pt负载催化剂可以有效地将甘油选择性催化氧化为二羟基丙酮,在最优条件下,可获得较高的甘油转化率和二羟基丙酮选择性,但催化剂稳定性较差,有待进一步提高。杂多酸催化剂以及非金属催化剂也存在稳定性差的问题。指出改善催化剂的稳定性将是未来研究的主要方向。     

固体酸催化剂脱附活化能动力学模型研究及酸强度表征

基于脱附动力学,确定了脱附活化能动力学模型方程,建立了基于一套程序升温脱附(TPD)数据确定固体酸催化剂脱附活化能的动力学模拟方法。不同温度活化的催化剂TPD实验数据模拟计算结果指出,催化剂的脱附过程符合2级脱附规律;随着活化温度的提高,催化剂的脱附活化能（或酸强度）呈先增大后降低的变化趋势。比较单套数据法和多套数据法的计算结果可知,两种方法测定的脱附级数相同,各活化催化剂的脱附活化能有相似的变化趋势,单套数据法具有操作简便和结果可靠的优点。     

甘油法制备环氧氯丙烷中间体二氯丙醇催化剂的研究

对甘油制环氧氯丙烷中间体二氯丙醇的催化剂进行了研究。考察了以冰醋酸、草酸、丁二酸、己二酸、辛酸五种有机酸为催化剂时,时间、温度、催化剂用量对目的产物二氯丙醇的收率以及反应速率的影响。研究结果表明,以己二酸为催化剂,甘油用量为3mol/kg,反应温度为110℃,反应时间为3h左右时达到平衡,二氯丙醇收率可达到85%。     

A novel catalyst system based on quadruple silicoaluminophosphate and aluminosilicate zeolites for FCC gasoline upgrading

To develop a novel catalyst system that has excellent olefin reduction capability for FCC gasoline without loss in octane number, different catalysts supported on multiple composite carriers consisting of SAPO-11, Hβ, HMOR and HZSM-5 were prepared and their catalytic performances for FCC gasoline upgrading were assessed in the present investigation. The pore structure and acidity of the catalysts were characterized by N₂ adsorption and pyridine adsorption FTIR, respectively. Based on the results obtained over the catalysts supported on binary-zeolite carriers (Hβ/HZSM-5, HMOR/HZSM-5 and SAPO-11/HZSM-5) using FCC gasoline as the feedstock, various multiple-zeolite supported catalysts were developed from different combinations of the binary-zeolite systems. It was found that the SAPO-11/HMOR/β/ZSM-5 quadruple composite zeolite supported catalyst gave higher liquid yield, improved gasoline RON, and lower coke deposit amount for the hydro-upgrading of FCC gasoline and thus can be considered as a potential catalyst system. A comprehensive analysis based on the catalytic activities and acidity measurements revealed that acid strength and acid type were two very important factors influencing hydroisomerization and aromatization activities, and the difference in catalyst acid strength determined which factor predominates.     

醇酸酯化反应催化剂研究进展

有机羧酸酯是重要的化工产品和药物中间体。传统生产工艺是用浓硫酸作催化剂的醇酸酯化反应,开发环境友好的高效酯化反应催化剂替代传统催化剂成为近年的研究热点之一。本文介绍了近年醇酸酯化反应各种催化体系的研究进展,对分子筛、杂多酸、固体超强酸、树脂等多相催化剂和离子型有机金属化合物、有机(酸)与无机盐等催化剂作了综述,对酸性离子液体在酯化反应中兼作溶剂和催化剂的应用研究进展进行了重点评述,并对其今后的研究方向进行了展望。     

适用于丙烯二聚反应非均相催化剂的研究进展

丙烯二聚反应是生产4-甲基-1-戊烯、1-己烯等端碳烯烃的重要手段,其产物可作为特种高分子材料单体、汽油添加剂和化工有机中间体,关键技术在于高效催化剂的开发。非均相催化剂相比于均相催化剂因易回收、对环境污染小等优点受到了学者们的广泛关注。本文综述了丙烯二聚非均相催化剂的研究进展,依据固体碱催化剂与固体酸催化剂在丙烯二聚反应中不同的反应机理,比较了两者各自的优缺点。回顾了固体碱催化剂的发展历程及工业化应用,并以碱金属钾为例总结了反应机理。详细介绍了固体酸催化剂中的固体磷酸催化剂、分子筛催化剂和负载型过渡金属催化剂。针对固体碱催化剂制备条件苛刻等问题,提出了改善催化装置的新思路;针对固体酸催化剂选择性不足的劣势,指出了应该进一步完善机理,并合理设计酸性载体与过渡金属相结合的催化剂。     

Kinetic and diffusion study of acid-catalyzed liquid-phase alkyl formates hydrolysis

Alkyl formates are typically hydrolyzed with the aid of homogeneous catalysts, but heterogeneous catalysts provide a promising pathway for the process. The hydrolysis of alkyl formates by a solid acid catalyst, ion-exchange resin was accomplished in a batch reactor, a stirred autoclave operating isothermally at 60 °C and 90 °C with a constant initial water-to-ester molar ratio. A mathematical model, which incorporates the particle size distribution of the solid catalyst, was developed to study the kinetics and internal mass transfer effects in the porous particles and it was able to predict the concentrations in the bulk phase and inside the catalyst particles. A combined reaction–diffusion model is necessary to describe the behavior of the system. The model was able to predict well the experimental results.