甲醇直接脱氢制甲醛催化剂研究进展

简要叙述了甲醇直接脱氢制甲醛催化剂的研究进展情况,介绍了甲醇脱氢反应所用3类催化剂：金属及其氧化物、碱金属盐和分子筛催化剂。讨论了各类催化剂对甲醇直接脱氢制甲醛的选择性及转化率的影响,并从催化剂的活性、寿命和经济性等方面分析了其优缺点及应用前景。     

甲醇脱氢制无水甲醛钠催化剂研究

0前言 甲醛是化学工业中的一种重要的大宗产品，由于它具有较强的反应性，所以甲醛非常广泛地用于如薄膜的研究开发、纺织工业和皮革工业，用作杀菌剂、或在无碳复写纸的生产中用作黑墨汁母体的微囊包封过程中的鞣剂。不过，生产的甲醛大部份用于各种树指和塑料的制取。     

甲醇脱氢制无水甲醛的研究进展

甲醇直接脱氢制无水甲醛是具有工业化前景的新工艺。介绍了该领域催化剂及相关工艺的研究现状。利用金属、金属氧化物、金属难熔盐和分子筛催化剂以及相关工艺技术制得定量的无水甲醛,该技术目前处于研发阶段,离工业化尚有一定距离,在催化剂的选择性、稳定性及使用寿命等方面有待于改进。     

甲醇脱氢制甲酸甲酯的催化剂和反应性能研究

甲醇脱氢制甲酸甲酯的催化剂和反应性能研究王乐夫，谭凤仙，张映珊，庞先 ，黄仲涛（华南理工大学化学工程系，广州５１０６４）关键词：甲醇，脱氢，甲酸甲酯，催化剂，反应性１前言甲酸甲酯是一种重要的化工产品，可用作醋酸纤维素溶剂、杀虫剂、杀菌剂等．同时由于甲?..     

多级孔二氧化硅负载铜催化剂制备及甲醇脱氢性能

甲酸甲酯是一种重要的煤化工下游化学品,甲醇脱氢制甲酸甲酯主要使用铜基催化剂,金属铜易发生团聚、烧结是限制催化剂性能的关键因素。通过水热合成法制备有序多级孔氧化硅载体(HPS-x),采用蒸氨法和浸渍法分别制得Cu/HPS-x(x=100、130和160)和Cu/HPS-130-W催化剂,考察不同水热温度对催化剂在甲醇脱氢制甲酸甲酯的催化性能的影响,催化剂活性顺序为：Cu/HPS-130> Cu/HPS-160> Cu/HPS-100> Cu/HPS-130-W。表征结果显示,水热温度对HPS载体的织构性质有显著影响,HPS-100以微孔为主,介孔较少,HPS-160比表面积较低,HPS-130载体有适宜孔径分布的有序微介孔结构,能有效促进Cu粒子分散,防止活性组分团聚,进而提高催化剂活性。采用蒸氨法制备的Cu/HPS-130催化剂在0.2 MPa、300℃反应条件下,甲醇转化率和MF选择性分别达38.7%和79.8%,明显优于浸渍法制备的Cu/HPS-130-W催化剂。结果表明蒸氨法比浸渍法更有利于活性组分的分散,载体和金属间相互作用更强,避免活性组分的团聚和剥离。     

甲醛溶液中甲醇回收技术研究

通过对吉化股份有限公司化肥厂甲醛生产过程中所采用不同催化剂的工艺路线和产品产量，质量及特殊用户的具体要求进行分析和研究。寻找出了最佳的从甲醛溶液中回收甲醇的方法，即在甲醛生产系统增建一套脱醇装置，将甲醛第一吸收塔底采出的甲醛溶液送入脱醇塔，利用混合液中各组分的挥发度不同，将甲醇和甲醛分开。该方法实验后取得了显著的经济效益。     

改进共沉淀法制Cu基甲醇催化剂

采用传统共沉淀法和加表面活性剂改进共沉淀法制备了两种超细 Cu/ Zn O/ Al2 O3 催化剂 ,并应用 XRD,TEM对催化剂的结构和形貌进行了表征 ,同时用流动固定床微型反应器在3.0 MPa和体积空速 760 0 h-1下考察了其催化合成气合成甲醇的活性 .结果表明 ,改进共沉淀法制备的超细 Cu/ Zn O/ Al2 O3 催化剂具有比传统共沉淀法制备的催化剂更细的粒径和更高的催化活性 .同时从理论上对表面活性剂的作用机制进行了讨论 .     

CuO/SiO2催化剂用于CO2加氢合成甲醇的研究

采用等容浸渍法,分别以水、乙醇、丙酮为分散剂制备CuO/SiO2催化剂,用H2-TPR,H2-TPD技术及CO2加氢合成甲醇反应对催化剂还原性能、H2吸附性能和催化性能进行了研究.TPR结果表明,以水为分散剂制备催化剂时,CuO分散不均匀,且难还原;以丙酮为分散剂时,CuO分散较均匀,且易还原;以乙醇为分散剂时,CuO的分散性和还原性介于水与丙酮制得的催化剂之间.TPD结果表明,以乙醇、丙酮为分散剂制备催化剂时,只增加H2的吸附量,而不改变H2的吸附强度.CO2加氢反应的结果表明,以乙醇和丙酮做分散剂,有利于CO2转化率、甲醇产率的提高,同时降低了反应的甲烷化.随CuO含量增加,CO2的转化率和甲醇的产率得到了提高.     

甲乙苯脱氢催化剂的研制

本试验研制的F—601甲乙苯脱氢非铬催化剂具有较高的活性和较好的选择性、用于间、对—甲乙苯脱氩,在640℃单程收率可达39.96％,用于对—甲乙苯脱氢,在620℃单程收率可达46.64％,640℃时可达48.29％。选择性均大于90％。     

在Pt—Sn／Al2O3催化剂上丙烷脱氢反应动力学

研究了丙烷在Pt-Sm／Al2O3催化剂上的脱氢反应动力学。在氮烃比1．0,反应温度460～500℃范围内,验证了该反应机理,获得反应速率表达式。     

STEADY STATE AND DYNAMIC MODELLING OF A PACKED BED REACTOR FOR THE PARTIAL OXIDATION OF METHANOL TO FORMALDEHYDE II. EXPERIMENTAL RESULTS COMPARED WITH MODEL PREDICTIONS

Heterogeneous and pseudohomogeneous two-dimensional models are compared to steady state and dynamic experimental data from a packed bed reactor for the partial oxidation of methanol to formaldehyde over an iron oxide-molybdenum oxide catalyst. Highly effective parameter estimation software was used to fit selected model parameters to large sets of experimental data so as to obtain small residuals. Heat transfer parameters which were successful in matching data from experiments without reaction were not capable of fitting data from experiments with reaction, and it was necessary to increase the radial heat transfer for higher temperatures or reaction rates. Axial composition profile data was represented by estimating the preexponential factors and activation energy in a half-order redox rate expression for methanol oxidation. After some decline in catalyst activity, a time-varying axial catalyst activity profile was determined from the data. A redox-type rate expression for the oxidation of formaldehyde to carbon monoxide was proposed to fit the data. The dynamics of the reactor temperature profile were accurately represented by the model. The heterogeneous and pseudohomogeneous models gave similar results in fitting experimental data, although the parameters determined for the two models were somewhat different.     

THE PROMOTER EFFECT OF ALKALI METAL TO SUPPORTED IRON CATALYST IN CARBON MONOXIDE HYDROGENATION, THE INFLUENCE OF ALKALI ON CARBON DEPOSITIONS

The promoter effect of alkali metals on CO hydrogenation was studied on a series of silica supported iron catalysts. Mossbauer spectra of the catalysts show that iron is well dispersed on the silica support. The decrease in chemisorption of carbon monoxide on addition of promoters reveals that alkali covers part of the iron metal surface. The production of olefins, carbon dioxide and long chain hydrocarbons increases with decreasing ionization potentials of the alkali metals added. Hydrogenative decarbidation of catalysts after CO/H₂ reaction show that the hydrogenation of the carbon depositions on iron catalysts can be well explained by a series reaction model. The relative reactivity of carbon depositions on well dispersed iron catalysts are strongly affected under the influences of alkali. Addition of alkali metals to iron catalyst may depress the hydrogenation ability of the catalysts.     

EFFECT OF SULPHIDING PARAMETERS ON THE INITIAL ACTIVITY BEHAVIOR OF A SUPPORTED NICKEL MOLYBDATE HYDROSULPHURIZATION CATALYST

The influence of some sulphiding parameters on the activity of a supported nickel-molybdate catalyst was studied for the gas phase hydrodesulphurization of thiophene carried out at atmospheric pressure. The optimum activation procedure involved prereduction with hydrogen at 300^°C followed by presutphidation with pure H₂S at 400^°C. The differences in activity observed were substantially maintained over the testing time when the reaction temperature was 300^°C. At 400^°C they were maintained only for limited periods. Catalyst deactivation was observed under either sulphiding or reducing atmospheres. The results are discussed in terms of possible structural changes involving molybdenum sulphide nucleation and crystal growth, which ted to the proposal of three stages for the initial catalyst transformation: oxide monolayer sulphidation, formation of small defected sulphide crystallites, and sulphide multilayer growth.     

铜系甲醇催化剂母体物相研究

研制了一种新型甲醇催化剂，它由分解类孔雀石（ＭＬ）相和ＦＣ型化合物组成的母体而制得。实验结果证明制备方法和组分配比对母体结构有重要的影响，由ＭＬ和ＦＣ双相结合母体制得的催化剂合成甲醇活性优良。