甲基叔丁基醚（MTEB）的合成

介绍了甲醇，异丁烯合成甲基叔丁基醚的催化剂，热力学，动力学。综述了合成ＭＴＢＥ的主原原料异丁烯的生产过程，并总结了甲醇，异丁醇和甲醇，叔丁醇合成了ＭＴＢＥ的研究开发进展，参考文献１６篇。     

分了筛催化合成MTBE的反应性能研究

在开发出催化性能良好的合成ＭＴＢＥ沸石分子筛催化的基础上,详细考察了反应条件：包括温度、压力、空速、醇烯比等操作条件对改性β沸石分子筛催化剂的合成ＭＴＢＥ反应性能的影响。结果表明：反应条件对催化剂活性、ＭＴＢＥ选择性及活性稳定性都有一定影响。在一定范围内反应温度升高,烯烃的转化率增加、ＭＴＢＥ的选择性不变,但反应温度过高,ＭＴＢＥ的选择性和催化剂的稳定性变差;反应压力必须大于系统完全液化压力;醇烯     

中孔MCM—41分子筛在微孔沸石ZSM—5上附晶生长的研究

首次在微孔沸石ＺＳＭ５表面进行了ＭＣＭ４１分子筛的附晶生长，并首次提出中孔材料ＭＣＭ４１分子筛静电组配理论的新形式（ＸＳ＋Ｉ）；同时利用ＸＲＤ、ＴＥＭ、ＢＥＴ等测试手段表征了合成样品，并讨论了微孔沸石表面附晶生长中孔分子筛ＭＣＭ４１的合成化学，考察了Ｆ离子效应、ｐＨ值及表面活性剂ＣＴＡＢ（十六烷基三甲基溴化铵）的影响。     

低温液相合成甲醇及甲酸甲酯用Cu—Cr—M—O催化剂的制备 …

采用共沉淀法和配合物沉淀法制备了分别添加Ｂa,Ｍn,Ｖ,Ｂi,Ｎi和Ｚn的Ｃu－Ｃr－ Ｍ－Ｏ三组分催化剂,采用ＢＥＴ,ＸＲＤ和ＴＥＭ对催化剂进行了表征,并考察了其对合成甲醇及甲酸甲酯反应的活性及选择性。结果表明,添加第三种金属使催化剂的稳定性及甲酸甲酯选择性有所提高,但使催化活性有所下降,配合物沉淀法制备的催化剂的比表面积较大,粒径较小,热分解温度越高,催化剂的比表面积越小,除Ｃu－Ｃr－Ｖ－Ｏ催化剂为纳     

以混合模板剂合成TS-1分子筛及其性能研究

以四丁基溴化铵（ＴＢＡＢｒ）＋四乙基氢氧化铵（ＴＥＡＯＨ，ｎ（ＴＢＡ＋）／ｎ（ＴＥＡ＋）＝１）或以四丙基溴化铵（ＴＰＡＢｒ）＋ＴＥＡＯＨ为模板剂，钛酸四丁酯和正硅酸乙酯为原料，于１７０℃水热合成出ＴＳ１分子筛．对合成的ＴＳ１样品进行了ＸＲＤ，ＦＴＩＲ，ＳＥＭ和ＢＥＴ比表面积分析，证实了样品中钛已进入Ｓｉｌｉｃａｌｉｔｅ１骨架．选择戊烷氧化为探针反应，考察了ＴＳ１的催化活性．结果表明以ＴＥＡＯＨ为碱，合成的样品晶粒较大，达到４～１０μｍ，用氨水和ＴＥＡＯＨ调节反应液的碱度，对晶体的生长和形貌的影响各不相同．文中还就ＴＥＡＯＨ引入的作用进行了讨论．     

以混合模板剂合成TS—1分子筛及其性能研究

以四丁基溴化铵（ＴＢＡＢｒ）＋四乙基氢氧化铵（ＴＥＡＯＨ，ｎ（ＴＢＡ＾＋）／ｎ（ＴＥＡ＾＋）＝１）或以四丙基溴化铵（ＴＰＡＢｒ）＋ＴＥＡＯＨ为模板剂，钛酸四丁酯和正硅酸乙酯为原料，于１７０℃水热合成出ＴＳ－１分子筛。对合成的ＴＳ－１样品进行了ＸＲＤ，ＦＴ－ＩＲ，ＳＥＭ和ＢＥＴ比表面积分析，证实了样品中钛已进入Ｓｉｌｉｃａｌｉｔｅ－１骨架。选择戊烷氧化为探针反应，考察了ＴＳ－１的催化活性。结果表明以     

SUBSTITUTE CALIBRATION APPLIED TO ISOTOPIC RATIO MEASUREMENT OF ERBIUM

ＳＵＢＳＴＩＴＵＴＥ　ＣＡＬＩＢＲＡＴＩＯＮ　ＡＰＰＬＩＥＤ　ＴＯ　ＩＳＯＴＯＰＩＣ　ＲＡＴＩＯ　ＭＥＡＳＵＲＥＭＥＮＴ　ＯＦ　ＥＲＢＩＵＭＳＵＢＳＴＩＴＵＴＥＣＡＬＩＢＲＡＴＩＯＮＡＰＰＬＩＥＤＴＯＩＳＯＴＯＰＩＣＲＡＴＩＯＭＥＡＳＵＲＥＭＥＮＴＯ...     

铜基甲醇合成催化剂的失活研究

选用了两个化肥厂的失活甲醇合成催化剂,采用ＸＲＤ、ＳＥＭ、ＳＥＭ－ＥＤＳ、ＴＥＭ、ＸＰＳ、ＴＲＰ、ＣＯ－ＴＰＤ和化学吸附等方法对催化剂进行比较测试。结果表明,硫中毒、积炭、铜粒长大和杂质金属沉积等是造成甲醇合成催化剂失活的因素。由于某一种或几种因素都导致催化剂活性表面积的降低,对反应物ＣＯ吸附量减少,或造成催化剂对ＣＯ吸附能力的降低,从而降低合成甲醇反应的活性。硫中毒和铜粒长大是普遍存在的最主要因     

低温液相合成甲醇及甲酸甲酯用Cu-Cr-M-O催化剂的制备与表征

采用共沉淀法和配合物沉淀法制备了分别添加Ｂａ, Ｍｎ,Ｖ,Ｂｉ,Ｎｉ 和Ｚｎ 的ＣｕＣｒＭＯ三组分催化剂,采用ＢＥＴ,ＸＲＤ和ＴＥＭ 对催化剂进行了表征,并考察了其对合成甲醇及甲酸甲酯反应的活性及选择性． 结果表明,添加第三种金属使催化剂的稳定性及甲酸甲酯选择性有所提高,但使催化活性有所下降． 配合物沉淀法制备的催化剂的比表面积较大,粒径较小． 热分解温度越高,催化剂的比表面积越小． 除ＣｕＣｒＶＯ 催化剂为纳米非晶态之外,其它催化剂均呈晶态． 催化剂的最小平均粒径为３８ ｎｍ , 最大平均粒径为６８ ｎｍ , 属纳米级催化剂．     

用于CO2加氢合成甲醇超细CuO-ZnO/SiO2-ZrO2催化剂

用溶胶－凝胶法制备了ＣｕＯ－ＺｎＯ／ＳｉＯ２－ＺｒＯ２复合氧化物催化剂，使用ＩＲ，ＸＲＤ，ＴＥＭ和ＢＥＴ等手段对催化剂的结构及表面性能进行了表征，考察了ＺｒＯ对该体系的表面性质，结构，ＣｕＯ分散状态以及二氧化碳加氢合成甲醇的催化性能的影响。结果表明，该体系催化剂的比表面积大，活性组分分散均匀。     

Acetone adsorption on hydroxylated silica gel: Correlation of sorption isotherms and IR spectra

The synthesis of MTBE from methanol and isobutene has been carried out over a ZSM-5 based catalyst, in two types of continuous flow catalytic reactors, fixed-bed and fluidized-bed. We have studied the influence of the molar ratio methanol to isobutene, the temperature and the weight hourly spatial velocity (WHSV) on the yield of MTBE.     

Pyrolysis of methyl tert-butyl ether (MTBE). 2. Theoretical study of decomposition pathways

The thermal decomposition pathways of MTBE have been investigated using the G3B3 method. On the basis of the experimental observation and theoretical calculation, the pyrolysis channels are provided, especially for primary pyrolysis reactions. The primary decomposition pathways include formation of methanol and isobutene, CH4 elimination, H2 elimination and C-H, C-C, C-O bond cleavage reactions. Among them, the formation channel of methanol and isobutene is the lowest energy pathway, which is in accordance with experimental observation. Furthermore, the secondary pyrolysis pathways have been calculated as well, including decomposition of tert-butyl radical, isobutene, methanol and acetone. The radicals play an important role in the formation of pyrolysis products, for example, tert-butyl radical and allyl radical are major precursors for the formation of allene and propyne. Although some isomers (isobutene and 1-butene, allene and propyne, acetone and propanal) are identified in our experiment, these isomerization reaction pathways occur merely at the high temperature due to their high activation energies. The theoretical calculation can explain the experimental results reported in part 1 and shed further light on the thermal decomposition pathways.     

Layered Group(IV) Metal Phosphates as Catalysts for MTBE Synthesis

Layered group(IV) metal phosphates and their phenylsulfonic acid derivatives were used as catalysts for the synthesis of methyl tert-butyl ether (MTBE) from methanol and isobutene. Because zirconium and titanium phosphates have only moderate acidic strength, relatively high temperatures are required to activate their Brønsted acidic sites. The optimal activity was obtained at ca. 443 K. Their phenylsulfonic acid derivatives, however, demonstrated higher acidic strength by giving much higher activity toward MTBE formation at relatively low temperaures. The catalysts were characterized in terms of their structure, thermal stability, surface area and acidic strength.     

Multiple steady states in a CSTR with total condenser: Comparison of equilibrium and nonequilibrium models

Comparison of equilibrium and nonequilibrium models of a CSTR with total condenser focused on the multiple steady states and dynamic behaviour was carried out. The steady-state behaviour of the model system, MTBE synthesis from methanol and isobutene in a reactive distillation column, was studied in terms of the input parameters, i. e. feed flow rate of methanol or butenes, reflux ratio, and mass of catalyst. The dynamic behaviour of the system during the start-up was investigated and perturbations of manipulated variables were found to cause transitions between the parallel steady states. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

等离子体辅助合成分子筛膜及其催化性能的研究

首次将等离子体技术应用于分子筛膜的制备，研究了以微波等离子体处理基材表面分子筛膜前驱体辅助水热反应合成支撑β型分子筛膜．利用XRD、SEM、XPS、BET、TPD表征了分子筛膜的物相、形貌、孔结构、表面元素组成和表面酸性，并通过甲醇与异丁烯液相反应体系实验考察了分子筛膜的催化性能．结果表明，等离子体处理能有效改善分子筛膜前驱体在基材表面的分散状况，减小了分子筛膜晶体的尺度，使晶体大小均匀，形成的膜致密、牢固．与采用常规方法合成的分子筛膜相比，等离子体辅助合成的分子筛膜对甲醇与异丁烯的反应有更好的催化活件．     

Catalytic Oxidative Dehydrogenation of Isobutane over KF-Zn_3(PO_4)_2

ＩｎｔｒｏｄｕｃｔｉｏｎＡｌｔｈｏｕｇｈｔｈｅｃａｔａｌｙｔｉｃｄｅｈｙｄｒｏｇｅｎａｔｉｏｎｏｆｉｓｏｂｕｔａｎｅｉｎｔｏｉｓｏｂｕｔｅｎｅｈａｓｂｅｅｎｃａｒｒｉｅｄｏｕｔｉｎｃｏｍｍｅｒｃｉａｌｐｌａｎｔｓｏｖｅｒＣｒ２Ｏ３－Ａｌ２Ｏ３ｏｒｎｏ...     

Trimerization of Isobutene Over Solid Acid Catalysts

Oligomerization of isobutene is a very promising reaction not only for the production of isobutene oligomers such as trimers but also for the separation of isobutene from C₄ mixtures. Several solid acid catalysts have been applied for the continuous oligomerization of isobutene in liquid phase. This review analyzes the trimerization of isobutene over various solid acid catalysts such as zeolites, oxides (zirconias and titanias) and acid resins. Trimers selectivity increases with increasing isobutene conversion, irrespective of catalysts such as zeolites and acid resins. Very stable operation with high trimers selectivity is accomplished with WO _x /ZrO₂ catalyst having tetragonal zirconia or various zeolite catalysts with high Lewis acid site-to-Brønsted acid site ratio (LA/BA ratio). For a good performance, acid resins should be macroporous and strong acid (sulphonic acid group) with high acid concentration. Inorganic catalysts are superior to acid resins because the deactivated inorganic materials can be regenerated by simple calcination. The WO _x /ZrO₂ catalyst may be applied to a commercial process because about several thousand tons of isobutene can be oligomerized per one ton of zirconia catalyst in a catalytic cycle without regeneration. The oligomerization of isobutene may be improved further because the reaction has been started only recently and no research has been done for the optimization of the reaction and catalysts. It is expected to develop a new inorganic catalyst having suitable acidity, LA/BA ratio and phase, etc. by further research. The isobutene trimers, with or without hydrogenation, may be used for various purposes, and the importance of this trimerization reaction will be increased considering the expected surplus of isobutene due to the banned use of methyl-tert-butyl ether.     

MCM-49分子筛催化剂上1-丁烯的骨架异构化反应

 采用动态和静态水热合成法合成了不同Si/Al比的MCM-49分子筛,并考察了合成分子筛对1-丁烯骨架异构化反应的催化性能. 结果表明,除目的产物异丁烯外,主要副产物为丙烯和戊烯,产物中没有检测到C6以上的副产物. 异丁烯收率随着反应温度的升高、分子筛晶粒的增大和1-丁烯分压的降低而升高. NH3-TPD 结果表明,随着分子筛Si/Al比的增加,分子筛的酸中心数减少,导致副产物选择性下降,异丁烯选择性升高. 根据反应结果讨论了异丁烯及副产物形成的机理.     

Copolymerization of isobutene and α-methylstyrene as a function of reaction conditions

The influence of reaction conditions (solvent, Lewis acid, temperature) on the cationic copolymerization of isobutene and α-methylstyrene was investigated. The crude product consists of low molecular nonprecipitable oligomers, polyisobutene, and poly(isobutene-co-α-methylstyrene). The amount of poly(α-methylstyrene) formed under the reaction conditions used was negligible. The degree of charge separation in the propagating cationic intermediate determines the selectivity of the reaction; that is, incorporation of monomer units into the polymer, ratio of different product fractions, and microstructure. Molecular weight distribution, copolymerization parameters, and sequence-length distribution functions were determined. The softening range of the copolymers depended on their isobutene content but appeared to be constant up to 15% isobutene in copolymers. The degradation temperature of the copolymers was between 340 and 390°C.     

Adsorptive separation of isobutene and isobutane on Cu3(BTC)2

The metal organic framework material Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate) has been synthesized using different routes: under solvothermal conditions in an autoclave, under atmospheric pressure and reflux, and by electrochemical reaction. Although the compounds display similar structural properties as evident from the powder X-ray diffraction (XRD) patterns, they differ largely in specific surface area and total pore volume. Thermogravimetric and chemical analysis support the assumption that pore blocking due to trimesic acid and/or methyltributylammoniummethylsulfate (MTBS) which has been captured in the pore system during reaction is a major problem for the electrochemically synthesized samples. Isobutane and isobutene adsorption has been studied for all samples at different temperatures in order to check the potential of Cu3(BTC)2 for the separation of small hydrocarbons. While the isobutene adsorption isotherms are of type I according to the IUPAC classification, the shape of the isobutane isotherm is markedly different and closer to type V. Adsorption experiments at different temperatures show that a somewhat higher amount of isobutene is adsorbed as compared to isobutane. Nevertheless, the differential enthalpies of adsorption are only different by about 5 kJ/mol, indicating that a strong interaction between the copper centers and isobutene does not drive the observed differences in adsorption capacity. The calculated breakthrough curves of isobutene and isobutane reveal that a low pressure separation is preferred due to the peculiar shape of the isobutane adsorption isotherms. This has been confirmed by preliminary breakthrough experiments using an equimolar mixture of isobutane and isobutene.