An infrared spectroscopic study of the mechanism of chloromethane conversion to higher hydrocarbons on HZSM5 catalyst

Investigation of the reaction mechanism of chloromethane on ZSM5 is a new topic. In this work an in situ FTIR technique was employed to study the conversion processes of chloromethane, the active sites on HZSM5, and the desorption state of surface species. The catalytic conversion of chloromethane to higher hydrocarbons was also studied. It is demonstrated that chloromethane can be reversibly adsorbed on acidic sites of HZSM5 at room temperature. At 100°C chloromethane is irreversibly and dissociatively adsorbed on the strong acidic sites of HZSM5, on which surface methoxyl is formed as proved by infrared characteristic C-H stretchings of-CH₃ at 2960 and 2870 cm^–1. Alkoxyls are produced and adsorbed on the catalyst surface as characterized by the infrared absorption bands of -CH₂-groups at 1460 and 2930 cm^–1. At 100°C the adsorbed methoxyl and alkoxyls are the main surface species, and a small amount of aromatics might exist as detected by a characteristic absorption band at 1510 cm^–1. Between 100 and 200°C the adsorbed surface methoxyl and alkoxyls are converted to aromatics, and the occupied OH groups partially appear. At temperature higher than 300°C the adsorbed aromatics are thermally desorbed into the gas phase. Aromatics and alkanes are the main products in catalytic conversion. These results reveal that the formation of aromatics from methoxyl and alkoxyls is easier than the desorption of aromatics from HZSM5 catalyst. An alkoxyl mechanism is proposed for the conversion of chloromethane on HZSM5 based upon the experimental results and the three assumptions: (a) The primary C-C bond is formed from surface methoxyl groups via the methoxyl group polarization and C-H bond weakening, (b) The adsorbed alkoxyls are converted to aromatics via hydrogen transfer and bond rearrangement similar to the conventional carbenium ion mechanism for the aromatization of olefins and alkanes on HZSM5. The hydrogen atoms from the aromatization stimulate the desorption of alkoxyls to alkanes. (c) At temperature higher than 300°C surface reactions and desorption of adsorbed species take place simultaneously, determining the product distribution in the catalytic conversion.     

Trifluoromethanesulphonic acid catalysed transalkylation between tetrabromobisphenol-a and toluene for the production of 2,6-dibromophenol

The preparation of 2,6-dibromophenol is described. This compound, useful as raw material for brominated poly(phenyleneoxide) and pyrogallol or derived pharmaceuticals/pesticides, was prepared in 80% (isolated) yield by a transalkylation reaction between tetrabromobisphenol-A and toluene. The catalyst, trifluoromethanesulphonic acid, can be simply recovered and recycled. Perfluorinated resin sulphonic acid (NAFION-H®, DuPont) did not effectively catalyse this transalkylation.     

Preparation and characterization of oxygen deficient perovskites,BaBiO3−x

Oxygen nonstoichiometry in the distorted perovskite BaBiO₃ has been studied by thermogravimetric analysis using controlled oxygen pressures. Three distinct regions of nonstoichiometry are observed with composition ranges which narrow as the temperature is lowered. Samples isolated from each region were shown by powder X-ray diffraction to retain the perovskite subcell but show different types of framework distortion. Low temperature reoxidation of the oxygen deficient phases is also described.     

催化氧化法合成脂肪醇醚羧酸盐的研究进展

详细介绍了氮氧自由基催化氧化法和贵金属催化氧化法合成脂肪醇醚羧酸盐。氮氧自由基催化时,反应温度20～60℃,反应时间3～6 h,得到酸型产品。贵金属催化剂中,钯的催化活性比铂高。贵金属催化时,加入铅、铋等助催化剂,并以活性炭为载体,碱性条件下于50～90℃反应2～6 h,得到盐型产品。在适当的条件下,这两种方法均可使醇醚转化率达95％,选择性达90％以上。     

乙烯直接氧化合成乙酸

用常规固定床反应器考察了Pd-SiW12/SiO2催化剂还原条件对乙烯直接氧化合成乙酸催化性能的影响。催化剂用H2在200－300℃还原后Pd 的分散度较高，其催化活性远高于肼在液相中还原的催化剂，在乙烯气相氧化合成乙酸反应的原料气中，适量1，2－二氯乙烷的存在有助于提高乙酸的选择性和时空产率，初步考察了Pd-Se-SiW12/SiO2催化剂连续206h运转的稳定性，结果表明，催化剂中Pd晶粒的长大和硅钨酸的流失是造成催化剂失活的主要原因。     

重油接触裂解制乙烯的HCC工艺研究

重油裂解制乙烯的HCC技术采用与FCC类似的“反应—再生”工艺技术,利用重油直接裂解制乙烯,兼产丙烯、丁烯和轻质芳烃,既可扩大乙烯的原料的来源,又可降低生产成本。HCC工艺的乙烯产率可达19%～27%,总烯烃产率大于50%。     

固体碱催化戊醛缩合的研究

自制了固体碱催化剂用于催化戊醛缩合反应 ,考察了碱金属、载体、反应温度、反应压力、空速等条件对反应的影响。研究表明 ,以介孔分子筛为载体的催化剂活性尤其是低温活性明显高于以硅胶为载体的催化剂。自制的固体碱催化剂性能稳定 ,在 2 0MPa ,2 60℃ ,1 0h-1条件下连续运转 2 7d,仍能保持转化率高于 90 %、选择性约 80 %的良好效果。     

聚酯新型催化剂乙二醇锑的工业应用

介绍了国产新型催化剂惭二醇锑在洛阳石油化工总厂聚酯装置上的使用情况，结果表明：乙二醇锑催化剂活性高、易溶解；以乙二醇锑催化剂合成的聚酯产品质量稳定，纺丝时的加工性能明显得到改善。     

甲醇氧化制甲醛铁钼催化剂的研究

采用共沉淀法制备甲醇氧化制甲醛无载体铁钼催化剂,并考察了催化剂制备老化条件、焙烧温度、外型尺寸以及活性测试反应温度、空速对催化剂性能的影响。该催化剂在280~300℃、气空速7000 h-1~8000 h-1、进料φ(甲醇)为5.5%的下,可获≥98%的甲醇转化率,≥92%的甲醛选择性和≥90%的甲醛产率。催化剂活性高,强度好,性能稳定。     

抽余C_4烃中异丁烯催化逆流水合制叔丁醇

采用大颗粒离子交换树脂催化剂,在φ100mm×10m的反应器中进行了异丁烯催化逆流水合制叔丁醇的中间试验。考察了反应温度、水油体积比和抽余C4烃的流速等对异丁烯转化率的影响。试验结果表明,异丁烯催化逆流水合制叔丁醇的适宜操作条件为:反应温度80~90℃,水油体积比为4~5,抽余C4烃的流速为0.45~0.55mm/s。在此条件下,异丁烯的转化率可达88.8%。工业装置运转结果表明,异丁烯转化率大于75%。