Isobutane/2-butene alkylation on MCM-22 catalyst. Influence of zeolite structure and acidity on activity and selectivity

The catalytic behavior of the novel MCM-22 zeolite for the continuous alkylation of isobutane with 2-butene has been investigated at a temperature of 50°C, 2.5 MPa total pressure, and a variety of olefin space velocities. At high olefin conversions the MCM-22 zeolite showed a very high initial cracking activity attributable to strong Brønsted acid sites, as well as to the existence of strong diffusional restrictions of the TMP's (formed inside the zeolite) to exit through the channels. At short times on stream (TOS), TMP's account for ca. 40% of the C₈ fraction. The olefin conversion and the cracking activity rapidly decline with TOS, while the alkylate product became richer in dimethylhexenes, indicating a predominance of 2-butene dimerization and a loss of hydrogen transfer activity as the catalyst aged. Moreover, MCM-22 gives less TMP's than large-pore zeolites (USY, beta, mordenite), but more than the mediumpore ZSM-5 at similar 2-butene conversion. The latter catalyst was much more selective for olefin dimerization than for isobutane alkylation, presumably because formation of the bulkier TMP's was strongly impeded in its smaller pores.     

胺化反应合成乙二胺催化剂的研究

研究了丝光沸石脱铝及金属改性等对合成乙二胺反应性能的影响,通过X荧光和XRD等手段对所得催化剂进行了表征。实验表明,脱铝改性时HCl溶液的最佳浓度为0.2 mol·L^－1。Cu和Zn改性可极大的提高催化剂的活性和选择性。改性后,催化剂的骨架结构基本维持不变,Cu和Zn高度分散于催化剂中。     

丝光沸石择形催化合成甲胺反应的性能研究

制备了经阳离子改性的合成丝光沸石催化剂 ;以氨和甲醇为原料 ,在常压固定床上进行了合成甲胺反应研究 ,考察了工艺条件对催化剂催化性能的影响 ,并通过正交试验筛选出最佳工艺条件。结果表明 :经钙、镁离子交换的丝光沸石催化剂具有较高活性和良好选择性 ,甲醇转化率 >90 % ,对二甲胺的单程选择性 >40 %。自制的这种钙离子改性丝光沸石催化剂(CaHM)的催化性能优于目前国内工业化的甲胺生产催化剂 ,而且CaHM是经添加粘接剂焙烧成型的样品 ,可直接供产品的中试放大。     

改性天然丝光沸石对氨的吸附性能

以缙云天然丝光沸石为载体,考察了载体预处理、不同活性组分、负载量等因素对氨、吡啶、二乙胺吸附容量的影响。结果表明,负载CuSO_4对氨的吸附容量明显提高,具有物理吸附和化学吸附双重功能,但吡啶、二乙胺略有下降。随着焙烧温度的提高,其对氨的吸附能力也提高,水份的存在对氨的吸附容量影响不大。     

H型丝光沸石催化剂催化甲苯与叔丁醇的烷基化反应

针对合成对叔丁基甲苯传统工艺中存在的缺点,采用环境友好、可重复利用的H型丝光沸石催化剂(以下简称催化剂)进行了甲苯与叔丁醇的烷基化反应,并用X射线衍射和氨程序升温脱附等方法对不同焙烧温度下得到的催化剂的物相结构和酸性质进行了表征,研究了各种反应条件对催化剂的催化性能的影响。实验结果发现,在适宜的操作条件下,即催化剂的焙烧温度823K、反应温度180℃、反应时间3h、初始压力1.0MPa、原料与催化剂的质量比为8、叔丁醇与甲苯的摩尔比为4、溶剂环己烷与甲苯的摩尔比为5时,甲苯转化率达42.73%,叔丁基甲苯的选择性为96.30%,对叔丁基甲苯的选择性为80.37%。     

Lean selective catalytic reduction of NO2 by methane over Co‐zeolites

The reaction of NO₂, CH₄ and O₂ was studied using low levels of methane compared to NO₂ and O₂ over protonic and cobalt‐exchanged ferrierite, ZSM‐5 and mordenite zeolites. Results suggest that two reaction pathways at low and high temperatures may be involved in the lean selective catalytic reduction (SCR) of NO₂ by methane. At low temperatures, the reduction of NO₂ to NO and N₂ might be the initial reaction step. It is likely that NO₂ or its adsorbed precursors initiate the reaction of methane at low temperatures. At high temperatures, the oxidation of NO and combustion of methane with oxygen might be involved. No appreciable differences were observed in the reduction of NO₂ over Co‐zeolites as compared to known results of NO reduction over these materials. However, enhanced N₂ formation rate was observed on H‐zeolites starting from NO₂ instead of data reported for NO. Furthermore, it appears that the active sites for SCR are both acid and metal sites. This revised version was published online in July 2006 with corrections to the Cover Date.     

双非贵金属催化nC_5异构化反应条件探索

考察正戊烷异构化应用双非贵金属丝光沸石催化剂的反应条件,实验在反应温度270～320℃,空速0.2～2.5h~(-1),氢油摩尔比2.0～6.0,反应压力1.4～4.0MPa的范围内进行。首先分析单因素对正戊烷异构化反应的影响,然后应用正交法获取了正戊烷异构化最佳反应条件和结果,即在反应温度300℃,反应压力3.0MPa,空速1.0h~(-1),氢油摩尔比4.0条件下,达到反应转化率0.6754,选择性0.9750;≥C_5异构烷产率0.6382;≥C_5液体收率0.9650。在100mL实验装置上连续进行1000h催化剂活性稳定性试验,证明双非贵金属丝光沸石异构化催化剂性能稳定。     

Mo－Ni／HM催化剂的研究

研制应用于正戊烷异构化的非贵金属催化剂Ｍｏ－Ｎｉ０／ＨＭ。以丝光沸石作载体，经两次２ｍｏｌ／Ｌ的ＮＨ４ＮＯ３铵交换，一次质量分数为０．３６的乙酸交换；用常规方法在室温下先后浸渍活性组分Ｍｏ，助催化剂组分Ｎｉ，ｗ（Ｍｏ）与ｗ（Ｎｉ）的最佳配比为３．２％：１．０％，焙烧温度为４７５℃。在临氢高压微反－色谱联合装置上对该催化剂进行考察，工艺条件为：反应温度３４０℃，压力３．０ＭＰａ，空速１．０ｈ－１，氢油摩尔比４：１。结果为：异戊烷收率达到５５．２％，≥Ｃ５液体收率为９５．２％。研究表明，此催化剂具有活性高，选择性好，成本低等特点，异构化性能优于只用两次铵交换、不同焙烧温度的其它催化剂。     

Mo－Ni／HM催化剂的研究

研制应用于正戊烷异构化的非贵金属催化剂Ｍｏ－Ｎｉ０／ＨＭ。以丝光沸石作载体，经两次２ｍｏｌ／Ｌ的ＮＨ４ＮＯ３铵交换，一次质量分数为０．３６的乙酸交换；用常规方法在室温下先后浸渍活性组分Ｍｏ，助催化剂组分Ｎｉ，ｗ（Ｍｏ）与ｗ（Ｎｉ）的最佳配比为３．２％：１．０％，焙烧温度为４７５℃。在临氢高压微反－色谱联合装置上对该催化剂进行考察，工艺条件为：反应温度３４０℃，压力３．０ＭＰａ，空速１．０ｈ－１，氢油摩尔比４：１。结果为：异戊烷收率达到５５．２％，≥Ｃ５液体收率为９５．２％。研究表明，此催化剂具有活性高，选择性好，成本低等特点，异构化性能优于只用两次铵交换、不同焙烧温度的其它催化剂。     

介孔丝光沸石组装钯物种催化有机反应的研究

随着绿色化学的不断发展,绿色有机合成成为现在及以后有机合成发展的重要方向。本文利用丝光沸石负载金属钯这种非均相催化剂替代传统的均相催化剂对Fujiwara-Moritani反应进行了探索并取得了非常好的效果。