苯丙苯基化β沸石催化剂上沉积物的组成和性质

 改性β沸石是高压液相苯－丙烯异丙基化合成异丙苯反应的优良催化剂,具有催化活性高和选择性高及稳定性好等优点,已成功进行了中试．用13CNMR,IR,GC－MS,TG等手段,并结合溶剂萃取法、TPO和结构分析等方法,确定了改性β沸石催化剂上沉积物的主要成分是多异丙基苯和四氢化萘,且主要分布在沸石孔道内;同时,快速升温后恒温烧炭的效果优于慢速升温后恒温烧炭的效果．     

甲苯和丙烯烷基化合成对异丙基甲苯催化剂的研究

本文考察了ＨＭ、ＨＹ、Ｈβ、ＨＺＳＭ－５和反应条件对丙烯烷基化反应的影响，结果表明在选定的较佳反应条件下：１００－１１０℃、甲苯／丙烯（Ｙ洋比）＝５－６，ＷＨＳＶ１．７＝３．５ｈ＾－１，ＨＭ和ＨＹ沸石具有较主的活性，对异丙基选择性（〉８３％）和较低的副产物含量，研究了高温焙烧、水热处理和有机预中毒等方法对ＨＭＩ沸石烷基化性能的影响，并探讨阱一步提高反应产物中对位选择性的可能性。     

MCM－22沸石的孔结构和酸分布特性对苯与丙烯烷基化反应产物分布的影响

 根据测试结果，得到了MCM－22和具有相同硅铝比的β沸石的酸中心数及其分布，系统地研究了反应条件对苯与丙烯烷基化反应产物分布的影响；结合扩散系数与扩散势能，讨论了产物分布与MCM－22沸石孔道及酸性质的关系，并与β沸石进行了比较．苯烷基化反应发生在MCM－22沸石的外表面上，其空间位阻较小；在相同的反应条件下，与发生在β沸石十二元环孔道内的苯烷基化反应相比，异丙苯的选择性低2％～4％，二异丙苯的选择性高0．5％～5％，三异丙苯的生成量多10余倍．位于MCM－22沸石十元环二维正弦波形孔道的B酸中心，由于空间位阻大，很难发生苯烷基化反应，但可发生丙烯齐聚反应，故MCM－22沸石上有较多的丙烯齐聚物生成．β沸石上生成正丙苯的量是MCM－22沸石上的3～4倍．     

在杂多酸催化剂上苯和1-十二烯的烷基化合成十二烷基苯

对比研究了磷钨酸，ＳｉＯ２负载磷钨酸，ＨＹ及Ｈβ分子筛催化剂的酸性和苯与１－十二烯的烷基化反应的催化性能，结果表明，磷钨酸催化剂具有酸性强，低温活性高和２位异构体选择性好等突出特点，特别是将磷钨酸负载于ＳｉＯ２载体上之后，其活性和稳定性得到大大提高。     

柠檬酸改性Hβ分子筛上的苯与丙烯烷基化反应

研究了柠檬酸改性对Hβ分子筛上苯与丙烯烷基化反应性能的影响。通过比较分析改性前后催化剂寿命、二异丙苯选择性及其异构体组成分布等的变化。结果表明，二异丙苯的选择性及各异构体的分布与催化剂的酸密度和酸强度有关；较高酸密度和酸强度有利于烷基转移反应的进行，但却加快了催化剂的失活。柠檬酸改性处理可调节Hβ分子筛的酸密度和酸强度，改善苯烷基化的催化反应性能。经0.50mol/L的柠檬酸处理后，Hβ催化剂的寿命比原来延长30%，正丙苯的质量分数减少90%。     

不同模板剂制成的β沸石对苯与丙烯烷基化反应的影响

采用XRD和TPD技术对两种不同模板剂合成的β沸石(F-β沸石，W-β沸石)进行了孔结构的表征。通过实际体系烷基化反应活性评价和加速失活稳定性实验找出两种不同合成方法的β沸石在催化性能上的差异。并对工业失活和加速失活催化剂样品上沉积炭物种进行了分析，结果表明导致工业失活和加速失活的物质有相似之处。造成失活的主要物质均为二异丙苯的进一步反应产物——多环芳烃等物质，它们不易从孔道中传递出来，堵塞孔道，占据活性位，是造成失活的主要原因。由于两种不同β沸石的孔结构分布情况不同，对二异丙苯的进一步反应的产物的空间位阻和抑制作用不同，从而两样品的稳定性不同。F-β沸石的孔分布比W-β沸石合理，有较好的抑制炭物质生成的作用，故有较好的稳定性。     

β沸石催化苯酚甲基化反应

研究了氢型β沸石和改性β沸石对苯酚－甲醇烷基化反应的催化性能。发现β沸艇下的反应网络与复合氧化物基本相同。沸石的酸碱性影响反应的活性和选择性；提高沸石硅铝比，反应活性降低，氧上烷基化反应的选择性提高。β沸石改性调变酸性后，可有效地抑制甲醇高温分解和生成积炭等副反应；酸碱中心的协同作用，降低了氧上烷基化反应的选择性。     

近临界条件下苯/丙烯烷基化反应的研究

以Hβ分子筛为催化剂,对比研究了苯与丙烯分别在超临界相和近临界液相的烷基化反应.结果发现,由于超临界流体对焦炭前驱物具有良好的溶解性能,超临界条件下催化剂稳定性明显提高,经114h反应后仍保持较高活性,催化剂结焦率则明显降低.     

用TPD、TPSR研究苯、丙烯和异丙苯在Hβ沸石上的吸附和脱附行为

用程序升温脱附(TPD)和程序升温表面反应(TPSR)技术研究了苯,丙烯和异丙苯在Hβ沸石上的吸附和脱附行为。结果表明,苯的脱附峰为一单峰,T_M值为260℃。在TPSR过程中,丙烯和异丙苯在Hβ沸石上分别发生聚合和裂解反应。用氨中毒法研究表明,强酸中心对聚合和裂解反应影响明显。文中讨论苯在Hβ沸石上的吸附模型和改进催化剂稳定性的可能途径。     

TEAOH-TMABr-Al2O3-SiO2-H2O体系中小晶粒offretite沸石的合成研究

不加无机强碱，在纯有机胺体系中合成了小晶粒offretite沸石，并采用XRD、SEM、FT-IR以及苯与丙烯烷基化制异丙苯探针反应对典型样品进行了结构性能表征。结果表明，采用四乙基氢氧化铵TEAOH与四甲基溴化铵TMABr为双模板剂时，TEAOH的量对合成产物影响很大，而TMABr的量增大容易导致生成Beta沸石。所合成的offretite沸石在苯与丙烯烷基化制异丙苯反应中活性和选择性较高。     

Structures and reaction mechanisms of cumene formation via benzene alkylation with propylene in a newly synthesized ITQ-24 zeolite: an embedded ONIOM study

The cumene formation via benzene alkylation with propylene on the new three-dimensional nanoporous catalyst, ITQ-24 zeolite, has been investigated by using the ONIOM2(B3LYP/6-31G(d,p):UFF) method. Both consecutive and associative reaction pathways are examined. The contributions of the short-range van der Waals interactions, which are explicitly included in the ONIOM2 model, and an additional long-range electrostatic potential from the extended zeolite framework to the energy profile are taken into consideration. It is found that benzene alkylation with propylene in the ITQ-24 zeolite prefers to occur through the consecutive reaction mechanism. The benzene alkylation step is the reaction rate-determining step with an estimated activation energy of 35.70 kcal/mol, comparable with an experimental report in beta-zeolite of 34.9 kcal/mol. The electrostatic potential from the extended zeolite framework shows a much more significant contribution to the transition state selectivity than the van der Waals interactions.     

Alkylation of benzene with propylene over MCM-36: A comparative study with MCM-22 zeolite synthesized from the same precursors

Pillared layered MCM-36 zeolite was prepared from MCM-22 precursor with polymeric silica as pillaring agent. Both MCM-36 and MCM-22 zeolites are very active for the alkylation of benzene with propylene, and MCM-36 shows higher selectivity to cumene compared with MCM-22 zeolite.     

Synthesis of Cumene from Lignin by Catalytic Transformation

Cumene is an important intermediate and chemical in chemical industry.In this work,directional preparation of cumene using lignin was achieved by a three-step cascade process.The mixture aromatics were first produced by the catalytic pyrolysis of lignin at 450℃ over 1% Zn/HZSM-5 catalyst,monocyclic aromatics with the selectivity of 85.7 wt% were obtained.Then,the catalytic dealkylation of heavier aromatics resulted in benzene-rich aromatics with 93.6 wt% benzene at 600℃ over Hβ catalyst.Finally,the cumene synthesis was performed by the aromatic alkylation,giving cumene selectivity of 91.6 C-mol% using the[bmim]Cl-2AlCl₁₃ ionic liquid at room temperature for 15 min.Besides,adding a small amount of methanol to the feed can efficiently suppress the coke yield and enhance the aromatics yield.The proposed transformation potentially provides a useful route for production of cumene using renewable lignin.     

MFI分子筛前驱体对Y型沸石分子筛表面的修饰及其催化性质

间、对-甲基异丙苯是生产间、对-苯酚的反应中间体,因此其制备受到国内外广泛关注．ZSM-5,Y型,betn等沸石分子筛和掺杂zn的Al-MCM-41介孔分子筛在此反应中表现出不同的择形性．近年来利用沸石分子筛前驱体自组装技术合成的新型介孔材料已显示出优异的催化性能,     

在H型分子筛上萘与正己醇的烷基化反应

制备了H型分子筛HY,Hβ和HM,通过XRD,NH₃-TPD和Py-IR对其进行了表征,考察了其对萘与正己醇的烷基化反应的催化性质.结果表明,HY可作为己基化反应的催化剂,较高的反应温度和较长的反应时间对β-己基萘的生成有利.     

Transition metal-catalyzed olefin arylation via C–H bond activation of arenes

In this article, two kinds of our transition metal-catalyzed olefin arylations are summarized and discussed. The first one is Ir-catalyzed novel anti-Markovnikov hydroarylation of olefins with benzene. Using this reaction catalyzed by [Ir(μ-acac-O,O′,C₃)(acac-O,O′)(acac-C₃)]₂ (acac = acetylacetonato), 1, straight-chain alkylarenes, which were not obtainable by the conventional Friedel-Crafts aromatic alkylation with olefins, were able to be successfully synthesized directly from arenes and olefins with the higher selectivity than that of branched alkylarenes. This is the first efficient catalyst which shows the desirable high regioselectivity. The reaction of benzene with propylene gave n-propylbenzene and cumene in 61% and 39% selectivities, respectively, and the reaction of benzene and styrene afforded 1,2-diphenylethane in 98% selectivity. The reaction of alkylarene and olefin showed meta and para orientations. A wide range of olefins and arenes can be employed for the synthesis of alkylarenes. The mechanism of the reaction involves C–H bond activation of benzene by Ir center to form Ir–phenyl species. The second reaction is Rh-catalyzed oxidative arylation of ethylene with benzene to directly produce styrene, namely one-step synthesis of styrene. The reaction of benzene with ethylene catalyzed by Rh(ppy)₂(OAc) (ppyH = 2-phenylpyridine, OAc = acetate), 3 with Cu oxidizing agent gave styrene and vinyl acetate in 77% and 23% selectivities, respectively, in contrast to those by Pd(OAc)₂, 47% of styrene and 53% of vinyl acetate. The mechanism of the reaction involves Rh-mediated C–H bond activation of benzene, which appears to be a rate-determining step. Furthermore, Rh complexes in a Rh(I) oxidation state at the beginning of the reaction work as catalysts for the reaction by addition of acacH and O₂ without any oxidizing agent, like Cu salt.     

Direct Dual‐Template Synthesis of MWW Zeolite Monolayers

A two‐dimensional zeolite with the topology of MWW sheets has been obtained by direct synthesis with a combination of two organic structure‐directing agents. The resultant material consists of approximately 70 % single and double layers and displays a well‐structured external surface area of about 300 m² g^?1. The delaminated zeolite prepared by means of this single‐step synthetic route has a high delamination degree, and the structural integrity of the MWW layers is well preserved. The new zeolite material displayed excellent activity, selectivity, and stability when used as a catalyst for the alkylation of benzene with propylene and found to be superior to the catalysts that are currently used for producing cumene.     

Pt改性分子筛催化剂上丙烷与苯的烷基化反应

研究了不同分子筛负载的Pt催化剂上丙烷与苯的烷基化反应.结果表明,Pt/HZSM-5具有较好的催化性能.在0~0.3%范围内提高Pt负载量可以提高催化剂的催化活性和生成C9以及C10 芳烃的选择性,降低非芳烃产物的选择性.较低的反应温度、较高的苯/丙烷摩尔比和较高的空速有利于烷基芳烃的生成.