Pt/SAPO-11催化剂载体的改性对正十四烷临氢转化性能的影响

以Pt/SAPO-11双功能催化剂为基础,对催化剂载体进行柠檬酸、炭黑改性,以正十四烷为模型化合物,通过催化剂表征和反应评价,探索了催化剂载体的改性对正十四烷临氢转化性能的影响。结果表明,异构化产物以单甲基异构物为主,改性没有改变催化剂的酸强度,但使得酸浓度有所下降。通过柠檬酸调变催化剂的酸性使得催化剂的低温催化活性显著提高,采用炭黑扩孔改性,有效改善了催化剂的传质性能,提高了催化剂的单甲基异构体选择性。柠檬酸和炭黑改性的催化剂裂化产物均以C6为主,改性并没有改变SAPO-11分子筛的孔道限制效应,裂化产物呈现一定的择型效应,裂化产物分布呈现出不对称分布的特点。     

诱捕在沸石超笼内的金属卟啉的催化性能

诱捕在沸石超笼内的金属卟啉的催化性能＊王杏乔高爽曹昌盛于连香曹锡章（吉林大学化学系，长春１３００２３）关键词诱捕的金属卟啉，分子筛，苯乙烯，对甲酚，氧化众所周知，金属卟啉是一种共轭的大环化合物，这种化合物具有特殊的性能，尤其在氧化－还原反应中的催化性...     

微波辅助催化氧化苯高性能催化剂实验研究

采用传统浸渍法制备分子筛负载过渡金属和稀土元素催化剂,通过微波辅助催化氧化苯性能实验考察其催化活性。研究表明,天津科密欧的5A分子筛为优良的催化剂载体,分子筛负载铜-锰-铈催化剂对苯的完全燃烧温度为230℃,铜(Cu)锰(Mn)双金属催化剂中晶相与非晶相Cu_1.5Mn_1.5O₄尖晶石提高了催化剂的催化活性,稀土铈(Ce)的助催化效果显著;30 h的连续性实验表明,Cu-Mn-Ce/分子筛催化剂具有良好的稳定性和高的催化活性。催化剂的比表面积和表面形貌表征表明,催化剂比表面积和孔径受高温煅烧和氧化反应而增大,从而有助于苯的吸附与氧化降解;X射线衍射表明,实验前后分子筛结构未发生明显变化,铜锰主要以二价和三价的氧化物形态分布于催化剂表面。     

铜磷铝分子筛的合成及其对苯液相氧化制苯酚的催化性能

 以水热法合成了铜磷铝分子筛(Cu-AlPO4-5),并用XRD,ICP,SEM,FT-IR,NH3-TPD,H2-TPR,ESR和N2吸附-脱附等手段对样品进行了表征. 结果表明,所合成的Cu-AlPO4-5分子筛具有AFI拓扑结构,结晶度高,无结晶态杂质; Cu2+进入到分子筛的骨架结构中,并使其Lewis酸和Brnsted酸中心数量增加,弱酸性中心大大增强,强酸性中心消失; 样品中的Cu存在多种形式,以骨架Cu物种为主,还存在 泄羌芡釩uO和双核Cu物种,部分样品具有缺陷结构. Cu-AlPO4-5分子筛中存在着骨架Cu和缺陷结构两种可能的活性中心,对苯液相氧化具有良好的催化性能,苯酚选择性可达96%,收率可达6.9%.     

Ti-HMS和TS-1分子筛结构和催化性能的对比研究

 采用长链十二烷基胺为模板剂,成功合成出含钛中孔分子筛Ti-HMS, 并针对其晶化过程、结构特征以及催化性能与修正经典法制备的微孔分子筛TS-1进行了对比. 结果表明,中孔分子筛Ti-HMS的晶化机理不同于微孔分子筛TS-1的晶化机理. 随着晶化温度的提高, Ti-HMS分子筛的相对结晶度降低,且晶化过程中母液的pH值变化不大. TEM照片显示, Ti-HMS分子筛的孔壁整体上呈无定形,在局部区域可能存在晶态或者类晶态物种. 与TS-1分子筛相比, Ti-HMS分子筛的活性中心(骨架钛)处在畸变的四面体环境中. 中孔分子筛Ti-HMS可以满足大分子硫化物(如苯并噻吩)氧化反应的要求; 对于小分子硫化物(如噻吩)的氧化反应,微孔分子筛TS-1催化剂效果更好.     

MCM-48掺杂铬对催化活性的影响

中介孔分子筛MCM-48因其具有三维螺旋孔道结构,且孔径均匀,长程周期性良好及骨架结构稳定等特征而有可能成为有应用前景的工业催化剂^[1～11].纯硅MCM-48分子筛因无酸性,催化活性极低.     

铈掺杂对Co_3O_4/微孔-介孔分子筛催化剂催化性能的影响

采用水热法制备了微孔-介孔分子筛,并以Ce掺杂改性后制备了Co3O4/Ce-微孔-介孔分子筛催化剂,考察了Ce掺杂微孔-介孔分子筛催化剂对苯催化完全氧化性能的影响,并采用BET,XRD,TPR等技术对催化剂进行了表征。研究结果表明:Ce的加入有利于提高MSZ-B催化剂的催化活性。XRD分析显示Ce的加入不会阻塞Co3O4在微孔-介孔分子筛孔道内的分布;TPR分析表明:Ce的加入提高了MSZ-B催化剂的可还原性能,催化剂的可还原性能是影响催化活性的主要因素;另外,介孔的存在不利于Ce改性Co3O4/ZSM-5微孔分子筛催化剂活性的提高。     

低共熔体中微波离子热法合成TAPO-5分子筛

以丁二酸、氯化胆碱与四乙基溴化铵复配形成的低共熔体作为溶剂和模板剂,采用微波辐射-离子热法合成了TAPO-5分子筛.考察了钛源、铝源、原料配比、晶化条件等因素对TAPO-5分子筛合成的影响.采用XRD、N2物理吸脱附、SEM和DRS UV-Vis等方法对产物的结构、织构、形貌和钛的配位状态等性质进行了表征.结果表明,TAPO-5分子筛的合成受铝源、钛源影响较大,最佳钛源为六氟钛酸铵,最佳铝源为异丙醇铝.所得分子筛在苯乙烯的氧化制苯甲醛反应中表现出较好的催化性能,苯甲醛的选择性达到91.4%.     

In-situ Synthesis of Gallium-Containing SAPO-11 Molecular Sieves and Superior Catalytic Performance of Their NiWS Supported Catalysts for Hydroisomerization of n-Hexadecane

In order to prepare a high-performance SAPO-11 (silicoaluminophosphate-11) based non-noble metal supported catalyst for the hydroisomerization of long-chain n-alkanes, gallium-modified SAPO-11 molecular sieve was successfully synthesized by the in-situ synthesis method, and the NiWS supported catalyst was prepared for the hydroisomerization of n-hexadecane. The effects of Ga-modification on the physicochemical properties of SAPO-11 molecular sieve, the active phase properties, and the catalytic performance of the catalyst were studied. Through a series of physicochemical characterizations, it was found that the introduction of Ga increased the mesoporous volume of SAPO-11 molecular sieve, reduced their acid density and strength, but improved the amount of medium-strong Brønsted acid. The Ga-modification weakened the interaction between the active metals and the support, increased the sulfidation degree of active metals, and increased the stacking number and dispersion of active phase. The results of catalytic performance evaluation showed that the catalytic activity and isomerization selectivity of the Ga-modified SAPO-11 molecular sieve based catalysts were improved, and the yield of i-hexadecane of NiW/2Ga-SAPO-11 was the highest, which was 40.30 % higher than that of NiW/SAPO-11. By analyzing the distribution of isomeric products, it was found that the Ga-modified SAPO-11 molecular sieve was helpful in improving the hydroisomerization depth of n-hexadecane over the catalyst.     

Nanosheets of Ni-SAPO-34 Molecular Sieve for Selective Oxidation of Cyclohexanone to Adipic Acid

Nanosheets of nickel doped SAPO-34 molecular sieves in thickness of ∼10 nm (denoted as NS−Ni-SAPO-34) has been successfully prepared through a morphology-reserved method of synthesis. A special aluminum phosphate in two-dimensional layered structure is used as precursor and converts to crystallized SAPO-34 molecular sieve, in nanosheet morphology reserved from the aluminum phosphate precursor, under hydrothermal conditions with tetraethyl orthosilicate and templates of mixed amines added. It is found that adequate amount of nickel, ∼5 wt %, added to the synthetic system is a key factor for the morphology-reserved synthesis. By characterization, the nickel is proved to be doped in the framework of the molecular sieve, which more likely helps to balance the high surface energy of nanosheet products. The NS−Ni-SAPO-34 shows excellent catalytic performance for oxidation of cyclohexanone to adipic acid by gaseous oxygen.     

Au/TS-1选择性催化氧化NO性能研究

制备了负载型Au/TS-1催化剂,采用XRD、SEM、TEM等方法进行了表征,并将其应用于选择性催化氧化NO反应,考察了各工艺条件对NO催化氧化效率的影响。结果表明,Au/TS-1催化剂具有良好的结晶度,Au粒子成功地负载在TS-1上。该催化剂在选择性催化氧化NO反应中具有优异的低温催化氧化活性,在NO体积分数为1×10-3,O2含量为10%,空速为5 000 h-1,Au的负载量为1.0%,180℃时,NO的氧化率高于55%(此时最适宜吸收处理);260℃时,氧化率可达到78%。     

氧化-萃取脱除柴油中噻吩类硫化物研究进展

近年来针对柴油中噻吩类硫化物的脱除问题国内外进行了多种非加氢脱硫技术研究,其中氧化脱硫、萃取脱硫、氧化-萃取脱硫技术是研究较多、具有应用前景的脱硫方法。本文从柴油氧化-萃取脱除噻吩类硫化物的反应机理出发,重点概述了有机酸、酸酐催化体系、离子液体催化体系及分子筛催化体系氧化-萃取脱除噻吩类硫化物获得低硫柴油的最新研究成果,并提出了目前存在的问题及该领域未来的研究方向。     

醋酸溶液中Pd-CuPc/Y催化甲烷选择氧化制甲醇

以氯化铜、钼酸铵、苯酐、氯化铵、尿素和NaY分子筛为原料,采用苯酐-尿素法制备了酞菁铜/分子筛复合物CuPc/Y.采用等体积浸渍法将金属钯担载在CuPc/Y上制备了Pd-CuPc/Y催化剂,并在醋酸水溶液中考察了其催化甲烷选择氧化合成甲醇反应的性能,结果表明,催化性能与反应温度、溶剂中CH₃COOH与H₂O的混合比例、对苯醌用量、反应时间等因素有关,在0.5%Pd-0.5%CuPc/Y添加量0.5 g、CH₃COOH与H₂O体积比4∶1、对苯醌用量1 000 μmol、反应时间3 h、反应温度150 ℃的条件下,甲醇的最佳生成量为1 840 μmol.Pd-CuPc/Y催化剂可以多次循环使用,但由于催化剂流失和催化剂表面的钯粒子聚集的原因,循环使用后的催化剂催化活性有所下降.Pd-CuPc/Y在醋酸溶液中催化甲烷选择氧化合成甲醇是亲电取代反应和活性氧物种氧化共同作用的结果.     

Challenges and Development Opportunities for Catalytic Technologies in Petrochemical Industry in the 21st Century

The propellent drive and development opportunities for future catalytic technologies in petrochemical industry in the 21st century are reviewed in this paper. It focuses on the following five aspects:(1) The environmentally-friendly catalytic technologies, such as new technologies for the production of organic chemicals changing the raw material and synthetic process, the chemicals production replacing phosgene and hydrogen cyanide toxicant, and the conversion and utilization of organic wastes etc.(2) Utilization and development of cheaper light alkanes, for example, the chemical use of natural gas and the development technologies of methane chain, the production of acetic acid, ethylene and vinyl chloride from selective oxidation of ethane, as well as the manufacture of acrolein and acrylonitrile from the oxidation and ammoxidation of propane.(3) The new propylene-plus technologies of the low value higher olefins, such as catalytic cracking of C4,C5 olefins and metathesis of C4 olefin.(4) The technologies of high selective oxidation, e.g. production of propylene oxide with TS-1 molecular sieve, oxidation process by lattice oxygen and direct oxidation of benzene to phenol etc.(5) Development and application of novel catalytic materials, especially, mesopore molecular sieve materials for a larger molecule reaction, zeolite catalyst with MWW structure for alkylation of benzene and propylene, ionic liquid, and membrane reactor catalyst etc.Meanwhile,the challenging research subjects for future industrial catalysis and the several viewpoints for development strategy of new catalytic technologies are proposed. These viewpoints are as follows:(1) Catalysis discipline must be integrated with many other disciplines and should be multidisciplinary and transdisciplinary.(2) New preparation methods of catalytic materials must be originally developed.(3) The instrumentation having better time resolution and spatial resolution and applying under reaction conditions must be improved further.(4) Fundamental research for catalysis and catalytic theory must be enhanced.(5) Catalysis science must be closely integrated with catalytic reaction engineering.(6) Knowledge innovation and technical progress must be accelerated.(7) Scientific and technological co-operation between academic, industrial circles and public organization having a common interest in catalysis must be intensified.     

自制Ti/W-MCM-41介孔分子筛催化制备乳酸戊酯

采用自制的介孔分子筛Ti/W-MCM-41催化乳酸与正戊醇的酯化反应,合成了乳酸正戊酯;利用红外光谱仪分析了催化剂的化学特征,考察了分子筛的WO3质量分数、催化剂用量、醇酸物质的量比、反应时间、催化剂重复使用性能等因素对目标产物酯化率的影响.结果表明,在nSi∶nTi=30∶1,WO3质量分数10%,550℃下焙烧6h条件下制得的催化剂具有良好的催化性能;其催化合成乳酸正戊酯适宜的反应条件为:0.2mol乳酸,催化剂用量0.5g,n(正戊醇)∶n(乳酸)=1.6∶1,反应时间100min,酯化率可达94.4%.该催化剂使用7次酯化率仍可达86.6%.     

Synthesis,characterization and catalytic properties of trivalent iron substituted hexagonal mesoporous aluminophosphates

Trivalent iron substituted hexagonal mesoporous aluminophosphate molecular sieve has been synthesized and characterized for the first time, which showed excellent catalytic activity and reusability for the cyclohexane oxidation reaction under mild conditions.     

磷酸铝分子筛AlPO4-12的合成与性能研究

用乙二胺作模报剂,在水热体系中合成了磷酸铝分子筛ＡＩＰＯ４－１２,考察了反应混合物的初始ＰＨ值和乙二胺用量对产物结晶相的影响,产品的化学组成与文献值吻合。用ＸＲＤ、ＳＥＭ、ＩＲ、ＤＴＡ、化学分析和吸附等方法,对样品进行了表征及物化性能的研究,用丙酸与正丁醇的酯化为典型反应,考究了ＡＩＰＯ４－１２分子筛的催化性能,实验结果表明,ＡＩＰＯ４－１２具有良好的吸附性能、很高的热稳定性（骨架倒塌温度为９９７     

SAPO-11/Beta复合分子筛的合成及其异构化性能研究

以Beta分子筛为硅源通过水热合成法合成了SAPO-11/Beta复合分子筛,采用X射线衍射、N2物理吸脱附、扫描电镜、透视电镜-能谱分析、固体核磁及吡啶红外等方法对单分子筛、复合分子筛和机械混合分子筛的物化性质进行了表征.以正十二烷为模型化合物,在固定床反应器上考察了铂负载型分子筛催化剂的异构化性能.结果表明,复合分子筛的物理化学性质明显不同于单分子筛和机械混合分子筛,其呈现核壳结构,SAPO-11和Beta间存在化学作用,使得复合分子筛具有适宜的B酸分布.在正十二烷异构化反应中,复合分子筛催化剂的异构化性能优于单分子筛催化剂和机械混合分子筛催化剂,多支链异构体收率高.     

LaSrMO4复合氧化物的结构及其己烷完全氧化性能

采用分解无定形柠檬酸和乙二胺四乙酸聚合体法,合成了具有类钙钛矿型结构的LaSrMO4(M=Mn,Fe,Co,N i,Cu)催化材料,以己烷完全氧化为探针反应,运用XRD、BET、TPR、TPD、FT-IR、XPS等手段进行表征.结果表明:对己烷完全氧化性能的顺序为LaSrCoO4>LaSrN iO4>LaSrCuO4>LaSrFeO4>LaSrMnO4,且氧空穴和可移动晶格氧越多、比表面积越大及颗粒度越小,均有利于提高己烷完全氧化活性.     

用TEAOH-C4H9NO复合模板剂合成SAPO-34分子筛的研究Ⅱ.SAPO-34分子筛的表面酸性和催化性能

 以吗啉(C4H9NO)为主要模板剂,以少量四乙基氢氧化铵(TEAOH)为辅助模板剂合成了SAPO -34分子筛,并用氨吸附红外、核磁共振和氮吸附等手段对合成的SAPO-34分子筛进行了表 征. 结果表明,与单独以吗啉为模板剂合成的样品相比,用复合模板剂合成的分子筛样品的比 表面积和孔体积均有所增大; 由于在分子筛骨架中形成了“硅岛”,使其B酸量有所增加 ,对甲醇制低碳烯烃反应的催化性能有所改善.