负载铂催化剂中沸石载体酸性对甲烷两步转化的影响

考察了具有相同金属分散度的Pt/NaY、Pt/HNaY、 Pt/HY、Pt/NaBeta和Pt/HBeta催化剂中沸石载体的酸性对在低温下(≤250℃)甲烷两步等温转化反应以及由甲烷解离吸附产生的表面碳物种分布的影响.由甲烷等温两步转化生成的C2+烃类产物的总量随着载体酸性的增加而明显增加;C2～C6产物的分布也发生了变化.由表面碳物种的程序升温加氢结果表明,在各种催化剂上碳物种的形式是相似的,其总量和具有活性的Cα物种的量均因载体酸性增加而增加,反应性也增大.这种因沸石载体酸性变化而引起的载体效应是由金属和载体的相互作用造成负载在酸性载体上铂粒子的贫电子性而引起,即由金属粒子电子性质的变化而引起的催化性质的变化.

酸性沸石催化剂上丙烯与异丙醇合成异丙醚的研究

考察了Ｈβ、ＨＹ、ＨＺＳＭ－５及ＨＭ等４种沸石对丙烯酸化反应制备异丙醚的催化活性。并研究了焙烧温度和水蒸汽处理条件的影响。结果表明，反应的总活性按下列顺序增加：ＨＹ＜ＨＺＳＭ－５＜ＨＭ＜Ｈβ．高温焙烧的沸石可提高丙烯转化率，降低异丙醇的脱水活性。水蒸汽处理的Ｈｅ＄石降低了反应总活性。丙烯醚化反应要求沸石的徽孔具有较大的体积，以Ｈβ沸石的效果最好。探讨了各沸石酸性与反应性能的关系。

酸性沸石分子筛催化Knoevenagel缩合反应

在高硅 /铝比的酸性沸石分子筛HY上实现了Knoevenagel缩合反应 .Br nsted酸和Lewis酸均可催化Knoevenagel缩合反应 .考察了羰基化合物和活泼亚甲基化合物的反应活性顺序 .结果表明 ,羰基化合物的羰基极化程度越高 ,反应越容易进行 ;不同于碱催化时的Knoevenagel缩合反应 ,活泼亚甲基化合物的活泼氢的酸性并不是影响其反应活性的重要因素 .

酸性沸石催化葡萄糖制备5-羟甲基糠醛研究

以酸性沸石为催化剂,催化葡萄糖脱水制备5-羟甲基糠醛(5-HMF)。沸石催化剂采用固载磷钨酸(PW)和脱铝两种方法制备,固载PW方法用3种类型沸石:HY、MCM-41和HMOR,脱铝方法用HY型沸石,共制得产物PW/MCM-41、PW/HMOR、PW/HY、HY-D0.2和HY-D1.0,考察沸石结构、反应温度、葡萄糖与水质量比、催化剂与葡萄糖质量比对制备5-HMF的影响。结果表明,沸石固载PW后5-HMF的产率均有所提高,其中,以Y型沸石(HY)固载PW后(PW/HY)作为催化剂时5-HMF产率最高,为27.9%;HY特殊的结构对提高5-HMF的产率具有重要的作用。另外,提高反应温度有利于加快5-HMF的生成;葡萄糖与水质量比为3.0∶100时5-HMF产率最高,反应2.5h时达到30.4%,说明适当的葡萄糖与水质量比有利于5-HMF的制备。

酸性沸石催化的香豆素类化合物的合成

制备多种酸性沸石,并通过X射线粉末衍射实验对沸石结构进行表征。通过试验为香豆素类化合物的合成选定了HY9沸石作为理想催化剂,选定了沸点较高的二甲苯作为理想溶剂。在理想条件下,多种香豆素类化合物的合成有着较高的产率和较好的选择性。

表面修饰的酸性丝光沸石催化油酸支链化

利用三苯基膦将合成的酸性丝光沸石进行表面修饰处理,使酸性丝光沸石外表面的部分酸性中心被三苯基膦吸附而失活,经过外表面修饰的酸性丝光沸石用于催化油酸支链化的反应,可明显提高目标产物C18饱和支链脂肪酸的选择性,加氢产物的C18饱和支链脂肪酸产率可提高约5个百分点。经过响应面法优化后,表面修饰的酸性丝光沸石催化油酸支链化反应最优工艺条件为:催化剂用量7.0%(基于油酸质量),加水量4.5%(基于油酸质量),反应温度270℃,反应时间4.5 h。在最优反应条件下,C18饱和支链脂肪酸产率可达到87.25%。反应动力学研究表明,该油酸支链化反应的反应活化能为22.46 k J/mol,指前因子为3.2×103。

高活性低硅铝比中空ZSM-5沸石研究获进展

近日,中国科学院金属研究所沈阳材料科学国家研究中心生物基材料与仿生构筑研究部与英国曼彻斯特大学合作制备出高活性低硅铝比中空ZSM-5沸石,该研究成果刊登在《德国应用化学》杂志上。ZSM-5沸石由于其微孔结构(孔径为0.51~0.56 nm)和可调变的固体酸特性,在石油裂解、石化产品精制方面发挥着重要的作用。由于沸石微孔限制反应物传质,近几十年以来研究重点一直是提高反应物对沸石酸性位的可接触性以提高其催化活性。通常采用碱液后处理选择性脱硅刻蚀出晶内介孔来提高沸石酸性位的可接触性。但是由于沸石母相中四配位铝对脱硅起抑制作用,这种方法只适用于合成硅铝比较高的ZSM-5沸石,合成具有良好可接触性的低硅铝比ZSM-5沸石仍是一个具有挑战性的课题。

Cu或Ag氧化物对碱性沸石上对二甲苯与甲醇侧链烷基化反应的影响

本文研究了对二甲苯与甲醇在Cu或Ag氧化物改性的碱金属离子沸石上的侧链烷基化反应。研究结果表明,在碱金属离子沸石上引入Cu或Ag氧化物,对侧链烷基化初活性有明显的促进作用。研究还表明,在反应条件下Cu或Ag氧化物中的Cu或Ag元素以还原态存在,它们对反应的助催化作用不是由于调变了催化剂的酸碱性,而是还原态Cu°或Ag°使甲醇脱氢成为甲醛。

沸石催化剂制备烷基苷的研究

以酸性沸石作为催化剂进行了葡萄糖与醇的苷化反应 ,反应过程中同时生成烷基呋喃型葡萄糖苷和吡喃糖苷。氢型β -沸石等具有三维孔道结构的沸石催化剂用于苷化反应可以得到 95 %左右的苷化收率 ,对烷基呋喃型葡萄糖苷和吡喃糖苷总选择性可达

强氢氟酸介质中结晶的沸石的独特性质

将分子筛水热结晶合成的化学体系由传统的碱性和中性介质拓展至强酸性范围,为所形成的分子筛带来一系列独特的性质,包括显著的完美晶格结构、憎水性表面、增强的热稳定性以及稳定可靠的微孔扩散性能等。本文结合前期发表的数据和新研究获得的结果详细演示,酸性体系结晶是普适性的分子筛合成方法,所获得的分子筛产品可具有前所未有的完美晶格结构。

由烯烃直接胺化合成脂肪胺的研究进展

烯烃与氨或胺直接胺化合成脂肪胺的反应在热力学上是有利的,但在动力学上需要适宜的催化剂进行活化。多种均相催化剂和多相催化剂已被尝试用于此反应,其中酸性沸石催化剂在催化氨与小分子烯烃(主要是乙烯和异丁烯)的反应中表现出了较好的活性和很高的选择性,且清洁无污染。提出应通过对此反应机理的深入研究以筛选出新的、高选择性的沸石催化剂以提高反应的转化率。

Modifying the acidity of H-MOR and its catalytic carbonylation of dimethyl ether

Among the reactions catalyzed by zeolites there are some that exhibit high selectivity due to the spatial confinement effect of the zeolite framework.Tailoring the acidity,particularly the distribution and location of the Bronsted acid sites in the zeolite is effective for making it a better catalyst for these reactions.We prepared a series of H-mordenite（H-MOR） samples by varying the composition of the sol-gel,using different structure directing agents and post-treatment.NH3-TPD and IR characterization of adsorbed pyridine were employed to determine the amount of Bronsted acid sites in the 8-membered ring and 12-membered ring channels.It was shown that controlled synthesis was a promising approach to improve the concentration of Bronsted acid sites in MOR,even with a low Al content.Using an appropriate composition of Si and Al in the sol-gel favored a higher proportion of Bronsted acid sites in the 8-membered ring channels.HMI as a structure-direct agent gave an obvious enrichment of Bronsted acid sites in the 8-membered ring.Carbonylation of dimethyl ether was used as a probe reaction to examine the modification of the acid properties,especially the Bronsted acid sites in the 8-membered ring channels.There was a linear relationship between methyl acetate formation and the number of Bronsted acid sites in the 8-membered ring channels,demonstrating the successful modification of acid properties.Our results provide information for the rational design and modification of zeolites with spatial constraints.

Ammonia nitrogen removal from aqueous solution using zeolite modified by microwave-sodium acetate

The characteristics of the zeolite modified by microwave and sodium acetate and its sorption of ammonia-nitrogen from simulated water sample were investigated.The results show that the modified zeolite by microwave-sodium acetate(SMMZ)has a high sorption efficiency and removal performance.The ammonia-nitrogen removal rate of SMMZ reaches 92.90%.The surface of SMMZ becomes loose and some pores appear,the specific surface area,total pore volume and average pore diameter increase after modification.Compared to the natural zeolite,SMMZ has a more concentrated pore size distribution in the range of 0-10 nm.The cation exchange capacity(CEC)of SMMZ is higher than that of the natural zeolite.And the ammonia nitrogen removal rate is consistent with the change of CEC.The SMMZ possesses rapid sorption and slow balance characteristics and ammonia-nitrogen sorption is consistent with both Langmuir adsorption isotherm model and Freundlich adsorption isotherm model.The adsorption kinetics of ammonia-nitrogen follows the pseudo-second order kinetic model.

Thermodynamics and kinetics of fluoride removal from simulated zinc sulfate solution by La(Ⅲ)-modified zeolite

To understand the mechanism of fluoride removal from the simulated zinc sulfate solution by the La(III)-modified zeolite,the adsorbent was characterized by XRD,SEM and EDS.The effects of absorbent dose and contact time,the adsorption isotherms and the sorption kinetics were investigated.The experimental results were compatible with the Langmuir isotherm model.The theoretical maximum adsorption capacities are 20.83 and 23.04 mg/g at 303 and 313 K,respectively.And the physisorption is revealed using the Temkin isotherm model and the D-R isotherm model.The sorption process is more suitable by the pseudo-second-order kinetic models.Thermodynamic parameters such as standard free energy change(ΔGΘ<0 kJ/mol),standard enthalpy change(ΔHΘ=8.28 kJ/mol)and standard entropy change(ΔSΘ=0.030 kJ/(mol?K))indicate the spontaneity of adsorption and endothermic physical sorption.Furthermore,the fluoride concentration in the industrial zinc sulfate solution decreases from 98.05 to 44.09 mg/L with the adsorbent dosage of 15 g/L.

Preparation, Characterization and Catalytic Behavior of 12-Molybdophosphoric Acid Encapsulated in the Supercage of Cs^＋-exchanged Y Zeolite

In order to solve the serious leaching problem of supported heteropoly acid catalysts in polar reaction media, 12-molybdophosphoric acid encapsulated in the supercage of Cs^＋-exchanged Y zeolite was prepared by the ＂ship in the bottle＂ synthesis. The influence of ion-exchange conditions and the synthesis parameters on the encaosulation of PMo12 were investigated. The obtained solid sample was characterized by X-ray diffraction （XRD）, 31p magic angle spin nuclear magnetic resonance （MAS NMR） and Fourier Transform Infrared Spectroscopy （FT-IR）, and its catalytic activity in the esterification of acetic acid and n-butanol was tested. The ion-exchange time, concentration of aqueous Cs^＋ solution, pH value, and amount of Mo added in the synthesis mixture were revealed to influence the encapsulation very remarkably. Under the optimal conditions, 12-molybdophosphoric acid could be successfully encapsulated in the supercage of CsY zeolite, and the samples showed considerable catalytic activity and excellent reusability in the esterification reaction.

法国-瑞士团队提出甲醇制烯烃反应的引发机理

甲醇制烯烃（MTO）工艺于1970年代首先被开发，它藉于酸性沸石将甲醇或二甲醚转化为烯烃，然而，该活性中心和第一个碳-碳键的形成机理仍然是一个有争议的问题。瑞士苏黎世联邦理工学院的科学家团队详细描述了MTO反应是如何引发的。

The Activity and Theoretical Interpretation of Role of Trimethyl Phosphite Modified HZSM-5 Zeolite

The catalytic activity of trimethyl phosphite modified HZSM-5 zeolite and un-modified HZSM-5zeolite treated with 100% steam at 673,773,873,973 and 1073K, respectively, were investigated using heptanecracking as a probe reaction. The results showed that the heptane conversion of both trimethyl phosphitetreated samples and un-phosphated samples decreased with an increase in treating temperature, but trimethylphosphite modified samples showed higher activity in comparison with the un-modified samples, which weresteam-treated at a higher temperature. The results were firstly elucidated by the model cluster method andcomputational quantum chemistry method. Full optimization and frequency analysis of all cluster model havebeen carried out using the Gaussian 94 software-package with the PM 3 semi-empirical method performed onsmall cluster models. The computational results showed that the dealumination of trimethyl phosphite modi-fied zeolite model cluster was more difficult than that of un-modified zeolite model cluster when they weretreated with steam while investigating the heat of reaction.

Adsorption of acid fuchsin onto LTA-type zeolite derived from fly ash

A facile strategy without organic template was developed for the conversion of fly ash to LTA-type zeolite(LTA-Z),which could be used as a good adsorbent for the removal of acid fuchsin(AF).XRD results indicated that the pure crystalline product was obtained with the structure of LTA-type zeolite.SEM investigations showed that the well-defined LTA-Z crystals exhibited uniform size with the same cubic shape.The maximum AF adsorption amount was observed at pH=5,slightly lower than pHPZC of LTA-Z.Higher temperature favored AF adsorption onto LTA-Z and it was an endothermic process.Furthermore,AF adsorption amount increased with initial AF concentration increasing and LTA-Z dosage decreasing.Surface sorption governed this process at the initial 120 min period,followed by the internal diffusion of AF molecules between porous sites.The Langmuir model was determined as the adsorption isothermal,suggesting that the monolayer coverage of AF on LTA-Z surface was involved.

Preparing amphiphilic acidic zeolite via chemically coating alkylamine

Amphiphilic ODA/HY and ODA/ Hβ zeolites have been prepared via chemically coating octadecylamine (ODA) with alcohol as solvent. IR and titrimetric results indicate that ODA molecules are chemisorbed on the acidic sites in zeolite, showing the higher thermostability and alcohol-resistance. These am- phiphilic zeolites contain both the hydrophobic and hydrophilic groups, orient at the liquid-liquid phase-boundary in both cyclohexane/water and water/carbon tetrachloride systems, and exhibit the potential to be used in the phase-boundary catalysis and adsorption. No by-products with strong acid- ity are formed in this approach, therefore, it can be used to prepare amphiphilic acidic zeolites with low Si/Al ratio.