Elucidating the effect of oxides on the zeolite catalyzed alkylation of benzene with 1-dodecene

In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.

Titanium-rich TS-1 zeolite for highly efficient oxidative desulfurization

The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.

无溶剂快速合成S-1和TS-1分子筛

Silicalite-1(S-1)和Titanium Silicalite-1(TS-1)沸石分子筛因其良好的疏水性、热稳定性和择形性等特点,作为环境友好的绿色催化剂在工业应用上极具优势和价值.采用无溶剂法成功合成了TS-1分子筛,并利用X-射线衍射仪、全自动比表面和孔隙分析仪、紫外可见光谱仪和扫描电镜等表征仪器研究了晶化时间和硅钛摩尔比对所制备TS-1分子筛的物化性质的影响.结果表明,合成的TS-1沸石分子筛具有较高的结晶度和纯度、均一的晶粒大小、高的比表面积和在分子筛骨架中四配位和六配位的钛物种.无溶剂合成TS-1沸石具有低成本、环境友好和高效的优点,研究将为工业上沸石的规模合成提供一定的理论借鉴.

Pt supported on Zn modified silicalite-1 zeolite as a catalyst for n-hexane aromatization

Platinum(Pt)supported on Zinc(Zn)modified silicalite-1(S-1)zeolite(denoted as Pt-Zn/S-1)was prepared by using a wetness-impregnation method and applied in the n-hexane aromatization reaction for the first time.Both Lewis and Bronsted acid sites were detected in Pt-Zn/S-1 catalyst by means of FT-IR adsorption of NH3 experiment,which were identified as mostly weak and medium ones.Besides,Pt and Zn species showed strong interaction,as revealed by the TPR(Temperature-programmed reduction)and XPS(X-ray photoelectron spectroscopy)experiments.Pt-Zn/S-1 catalyst exhibited excellent aromatization function rather than isomerization and cracking side reactions in the conversion of n-hexane.Pulse experimental study showed that 75.6%of n-hexane conversion and 76.8%of benzene selectivity were obtained over Pt0.1-Zn60/S-l catalyst at 550℃ and under atmospheric pressure.By spectroscopy tests and pulse experimental results,it was concluded that the n-hexane aromatization over Pt-Zn/S-1 catalyst follows a metal-acid bifunctional mechanism.Furthermore,with the assistance of Zn,the electron-deficient Pt species in Pt-Zn/S-1 showed good sulfur tolerance performance.

The synthetic strategies of hierarchical TS-1 zeolites for the oxidative desulfurization reactions

With the increasingly stringent standards for limiting sulfide content in liquid fuels,oxidative desulfurization(ODS)has become a promising ultra-deep desulfurization process in fuel desulfurization.TS-1 zeolites show great potential as catalysts for ODS reactions,due to its remarkable oxidation activity at low temperatures and pressure.However,the inherent microporous structure of conventional TS-1 zeolites restricts the mass transportation and renders the active sites in the microporous space of TS-1 zeolites inaccessible for bulky aromatic organosulfur compounds.Fabrication of hierarchical TS-1 zeolites by incorporating meso-/macropores into microporous TS-1 zeolites is an effective strategy to improve mass transportability.In recent years,abundant efforts have been dedicated to developing synthetic strategies of hierarchical TS-1 zeolite,thereby improving its catalytic performance in the ODS process.This mini-review addresses the synthetic methods of hierarchical TS-1 catalysts and their catalytic performance in the ODS reactions.In addition,some current problems and prospects of synthesis routes for constructing hierarchical TS-1 catalysts have also been revised.We expect this mini-review to shed light on the more efficient preparation strategies of hierarchical TS-1 zeolites for the ODS process.

Quasi-solid state synthesis of EU-1 zeolite and its catalytic properties for the isomerization of C_8 aromatics

In this study,EU-1 zeolite was successfully synthesized via a quasi-solid state approach and assembled to catalyst for the C 8 aromatics isomerization process.The catalytic properties were tuned through careful modification of the acidity of EU-1 zeolites and metal-doping of the catalyst.It was shown that EU-1 was an excellent candidate for the C 8 aromatics isomerization process due to its unique structure.In addition,steam treatment of EU-1 at 450-500 ℃ could optimize the acidic properties of the catalyst,hence enhance its catalytic performance.The effect of the amount of Pt on ethylbenzene conversion was studied and the optimum amount was determined to be about 0.3-0.4 wt%.It was confirmed that EU-1 zeolite prepared via a quasi-solid state approach and then dealuminated by steam treatment had better activity and selectivity than conventional mordenite（MOR） zeolite and could be an excellent candidate for C 8 aromatics isomerization.

MCM-36 zeolites tailored with acidic ionic liquid to regulate adsorption properties of isobutane and 1-butene

Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impact on the adsorption properties. In this study, a novel acidic ionic liquid, 1-butyl-3-(triethoxysilylpropyl)imidazolium hydrogen sulfate(i.e., [BTPIm][HSO_4]), was synthesized and subsequently grafted onto the MCM-36 zeolite for the regulation of its adsorption properties towards isobutane and 1-butene. The resultant [BTPIm][HSO_4]-immobilized MCM-36(i.e., MCM-36-IL) was characterized by FT-IR, XPS, XRD, SEM, TG/DTG and N_2 adsorption–desorption measurement. It was found that the specific surface area, micropore volume and mesopore volume of the MCM-36 support underwent a reduction upon the immobilization of ionic liquid,while the surface density of acid increased from 0.0014 to 0.0035 mmol·m^(-2). The adsorption capacity of isobutane and 1-butene on the MCM-36-IL was determined by a static volumetric method. Results demonstrated that the interaction between isobutane and MCM-36-IL was enhanced and the interaction between 1-butene and MCM-36-IL was reduced. As a result, a tunable adsorption ratio of isobutane/1-butene on MCM-36 was achieved.With the increase in surface density of acid and the tunable adsorption ratio of isobutane and 1-butene on the functionalized MCM-36, the acidic ionic liquid-immobilized zeolites are beneficial to obtain an improved reaction yield and a prolonged catalyst life in the reactions catalyzed by solid acid.

Synthesis, characteristics of hierarchical EU-1 zeolite for xylene isomerization probe reaction

Introduced a method of synthesizing hierarchical EU-1 zeolite with organosilanes as additive, and studied the influences of following different kinds of organosilanes on the synthesis of hierarchical EU-1 zeolite: γ-glycidoxy propyl trimethoxy silane(GPTMS), N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxyl silane(APAEDMS),and N-(β-aminoethyl)-γ-aminopropyl dimethoxyl(ethyoxyl) silane(TMPED). The hierarchical EU-1 samples were characterized by XRD, SEM, N_2 adsorption, FT-IR and NH_3-TPD to analyze the crystallinity, morphology, surface area, pore size distribution and acidity. The results showed that hierarchical EU-1 zeolites were successfully synthesized; organosilanes have great influence on crystal morphology of EU-1 zeolites; the exterior surface area of hierarchical EU-1 zeolite, which synthesized with organosilanes(APAEDMS) adding into synthesis system, increased by 62.1% and mesopore volume increased by 129.1% compared with conventional EU-1 zeolites, thus can reduce the diffusional restriction markedly in catalytic reaction. The catalytic performance of hierarchical EU-1zeolites were evaluated in m-xylene isomerization on fixed bed reactor. The catalytic data showed that the isomerization activity PX/X of the hierarchical EU-1 zeolites reached around 24.09% in theoretical thermodynamic equilibrium from 23.83%, and the selectivity of C_8 aromatic hydrocarbon increased from 75.16% to 84.87%. The conversion of p-xylene increased from 16.30% to 18.41%.

过渡金属负载Silicalite-1分子筛的制备及其催化糠醛加氢性能研究

糠醛是一种重要的生物质平台分子,研发具有高活性和稳定性的糠醛加氢催化剂是当前的研究焦点,但贵金属催化剂的高成本问题使得其难以满足大规模工业生产的需求。利用一步水热法成功地合成了过渡金属负载Silicalite-1分子筛催化剂,并探讨了引入不同类型的过渡金属(如Ni、Co、Cu和Fe)对Silicalite-1分子筛结构产生的影响。研究结果表明:低金属负载量并不会对分子筛结构的形成产生影响,同时金属物种在分子筛载体的表面也能均匀分布。在糠醛的加氢转化过程中,Ni基催化剂S-Ni2展现出优异的糠醛转化能力,糠醛的转化率高达96%,产物呋喃的选择性保持在71%左右。Cu基催化剂S-Cu1表现出优异的糠醇选择性,产物选择性接近100%,这一性能明显优于通过浸渍法制得的铜基催化剂(76%)。因此,与浸渍法相比,采用一步水热法可以获得具有高选择性的催化剂,且该方法简单易操作。本研究为寻找高效、稳定且经济的金属加氢催化剂开辟了新的方向,并促进了生物质资源的高值化应用。

Experiment and Modeling of Pure and Binary Adsorption of n-Butane and Butene-1 on ZSM-5 Zeolites with Different Si/Al Ratios

Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gra- vimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir(DL)model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory(IAST),the IAST-DL model was applied to model the butene-1(1)/n-butane(2)binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorp- tion over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.

A convenient synthesis of 1,5-diarylpyrazoles from Baylis-Hillman adducts using HY-zeolite

A facile and convenient protocol was developed for the synthesis of 1,5-diarylpyrazoles using Baylis-Hillman adducts in the presence of HY-zeolite as an efficient recyclable heterogeneous catalyst in reasonable reaction times(1.5-2.5 h) and high yields (78-90%).

Modification and sequential treatment of EU-1 zeolite in mild alkali and alkaline-acid conditions

EU-1 zeolites were sequentially treated with low-concentration sodium carbonate(Na_2CO_3) and hydrochloric acid(HCl) solutions.The obtained samples were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),N_2 adsorption/desorption,temperature programmed desorption of NH_3(NH_3-TPD),solid state^(27)A1 nuclear magnetic resonance(^(27)A1 NMR),and the catalytic performances of the treated samples were tested in the xylene isomerization reaction.The results showed that the external surface area and mesoporous volume of the sample sequentially treated with 0.05 mol·L^(-1) Na_2CO_3 and 0.1 mol·L^(-1) HCl solutions reached73.9 m^2·g^(-1) and 0.162 cm^3·g^(-1),respectively.The catalytic performances of EU-1 zeolites were significantly improved,that the activity of the probe reaction increased from 23.03%to 23.61%and the selectivity increased from85.09%to 87.14%compared with those of parent sample.Furthermore,it was found that only amorphous silica and alumina species was dissolved during the post-treatment process,but the framework structure and the acidic properties of EU-1 zeolite remained intact.

Studies of Cyclohexane Catalytic Oxidation Processes over Titanium Silicate-1 Zeolite

The catalytic oxidation processes for cyclohexane/H2O2/acetone system over the TS-1 zeolite was studied. Study results have revealed that the cyclohexane conversion was 27% after the reaction proceeded at 100C for 2 hours at a cyclohexane/H2O2 molar ratio of 0.8. The cyclohexanol/cyclohexanone molar ratio was 1.3along with a certain amount of organic acids and esters, the formation of which was closely associated with the oxidation of reaction solvent and deep oxidation of cyclohexanone and cyclohexanol contained in the reaction products. With respect to the catalytic oxidation of cyclohexane/H2O2 system the selection of appropriate solvent was critically important.

Skeletal Isomerization of 1-Hexene over MCM-22 Zeolite Catalyst

The performance of MCM-22 zeolite for catalytic isomerization of 1-hexene has been studied. At a n(H2)/n(1-hexene) ratio of 8, the influence of steam treatment temperature, reaction temperature and reaction pressure on the performance of MCM-22 zeolite for catalytic skeletal isomerization of 1-hexene was examined. The experimental results showed that at a steam treatment temperature of 500℃, a reaction temperature of 270℃, a space velocity of 1.0 h-1 and a reaction pressure of 0.2 MPa, the MCM-22 zeolite exhibited excellent performance for catalytic skeletal isomerization of 1-hexene with the i-hexene yield reaching 66.15%. Compared with other commonly used molecular sieve catalysts, the MCM-22 zeolite catalyst exhibited better catalytic performance for skeletal isomerization of 1-hexene.

Synthesis and Characterization of Zeolite Hexanediamine-Theta-1

The synthesis of zeolite HXDM-Theta-1(HXDM = hexanediamine) from the reaction mixture HXDM-Al2O3-SiO2-HF-H2O is described. The formation of HXDM-Theta-1 is favoured at 150℃, and a mixture of Theta-1 and ZSM-5 is obtained at a higher temperature. The asynthesized Theta-1 was characterized by means of scanning electron micrography, thermal analysis and 13C MAS NMR techniques. Keywords Theta-1, Hydrothermal crystallization, Hexanediamine template, Thermal analysis, 13C MAS NMR

盐酸溶液和水热脱铝HEU-1分子筛的表征及其催化裂解性能

采用HCl溶液和/或水热处理HEU-1分子筛,利用X射线衍射、N2吸附-脱附、X射线荧光光谱、NH3程序升温脱附、吡啶吸附傅里叶变换红外光谱和铝固体核磁共振等对脱铝处理的HEU-1分子筛进行了表征,并考察了脱铝HEU-1分子筛上正己烷的催化裂解性能.结果表明,采用HCl溶液处理HEU-1分子筛,能有效脱除非骨架铝,可调变样品的弱酸中心;而水热处理HEU-1分子筛,能有效脱除骨架铝,可调变样品的强酸中心.水热处理和HCl溶液处理有效结合可以达到同时调变HEU-1分子筛的酸类型和酸密度的目的.脱铝HEU-1分子筛上正己烷催化裂解反应结果表明,氢转移反应被明显抑制,丙烯选择性提高.600°C水热处理后再用HCl溶液处理的HEU-1分子筛于625°C反应时丙烯选择性由未改性的21.9%提高到35.2%,活性稳定性也由不足10h提高到40h.

氧化石墨烯/金属离子复合改性沸石体外吸附花生粕中黄曲霉毒素B_(1)性能研究

在动物饲料中添加吸附剂是减轻真菌毒素污染不良影响的有效途径。为了制备饲料黄曲霉毒素B_(1)(AFB_(1))高效脱毒剂,采用固相分散法制备了氧化石墨烯/金属离子复合改性沸石,通过研究其在模拟胃环境(pH=2)和肠环境(pH=6.8)下对花生粕中AFB_(1)的体外吸附率,筛选出最优复合改性沸石,并对其进行结构表征及吸附性能研究。结果表明:氧化石墨烯/钙离子复合改性沸石(GO-Ca-Z)对花生粕中AFB_(1)的吸附率最高;其具有丰富的孔隙;在pH为2和6.8的环境下,GO-Ca-Z(2∶1)(GO与Ca-Z的质量比为2∶1)的最大吸附量分别为0.046 mg/g和0.036 mg/g,与未改性的沸石相比,吸附量分别提高了2.42和3倍;吸附过程符合准二级模型,说明化学吸附在吸附体系中起到主要作用;经过酸浸泡后GO-Ca-Z(2∶1)比表面积和总孔体积显著增加,说明酸处理有利于提高材料的吸附性能。

Ultra-deep adsorptive removal of thiophenic sulfur compounds from FCC gasoline over the specific active sites of CeHY zeolite

Adsorption desulfurization performance of Na Y,HY and Ce HY zeolites is evaluated in a miniature fixedbed flow by model gasoline containing with thiophene,tetrahydrothiophene,2-methylthiophene,benzothiophene or mixed sulfur compounds.The structural properties of adsorbents are characterized by XRD,N2-adsorption and XPS techniques.Adsorption desulfurization mechanisms of these sulfur compounds over the specific active sites of adsorbents as a major focus of this work,have been systematically investigated by using in situ FT-IR spectroscopy with single and double probing molecules.Desulfurization experimental results show that the Ce HY adsorbent exhibits superior adsorption sulfur capacity at breakthrough point of zero sulfur for ultra-deep removal of each thiophenic sulfur compound,especially in the capture of aromatic 2-methylthiophene(about ca.28.6 mgS/gadsorbent).The results of in situ FT-IR with single probing molecule demonstrate an important finding that high oligomerization ability of thiophene or 2-methylthiophene on the CeHY can promote the breakthrough adsorption sulfur capacity,mainly resulting from the synergy between Br?nsted acid sites and Ce(III)hydroxylated species active sites located in the supercages of Ce HY.Meanwhile,the result of in situ FT-IR with double probing molecules further reveals the essence of oligomerization reactions of thiophene and 2-methylthiophene molecules on those specific active sites.By contrast,the oligomerization reaction of benzothiophene molecules on the active sites of Ce HY cannot occur due to the restriction of cavity size of supercages,but they can be adsorbed on the Br?nsted acid sites via protonation,and on Ce(III)hydroxylated species and extra-framework aluminum hydroxyls species via direct"S-M"bonding interaction.As to the tetrahydrothiophene,adsorption mechanism is similar to that of benzothiophene,except in the absence of protonation.The paper can provide a new design idea of specific adsorption active sites in excellent desulfurization adsorbents for elevating higher quality of FCC gasoline in the future.

silicalite-1分子筛载体在丙烷脱氢中的应用

以正硅酸乙酯为硅源,合成了具有MFI结构的球形和六方片状silicalite-1全硅分子筛,并将其作为载体制备了负载型催化剂用于丙烷脱氢制丙烯反应;采用SEM、XRD、TEM、N_(2)吸附-脱附、Py-FTIR、NH_(3)-TPD、^(29)Si MAS NMR和H_(2)-TPR等方法对两种分子筛载体及负载型催化剂的结构和表面性质进行表征,研究了不同形貌silicalite-1载体对催化剂性能的影响机制。实验结果表明,球形silicalite-1分子筛载体具有更大的外比表面积和更多的表面硅羟基,进而增强了活性组分与载体间的相互作用,提高了活性金属在载体表面的分散度,因此在丙烷脱氢制丙烯反应中球形silicalite-1载体负载的催化剂具有更高的活性。

多级孔NiMo负载TS-1分子筛催化剂的制备及其加氢脱硫性能

钛硅(TS-1)分子筛的微孔孔道严重限制了其在复杂分子催化转化中的应用,为了克服这一问题,通过酸洗脱、碱刻蚀及二者相结合的方法制备了多级孔TS-1分子筛,并采用等体积共浸渍法制备了相应的NiMo负载型催化剂;使用X射线衍射(XRD)、N2吸附-脱附、吡啶吸附红外光谱(Py-FTIR)、氢气程序升温还原(H_(2)-TPR)、X射线光电子能谱(XPS)和高分辨透射电子显微镜(HR-TEM)等方法对多级孔TS-1分子筛的理化性质进行了表征;以二苯并噻吩(DBT)为探针对催化剂的加氢脱硫(HDS)性能进行了评价。结果表明,和常规TS-1分子筛相比,多级孔TS-1分子筛保持了MFI拓扑结构,比表面积增大且具有介孔结构,分子筛表面形成了适量的Br?nsted酸中心;相应催化剂上活性金属与载体间相互作用得以改善,MoS_(2)片晶长度和堆垛层数适宜,形成了更多的NiMoS活性相;催化剂活性和选择性均有所提升,尤其是酸洗脱获得的NiMo/AT-TS-1催化剂的活性相较未经处理的NiMo/TS-1催化剂提升了1.2倍,直接脱硫(DDS)路径选择性提升了22%。