Post-treatment of TS-1 with Mixtures of TPAOH and Ammonium Salts and the Catalytic Properties in Propylene Epoxidation

TS-1/SiO_2 extrudate was post-treated with mixed solution of tetrapropyl ammonium hydroxide(TPAOH)and various ammonium salts solution(NH_4F,(NH_4)_3PO_4,(NH_4)_2CO_3,(NH_4)_2SO_4,NH_4CH_3CO_2,NH_4NO_3,NH_4Cl and(NH_4)_2TiF_6).The obtained hierarchical TS-1 catalysts were characterized by many techniques and tested for propylene epoxidation using hydrogen peroxide as an oxidant in a fixed-bed reactor.It was shown that the physicochemical and catalytic properties of the treated TS-1/SiO_2 extrudate depended on the types of ammonium salts added.Compared to the treatment with TPAOH alone,the treatment with a mixed solution of TPAOH and some ammonium salts can greatly improve the catalytic properties of the treated TS-1/SiO_2 extrudate.Some of these ammonium salts were favorable for the incorporation of titanium in the framework,and the beneficial effect depended on the types of ammonium salt.TS-1/SiO_2 extrudate treated with a mixed solution of TPAOH and(NH_4)_3PO_4 exhibited the highest catalyst stability in propylene epoxidation.Such catalytic property can be correlated to high crystallinity,more framework titanium,large specific surface area and large external surface area.     

Effect of TS-1 Treatment by Mixed Alkaline on Propylene Epoxidation

Titanium silicate-1(TS-1) was treated with a mixed alkaline of tetrapropyl ammonium hydroxide(TPAOH) and NaOH. It was characterized by XRD, nitrogen physical adsorption, SEM, FT-IR, UV-Vis and ICPOES, and studied in propylene epoxidation. The mixed alkaline treatment with TPAOH/NaOH solution did not destroy the MFI structure of TS-1. With increasing NaOH concentrations, the relative crystallinity and the framework titanium decreased to some extent while the mesopore volume, mesopore diameter, and extra-framework titanium increased appreciably. When NaOH concentration was 0.0333 mol L~(-1), the best catalytic performance was obtained.     

Synthesis of mesoporous titanium silicalite-1 with high stability in cyclohexanone ammoximation

Mesoporous titanium silicalite-1(TS-1)was hydrothermally synthesized with the addition of triethanolamine( TEA)in the conventional process, and used in the cyclohexanone ammoximation in a continuous slurry reactor. The as-prepared TS-1 was characterized with X-ray diffraction(XRD), scanning electron microcopy( SEM), N₂ adsorption-desorption, Fourier transform infrared (FT-IR)spectroscopy, UV-Visible(UV-Vis) diffuse reflectance spectra and UV Raman spectroscopy. The results indicated that the addition of TEA resulted in the formation of mesopores and the slight increase of framework titanium in TS-1. TS-1 synthesized with the addition of TEA exhibited a higher stability in the cyclohexanone ammoximation than that without the addition of TEA, attributing to the increase of mesopore volumes and the slight increase of the framework titanium in TS-1. However, when the addition of TEA was up to TEA/SiO₂ ratio of 0.24, the crystallinity and framework titanium of TS-1 decreased markedly, and the average crystal sizes of TS-1 increased, with the catalyst stability becoming poor.     

钛硅分子筛TS—1的合成及催化性能研究

钛硅分子筛在环境友好工艺过程中发挥着越来越大的作用。该文以TPAOH为模板剂，TEOS，硅溶胶，无定形氧化硅为硅源，合成了TS－1分子筛，重点考察了合成条件对TS－1分子筛晶粒度的影响，并针对苯乙烯氧化反应体系分析了TS－1晶粒度对催化性能的影响。     

Effect of Extra-Framework Titanium in TS-1 on the Ammoximation of Cyclohexanone

Titanium silicalite (TS-1) without and with extra-framework titanium have been prepared and TiO_2 is also prepared under the same conditions.All the samples are characterized with XRD,FT-IR,and UV–Vis.The effects of extra-framework titanium in TS-1 on the ammoximation of cyclohexanone have been studied in a continuous slurry reactor.The characterization results reveal that the extra-framework titanium exists as anatase.The catalytic evaluation results show that the anatase has a positive effect on the ammoximation of cyclohexanone by extending the catalytic life because it also exhibits some activity,while the conversion of cyclohexanone and the selectivity to cyclohexanone oxime are not influenced.The anatase TiO_2 does not catalyze H_2O_2 decomposition appreciably compared with TS-1 without extra-framework titanium.The results are very useful in guiding the TS-1 production.     

TiC对Ti:Al:C=2:2:1系燃烧产物的影响

Ti、Al和C粉的燃烧合成实验结果表明,在Ti:Al:C=2:2:1体系中,添加TiC≤10wt.％时,燃烧产物中Ti3AlC2的含量与未添加TiC的相比,有大幅度增加;添加TiC≥20wt.％时,燃烧产物中Ti3AlC2的含量略有减少,而TiC的含量增多.从燃烧温度的角度探讨了TiC对燃烧合成产物相组成的影响.     

山梨酸乙酯的合成研究

以对甲苯磺酸为催化剂,催化合成山梨酸乙酯。考察了原料配比、催化剂的用量、带水剂的用量以及反应时间等条件对反应的影响。实验结果表明,合成山梨酸乙酯的最佳反应条件是：n（山梨酸）：n（乙醇）=1：5,催化剂用量占山梨酸质量的25％,反应时间3h,带水剂用量为15mL,产物收率75．04％,纯度达98％。     

不同气氛和素坯密度对燃烧合成Ti_3AlC_2粉体的影响

实验结果表明 ,Ti:Al:C =2 :2 :1(摩尔比 )体系燃烧合成Ti3AlC2 的环境气氛若为真空 ,燃烧产物主要为TiC ,若为氩气 ,燃烧产物主晶相为Ti3AlC2 ;增加反应物原料的素坯密度 ,可较大程度地提高燃烧产物中Ti3AlC2 的含量。     

木炭颗粒对水溶液中Cd2+和Cr3+质量浓度的影响

目的及方法:采用室内模拟试验,研究木炭不同粒径和用量及不同吸附时间对水溶液中Cd2+和Cr3+质量浓度的影响。结果:木炭粒径为0.25 mm时,溶液中的Cd2+、Cr3+质量浓度最高;粒径大于0.25 mm时,Cd2+、Cr3+质量浓度随着粒径增大而减小;粒径小于0.25 mm时,Cd2+、Cr3+质量浓度随着粒径减小而减小,表明只有在粒径小于0.25 mm时,粒径越小,吸附效果越好。木炭用量达到20 g.L-1时,水溶液中Cd2+、Cr3+剩余质量浓度显著低于对照,且随着用量增加,Cd2+、Cr3+剩余质量浓度有所降低;木炭用量为40 g.L-1时,第1天至第4天,4种不同浓度Cr3+水溶液中,Cr3+质量浓度随着时间的递增而递减,随后随着时间的推移,Cr3+质量浓度呈小幅增长趋势。结论:使用木炭对水溶液中的重金属离子浓度进行吸附,需要对粒径大小、用量、吸附时间等因素进行优化,才能保证吸附效果。     

SBA-15固载离子液体催化合成碳酸丙烯酯的研究

采用原位合成法和后嫁接法将[SiPMIm] Cl固载在SBA-15材料上,制得SBA-15固载离子液体催化剂SBA-15-[SiPMIm] Cl.用N2吸附-脱附、透射电镜、小角X射线衍射和红外光谱等手段表征催化剂,并考察其在CO2与环氧丙烷（PO）环加成合成碳酸丙烯酯（PC）反应中的催化性能.结果表明：固载等量离子液体后,原位合成法制备的SBA-15固载离子液体催化剂体系对CO2环加成合成PC反应的催化活性优于后嫁接法制备的SBA-15固载离子液体催化剂体系.在最优工艺条件下,PO的转化率高达52.8％,且反应后催化剂经过滤即可分离回收利用,多次使用仍保持较高的反应活性.     

改性固体超强酸催化合成原油降凝剂单体甲基丙烯酸高级酯

首次将稀土元素镧改性并以HZSM-5分子筛担载制备的固体超强酸催化剂SO24-/ZrO2/La2O3-HZSM-5(SZLH),用于合成原油降凝剂单体甲基丙烯酸高级酯。合成了3种甲基丙烯酸酯,考察了催化剂用量、带水剂种类、醇酸比和反应时间等因素对酯化率的影响。结果表明,在最佳工艺条件下,酯化率可达95.6%以上。酯化产物经红外光谱测定,证明为甲基丙烯酸高级酯,且该催化剂具有良好的重复使用性。     

新型片状氧化铁的合成以及在珠光颜料中的应用

介绍了以熔盐法制备珠光颜料用片状氧化铁的最佳制备条件的探讨过程,通过在不同条件如熔盐种类、熔盐用量、煅烧温度和煅烧时间下进行合成,并使用光学显微镜对产品形貌和尺寸进行观察,从而推断出助熔剂法合成片状氧化铁的最佳条件.通过研究发现,在采用Na2SO4＋K2SO4作为复合熔盐,并且熔盐用量与三氯化铁的摩尔比为5的条件下制备前驱体,在1 100℃下煅烧4 h,可得到平均粒径约为20μm,表面平整,形貌良好的六角形片状氧化铁晶体.并对制备的片状氧化铁进行了包覆二氧化钛应用尝试,表明该法制备的片状氧化铁满足珠光颜料的要求.     

用作珠光颜料基材的片状氧化铝的制备

以十八水合硫酸铝作为铝源,采用熔盐法制备了片状六方形氧化铝晶体．通过激光粒度仪、XRD和光学显微镜等检测手段,系统考察了复合熔盐的用量,磷化剂的用量,钛盐的用量,煅烧过程的升温速率以及添加晶种等对晶体的生长过程的影响．研究结果表明：在熔盐与铝盐的比例为4,磷化剂的用量为1．0％,钛盐的用量为1．O％的情况下,可以制备出具有粒径为12μm的六角片状氧化铝．     

Preparation of SO4^2-/TiO2-La2O3 solid superacid and its catalytic activities in acetalation and ketalation

SO4^2- / TiO2-La2O3, a novel solid superacid, was prepared and its catalytic activities at different synthetic conditions are discussed with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. The optimum conditions have also been found, mole ratio of n（La^3＋）：n（Ti^4＋） is 1：34, the soaked consistency of H2SO4 is 0.8 tool/L, the soaked time of HESO4 is 24 h, the calcining temperature is 480 ℃, the calcining time is 3 h. Then it was applied in the catalytic synthesis often important ketals and acetals as catalyst and revealed high catalytic activity. Under these conditions on which the molar ratio of aldehyde/ketone to glycol is l： 1.5, the mass ratio of the catalyst used in the reactants is 0.5%, and the reaction time is 1.0 h, the yields of ketals and acetals can reach 41.4%-95.8%.     

Ethylene polymerization with novel silicon bridged homo-dinuclear cyanoethyl cyclopentadienyl complexes of titanium and zirconium

Novel homo-dinuclear silicon bridged cyanoethyl cyclopentadienyl complexes of titanium and zirconium (CH₃)₂Si((η⁵ ? C₅H₃CH₂CH₂CN)(C₅H₅)MCl₂)₂(M = Ti(1), Zr(2)) were synthesized and developed for the polymerization of ethylene. Compared with their corresponding mononuclear complexes (η⁵ ? C₅H₄CH₂CH₂CN)(C₅H₅)MCl₂(M = Ti(3), Zr(4)), the dinuclear complexes had higher catalytic activity. And the polyethylene produced had a higher molecular weight than that obtained with mononuclear catalysts. Effects of conditions on the ethylene polymerization catalyzed by (2)/MAO (methylaluminoxane) were studied in detail. The catalyst showed a very high activity (> 10⁶ g PE/mol Zr·h) under low catalyst concentration and high molar ratio of Al/Zr.     

Synthesis of novel electron donors and their application to propylene polymerization

A series of electron donors,including 1,1-cyclopentanecarboxylic acid diethyl ester (CPCADEE),1,1cyclopentanedimethanol acetic diester (CPDMAD),1,1-biethoxymethyl pentane (BEMP),2,2-diethyl diethylmalonate (DEDEM)and 2,2-diethyl-1,3-propanediol acetic diester (DEPDADE),were synthesized by diethyl malonate (DEM).The purities and structures of the above products were characterized by gas chromatography (GC) and gas chromatography-mass spectrometer (GC-MS),respectively.Furthermore,the possible optimal three-dimensional structures of these donors were simulated by means of Gaussian 03 and Chem 3D.Then these electron donors were coordinated with tetrachloro titanium (TiCl 4) and chloride magnesium (MgCl 2)to obtain the catalysts for the polymerization of propylene.The catalytic activities and properties of polypropylene are greatly improved by adding external donor(ED) when CPCADEE or DEPDADE is used as internal donor(ID).However,when BEMP was used as ID,the highest catalytic activity is obtained without adding ED,which can reduce production costs and simplify catalytic synthesis.The experiments indicate that BEMP has the shortest distance of oxygen atoms and the highest electronegativity.     

柠檬酸三辛酯（TOC）的催化合成研究

研究了几种固体酸催化合成柠檬酸三辛酯的催化活性。结果表明：四氯化锡的催化酯化活性最好,并讨论了以四氯化锡为催化剂时,醇酸物质的量比、催化剂用量、反应时间与酯化程度的关系,确定了合成柠檬酸三辛酯的最佳条件：醇酸物质的量比为5：1,催化剂用量为0.2g,反应时间为50min。在最佳条件下,酯化率可达95.58%。     

SO_4~(2-)/La_2O_3-ZrO_2-HZSM-5催化合成肉桂酸酯

首次将SO42-/La2O3-ZrO2-HZSM-5催化剂用于合成柠檬酸酯,合成了五种肉桂酸酯。考察了催化剂用量、醇酸比、反应时间等因素对酯化率的影响。结果表明:肉桂酸酯的酯化率最高可达93.6%,高碳醇的酯化率高于低碳醇的酯化率,且该催化剂具有良好的重复使用和再生能力。     

SO4^2--/La2 O3-ZrO2-HZSM-5催化合成柠檬酸酯

首次合成了固体超强酸催化剂SO4^2--/La2O3-ZrO2-HZSM-5,并用其合成了六种柠檬酸酯,分析了催化剂用量、焙烧温度、反应时间、醇酸比等因素对酯化率的影响。结果表明：500℃焙烧3 h所得催化剂活性最好,柠檬酸酯的酯化率可达91.5%以上,高碳醇的酯化率高于低碳醇的酯化率,且该催化剂具有良好的重复使用和再生能力。     

Screening study of transition metal oxide catalysts supported on ceria-modified titania for catalytic oxidation of toluene

Six transition metal oxides were added in ceria-modified titania using a sol-gel method for catalytic oxidation of toluene. An MnOx based catalyst was found to be the most active one, with which toluene could be decomposed completely at 200 °C. The greatest Mn/Ti and molar ratio of the mobile oxygen to the total oxygen concentration, together with a large surface area and a low reduction peak-starting temperature, would result in its best activity in toluene oxidation.