Cu/Zn/Ce/ZSM-5分子筛的碱改性及催化性能研究

采用NaOH溶液和金属离子(Cu~(2+)、Zn~(2+)、Ce~(4+))改性ZSM-5分子筛。通过SEM、XRD等表征手段,探讨NaOH溶液浓度、Cu/Zn/Ce物质的量比以及不同制备方法对ZSM-5分子筛形貌及性能的影响。以光催化辅助降解酸性大红GR模拟废水,考察改性后的ZSM-5分子筛的催化活性。结果表明,当NaOH溶液的浓度为0.2mol/L、Cu负载量为8%、Cu/Zn/Ce物质的量比为8∶4∶1、制备方法为溶胶-凝胶法时,分子筛的催化性能最佳,离子溶出量较小。     

Cu含量对Cu/ZSM-5催化剂氨选择性催化还原NO影响的研究

采用浸渍法将铜(Cu)负载在ZSM-5分子筛上,制备了一系列不同Cu含量的Cu/ZSM-5分子筛催化剂。对ZSM-5及Cu/ZSM-5分子筛催化剂的氨选择性催化还原一氧化氮(NO)性能进行评价,并对Cu/ZSM-5分子筛催化剂进行表征分析。结果表明,Cu含量变化对Cu/ZSM-5分子筛催化剂的氨选择性催化还原反应(NH3-SCR)活性影响较大,Cu含量为0.75%(wt,质量分数)制得的Cu/ZSM-5具有最佳的中低温活性,在190℃条件下对NO的转化率为91%。     

ZSM-5分子筛膜/SiSiC复合材料的制备与表征

以生物形态多孔木材SiSiC陶瓷为载体,采用二次生长法在其孔道内壁合成了薄且连续、致密的ZSM-5分子筛膜.采用SEM、EDX、BET对多孔ZSM-5/SiSiC复合材料进行了表征.研究结果表明,采用静电组装技术,在木材陶瓷孔道内表面形成了单层、致密的分子筛晶种层.在100℃水热合成48h可在SiSiC陶瓷孔道内壁形成平均厚度为120nm的ZSM-5分子筛膜,且很好地复制了陶瓷载体的孔道结构,表现为连续致密的管状结构.制得的分子筛陶瓷复合材料的BET比表面积、微孔体积、ZSM-5分子筛负载量分别为17.8m2/g、0.00413cm3/g、2.36%.延长水热合成时间并不能增加膜的厚度,但ZSM-5分子筛膜表面的n(SiO2):n(AL2O3)会降低.     

对NaZSM-5分子筛盐酸改性制备TiO2/ZSM-5光催化剂

用盐酸改性处理NaZSM-5得到HZSM-5分子筛载体,再用溶胶-凝胶法在NaZSM-5和HZSM-5表面合成TiO_2前驱体,将其煅烧制备出TiO_2/ZSM-5负载型光催化剂。分别用扫描电镜、X射线衍射、傅里叶变换红外光谱和BET氮吸附对光催化剂的表面形貌、晶相结构和比表面积进行表征,研究了NaZSM-5分子筛盐酸改性对TiO_2/ZSM-5光催化剂的影响。结果表明,盐酸改性对NaZSM-5分子筛骨架结构的影响不大,但是使其结晶度有所降低。负载后TiO_2的晶粒尺寸明显减小,TiO_2/ZSM-5光催化剂的比表面积比纯TiO_2有较大增长。对NaZSM-5分子筛盐酸改性提高了TiO_2/ZSM-5对甲基橙的吸附和光催化降解能力。重复使用四次后,TiO_2/ZSM-5光催化剂的光催化降解率下降为初次使用时的82.4%。     

ZSM-5分子筛膜/多孔SiSiC陶瓷复合孔结构微反应器的制备

以生物形态多孔SiSiC陶瓷为载体,采用原位水热法在多孔陶瓷微孔道内壁形成了一层2～5μm厚的b轴取向生长的ZSM－5分子筛膜. 利用XRD、SEM EDX、BET分析对复合材料的相组成、微观结构和比表面积进行了表征,研究了水热晶化时间、载体预处理对原位合成分子筛膜的影响. 结果表明,随晶化时间从5h增加到15h,从不连续的单层膜演变到～5μm厚的b轴取向的连续致密多层膜,该膜层是由粒径在1μm左右的ZSM-5分子筛颗粒堆积交联而成. 载体表面Si-OH浓度越高,分子筛膜和载体的结合力越强,但是较难控制分子筛膜的定向生长. ZSM-5/SiSiC复合孔结构材料的微孔体积为0.015cm3/g,BET面积为42.8m2/g,而相应的分子筛负载量为8.6%.     

非均匀沉淀法制备Cu包覆ZrW2O8复合粉体的研究

通过分部固相法制备ZrW2O8粉体。以ZrW2O8、CuSO4·5H2O（分析纯）和无水Na2CO3（分析纯）为原料，采用非均匀沉淀法制备了Cu包覆ZrW2O8复合粉体，并利用XRD、SEM、EDS测试手段，分析包覆粉的物相和形貌，研究了反应液浓度、表面活性剂、反应液滴加速度等反应条件对包覆效果的影响。研究表明：通过非均匀沉淀法可以制备Cu包覆ZrW2O8复合粉体，其关键是控制反应液的浓度和滴加速度，同时，不同分子量的表面活性剂对包覆前驱体的分散性影响很大．     

一步合成核壳结构ZSM-5/EU-1复合分子筛及其表征

在添加适量柠檬酸的条件下采用双模板剂一步法, 一次晶化合成ZSM-5/EU-1核壳共生复合分子筛, 对其物理化学性质进行表征, 结果显示: 核壳分子筛中存在ZSM-5和EU-1两种分子筛晶相, 且EU-1分子筛在ZSM-5分子筛表面缺陷处外延生长; 复合以后核壳分子筛为微孔-介孔多级孔道结构, 且其微孔孔径达到0.94 nm; 相比于单一分子筛, 核壳分子筛的强酸量相对提高, 酸性质有所改善。通过对柠檬酸加入量、晶化时间影响因素的分析, 得到合成核壳共生结构的最佳条件为: n(citrate)/n(Al₂O₃)=0.8~1.2, 晶化时间为72~96 h, 并推测核壳分子筛可能的生长过程。     

基于双模板剂B-EU-1/ZSM-5复合分子筛的合成与表征

首次在Na2O-SiO2-Al2O3-TPABr(四丙基溴化铵)-HMBr2(溴化六甲双铵)-H2O合成体系中,以溴化六甲双铵(HMBr2)和四丙基溴化铵(TPABr)为双模板剂,采用一步晶化法合成了具有微-微孔道结构的B-EU-1/ZSM-5复合分子筛,并通过XRD,FT-IR,SEM等手段对合成样品的物性进行表征;分析发现合成的复合分子筛同时具有ZSM-5和EU-1的特征衍射峰,结晶度较好,是两种晶相相互作用的分子分散晶相材料;通过合成条件的探究,发现复合分子筛的生长过程与两种模板剂的比例有关,在0.2n(四丙基溴化铵)/n(溴化六甲双铵)0.5的范围内是复合分子筛适宜的生长环境,得到合成的最佳条件为:n(四丙基溴化铵)/n(溴化六甲双铵)=0.4,晶化时间72h。     

Cu(Ⅰ)/AC(HZSM)吸附剂的制备及变压吸附CO的性能研究

选择活性炭(AC)或分子筛(HZSM-5)为吸附剂载体,采用等体积浸渍法制备Cu(I)/AC(HZSM)吸附剂.利用比表面积(BET)及H2程序升温还原(H2-TPR)表征手段.结合固定床评价了装置,研究了载体类型、预处理方法以及还原温度对吸附剂性能的影响.结果表明,以活性炭为载体时吸附性能优于分子筛为载体时的吸附性能;水洗处理降低了吸附剂的吸附能力;吸附剂原位活化还原温度过低不利于Cu2+→Cu+的还原,350℃时吸附剂的吸附性能最好.     

表面负载不同金属离子的活性炭吸附二苯并噻吩

主要研究活性炭表面负载不同金属离子以提高其对二苯并噻吩吸附性能.通过浸渍法制备5种负载过渡金属离子活性炭Ag(Ⅰ)/AC、Cu(Ⅱ)/AC、Ni(Ⅱ)/AC、Zn(Ⅱ)/AC和Fe(Ⅲ)/AC.用静态吸附法测定了二苯并噻吩在不同活性炭上的吸附平衡等温线,并应用软硬酸碱理论分析和讨论活性炭表面负载不同金属离子对二苯并噻吩吸附性能的影响.结果表明活性炭表面负载Ag ,Ni2 、Cu2 或Zn2 离子,可提高其对二苯并噻吩的吸附,而活性炭表面负载Fe3 ,反而降低了其对二苯并噻吩的吸附能力.由于Ag 价格昂贵,而Ni2 、Cu2 和Zn2 价廉易得,而且Zn(Ⅱ)/AC、Cu(Ⅱ)/AC和Ni(Ⅱ)/AC对二苯并噻吩又具有良好的吸附能力,故表面负载Ni2 、Cu2 和Zn2 可改善活性炭吸附脱除油品中有机硫化物的能力.     

酸碱复合处理制备多级孔ZSM-5分子筛及其甲醇制汽油反应性能

以商业ZSM-5分子筛为原料, 分别采用碱处理和酸碱复合处理法制备了多级孔ZSM-5分子筛。利用XRD、FT-IR、SEM、TEM以及氮气吸-脱附等手段对样品进行了表征, 并评价了样品的MTG反应性能。结果表明: 利用单纯碱处理或酸碱复合处理商业ZSM-5分子筛均可制备晶体内富含介孔和大孔的多级孔ZSM-5分子筛。与商业ZSM-5原料相比, 多级孔ZSM-5分子筛催化剂的介孔比表面积、介孔孔容以及酸性位“可接近性指数”等显著增加, 酸量明显减少, 酸强度降低。催化评价结果显示, 多级孔ZSM-5分子筛催化剂在大幅提高汽油产品收率、延长使用寿命的同时降低了芳烃收率。与碱处理样品相比, 酸处理能够进一步调节样品的酸性质和孔结构, 因此酸碱复合处理所得多级孔ZSM-5分子筛催化剂的物化性质和催化性能得以进一步提升。     

Investigation of the catalytic wet peroxide oxidation of phenol over different types of Cu/ZSM-5 catalyst

In this work oxidation of phenol with hydrogen peroxide on Cu/ZSM-5 catalysts was studied. The catalysts samples were prepared by two different methods: by ionic exchange from the protonic form of commercial ZSM-5 zeolite, and by direct hydrothermal synthesis. Characterization of the catalysts extends to X-ray diffraction (XRD), while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and the temperature range from 50 to 80 degrees C. The mass ratio of the active metal component on the zeolite was in the range of 1.62-3.24 wt.%. for catalyst prepared by direct hydrothermal synthesis and 2.23-3.52 wt.% for catalyst prepared by ion exchange method. The initial concentration of phenol and hydrogen peroxide was 0.01 and 0.1 mol dm(-3), respectively. The influence of different methods of Cu/ZSM-5 preparation on their catalytic performance was monitored in terms of phenol conversion and degree of metal leached into aqueous solution.     

甲醛湿式氧化催化剂的制备及性能研究

用FTIR和N2吸附法对活性炭进行表面分析,通过原子吸收光谱考察了铜在活性炭表面的吸附行为,制备了几种甲醛湿式氧化的催化剂,对比研究了它们在常温常压下对甲醛氧化的催化性能。结果表明,活性炭氧化改性后表面含氧基团增加,对铜和甲醛的吸附性能提高。活性炭表面负载的铜、银、铁对甲醛湿式氧化都有一定的催化能力,其中栽铜活性炭的催化效果最好,载铁活性炭的催化性能优于载银活性炭,催化动力学曲线表明,氧化改性后,载铜活性炭的催化性能进一步提高。     

汽相转化法制备纳米晶组成的块状ZSM-5多孔沸石

在ZSM-5沸石前驱体中加入羧甲基纤维素钠并制得干胶, 然后通过蒸汽相转化制得了大块状ZSM-5沸石。由于羧甲基纤维素钠与硅铝物种之间的相互作用干扰了沸石晶体的正常生长, 这种干扰所产生的“键阻断”作用导致合成的大块状ZSM-5沸石由100~150 nm的初级ZSM-5沸石晶体组成, 在这些初级粒子之间存在2~20 nm的二次介孔结构。异丙苯催化裂化结果表明, 由于纳米沸石具有较高的外表面积和较大的介孔孔容, 比参比催化剂表现出更高的异丙苯转化率。     

Photo-degradation of acid green dye over Co-ZSM-5 catalysts prepared by incipient wetness impregnation technique

Co-ZSM-5 catalysts with different Co-loadings (2-30wt.%) were prepared by incipient wetness impregnation method. The prepared solid catalysts were characterized by X-ray diffraction, FTIR, in situ FTIR of pyridine adsorption and surface area measurements. The XRD data presented disintegration in the zeolitic crystalline structure accompanied by an increase in particle size of the prepared solids. New phases, Co(3)O(4) and Co(2)SiO(4), were detected with increasing the Co-loading, which indicate the strong interaction of cobalt ions with the ZSM-5 zeolite. FTIR study proved the presence of Co ions in stabilized sites inside the ZSM-5 framework. The in situ FTIR of adsorbed pyridine determined the type and relative strength of acidity on the surface of the prepared solids. The acidity switched from B-acid sites to L-acid sites with impregnation of cobalt ions in ZSM-5 zeolite. The acidity decreased with increasing Co-loading, which might be due to the destruction of zeolite framework and presence of new phases such as cobalt silicate and cobalt oxide on the surface. The surface texture characteristics changed with the promotion of ZSM-5 by cobalt ions, since a decrease of surface area, mean pore radius and pore volume was observed. The assessment of the catalytic activity was performed by the use of the photo-degradation of acid green (AG) dye as a probe reaction in presence of H(2)O(2) as an oxidant. The pH value controlled the degradation rate since a gradual increase of AG degradation rate was observed with increasing pH value and the optimum H(2)O(2) concentration was 61.6 mmol/l. It was found that, the AG degradation rate increased until an optimum value of Co-loading (ca. 10 wt.%), beyond which a monotonic decrease of reaction rate was recognized. The experimental data pointed to the importance of both the cobalt moieties and the zeolite framework structure in the AG degradation reaction.     

ZSM-5 zeolite modified with vanadyl ions

Properties of the ZSM-5 zeolite modified with VO²⁺ ions in a one-step exchange reaction in water medium have been investigated. Physicochemical characterization (chemical analysis, XRD, MAS n.m.r., e.s.r.) shows that during the preparation the ZSM-5 zeolite structure remains preserved and the vanadyl ions enter the zeolite structure. Sample acidity is of Brönsted and Lewis types and can be reduced by treatment with NaCl solution. Doping with vanadyl ions produces catalysts active in ammoxidation of m-xylene.     

Phosphoric acid modified-Y zeolites: a novel, efficient and versatile ion exchanger

Large pore HY zeolite was modified with phosphoric acid by wet method. The modified zeolite was converted to Na(+) form using aqueous NaHCO(3) solution(.) The Na(+) form of modified zeolite, represented as PNa(2)Y, was characterized by XRD, BET surface area, SEM, and AAS techniques. The XRD analysis showed diffraction patterns same as that of parent HY zeolite, as a result there has been no structural degradation during modification. It was then tested for sorption of Cu(2+) ions from aqueous solution. The Cu(2+) content of the solution was analyzed by AAS. PNa(2)-Y shows higher sorption capacity ( approximately 40%) than the parent Na-Y ( approximately 23%) zeolite, which is attributed to the double of amount Na(+) content in PNa(2)-Y compared to the Na-Y zeolite. Equilibrium modeling data were found to fit more to the linear Langmuir model than the Freundlich model. The thermodynamic parameters such as change in free energy (DeltaG degrees ), enthalpy (DeltaH degrees ), and entropy (DeltaS degrees ), were also calculated. These parameters confirmed that the sorption of Cu(2+) is feasible, spontaneous and endothermic.     

A novel method for the growth of ZSM-5 zeolite membrane on the surface of stainless steel

Thin ordered micropore ZSM-5 zeolite membrane has formed on the stainless steel surface. The influence of three different pre-treatment methods for the growth of ZSM-5 zeolite membrane on the stainless steel was studied, including mechanical polishing, soaking in a 20 wt.% sulfuric acid aqueous solution and anodic oxidation treatment. It was found that the anodic oxidation technique was more favorable for the growth of ZSM-5 zeolite membrane on the stainless steel surface compared with the other two methods. By this appropriate pre-treatment process, ordered ZSM-5 zeolite membrane was immobilized on the stainless steel surface and it showed good interaction with the stainless steel. Energy-dispersive X-ray (EDX) spectroscopy result indicates that the ZSM-5 zeolite membrane has a Si/Al ratio of 37. X-ray diffraction (XRD), N₂ adsorption and scanning electron microscopy (SEM) were used to study the crystal structure, specific surface area and morphologies of the ZSM-5 zeolite membrane.     

The use of natural Kazakhstan zeolites for the development of gas purification catalysts

The results of investigation of catalysts based on natural zeolite in comparison with synthetic ZSM-5 zeolite used in reduction of nitrogen oxides and conversion of carbon monoxide are presented. It was found that rearrangement of the crystal structure of natural zeolite begins upon heating it above 500 °C in air. The structure of natural zeolite has been improved by introduction of various modifiers and selection of thermal regime of samples training. It has been shown that developed compositions of press-mass for preparation of carriers for gas purification catalysts in the form of granules and tablets satisfy the requirements on ductility and mechanical strength. The efficiency of synthesized granular and block Cu–Ce, Cu–Ni–Cr, Ti–V, Ti–VW, and TiO₂–V₂O₅ catalysts based on natural and synthetic zeolites was determined in conversion of CO and nitrogen oxides. The results of X-ray structure analysis of clinoptilolite of the Republic of Kazakhstan deposits—Chankanai and Taizhuzgen—are represented in comparison with synthetic ZSM-5 zeolite. The paper also comprises data about their thermal stability, ductility, and strength of compositions on their base. Metals particles morphology and dispersity are studied by the method of electronic microscopy. These particles were used as active components of synthesized catalysts.