纯固体配料体系中不同碱金属卤化物对ZSM－48沸石合成及性质的影响 Ⅱ．不同卤化钾的影响

纯固体配料体系中引入碱金属钾的不同卤化物ＫＸ（Ｘ＝Ｆ~－，Ｃｌ~－，Ｂｒ~－，Ｉ~－）对ＺＳＭ－４８沸石的晶化和性质有着显著的影响。ＸＲＤ测试结果表明：引入不同的卤化钾对合成沸石的结构基本没有影响，但均大大降低了沸石的晶化速率。通过等离子光谱和ＸＰＳ测试发现沸石的体相硅铝比基本相同，但沸石表面的硅铝比显著不同。合成体系中引入一定量的ＫＩ很难合成ＺＳＭ－４８沸石，或者需要很长时间才能合成，引入ＫＦ和ＫＢｒ不利于生成稳定的产物。ＴＧ／ＤＴＡ表明引入不同的卤化钾强烈影响着产物的热性质。ＳＥＭ测试表明产物的晶体形貌和晶粒大小与卤化钾的类型有关。     

QUICK SYNTHESIS OF ZSM-48 BY DIRECT TiO_2 ADDITION IN A SOLID REACTION MIXTURE SYSTEM

IntroductionZeoliteZSM-48wasfirstsuccessfullypreparedfromthehydrothermalanddouble-aminenoneque0ussysteminl980s[l'2].Rccently,ithasbeensynthesizedinapuresolidsysteml3].Comparedwlththcpreviousmcthods,synthesisofZSM-48inapuresolidsystem,orsolidreactionmixturesystem,cangreatlyincreasetheyteldofproductsperunitvolume,sirnplifythesynthesisproceduresanddecreasetheenvironmentalpollution.However,ittakesmoretimetocompletecrystalIiZationthantheOthersdo.Therefore,itisnecessarytostudyhowthecrystallizati…     

Synthesis of high-silica EU-1 zeolite in the presence of hexamethonium ions: a seeded approach for inhibiting ZSM-48

A seeded approach was developed to synthesize high-silica EU-1 zeolite via inhibiting the co-crystallization of ZSM-48 in the presence of hexamethonium (HM) ions. A systematic study was carried out to determine factors such as seed content and SiO(2)/Al(2)O(3) ratio, which influenced the crystallization of high-silica EU-1 and transformation of EU-1 into ZSM-48. Using EU-1 seeds, not only well-crystallized pure EU-1 zeolites with SiO(2)/Al(2)O(3) ratios more than 500 were synthesized, but also the co-crystalline of ZSM-48/EU-1 or pure ZSM-48 was obtained in control from silica-rich mixture gels. Furthermore, the kinetic features of the seeded synthesis of EU-1 zeolites with SiO(2)/Al(2)O(3) ratios of 55, 190, and 500 were examined. It was found that seeds played crucial roles in the decrease of apparent activation energy of EU-1 nucleation and inhibiting the transformation of EU-1 into ZSM-48. The HM and Al species performed synergistic roles to inhibit the formation ZSM-48 during high-silica EU-1 nucleation and crystal growth.     

纳米NaY分子筛的合成及其催化柴油加氢改质性能

在系统考察添加阳离子表面活性剂、凝胶陈化以及晶化温度和晶化时间等因素对NaY分子筛细化影响的基础上,对纳米NaY分子筛的合成规律进行了研究;合成出了n(SiO2)/n(Al2O3)=4.5,BET比表面积为620m2/g,孔容为0.34 cm3/g,微孔集中分布在0.55 nm附近,粒度分布范围在100 nm以内的纳米NaY分子筛.并采用XRD、BET、IR、TTEM和NH3-TPD等手段系统表征了纳米NaY分子筛的微观结构.分别采用合成的纳米NaY分子筛和微米NaY分子筛为原料制备负载型Ni-Mo-P催化剂,并以FCC柴油为原料,考察了催化剂的加氢改质性能,结果表明,与微米NaY分子筛基负载型Ni-Mo-P催化剂相比,纳米NaY分子筛基负载型Ni-Mo-P催化剂,在加氢脱氮率、密度和十六烷值相当的情况下,其加氢脱硫率较高,柴油收率较高.     

Effects of ammonium exchange and Si/Al ratio on the conversion of methanol to propylene over a novel and large partical size ZSM-5

One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on the reaction of methanol to propylene (MTP) over Na-ZSM-5 and H-ZSM-5 zeolites have been studied in a fixed-bed flow reactor under the operating conditions of T = 500 °C, P = 1 atm, and WHSV = 6 h-1. Ammonium exchange led to a rapid decrease in Na content for Na-ZSM-5 zeolite. The reaction results indicated that Na-ZSM-5 and H-ZSM-5 with different SiO2/Al2O3 molar ratios all exhibited high activity for methanol conversion. Ammonium exchange and the decreased SiO2/Al2O3 molar ratio of ZSM-5 zeolite led to an increase both in strong acid sites and weak acid sites. Na-ZSM-5 with high SiO2/Al2O3 molar ratio was favorable for the formation of propylene. The highest propylene selectivity (45.9%) was obtained over Na-ZSM-5 zeolite catalyst with SiO2/Al2O3 molar ratio of 220.     

CF-2沸石的表面酸性及催化性能

CF-2是一种新型的高硅沸石。1981年我们实验室首先在二乙醇胺-甘油-Na₂O-SiO₂-Al₂O₃-H₂O体系中制备成功^[1],以后才见到关于Theta-1^[2],ISI-1^[3],KZ-2^[4],NO-10^[5]和ZSM-22^[6]沸石的报道。     

以环己胺为模板剂的ZSM－35分子筛的合成及其催化性能

 采用环己胺为有机模板剂成功地合成出ZSM－35分子筛．反应釜的转速对ZSM－35的晶化过程有明显的影响．NH3－TPD结果显示ZSM－35的酸性分布与ZSM－5分子筛类似，但ZSM－35具有强于ZSM－5的酸性中心．酸碱浸泡试验及热分析结果表明ZSM－35具有良好的耐酸碱性和热稳定性．在连续流动的固定床反应装置上，将担载少量镍的ZSM－35分子筛催化剂用于催化裂化汽油的加氢异构化反应，结果表明，Ni／ZSM－35催化剂可降低汽油中的烯烃含量，增加异构烷烃和芳烃的含量，从而提高汽油的质量．     

TEAOH-TMABr-Al2O3-SiO2-H2O体系中小晶粒offretite沸石的合成研究

不加无机强碱，在纯有机胺体系中合成了小晶粒offretite沸石，并采用XRD、SEM、FT-IR以及苯与丙烯烷基化制异丙苯探针反应对典型样品进行了结构性能表征。结果表明，采用四乙基氢氧化铵TEAOH与四甲基溴化铵TMABr为双模板剂时，TEAOH的量对合成产物影响很大，而TMABr的量增大容易导致生成Beta沸石。所合成的offretite沸石在苯与丙烯烷基化制异丙苯反应中活性和选择性较高。     

晶化时间对ZSM-5分子筛物化性质及催化性能的影响

 考察了ZSM－5分子筛在晶化过程中的变化规律及其在苯与乙烯气相烷基化制乙苯反应中的催化性能．结果表明,当晶化时间为70h时,分子筛晶体开始出现;晶化90h时无定形物相基本消失．晶化时间从90h再延长至150h,ZSM－5分子筛晶粒的大小、形貌和体相硅铝比都基本不变,但分子筛表面的硅铝比逐渐降低．以晶化时间为90h的ZSM－5分子筛原粉为活性组元制备的催化剂,对苯与乙烯气相烷基化制乙苯反应表现出最佳的催化性能．     

超微NaY分子筛的合成(Ⅱ)——添加铝络合剂的影响

NaY分子筛合成体系中添加铝的络合剂(乙二胺四乙酸、柠檬酸和醋酸),可有效地减小分子筛的晶粒尺寸及增加分子筛的晶化速度和SiO2/Al2Oa物质的量比.在添加柠檬酸的合成体系中,考察了柠檬酸的添加量对NaY分子筛晶化行为的影响.发现存在着一个最佳的柠檬酸的添加量范围,即n(柠檬酸)：n(氧化铝)≤2：1,在此范围内,NaY的晶化速率和硅铝比较高,而晶粒尺寸较小.     

低硅铝比ZSM-48分子筛合成及其正构十二烷临氢异构催化性能研究

通过静态水热合成法,溴化六甲二铵作为结构导向剂合成出系列低硅铝比的ZSM48沸石分子筛(Si/Al100),所合成样品中最低硅铝比为38.6(ICP-AES),这将拓宽ZSM-48高硅沸石分子筛的应用范围。制备Pt负载双功能催化剂,用于正构十二烷临氢异构催化反应。结果表明,硅铝比的改变可以影响催化剂的活性,投料硅铝比为70的双功能催化剂具有最优的催化性能,但硅铝比改变对异构产物的分布没有明显的影响,其异构产物以支链在中间位的异构体为主。     

无粘结剂ZSM-11催化剂上异丁烯直接胺化生成叔丁胺

叔丁胺是一种重要的化工原料和中间体,广泛应用于制备橡胶促进剂、医药、农药和着色剂等下游产品.异丁烯在分子筛催化剂上直接胺化生产叔丁胺是一个经济环保过程,其中ZSM-5和BEA分子筛的催化性能优于其它系列分子筛.ZSM-11与ZSM-5分子筛具有相似的孔道结构,我们以前的实验结果表明,与ZSM-5相比,ZSM-11表现出更优越的芳构化反应性能,在干气中乙烯低温芳构化方面也有明显优势.在此基础上,我们进行无粘结剂ZSM-11分子筛催化剂合成,并应用于异丁烯直接胺化生产叔丁胺反应.传统水热技术合成的分子筛通常为粉末,机械强度不能达到实际应用的要求,在工业化过程中分子筛粉末一般需要加入粘结剂成型使其具备一定的机械强度和形状,但是粘结剂会降低分子筛催化剂的活性和选择性,有可能会引发一些副反应,因此无粘结剂分子筛催化剂引起人们广泛关注.无粘结剂分子筛是指分子筛颗粒中不含惰性粘结剂或只含有少量粘结剂,主要依靠分子筛晶粒间的相互作用支撑存在,具有一定形状、尺寸和机械强度的催化材料.无粘结剂分子筛催化剂中分子筛含量较高,可利用的有效表面积较大,在离子交换及工业催化等方面具有明显优势.本文采用水热合成的ZSM-11分子筛原粉与二氧化硅机械混合(ZSM-11/SiO2=70/30)挤条后,通过气固相合成法制备了无粘结剂ZSM-11分子筛催化剂(Cat-C).作为对比,还分别制备了ZSM-11和SiO2机械混合(ZSM-11/SiO2=70/30)样品HZSM-11+SiO2及ZSM-11和氧化铝机械混合(ZSM-11/Al2O3=70/30)样品HZSM-11+Al2O3.利用X射线衍射、透射电镜、NH3程序升温脱附和吸附吡啶红外光谱等对分子筛催化剂的物理化学性能进行了表征.同时,以这些分子筛样品为催化剂,在固定床反应装置上进行了异丁烯胺化反应评价,反应条件为270℃,5.0 MPa,氨烯比为4和异丁烯空速0.5 h?1.结果表明,与HZSM-11+SiO2和HZSM-11+Al2O3相比,Cat-C上叔丁胺生成速率最高.关联催化剂物化性能和反应性能发现,催化剂孔道结构与叔丁胺生成并不存在明显的关联性,而较多的Br?nsted酸和较少的Lewis酸才是Cat-C具有良好反应性能的主要原因.具有一定机械强度的无粘结剂ZSM-11分子筛催化剂制备简单,在异丁烯直接胺化过程中叔丁胺生成速率高,具有很好的工业化应用前景.     

Dealuminated ZSM-5 Zeolite Catalyst for Ethylene Oligomerization to Liquid Fuels

Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Bronsted acid sites in the formation of higher hydrocarbons. The oligomerization of olefins, dependent on the acidity of ZSM-5 zeolite, is an important step in the conversion of natural gas to liquid fuels. The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst. ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios. The FT-IR analysis revealed that the integrated framework aluminum band, non-framework aluminum band, and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated. The performance of the dealuminated zeolite was tested for ethylene oligomerization. The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion, but the gasoline selectivity was reduced compared to the performance     

混合胺体系中 MCM-49/ZSM-35 复合分子筛的晶化过程

 采用 X 射线衍射、N2 吸附-脱附、扫描电镜和傅里叶变换红外光谱等技术, 研究了 MCM-49/ZSM-35 复合分子筛在 Na2O-SiO2-Al2O3-CHA (环己胺)-HMI (六亚甲基亚胺)-H2O 合成体系中, 先在低温 80 ?C 老化 4 h, 再经 160 ?C 晶化不同时间的演变过程. 结果表明, 在该混合胺体系中, 首先生成 MCM-49 分子筛, 随着晶化时间的延长, 形成 ZSM-35 含量逐渐增加的 MCM-49/ZSM-35 复合分子筛, 最后生成纯 ZSM-35 分子筛; ZSM-35 的生成是以 MCM-49 分子筛的消耗为代价的.     

Design of effective zeolite catalysts for the complete hydrogenation of CO2

Ab initio molecular orbital calculations have been applied to the study of the three-stage zeolite-catalyzed hydrogenation of CO2 to methanol. The results present strong evidence that appropriate chemical modifications to ZSM-5 can lead to significantly lower energy barriers for the three component reactions, that is, hydrogenation of CO2, HCO2H, and CH2O. Zeolites incorporating either Na+ or Ge are more effective catalysts than conventional acidic zeolites for the hydrogenation of CO2 to give HCO2H, but amine-based zeolites do not lead to significantly lower barriers for any of the three hydrogenation reactions. However, we predict that when all three features, namely, Na+, N, and Ge, are incorporated in the zeolite, there is a dramatic improvement in catalytic activity for all three reactions.     

(K,Mo)Y分子筛中钼组分的EXAFS研究

应用同步辐射Extended X-ray Absorption Fine Structure (EXAFS)技术研究固态法制备的KHMoY分子筛的氧化态和硫化态样品以及硫化态KHY/MoO3样品中钼组分的局域配位环境结构,并与KHMoY和KHY/MoO3样品催化加氢活性结果进行对照.结果表明,随原子比(K+2Mo)/Al的变化,钼原子周围的配位环境有显著的差异.当(K+2Mo)/Al＜1时,KHMoY和KHY/MoO3硫化后,钼组分主要以MoS2小原子簇分散在分子筛超笼中;(K+2Mo)/Al＞1时,钼组分则有两种存在环境,即分子筛超笼中的和分子筛外表面的钼组分.分子筛超笼中的MoS2原子簇的催化加氢合成醇选择性较高;分子筛外表面的MoS2微小颗粒的尺寸相对于超笼中的要大许多,其合成醇选择性较低.     

ZSM－35分子筛的合成及模板效应的研究

以1,6-己二胺为模板剂合成了ZSM-35分子筛,通过对比ZSM-35、ZSM-5和丝光沸石的合成条件,采用化学组成分析、热重分析及¹³CNMR等技术研究了1,6-己二胺和乙二胺的模板效应。结果表明,二者均对ZSM-35有较好的模板作用,而1,6-己二胺对ZMS-5的模板效应更佳。     

Dealuminated ZSM—5 Zeolite Catalyst for Ethylene Oligomerization to Liquid Fuels

Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Broensted acid sites in the formation of higher hydrocarbons,The oligomeriztion of olefins,dependent on the acidity of ZSM-5 zeolite ,is an important step in the conversion of natural gas to liquied fuels,The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst,ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios,The FT-IR analysis revealed that the integrated framework aluminum band,non-framework aluminum band,and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated,The performanc of the dealuminated zeolite was tested for ethylene oligomerization.The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion,but the gasoline selectivity was reduced compared to the performance of a ZSM-5 zeolite ,The characterization results revealed the amount of aluminum in the zeolitic framework,the crystallinity of the ZSM-5 zeolite,and the Si/Al ration affected the formation of Broensted acid sites,The number of the Broensted acid sites on the catalyst active sites is important in the olefin conversion to liquied hydrocarbons.     

低硅铝比ZSM-5分子筛上C4烃的催化裂解反应

以低硅铝比(n(SiO2)/n(Al2O3)=20-45)的ZSM-5分子筛为催化剂, 研究了混合C4烃的催化裂解反应, 并对不同硅铝比的ZSM-5分子筛进行了酸性表征. 混合C4烃的催化裂解反应结果表明, 低硅铝比的ZSM-5分子筛具有较高的低温催化活性, 高硅铝比ZSM-5分子筛催化剂上乙烯和丙烯的收率高于低硅铝比ZSM-5分子筛催化剂, 低硅铝比ZSM-5分子筛上苯和甲苯的收率高于高硅铝比ZSM-5分子筛催化剂. 在反应温度为625 ℃时, 硅铝比为20的ZSM-5分子筛催化剂上乙烯、丙烯、苯和甲苯的总收率可达79.42%. 酸性表征结果表明, 硅铝比低的ZSM-5分子筛具有更多的Bronsted(B)酸酸量、Lewis(L)酸酸量及总酸酸量, 这是低硅铝比ZSM-5分子筛具有低温高活性及高的苯和甲苯收率的原因.     

不同硅铝比ZSM-5分子筛作为助催化剂在渣油裂化中的应用

采用不同方法表征了硅铝比(SiO2/Al2O3)为33、266和487的质子型ZSM-5分子筛,并研究了ZSM-5分子筛作为助催化剂在渣油裂解中的应用。与USY分子筛基催化剂混合后,在固定流化床上,评价了ZSM-5分子筛助催化剂的催化裂化性能。研究发现,提高ZSM-5分子筛硅铝比,可以有效抑制混合催化剂对汽油烯烃的裂解,从而避免了汽油烷烃的大量损失。加入ZSM-5助催化剂后,伴随着液化气(LPG)产率的增加,异丁烷和异戊烷产率增加,这可能是由USY基催化剂和ZSM-5助催化剂的综合效应引起的。汽油烷烃和芳烃含量的变化,引起了汽油辛烷值的增加。高硅铝比ZSM-5分子筛(硅铝比为266和487)不仅可以显著改善汽油的辛烷值,而且有效避免了汽油的大量损失。催化汽油辛烷值的改善主要是由于高硅铝比ZSM-5分子筛具有适宜的芳构化和异构化活性,这些变化主要源于高硅铝比ZSM-5分子筛小的孔道直径和适宜的酸性。