纳米Beta沸石的合成与表征及催化苯和丙烯烷基化性能

合成了纳米Beta沸石,并采用X射线衍射(XRD)、透射电镜(TEM)、比表面(BET)、程序升温脱附(NH3-TPD)以及吡啶-红外光谱(Py-IR)等方法对其结构和酸性进行了表征。比较了纳米Beta和常规大晶粒Beta沸石的催化性能,对纳米Beta沸石催化烷基化的关键参数进行了优化。结果表明:在硅铝物质的量比为25~30时,所合成的纳米Beta沸石具有较高的结晶度,晶粒尺寸在20 nm左右。同常规Beta沸石相比,纳米Beta沸石具有更大的BET比表面积和孔容,其比表面积可达600 m2/g,总孔容达0.42 cm3/g,介孔和大孔贡献超过50%。纳米Beta沸石具有较高的总酸量和B酸含量。作为苯和丙烯的烷基化催化剂,纳米Beta沸石具有更好的反应稳定性和选择性。在苯烯比3.0,反应温度150~160℃的条件下,异丙苯选择性可达89%,杂质正丙苯含量可降到极低水平。在工业试验中,纳米Beta沸石也表现出良好的综合性能,催化剂的稳定性和选择性优于同类Beta沸石催化剂。     

改性ZSM-5催化剂上苯与FCC干气中乙烯气相烷基化反应

考察了经过改性的ZSM-5沸石和参比催化剂催化苯与流化催化裂化(FCC)干气中乙烯的气相烷基化反应.结果表明,改性ZSM-5催化剂的乙基化选择性高于参比催化剂,产物中的二甲苯和总杂质含量小于参比催化剂,稳定性优于参比催化剂.通过考察比较改性ZSM-5沸石催化剂与参比催化剂在苯与稀乙烯气相烷基化反应的工艺条件,获得了匹配于该改性ZSM-5沸石催化剂的较佳工艺条件:反应温度350～380℃,反应压力0.5～0.9 Mpa.苯烯物质的量比4.0～7.0,乙烯空速0.4～0.7 h-1.并在选定的优化工艺条件下分别对改性催化剂和参比催化剂进行了1 000 h的寿命实验.结果显示,在1 000 h寿命实验内,反应产物中乙苯含量没有下降的趋势,改性催化剂和参比催化剂的乙烯转化率分别为99.99%和99.96%,乙基化选择性分别为80%和77%,二甲苯含量分别为871和2 223 mg/kg左右.     

无粘结剂MCM-22分子筛催化剂制备及其催化性能

采用NaOH溶液对含粘结剂的成型工业MCM-22分子筛催化剂进行后处理以脱除粘结剂,制备无粘结剂MCM-22分子筛催化剂,并实验考察了碱浓度、处理时间对催化剂的强度、活性组分的含量、酸量及催化性能的影响。结果表明:在NaOH溶液的质量分数为0.3%、150℃的条件下对圆柱形含粘结剂MCM-22分子筛催化剂处理4h,即可制得无粘结MCM-22分子筛催化剂。在苯与乙烯液相烷基化反应中,在苯与乙烯物质的量比为3.0,乙烯质量空速为9.0h~(-1),温度200℃,压力3.5 MPa的反应条件下,无粘结剂MCM-22分子筛催化剂的乙烯转化率维持在60%以上,催化性能与分子筛原粉相当,明显优于含粘结剂的催化剂(低于40%),且其强度能够满足工业应用的要求。     

MCM-22、MCM-49、β及Y分子筛在苯液相烷基化合成乙苯反应中的应用

采用10 L高压反应釜动态水热合成了 MCM-22、MCM-49及β分子筛,并利用X射线衍射(XRD)、NH_3-程序升温脱附(NH_3-TPD)、X射线荧光(XR F)、N_2-吸附脱附(BET)等手段对其结构物性进行了表征测试。考察了上述分子筛催化剂在苯和乙烯液相烷基化合成乙苯反应中的催化性能,并与进口Y分子筛进行了对比。结果表明,在n(苯):n(乙烯)=2.6、t=210℃、p=3.4 MPa条件下,MCM-22分子筛催化性能优于Y、MCM-49、β分子筛,其乙烯转化率与β分子筛相当,大于99%;同时获得最高的乙苯选择性(84 %),连续反应60 h催化性能稳定。     

CF-Mg分子筛的微波合成及催化性能研究

采用微波水热法合成了含Mg的磷铝结构单元MCM-41分子筛。考察了晶化温度和酸处理等因素对分子筛合成和性能的影响,通过XRD、NH₃-TPD、TEM和IR等分析手段对合成的样品进行表征。结果表明,当晶化温度为90 ℃时,合成的样品具有核壳结构和MCM-41特有的六方排列的孔道结构,酸处理和杂原子的掺入显著提高复合分子筛的酸性。含Mg的磷铝结构单元MCM-41分子筛催化苯与十二烯的烷基化反应时,十二烯的转化率可达到99%以上,2-十二烷基苯的选择性达到20%以上。     

甲苯甲醇烷基化合成对二甲苯催化剂研究进展

甲苯甲醇烷基化是新型高选择性合成对二甲苯的方法,可以解决石化行业甲苯和甲醇过剩问题,具有较高的工业开发价值。在具有B酸中心及特殊孔结构的分子筛催化下,甲苯甲醇发生苯环上亲电取代反应得到对二甲苯。甲苯甲醇烷基化催化剂主要有Y沸石催化剂、SAPO及MCM-22和ZSM-5分子筛催化剂等,研究较多的是ZSM-5分子筛催化剂。通过对ZSM-5分子筛进行金属、非金属或复合改性后,可以显著提高烷基化反应转化率和选择性。未来研究的主要目标是获得选择性高且稳定性好的催化剂。     

MCM-22沸石催化剂的苯与长链烯烃烷基化性能

用NH3-TPD法研究了4种不同硅铝摩尔比的MCM-22沸石的酸性质,在常压间歇式反应器中考察了它们在苯与长链烯烃烷基化反应中的催化性能,并与HY和HZSM-5沸石催化剂进行了比较。实验结果发现MCM-22的催化活性与其强酸量有一致的关系,与其硅铝摩尔比无对应关系;MCM-22的活性比HY低,但对2-P的选择性远远高于HY,这说明了MCM-22对2-P具有形状选择作用。     

苯和乙烯一步法合成苯乙烯反应研究

首次采用苯和乙烯在无氧存在下, 于多种固体酸和金属负载HZSM-5分子筛催化剂上反应直接得到苯乙烯与其它固体酸相比, HZSM-5分子筛催化剂表现出最高的反应活性和较高的对苯乙烯的选择性。HZSM-5分子筛负载不同金属后, 苯乙烯的选择性均有明显提高, 其中以Co/HZSM-5、Fe/HZSM-5和Pd/HZSM-5催化剂显示出较高的反应活性和苯乙烯选择性。反应温度、苯烯比、金属负载量、液空速、催化剂的焙烧及还原温度均会不同程度地影响反应转化率和产物分布。     

无硼体系MCM-22分子筛的合成

以哌啶(PI)为模板剂,在不添加晶化助剂下,采用动态水热晶化法合成MCM-22分子筛,考察了晶化时间、PI和Si O2、OH-和Si O2、Si O2和Al2O3的物质的量之比等对晶化产物的影响,结果表明,PI和Si O2,OH-和Si O2,Si O2和Al2O3的物质的量之比为0.50~0.70,0.09~0.10和30~40,晶化时间48~72 h的条件下,能较好地合成MCM-22分子筛。在苯与乙烯液相烷基化制乙苯反应中,以哌啶为模板剂与采用六亚甲基亚胺为模板剂合成的MCM-22分子筛的催化性能相当。     

制备条件对MCM-22分子筛催化异丁烯气相齐聚性能的影响

以六亚甲基亚胺为模板剂,硅溶胶为硅源,偏铝酸钠为铝源,采用动态水热法合成了MCM-22分子筛,并考察了MCM-22分子筛的Si与Al之比和制备条件对其催化异丁烯气相齐聚反应性能的影响.结果表明:Si与Al之比对其催化性能影响较小;MCM-22分子筛适宜的制备条件为晶化温度175 ℃、晶化时间72 h、焙烧温度500 ℃和离子交换浓度2 mol/L.异丁烯气相齐聚反应的实验结果表明, MCM-22分子筛具有较好的异丁烯齐聚活性,在反应温度225 ℃和体积空速240 h-1条件下, 异丁烯转化率大于50%,C8烯烃选择性大于95%.     

MCM-22、MCM-49和MCM-56三种分子筛的合成

MWW结构分子筛是一类新型的催化材料,具有独特的10元环孔道和12元环孔穴结构,在多种反应中表现出良好的催化活性。以六亚甲基亚胺作为模板剂,合成了MCM-22、MCM-49和MCM-56三种分子筛,并详细考察了不同硅源、凝胶配比、晶化温度和晶化时间对合成过程的影响。结果表明,凝胶配比和晶化温度对分子筛物相的影响较大。以硅胶粉为硅源,无论在何种晶化时间下都不能得到MCM-56,只能合成出MCM-49。而以碱性硅溶胶为硅源,在较短的晶化时间内就可以得到MCM-56。     

动态法合成MCM-22分子筛及其表征

以六亚甲基亚胺(HMI)为模板剂,采用动态水热晶化法合成出MCM—22沸石分子筛。采用XRD表征对其进行物相分析;采用氨脱附—程序升温脱附(NH3—TPD)法表征其酸性质。结果表明:合成过程中易生成混晶,而适宜的SiO2/Al203比和碱度可以合成出比较纯的MCM—22分子筛。采用常规的离子交换方法可以将其转变为氢型样品。     

Influence of synthesis method on the properties and catalytic performance of MCM-49 zeolites

Highly crystalline and pure MCM-49 was hydrothermally synthesized by dynamic and static methods, respectively. The properties of the samples were studied by N₂ adsorption, XRD, TEM and FT-IR techniques. The results indicated that MCM-49 synthesized by dynamic method showed much smaller crystal and lower concentration of acid sites. The Pd-supported catalyst on MCM-49 synthesized by static method showed higher acetone conversion in one-step synthesis of methyl isobutyl ketone from acetone, which was attributed to higher concentration of acid sites. While the higher selectivity to methyl isobutyl ketone for Pd-supported on MCM-49 synthesized by dynamic method might be related with the lower acidity and higher BET surface area.     

Synthesis, characterization and catalytic properties of MCM-36 pillared via the MCM-56 precursor

Pillared layered MCM-36 zeolite (MCM-36-I) was successfully synthesized from MCM-56 precursor with polymeric silica as the pillaring agent. The structure and properties of the sample was characterized by means of N₂ adsorption, XRD, TEM and IR spectroscopy of pyridine adsorption. The results showed that MCM-36-I has higher external surface area and more Brönsted acidic sites on external surface than that on the MCM-36 sample (MCM-36-II) which was synthesized from layered MCM-22 precursor. The catalytic properties of these samples were tested for alkylation of benzene with isopropanol. Compared with MCM-36-II catalyst, MCM-36-I showed higher conversion of benzene and selectivity to cumene. This should be mainly assigned to the fact that MCM-36-I possesses larger amount of accessible Brönsted acid sites which located on the external surface than that of MCM-36-II.     

PEG2000对MCM-22分子筛结构特性和催化性能的影响

以六亚甲基亚胺为模板剂,在动态水热合成MCM-22分子筛的过程中,加入有机辅助剂聚乙二醇2000(PEG2000),考察有机辅助剂PEG2000对MCM-22分子筛结构、酸性以及催化性能的影响。由X射线衍射谱图可以看出,合成时加入适量的PEG2000,可以得到结晶较好的MCM-22晶体,但结晶度稍微有些降低。由氮吸附脱附测试结果可以看出,适量助剂PEG2000的加入,改变了分子筛的最可几孔径分布,最可几孔径由0.556 nm提高至0.587 nm,孔容由0.35 m3/g增加到0.59 m3/g,BET比表面积由410 m2/g增加到456 m2/g。NH3-TPD方法测试样品的酸性结果显示,加入适量的PEG2000后,分子筛的强酸位得到加强。另外用合成的分子筛作为催化剂,以苯与丙烯烷基化为模型反应,考察了MCM-22分子筛的活性以及选择性,结果显示催化剂的活性有较大提高,然而对异丙苯的初始选择性降低,随着反应的进行,异丙苯的选择性却很快地增长。     

Liquid-phase thiophene adsorption on MCM-22 zeolite and activated carbon

The liquid-phase adsorption of thiophene from thiophene/iso-octane and toluene-rich thiophene/toluene/iso-octane solutions has been investigated in batch conditions at room temperature and atmospheric pressure on MCM-22 zeolite and activated carbon. The adsorption of toluene from toluene/iso-octane solutions has also been investigated on both the adsorbents. These were characterised by X-ray diffraction, nitrogen physisorption, scanning electron microscopy and adsorption microcalorimetry of ammonia. Both MCM-22 and activated carbon were able to adsorb thiophene and toluene from the corresponding single-adsorptive iso-octane solutions. MCM-22 appeared superior to activated carbon for the adsorption of thiophene from toluene-rich thiophene/toluene/iso-octane mixtures. The adsorption data for MCM-22 were correlated with the acid sites and silanol groups concentrations, as determined by microcalorimetric experiments. No such correlation was found for activated carbon. Apparently, on MCM-22 thiophene adsorption occurs first on the acid sites until they are saturated and then continues on the silanol groups. Toluene adsorption also occurs on the acid sites of MCM-22 until saturation, but no further adsorption by interaction of toluene with the silanol groups takes place. GC/MS investigation of the nature of the organosulphur material retained by the adsorbent revealed that the tiophene adsorbed on MCM-22 undergoes transformation into heavy products. Besides thiophene trimers and tetramers, these include other compounds formed by two and three thiophenic rings linked by alkyl groups, as well as a rather high molecular weight product where a trimer is linked to thiophenic ring by a cyclohexadienic ring. Reaction pathways leading to these products have been tentatively outlined.     

均三甲苯在MCM-22和MCM-56分子筛上的吸附和扩散

以MCM-22和MCM-56分子筛为研究对象,考察烃类均三甲苯在MWW型分子筛上的吸附和扩散,同时对分子筛进行XRD、N2吸附和TEM等表征,探究分子筛的结构特性与吸附和扩散之间的关系。研究表明,均三甲苯在MWW型分子筛中的吸附和扩散位置为外表面半超笼。单层和错层结构使MCM-56较MCM-22分子筛拥有更多的外表面酸性位,有利于均三甲苯的吸附。与MCM-22相比,MCM-56分子筛片层结构较薄,焙烧导致晶体外部结构的卷曲使烃类大分子均三甲苯在MCM-56分子筛中的扩散受阻。     

Pyrolysis of Polyethylene over Aluminum-Incorporated MCM-41 Catalyst

Aluminum-containing MCM-41 catalysts were synthesized in this study by impregnation of aluminum into hydrothermally synthesized MCM-41. Aluminum was loaded into the porous framework of silica with different Al/Si ratios, using aluminum isopropoxide as the aluminum source. These catalysts exhibited Type IV adsorption–desorption isotherms and had a pore diameter of 2.4 nm. Aluminum species were coordinated tetra- and octahedrally in the structure of catalysts. Diffuse Reflectance Fourier Transform Infrared Spectra (DRIFTS) analysis of the pyridine-adsorbed catalysts revealed the existence of Brönsted acid sites in the synthesized catalysts in addition to the Lewis acid sites. The performance of these catalysts was tested in the degradation of polyethylene using a thermogravimetric analyzer. Pure MCM-41 did not show a significant reduction in the degradation temperature of polyethylene, whereas aluminum-impregnated catalysts were successful in decreasing the temperature.