烯烃裂解中分子筛催化剂的稳定性研究进展

低碳烯烃催化裂解增产丙烯是一项新技术,高水热稳定催化剂的研究和开发是关键技术之一,硅酸铝分子筛催化剂因具有相对较好的稳定性而得到了广泛研究. 本文总结了HY, HZSM-5和 MCM-22等微孔、介孔以及具有微-介孔复合结构的新型分子筛在烯烃催化裂解反应中的稳定性,特别是水热稳定性方面的研究进展,归纳了提高酸性分子筛催化剂水热稳定性的方法,比较了不同方法制得分子筛的催化裂解性能,对高稳定性催化剂在实际应用中的问题和前景进行了探讨,为研发新一代低碳烯烃裂解催化剂提供参考.     

High-Flux Carbon Molecular Sieve Membranes for Gas Separation

Carbon membranes have great potential for highly selective and cost-efficient gas separation. Carbon is chemically stable and it is relative cheap. The controlled carbonization of a polymer coating on a porous ceramic support provides a 3D carbon material with molecular sieving permeation performance. The carbonization of the polymer blend gives turbostratic carbon domains of randomly stacked together sp² hybridized carbon sheets as well as sp³ hybridized amorphous carbon. In the evaluation of the carbon molecular sieve membrane, hydrogen could be separated from propane with a selectivity of 10 000 with a hydrogen permeance of 5 m³(STP)/(m²hbar). Furthermore, by a post-synthesis oxidative treatment, the permeation fluxes are increased by widening the pores, and the molecular sieve carbon membrane is transformed from a molecular sieve carbon into a selective surface flow carbon membrane with adsorption controlled performance and becomes selective for carbon dioxide.     

CuSAPO-5分子筛的合成、表征及对甲苯吸附性能

采用水热合成法,以三乙烯四胺（TETA）为模板剂,合成CuSAPO-5分子筛。通过扫描电子显微镜（SEM）、粉末X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）、热重（TG）、N₂吸附及元素分析等手段对分子筛样品进行表征,考察了不同硅铝比对合成分子筛晶体的影响,并测定了分子筛样品对甲苯的吸附性能。结果表明,将合成液的pH值调节为4.8～5.0,于150～170℃晶化1 d,可合成晶体形貌为球体的CuSAPO-5分子筛,粒径约为30 μm。分子筛样品具有较好的热稳定性,仍保持了SAPO-5分子筛的AFI骨架结构,属于微孔分子筛,孔径约为0.70nm,比表面积约为265 m²·g^-1。元素分析结果表明分子筛中P、Si、Al和Cu的含量分别为12.56%、4.48%、7.17%和6.25%。样品对甲苯的吸附约在120 min时达到饱和,吸附量约为180 mg·g^-1。     

CuSAPO-5分子筛的合成、表征及对甲苯吸附性能

采用水热合成法,以三乙烯四胺(TETA)为模板剂,合成Cu SAPO-5分子筛。通过扫描电子显微镜(SEM)、粉末X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、热重(TG)、N2吸附及元素分析等手段对分子筛样品进行表征,考察了不同硅铝比对合成分子筛晶体的影响,并测定了分子筛样品对甲苯的吸附性能。结果表明,将合成液的p H值调节为4.8~5.0,于150~170℃晶化1d,可合成晶体形貌为球体的Cu SAPO-5分子筛,粒径约为30μm。分子筛样品具有较好的热稳定性,仍保持了SAPO-5分子筛的AFI骨架结构,属于微孔分子筛,孔径约为0.70nm,比表面积约为265 m2·g-1。元素分析结果表明分子筛中P、Si、Al和Cu的含量分别为12.56%、4.48%、7.17%和6.25%。样品对甲苯的吸附约在120 min时达到饱和,吸附量约为180 mg·g-1。     

KOH/4A分子筛催化剂对环氧丙烷、二氧化碳和甲醇合成碳酸二甲酯反应的催化性能

 首次开发出对环氧丙烷、二氧化碳和甲醇合成碳酸二甲酯反应具有较高活性和稳定性的KOH/4A分子筛固体催化剂,考察了反应温度和催化剂活性组分KOH的负载量等因素对催化剂性能的影响. 在优化的实验条件下,环氧丙烷可以完全转化,碳酸二甲酯的收率为168%. 从实验结果推测,产物碳酸二甲酯是由环氧丙烷和二氧化碳加成生成碳酸丙烯酯,然后与甲醇发生酯交换反应生成的,甲醇对环氧丙烷和二氧化碳合成碳酸丙烯酯反应具有助催化作用.     

Kinetic Separation of Oxygen and Argon Using Molecular Sieve Carbon

A pressure-swing adsorption (PSA) simulation study was performed for the separation of a mixture of 95% O₂ and 5% Ar using a molecular sieve carbon (MSC) as the adsorbent. Two PSA cycles have been outlined to maximize the recovery of either argon or oxygen as a high purity product. The effect of cycle parameters such as cocurrent depressurization pressure, purge/feed ratio, pressure ratio and adsorption pressure on the separation of O₂/Ar has been studied. It was found that it is feasible to obtain an argon product of purity in excess of 80% with reasonably high recovery using one of the cycles. The other cycle is capable of producing high purity oxygen (>99%) at high recovery (>50%) with reasonably high product throughputs. The PSA process can be conducted at room temperature and hence has an advantage over conventional processes like cryogenic distillation and cryogenic adsorption.     

萘普生在介孔分子筛MCM-41中的负载及其溶出性能

用含氨基的偶联剂修饰介孔分子筛MCM-41的表面,将修饰前和修饰后的介孔分子筛分别负载难溶性药物萘普生（NAP）,利用X射线衍射、傅里叶变换红外光谱、差示扫描量热分析、扫描电子显微镜、透射电子显微镜和N2吸附 脱附分析等技术分别对其进行了结构表征和性能测试。 结果表明,药物分子存在于分子筛的孔道中。 负载在MCM-41中的萘普生溶出速率远优于原料药,60 min时大约溶出70%。 氨基修饰后的药物释放速率比修饰前有所减慢,表明可通过氨基修饰调节释放速率。     

碱改性ZSM-11分子筛及其催化裂化增产烯烃性能

通过晶种辅助法合成ZSM-11分子筛,并对其进行碱处理从而制备了改性样品ZSM-11-AT.采用XRD、 N₂吸附和脱附、 XRF、 TEM、 NH₃-TPD和Py-IR等表征手段对样品ZSM-5、 ZSM-11和ZSM-11-AT的物化性质进行了表征和对比分析,发现改性样品ZSM-11-AT的比表面积、孔隙结构和酸性质均得到了改善.采用固定床反应装置对样品的催化裂化性能进行了评价,对样品ZSM-5、 ZSM-11和ZSM-11-AT的反应物转化率和产物分布进行了对比研究.结果表明, ZSM-11和ZSM-11-AT在烯烃乙烯和丙烯产率方面优于ZSM-5.与ZSM-11相比, ZSM-11-AT的催化性能得到了进一步的提高.     

硅烷化对Ti/HMS分子筛催化性能的影响

分别用水热法和气相沉积法制备了Ti/HMS分子筛,采用三甲基氯硅烷(TMCS)和六甲基二硅氮烷(HMDSZ)对Ti/HMS样品进行了气相硅烷化,并用X射线衍射、N2吸附、红外光谱、29Si核磁共振和紫外-可见光谱对样品进行了表征.丙烯环氧化反应的测定结果表明,硅烷化可显著提高环氧化催化活性.水热法制备的Ti/HMS经HMDSZ硅烷化后的催化活性比经TMCS硅烷化后的稍高;气相沉积法制备的Ti/HMS经HMDSZ硅烷化后的催化活性远高于经TMCS硅烷化后的催化活性.这是由于TMCS不但能与分子筛表面的硅羟基反应,而且能破坏分子筛骨架中的Si-O-Ti甚至Si-O-Si键,形成新的羟基,导致样品的亲水性较强,同时还能对气相沉积法制备的Ti/HMS中的四配位骨架钛产生破坏作用.     

SO42-促进的中孔含锆分子筛催化合成乙酸松油酯的研究

合成了中孔含锆分子筛Zr-MCM-41，用H2SO4对Zr-MCM-41进行修饰，得到SO4^2-促进的中孔含锆分子筛SO4^2-／Zr-MCM-41．通过XRD、FT—IR表征了其结构．结果表明：Zr—MCM-41和SO4^2-／Zr—MCM-41具有中孔分子筛的特征结构、良好的长程有序性和结晶度；SO4^2-已进入Zr—MCM-41骨架内部，并与骨架原子形成了化学键，从而产生强酸中心，将SO4^2-／Zr—MCM-41用于催化合成乙酸松油酯，考察了催化剂的种类、反应温度、反应时间及反应物配比对松油醇酯化反应结果的影响．     

含Co纳米介孔分子筛的制备与表征

用两步水热法合成出了含Co介孔分子筛,采用XRD,FT-IR,TPR,AFM,BET,B JH等方法对样品的物化性能进行了表征.结果表明合成出了纳米级具有介孔结构的CoMCM-41.样品在550℃焙烧可以将模板剂有效去除而不影响孔结构.所得CoMCM-41比表面积大于500 m2/g,平均孔径分布为3.57 nm,粒径分布在20~40 nm范围内.     

不同碳源制备的介孔碳分子筛的性能研究

以介孔分子筛SBA-15为模板剂,分别采用蔗糖、糠醇和酚醛树脂作为碳源制备介孔碳分子筛.用TGA、XRD、N2吸附-脱附和TEM对制备的样品进行了表征和比较.结果表明,三种碳源制备的介孔碳分子筛的结构有序性明显不同.用蔗糖为碳源能够得到结构高度有序的介孔碳分子筛,其比表面积和孔容最大,分别为1 422 m2·g和1.15 cm3·g;用糠醇为碳源制备的样品次之;用普通酚醛树脂为碳源制备的样品其结构有序性最差.     

A Self-Consistent Model for Sorption and Transport in Polyimide-Derived Carbon Molecular Sieve Gas Separation Membranes

Demand for energy-efficient gas separations exists across many industrial processes, and membranes can aid in meeting this demand. Carbon molecular sieve (CMS) membranes show exceptional separation performance and scalable processing attributes attractive for important, similar-sized gas pairs. Herein, we outline a mathematical and physical framework to understand these attributes. This framework shares features with dual-mode transport theory for glassy polymers; however, physical connections to CMS model parameters differ from glassy polymer cases. We present evidence in CMS membranes for a large volume fraction of microporous domains characterized by Langmuir sorption in local equilibrium with a minority continuous phase described by Henry's law sorption. Using this framework, expressions are provided to relate measurable parameters for sorption and transport in CMS materials. We also outline a mechanism for formation of these environments and suggest future model refinements.     

以介孔分子筛为金属催化剂载体制备纳米碳管

 以不同的介孔分子筛作为金属催化剂载体,对催化合成纳米碳管进行了系统的研究,讨论了反应条件对纳米碳管纯度和产量的影响. 结果表明,不同的介孔分子筛对金属活性中心的形成、碳组分的扩散、纳米碳管的管径及形态均有明显的影响. 此外,金属的种类、状态和含量也影响纳米碳管的合成. 探索了合成高产量纳米碳管的条件,并对介孔分子筛上生长纳米碳管的特点进行了讨论.     

Comparative Studies of the Micropore Size Distributions of an Alumina Pillared Montmorillonite and a Molecular Sieve Carbon

The aim of this work is to applicate and to compare various analysis methods for the characterization of the microporous structure from nitrogen adsorption at 77 K of an alumina pillared montmorillonite and a molecular sieve carbon. The adsorption potential distribution (X(A)), the Horvath-Kawazoe (HK) method, the Jaroniec-Gadkare-Choma (JGC) one and a numerical algorithm for the reconstruction of the micropore size distribution (MPSD) from the adsorption equilibrium isotherm have been applied. Comparison of all distributions revealed that the molecular sieve carbon shows smaller micropores and smaller structural hetereogeneity than the alumina pillared montmorillonite.     

Effect of Structure and Pore Size of Mesoporous Molecular Sieve Materials on the Growth of Carbon Nanotubes

Microporous and mesoporous molecular sieve materials with different channel structures and pore sizes were applied as supports for Fe-loaded catalysts to catalytically synthesize carbon nanotubes. The deposited carbon materials were characterized by the TEM technique. It was shown that the structures and pore sizes of supports greatly influence the forms and quality of the deposited carbon materials. The larger the pore size of the support used, the larger the diameter and pore size of the carbon nanotubes formed. It seems that the growth of carbon nanotubes can be orientated by the one-dimensional mesoporous structure of hexagonal mesoporous molecular sieve materials.     

MCM-49分子筛催化剂上1-丁烯的骨架异构化反应

 采用动态和静态水热合成法合成了不同Si/Al比的MCM-49分子筛,并考察了合成分子筛对1-丁烯骨架异构化反应的催化性能. 结果表明,除目的产物异丁烯外,主要副产物为丙烯和戊烯,产物中没有检测到C6以上的副产物. 异丁烯收率随着反应温度的升高、分子筛晶粒的增大和1-丁烯分压的降低而升高. NH3-TPD 结果表明,随着分子筛Si/Al比的增加,分子筛的酸中心数减少,导致副产物选择性下降,异丁烯选择性升高. 根据反应结果讨论了异丁烯及副产物形成的机理.