Busting the efficiency of SAPO-34 catalysts for the methanol-to-olefin conversion by post-synthesis methods

As an effective non-petroleum based process for producing light olefins, the methanol-to-olefin (MTO) route has become an indispensable alternative to the industrial production of light olefins. The silicoaluminophosphate SAPO-34 zeolite (CHA-type structure) has proven to be an efficient industrial catalyst for the production of ethylene and propylene by the MTO reaction. However, the inherent structure and related diffusion limitations of SAPO-34 limit the mass transport and thus cause rapid deactivation of the catalyst. Fabrication of hierarchical SAPO-34 zeolite is one of the most effective strategies to address the intrinsic diffusion limitation. As simple, inexpensive, and efficient approach, the post-synthetic route has attracted considerable attention and widely used to introduce secondary meso-/macropores into the microporous SAPO-34 material. Significant effort has been dedicated to the development of post-synthesis strategies to prepare hierarchical SAPO-34 zeolite, thereby enhancing its catalytic performance in the MTO process. This mini-review addresses the post-synthesis preparation of hierarchical SAPO-34 catalysts and their MTO performance. Furthermore, some current problems and prospects of the post-synthesis route to hierarchical SAPO-34 catalysts are also revised. We expect this minireview to inspire the more efficient preparation of hierarchical SAPO-34 catalysts for the MTO process.     

用于甲醇制烯烃SAPO-34分子筛的研究进展

具有CHA结构的SAPO-34分子筛因其优异的理化性质被认为是甲醇制烯烃(MTO)工艺的最佳催化剂,但CHA结构中狭窄的八元环孔会限制扩散,使催化剂易于失活降低使用寿命.本文从构建多级孔结构和减小分子筛粒径入手,综述了具有优异的MTO催化性能的多级孔和纳米级SAPO-34分子筛的最新进展,分析不同制备方法对SAPO-3...     

水热合成法合成SAPO-34分子筛

采用吗啉和四乙基氢氧化铵为模板剂,研究了不同因素对水热合成法合成SAPO-34分子筛的影响。结果表明,陈化时间、晶化时间和搅拌对合成分子筛都有重要影响,最佳陈化和晶化时间均为24 h,适宜的搅拌速度为100r/min。以吗啉和吗啉-四乙基氢氧化铵为模板剂,采用先陈化后晶化并搅拌的方式均可得到SAPO-34分子筛,四乙基氢氧化铵的加入有利于合成小晶粒的分子筛。甲醇制烯烃(MTO)结果表明,甲醇转化率达98%以上,乙烯和丙烯总选择性达85%以上。     

利用合成SAPO-34分子筛的晶化残液合成SAPO-34分子筛

在制备SAPO-34过程中会产生大量的晶化残液,晶化残液中除了含有大量水之外,还含有残留的模板剂(有机胺)、硅源、铝源、磷源等组分,通过向合成SAPO-34分子筛产生的晶化残液中加入适量的铝源、磷源、硅源、模板剂等物料制备成凝胶混合物,经过老化、水热晶化、洗涤、干燥和焙烧等工序,即得到纯净的SAPO-34分子筛,既保护了环境又实现了晶化残液的再利用。     

Behaviors of coke deposition on SAPO-34 catalyst during methanol conversion to light olefins

The deposition of coke on SAPO-34 during methanol conversion to olefins at temperatures of 623–823 K was observed to be fast initially but moderate in the later stage. Micropores are blocked badly at coke contents of above 4 wt.%. The coke deposition influences olefins selectivity significantly and selectivities of ethylene plus propylene reach maximum at a coke content of about 5.7 wt.%. The coke formation can be attenuated by the presence of water, but the effect of water weakens gradually with the progress of the reaction. A model relating the coke content over SAPO-34 to cumulative amount of methanol fed to the catalysts is proposed and proved the validity to estimate the coke content on SAPO-34 at different reaction conditions. The coke deposited at different reaction temperatures has different compositions.     

模板剂对SAPO-34分子筛性能的影响

采用XRD、SEM、NH3-TPD等方法研究了以三乙胺(TEA)、四乙基氢氧化铵(TEAOH)及二者的混合物为模板剂合成的产物的结构及物化性能,并以甲醇为探针分子,在固定床反应器上对合成产物在甲醇制取烯烃(MTO)反应中的催化性能进行了评价。结果表明,模板剂的种类及配比对所得产物的晶相结构、晶粒大小、酸强度、酸量以及催化性能有重要影响。双模板体系中,当n(TEAOH)/n(TEA)=0.037～0.186时,得到纯相SAPO-34分子筛;且当n(TEAOH)/n(TEA)=0.093时,得到的SAPO-34分子筛晶粒较小(1.0μm左右)且均匀,酸度适中,低碳烯烃(C2=～C4=)的选择性94.98%,催化寿命415min,较单独以TEA〔n(TEA)/n(Al2O3)=2.15〕或TEAOH〔n(TEAOH)/n(Al2O3)=2.0〕为模板剂合成的催化剂的低碳选择性(88.22%和89.29%)和寿命(170min和165min)均有明显提高,且积炭速率(0.016%/min)明显降低。     

甲醇制烯烃催化剂SAPO-34分子筛的制备和喷雾成型

SAPO-34分子筛用于催化甲醇转化制烯烃,乙烯和丙烯选择性高,是很好的甲醇制烯烃催化剂。由于SAPO-34分子筛失活速率快,甲醇制烯烃反应器通常是连续循环再生的流化床反应器,SAPO-34分子筛必须喷雾成型并达到一定抗磨强度后才能使用。在50 L反应釜合成了SAPO-34分子筛,并在中试喷雾装置上,以SAPO-34为活性组分喷雾成型甲醇制烯烃催化剂。结果表明,喷雾成型甲醇制烯烃催化剂的抗磨损指数为1.58%·h-1,抗磨性能达到工业应用要求,与两种工业甲醇制烯烃催化剂对比,喷雾成型甲醇制烯烃催化剂寿命最长,达260 min,乙烯、丙烯选择性以及乙烯+丙烯总选择性在对应的各个反应时间点均最高,260 min分别达到49.09%、35.05%和84.98%。     

SAPO-34分子筛催化剂制备及发展现状

乙烯和丙烯作为重要的化工原料,在经济发展中的需求量越来越大。在石油资源越来越匮乏的今天,甲醇制烯烃作为一种可以代替常规石油路线生产低碳烯烃的新工艺受到广泛关注。SAPO-34分子筛因为高甲醇转化率和优良烯烃选择性成为当前甲醇制烯烃工艺催化剂的研究重点。合成SAPO-34分子筛的影响因素有模板剂、合成原料和反应条件等。通过调节分子筛粒径尺寸、酸性、金属改性可以实现分子筛的性能优化。介绍了SAPO-34分子筛催化剂常用的制备方法和一些分子筛催化剂改进的专利。使用一定时间后催化剂由于积炭而失活,再生工艺目前主要采用烧焦再生。2011年,神华煤制烯烃示范工程进入工业化运行,近年陆续有多套甲醇制烯烃装置投产和在建,煤制烯烃正在改变中国聚烯烃市场格局。     

硅改性拟薄水铝石合成SAPO-34分子筛的研究

SAPO-34分子筛常用于甲醇制烯烃（MTO）反应中。以硅酸钠、硝酸铝和氨水为原料采用碱滴酸加料方式制备一种硅改性拟薄水铝石,再以硅改性拟薄水铝石为硅源和铝源、磷酸（H₃PO₄）为磷源、四乙基氢氧化铵（TEAOH）为模板剂采用水热合成法制备SAPO-34分子筛。采用XRD、SEM、FT-IR、NH₃-TPD等表征手段对合成的硅改性拟薄水铝石及SAPO-34分子筛进行表征并对其MTO催化性能进行评价。结果表明,在硅铝物质的量比为0.08~0.5时,硅的引入对合成纯相拟薄水铝石无影响,但硅的引入量对拟薄水铝石的结晶度及形貌有一定影响;在硅铝物质的量比为0.2~0.5时,以硅改性拟薄水铝石为硅源和铝源可以合成纯相SAPO-34分子筛,MTO催化反应甲醇转化率可达99%以上,双烯选择性最高达87%以上,并拥有较高的乙烯选择性。     

Effect of temperature in the conversion of methanol to olefins (MTO) using an extruded SAPO-34 catalyst

The methanol-to-olefin (MTO) reaction was investigated in a bench-scale, fixed-bed reactor using an extruded catalyst composed of a commercial SAPO-34 (65 weight percentage, wt-%) embedded in an amorphous SiO₂ matrix (35 wt-%). The texture properties, acidity and crystal structure of the pure SAPO-34 and its extruded form (E-SAPO-34) were analyzed and results indicated that the extrusion step did not affect the properties of the catalyst. Subsequently, E-SAPO-34 was tested in a temperature range between 300 and 500 °C, using an aqueous methanol mixture (80 wt-% water content) fed at a weight hour space velocity (WHSV) of 1.21 h⁻¹. At 300 °C, a low conversion was observed combined with catalyst deactivation, which was ascribed to oligomerization and condensation reactions. The coke analysis showed the presence of diamandoid hydrocarbons, which are known to be inactive molecules in the MTO process. At higher temperatures, a quasi-steady state was reached during a 6 h reaction where the optimal temperature was identified at 450 °C, which incidentally led to the lowest coke deposition combined with the highest H/C ratio. Above 450 °C, surges of ethylene and methane were associated to a combination of H-transfer and protolytic cracking reactions. Finally, the present work underscored the convenience of the extrusion technique for testing catalysts at simulated scale-up conditions.     

草酸溶液处理对SAPO-34分子筛物性和催化性能的影响

用XRD、SEM、N₂物理吸附、XRF、ICP-AES以及NH₃-TPD、FT-IR、固体NMR和固定床甲醇制烯烃技术（MTO）反应评价等表征手段,研究了草酸溶液处理对SAPO-34分子筛的改性作用。结果表明,用草酸溶液对SAPO-34分子筛进行后处理可以通过刻蚀骨架在晶体中产生大孔,调变孔道结构,改善微孔扩散性能;选择性地降低分子筛的骨架硅含量,从而降低分子筛的酸强度和酸中心密度。将改性前后的分子筛应用于MTO反应中。评价结果表明,适度的酸处理能够在保证分子筛收率和乙烯、丙烯选择性的前提下,明显提高催化剂的单程寿命。草酸溶液处理是一种值得研究的SAPO-34分子筛后处理改性方法和MTO催化剂制备手段。     

Zeotype SAPO-34 Synthesized by Combination of Templates for the Gasification of Biomass

SAPO-34 is a crystalline microporous material, the characteristics of which are greatly influenced by synthetic parameters, especially the silica precursors and templates. In this study, the combination of templates and silica sources was optimized to obtain SAPO-34 phases in the purest form. The physicochemical properties of the thus-synthesized catalysts were characterized, and the Si environment in the SAPO-34 framework was analyzed. The catalytic performance in biomass gasification was investigated in a fixed-bed flow reactor. SAPO-34 synthesized with triethylamine/morpholine/tetraethylammonium hydroxide templates exhibited the highest total acidity, the smallest particle size, and high surface area, and produced a large amount of light hydrocarbons in biomass gasification.     

双模版剂法制备SAPO-5和SAPO-34分子筛

以二乙胺和四乙基氢氧化铵为混合模版剂,采用水热法合成了SAPO6和SAPO-34分子筛,并用XRD,SEM,XRF,NH3-TPD等手段对其表征,以氧化苯乙烯重排反应为探针反应评价其活性.分别讨论了加料顺序和晶化升温模式对合成SAPO-5和SAPO-34的影响.结果表明,改变加料顺序和晶化升温模式时,在原料和合成物料配比不变的条件下可以分别合成出纯相的SAPO6和SAPO-34分子筛.在氧化苯乙烯重排反应中,由于SAPO-34含有强酸位,会产生大量聚合物,使得苯乙醛的选择性较低,而只含有弱酸位的SAPO-5表现出较好的活性和选择性.     

Dimethyl ether conversion to light olefins over the SAPO-34/ZrO2 composite catalysts with high lifetime

The SAPO-34/ZrO₂ composite catalysts using ZrO₂ as a binder were prepared and their performance was investigated for the dimethyl ether to olefins (DTO) reaction. The composite catalysts showed higher catalytic lifetimes than the free SAPO-34 catalyst, while maintaining high selectivity toward light olefins. This suggests that the binder-filled space between the SAPO-34 crystals can provide additional diffusion paths for mass transfer. In the SAPO-34/ZrO₂ composite catalysts with different ZrO₂ contents, the SAPO-34(11 wt%)/ZrO₂ composite catalyst showed the highest catalytic lifetime. It can be concluded that ZrO₂ is one of the best binders for the preparation of SAPO-34/binder composite catalysts.     

二次生长法合成SAPO-34沸石膜及其气体渗透性能

以四乙基氢氧化铵(TEAOH)为模板剂,采用二次生长法在α-Al_2O_3多孔陶瓷管上合成了SAPO-34沸石膜.利用X射线衍射(XRD)、扫描电镜(SEM)以及气体渗透对合成的膜进行了表征.XRD结果表明合成的膜具有典型的CHA型沸石特征峰,无其它杂相存在.SEM显示膜厚大约为5 μm,膜表面晶粒交织共生完好,且连续、致密,没有发现明显的针孔和裂纹.室温下, 当膜两侧压降为0.1 MPa时,CO_2/CH_4的理想选择性和混合气体分离选择性分别为7和40.     

模板剂对SAPO-34分子筛性能的影响研究

采用XRD、SEM、NH3-TPD等方法深入研究了以三乙胺(TEA)、四乙基氢氧化铵(TEAOH)及二者的混合物为模板剂合成的产物的结构及物化性能。并以甲醇为探针分子,在固定床反应器上对合成产物在甲醇制取烯烃(MTO)反应中的催化性能进行了评价。结果表明,模板剂的种类及配比对所得产物的晶相结构、晶粒大小、酸强度、酸量以及催化性能有重要影响。双模板体系中,当TEAOH/ TEA=0.037～0.186时,可以得到纯SAPO-34分子筛;且当TEAOH/TEA=0.093时,得到的SAPO-34分子筛晶粒较小(1.0μm左右)且均匀,酸度适中,低碳烯烃(C2=～C4=)的选择性94.98%,催化寿命415min,较单独以TEA(TEA/Al2O3=2.15)或TEAOH(TEA/Al2O3=2.0)为模板剂合成的催化剂的低碳选择性 (88.22%和89.29%)和寿命(170min和165min)均有明显提高,且积炭速率(0.016%/min)明显降低。     

On the reaction mechanism for propene formation in the MTO reaction over SAPO-34

Three different feeds: methanol, methanol/ethanol/water (2 1 1 molar ratio) and¹³C-methanol/ethanol/water (2 1 1) have been converted to hydrocarbons over a SAPO-34 catalyst at 420 °C using argon carrier gas. The products were analyzed by GC-MS allowing the determination of the isotopic composition of the reaction products. The experiments show that the majority of the propene molecules are formed directly from methanol, and that only a minor part is formed by methylation of ethene.     

NaOH预处理对高岭土表面原位合成SAPO-34催化剂性能的影响

以高温煅烧高岭土微球(CKM)为载体,采用原位合成法制备了负载型SAPO-34催化剂(SCKM)。以质量分数2%～10%的NaOH水溶液对高岭土微球进行了预处理。采用XRD、XPS、SEM、N2吸附-脱附对NaOH处理的高岭土微球及原位合成的SAPO-34进行了表征,并在MTO固定床上对合成催化剂的活性进行了评价。结果表明,NaOH水溶液预处理对高岭土微球表面的化学组成、形貌结构以及原位合成SAPO-34负载型催化剂的性能均有显著影响。质量分数4%的NaOH水溶液处理高岭土微球表面合成的SAPO-34催化剂(4-SCKM)在MTO催化反应中的活性最佳,甲醇转化率达到100%,低碳烯烃选择性89.8%,单程寿命964 min,优于非原位合成的SAPO-34催化剂。     

用于催化甲醇制烯烃的SAPO-34分子筛合成的研究进展

介绍了用于催化甲醇制烯烃的SAPO-34分子筛合成的研究近况。SAPO-34分子筛的合成过程是影响其晶粒尺寸、酸性强弱等物化性能的重要因素, 因而是影响其催化性能的关键因素。本文详细叙述了原料配比及其种类、模板剂、F^-等合成因素对SAPO-34分子筛物化性能及其MTO反应催化性能的影响。针对SAPO-34合成及其催化性能优化的新技术, 综述了SAPO-34分子筛的金属改性及其超声波、微波辅助合成的特点和效果, 指出通过研发新的模板剂及其助剂、改性或制备新工艺进而改善分子筛的酸性、提高其烯烃选择性、延长催化反应寿命、降低合成成本是SAPO-34今后研发的重要方向。     

多级孔ZSM-5/SAPO-34复合分子筛制备及催化MTO性能研究

为制备性能更加优异的甲醇制烯烃（MTO）催化剂及进一步探究多级孔道对MTO催化反应的影响,采用柠檬酸溶液（CA）运用后处理方法对复合分子筛进行刻蚀,成功制备了具有多级孔道结构的ZSM-5/SAPO-34复合分子筛（CA-Z-S）。对复合分子筛的晶相、骨架、孔结构等理化性质进行了表征;将复合分子筛用于催化MTO反应,考察了复合分子筛的催化性能。表征结果表明,使用CA处理对ZSM-5/SAPO-34复合分子筛的形貌、结构会产生影响,使CA-Z-S具有更紧密的复合结构、适量的弱酸中心和多级孔道复合结构。催化测试结果表明,甲醇转化率达到100%时,CA-Z-S的寿命为1 200 min,较SAPO-34提高79%,较ZSM-5/SAPO-34提高30%;CA-Z-S对轻烯烃的选择性达到90.5%,较SAPO-34提高约3.7%。研究结果表明,利用CA对复合分子筛进行后处理,有利于复合分子筛催化MTO反应性能的提升。