[摘　　要]：

甲醇制烯烃（MTO）反应是最有希望替代常规石油路线生产低碳烯烃的新兴工艺路线。作为MTO反应的核心，催化剂的合成成为人们研究的重点。SAPO-34分子筛以其高甲醇转化率和优异的乙烯、丙烯选择性成为目前MTO反应催化剂研究重点。然而由于SAPO-34分子筛受到其微孔的限制，孔道容易被积碳堵塞从而造成较短的催化剂寿命。因此有效的提高SAPO-34分子筛的催化剂寿命对于推进MTO反应工业化有着极其重要的意义。本论文致力于研究SAPO-34分子筛的合成和改性，分别考察了不同单模板剂、双模板剂、单一金属离子和双金属离子改性对于SAPO-34分子筛结构的影响，采用XRD，SEM和NH3-TPD等手段进行分......更多

甲醇制烯烃（MTO）反应是最有希望替代常规石油路线生产低碳烯烃的新兴工艺路线。作为MTO反应的核心，催化剂的合成成为人们研究的重点。SAPO-34分子筛以其高甲醇转化率和优异的乙烯、丙烯选择性成为目前MTO反应催化剂研究重点。然而由于SAPO-34分子筛受到其微孔的限制，孔道容易被积碳堵塞从而造成较短的催化剂寿命。因此有效的提高SAPO-34分子筛的催化剂寿命对于推进MTO反应工业化有着极其重要的意义。本论文致力于研究SAPO-34分子筛的合成和改性，分别考察了不同单模板剂、双模板剂、单一金属离子和双金属离子改性对于SAPO-34分子筛结构的影响，采用XRD，SEM和NH3-TPD等手段进行分子筛结构表征，并考察了SAPO-34分子筛对MTO过程的影响。 考察了吗啡啉（MOR）、三乙胺（TEA）和四乙基氢氧化胺（TEAOH）三种模板剂及MOR和TEA双模板剂对于SAPO-34分子筛合成的影响。结果发现：（1）三种模板剂合成的催化剂晶粒大小由大到小为MOR-SAPO-34 > TEA-SAPO-34 > TEAOH-SAPO-34；（2）催化剂寿命由长到短为TEAOH-SAPO-34≈TEA-SAPO-34> MOR-SAPO-34；（3）采用MOR和TEA双模板剂两种模板剂混合使用可调节控制分子筛的晶粒大小和强、弱酸的比例，达到改善分子筛催化性能的目的。尽管以TEAOH为模板合成SAPO-34分子筛寿命最长，但是由于TEAOH价格昂贵不适合。（4）以TEA和MOR为双模板剂合成了晶化度较高的SAPO-34，酸性及晶粒大小都通过两种模板剂有效的得到控制，提高了催化剂的寿命。 本文考察了Mg、Co、Ni、Mn等金属离子的加入对SAPO-34的影响，重点考察了Co、Ni双金属催化剂对MTO反应的影响。结果表明：（1）在多种离子改性的MeSAPO-34分子筛中，Mn离子的加入可使分子筛的酸性降低，乙烯、丙烯的选择性提高并表现出最长的寿命。（2）Co、Ni双金属催化剂在450oC下具有较高的乙烯、丙烯的选择性，但其寿命有所降低。关闭

Methanol to olefins (abbr．MTO)is the most hopeful technology that substitute for the way of petroleum to olefins．The catalyst is the key to the MTO reaction.SAPO-34 molecular sieve is a potential catalyst for MTO reaction because of its high conversion of methanol and selectivity to ethane and propene. However, shorter catalytic lifetime caused limited its application. This paper is aimed to synthesize and modify the SAPO-34molecular sieve． The effect of different templates such as MOR, TEA and TEAOH on SAPO-34 synthesis, especiall......更多

Methanol to olefins (abbr．MTO)is the most hopeful technology that substitute for the way of petroleum to olefins．The catalyst is the key to the MTO reaction.SAPO-34 molecular sieve is a potential catalyst for MTO reaction because of its high conversion of methanol and selectivity to ethane and propene. However, shorter catalytic lifetime caused limited its application. This paper is aimed to synthesize and modify the SAPO-34molecular sieve． The effect of different templates such as MOR, TEA and TEAOH on SAPO-34 synthesis, especially using TEA and MOR as co-templates was investigated. The results show that the crystal grain size of catalyst synthesized with different templates is in the order: MOR-SAPO-34> TEA-SAPO-34>TEAOH-SAPO-34; the lifetime is in the order: TEAOH-SAPO-34≈TEA-SAPO-34>MOR-SAPO-34. The size of crystal and the intensity of the acid can be controlled by using the co-templates. The effect of metal ions such as Mg, Co, Ni, Mn on lifetime of SAPO-34 were carried out. The results show that MeSAPO-34 modified by Mg, Co, Ni or Mn metal ion has low acidity of catalyst and high of the selectivity to ethane; the lifetime of MnSAPO-34 shows the longest lifetime, 7.25 h. The synthesized CoNiSAPO-34 was used for methanol to olefin reaction (MTO) at 450 oC, and the results showed that the selectivity of ethylene of CoNiSAPO-34 is higher than that of pure SAPO-34, but the reactivity life is shorter than H-SAPO-34.关闭