本文選題：Cu-SSZ-13 + 分子篩　； 參考：《天津工業(yè)大學》2017年碩士論文

【摘要】：隨著石油資源的日益短缺以及乙烯、丙烯需求量的增長,開發(fā)出一條替代石油生產(chǎn)乙烯、丙烯的路線受到廣泛關注,甲醇制烯烴(MTO)技術就是一條從非石油資源制取烯烴的新路線。甲醇制烯烴工藝的核心是催化劑,主要有SAPO-34分子篩、SSZ-13分子篩等。盡管SSZ-13分子篩在MTO反應中具有優(yōu)異的催化性能,但是用于合成該分子篩的模板劑N,N,N-三甲基金剛烷銨(TMAdaO-H)價格昂貴且依賴進口。Cu-SSZ-13分子篩在催化氧化還原反應中具有非常好的催化性能和水熱穩(wěn)定性,但目前對Cu-SSZ-13分子篩的研究主要集中在氮氧化物的脫除領域,有關其催化MTO性能的研究,文獻報道褥得少。本論文以低廉的銅氨絡合物(Cu-TEPA)為模板劑,通過原位水熱合成法制備了 Cu-SSZ-13分子篩。系統(tǒng)研究了 Cu-SSZ-13分予篩的合成影響因素,包括氫氧化鈉和水的用量、硅鋁比以及晶化時間等,得出了合成Cu-SSZ-13分子篩的最優(yōu)反應原料和反應條件:14℃下晶化4d。當4.7≤n(Na20):n(Al203)≤5,10≤Si/Al≤11.5,185≤n(H2O):n(Al2O3)≤230時,合成的Cu-SSZ-i3分子篩結晶度最高且MTO催化性能最好。考察了硝酸銅和硫酸銅對Cu-SSZ-13分子篩的晶相結構和形貌的影響,測試了兩種銅鹽制備的Cu-SSZ-13分子篩和金屬改性的Cu-SSZ-13分子篩在甲醇制烯烴(MTO)中的催化性能。用X射線熒光光譜(XRF)、X射線衍射(XRD)、掃描電子顯微鏡(SEM)、N2等溫吸附-脫附(BET)和NH3程序升溫脫附(NH3-TPD)對催化劑進行了表征。結果表明:在MTO反應中,硝酸銅制備的Cu-SSZ-13分子篩的氫轉移反應劇烈,反應初期丙烷選擇性達到40%,遠高于硫酸銅制備的Cu-SSZ-13分子篩的19%。錳改性的Cu-SSZ-13分子篩明顯提高了抗積炭失活能力,在反應溫度440℃和質量空速5h-1條件下的催化壽命從未改性的30min延長到 65min。比較了不同濃度的稀硝酸改性的Cu-SSZ-13分子篩與氯化銨處理過的Cu-SSZ-13分子篩的MTO催化性能。結果表明,稀硝酸改性的Cu-SSZ-13分子篩雙烯選擇性略高于氯化銨處理過的Cu-SSZ-13分子篩。
[Abstract]:With the increasing shortage of petroleum resources and the increasing demand for ethylene and propylene, the route of developing a substitute for petroleum to produce ethylene has received extensive attention. Methanol to olefin (MTO) technology is a new route to produce olefin from non-petroleum resources. The core of methanol to olefin process is catalyst, mainly SAPO-34 molecular sieve SSZ-13 molecular sieve and so on. Although SSZ-13 molecular sieve has excellent catalytic performance in MTO reaction, However, the template for the synthesis of this molecular sieve, NZN- N- trimethyl amantadine (TMAdaO-H), is expensive and dependent on imported. Cu-SSZ-13 molecular sieve has very good catalytic performance and hydrothermal stability in the catalytic redox reaction. However, the research on Cu-SSZ-13 molecular sieve is mainly focused on the removal of nitrogen oxides, and the research on its catalytic MTO performance is seldom reported in the literature. In this paper, Cu-SSZ-13 molecular sieve was prepared by in situ hydrothermal synthesis with cupric ammonia complex (Cu-TEPA) as template. The factors affecting the synthesis of Cu-SSZ-13 sieve were systematically studied, including the amount of sodium hydroxide and water, the ratio of Si to Al and crystallization time, etc. The optimum reaction materials and reaction conditions for the synthesis of Cu-SSZ-13 molecular sieve were obtained. When 4.7 鈮，

本文編號：1883142