多级孔纳米SAPO-34分子筛制备及甲醇制烯烃性能研究
收稿日期: 2023-03-31
网络出版日期: 2024-01-18
基金资助
国家科技支撑计划项目(2013BAE11B03);江苏省产学研前瞻性联合研究项目(BY2016005-11)
Study on preparation of multistage pore nano-SAPO-34 molecular sieves and its methanol to olefin performance
Received date: 2023-03-31
Online published: 2024-01-18
为缩短SAPO-34分子筛的高温晶化时间，提高其在甲醇制烯烃（MTO）反应中的寿命和选择性，以三乙胺和四乙基氢氧化铵作为双模板剂，采用分步晶化法快速制备了粒径为300~500 nm的纳米SAPO-34分子筛，同时添加表面活性剂十六烷基三甲基溴化铵（CTAB）进一步对分子筛进行改性，得到多级孔纳米SAPO-34分子筛（C-ST1T2）。对制备的所有样品进行理化性质表征，并应用于甲醇制烯烃的催化反应，考察了其在一定条件下的催化性能。表征结果显示，分步晶化法可以有效缩短分子筛的晶化时间，并且得到纳米级SAPO-34分子筛。用CTAB改性后得到的多级孔纳米SAPO-34分子筛晶型完整，具有多级孔道结构和适中的酸强度。催化性能测试表明，C-ST1T2的甲醇转化率能够达到100%，并且催化寿命可以达到690 min，较单模板剂合成的分子筛有较大提升，同时低碳烯烃的选择性稳定在89%以上。研究结果表明，利用CTAB对纳米分子筛的多级孔改性，有利于分子筛的MTO反应性能进一步提升。
陈旭 , 杨刚 , 李海涛 . 多级孔纳米SAPO-34分子筛制备及甲醇制烯烃性能研究[J]. 无机盐工业, 2024 , 56(1) : 134 -140 . DOI: 10.19964/j.issn.1006-4990.2023-0183
In order to shorten the crystallization time of SAPO-34 molecular sieve at high temperature and improve its life and selectivity in MTO reaction，triethylamine and tetraethyl ammonium hydroxide were used as double templates to rapidly prepare nano-sized SAPO-34 molecular sieve with a particle size of 300~500 nm by step crystallization method.At the same time，the surfactant cetyltrimethyl ammonium bromide（CTAB） was added to further modify the molecular sieve，and the multiporous SAPO-34 molecular sieve（C-ST1T2） was obtained.The physicochemical properties of all the samples were characterized and applied to the catalytic reaction of methanol to olefin.The catalytic performance under certain conditions was investigated.The characterization results showed that the crystallization time of nano-sized SAPO-34 molecular sieve could be shortened by step crystallization.After modification by CTAB，SAPO-34 molecular sieve with multistage pore structure and moderate acid strength was obtained.The catalytic performance test showed that the methanol conversion rate of C-ST1T2 could reach 100%，and the catalytic life could reach 690 min，which was significantly improved compared with the molecular sieve synthesized by single template agent.Meanwhile，the selectivity of low carbon olefin was stable at more than 89%.The results showed that the multistage pore modification of molecular sieve using CTAB was beneficial to further improve the MTO reaction performance of molecular sieve.
Key words： SAPO-34; nano molecular sieves; step-by-step crystallization; MTO reaction
| 1 | 朱伟平，李飞，薛云鹏，等.甲醇制烯烃工艺技术研究进展［J］.天然气化工（C1化学与化工），2013，38（4）：90-94. |
| ZHU Weiping， LI Fei， XUE Yunpeng，et al.Technological advan-ces in methanol to olefins process［J］.Natural Gas Chemical Indu-stry，2013，38（4）：90-94. | |
| 2 | ZHONG Jiawei， HAN Jingfeng， WEI Yingxu，et al.Catalysts and shape selective catalysis in the methanol-to-olefin（MTO） reacti- on［J］.Journal of Catalysis，2021，396：23-31. |
| 3 | RIMAZ S， KOSARI M， ZARINEJAD M，et al.A comprehensive review on sustainability-motivated applications of SAPO-34 molecular sieve［J］.Journal of Materials Science，2022，57（2）：848-886. |
| 4 | YU Wenhe， WU Xiaowen， CHENG Bohao，et al.Synthesis and applications of SAPO-34 molecular sieves［J］.Chemistry：A European Journal，2022，28（11）：e202102787. |
| 5 | 季超，武鲁明，李滨，等.甲醇制烯烃催化剂SAPO-34分子筛的改性研究进展［J］.无机盐工业，2022，54（7）：1-9，90. |
| JI Chao， WU Luming， LI Bin，et al.Research progress on modification of SAPO-34 as catalyst for methanol to olefins［J］.Inorganic Chemicals Industry，2022，54（7）：1-9，90. | |
| 6 | SUN Chao， WANG Yaquan， ZHAO Aijuan，et al.Synthesis of nano-sized SAPO-34 with morpholine-treated micrometer-seeds and their catalytic performance in methanol-to-olefin reactions［J］.Applied Catalysis A：General，2020，589：117314. |
| 7 | RANJBARAN LODRIJEH S， ASKARI S， HALLADJ R.Seeding-induced nano-sized SAPO-34 synthesis with superior MTO performance：Energy-efficient approach with highly reduced OSDA consumption［J］.Powder Technology，2021，389：383-391. |
| 8 | WANG Chan， YANG Miao， TIAN Peng，et al.Dual template-directed synthesis of SAPO-34 nanosheet assemblies with improved stability in the methanol to olefins reaction［J］.Journal of Materials Chemistry A，2015，3（10）：5608-5616. |
| 9 | 邵川，王银忠，秦冬玲，等.酸掺杂原位合成多级孔SAPO-34及用于催化甲醇制烯烃反应［J］.南京工业大学学报（自然科学版），2021，43（5）：600-608. |
| SHAO Chuan， WANG Yinzhong， QIN Dongling，et al.Acid-doped in situ synthesis of hierarchical SAPO-34 and applied in the catalytic methanol to olefin reaction［J］.Journal of Nanjing Tech University（Natural Science Edition），2021，43（5）：600-608. | |
| 10 | 邵武俊，刘春燕，贺宁，等.草酸溶液处理对SAPO-34分子筛物性和催化性能的影响［J］.无机盐工业，2020，52（2）：84-90. |
| SHAO Wujun， LIU Chunyan， HE Ning，et al.Effect of oxalic acid solution treatment on physiochemical properties and catalytic performance of SAPO-34 molecular sieve［J］.Inorganic Chemicals Industry，2020，52（2）：84-90. | |
| 11 | HUANG Yuxuan， MA Hongfang， XU Zhiqiang，et al.Role of nano-sized sheet-like SAPO-34 in bifunctional catalyst for syngas-to-olefins reaction［J］.Fuel，2020，273：117771. |
| 12 | 李强，刘佳佳，李方倪，等.纳米级SAPO-34分子筛的制备及其在甲醇制烯烃反应中的应用进展［J］.化学通报，2019，82（7）：585-589. |
| LI Qiang， LIU Jiajia， LI Fangni，et al.Progress in preparation of nano-scale SAPO-34 molecular sieves and their application in methanol to olefins［J］.Chemistry，2019，82（7）：585-589. | |
| 13 | ASKARI S， BASHARDOUST SIAHMARD A， HALLADJ R，et al.Different techniques and their effective parameters in nano SAPO-34 synthesis：A review［J］.Powder Technology，2016，301：268-287. |
| 14 | LIU Haiyan， KIANFAR E.Investigation the synthesis of nano-SAPO-34 catalyst prepared by different templates for MTO process［J］.Catalysis Letters，2021，151（3）：787-802. |
| 15 | 聂晓明，袁波，贾聪娜，等.甲醇制烯烃（MTO）的生产技术现状及发展趋势［J］.山东化工，2021，50（1）：99-100，102. |
| 16 | RUI Peixin， WANG Baorong， CHEN Feibiao，et al.The hydrothermal synthesis of hierarchical SAPO-34 with improved MTO performance［J］.New Journal of Chemistry，2021，45（25）：11093-11100. |
| 17 | YI Honghong， YANG Kun， TANG Xiaolong，et al.Ultrasound-assisted modification of Al2O3@TiO2-Ce core-shell structure adsorbent for simultaneous desulfurization and denitrification［J］.Journal of Chemical Technology & Biotechnology，2020，95：2261-2271. |
| 18 | YUE Mingbo， JIAO Wenqian， WANG Yimeng，et al.CTAB-directed synthesis of mesoporous γ-alumina promoted by hydroxy polyacids［J］.Microporous and Mesoporous Materials，2010，132（1/2）：226-231. |
| 19 | 王磊，孙毯毯，闫娜娜，等.不同结构导向剂合成不同硅含量SAPO-34分子筛的酸性质［J］.物理化学学报，2022，38（4）：57-64. |
| WANG Lei， SUN Tantan， YAN Nana，et al.Acid properties of SAPO-34 molecular sieves with different Si contents templated by various organic structure-directing agents［J］.Acta Physico-Chimica Sinica，2022，38（4）：57-64. | |
| 20 | VARZANEH A Z， TOWFIGHI J， MOHAMADALIZADEH A.Com-parative study of naphtha cracking over SAPO-34 and HZSM-5：Effects of cerium and zirconium on the catalytic performance［J］.Journal of Analytical and Applied Pyrolysis，2014，107：165-173. |
| 21 | SHALMANI F M， HALLADJ R， ASKARI S.Physicochemical characterization to assess Ni and Zn incorporation into zeotype SAPO-34 nanoparticles synthesized with different mixing methods through ultrasound-promoted crystallization［J］.RSC Advan- ces，2017，7（43）：26756-26769. |
| 22 | VAN VREESWIJK S H， MONAI M， OORD R，et al.Nano-scale insights regarding coke formation in zeolite SSZ-13 subject to the methanol-to-hydrocarbons reaction［J］.Catalysis Science & Technology，2022，12（4）：1220-1228. |
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