本文主要研究内容
作者刘飘（2019）在《ZSM-5@t-ZrO2催化甲醇和硫化氢反应预硫化及失活行为研究》一文中研究指出：鉴于ZSM-5@t-ZrO2核壳催化剂优异催化性能,从新型结构催化剂设计开发和工业催化应用角度出发,为进一步揭示该催化剂预硫化作用机制和失活行为,论文首先研究预硫化条件对ZSM-5@t-ZrO2核壳催化剂物化性质及催化性能的影响,揭示了预硫化作用机制;以t-ZrO2、ZSM-5及ZSM-5/t-ZrO2物理混合催化剂为参考对比,研究了反应条件对ZSM-5@t-ZrO2核壳催化剂积碳积硫量和物种的影响,揭示了核壳催化剂积碳积硫失活规律。论文率先考察了不同预硫化时间对ZSM-5@t-ZrO2核壳催化剂硫醇化反应性能的影响,预硫化3h甲醇转化率92.09%,甲硫醇选择性90.95%,与未预硫化催化剂相比,甲醇转化率和甲硫醇选择性分别提高了3.83%和3.32%。借助TEM、XRD、XPS、NH3/CO2-TPD和NH3/CO2-IR等表征手段,以ZSM-5/t-ZrO2物混催化剂为对比参考,对比研究了未硫化和预硫化3h对ZSM-5@t-ZrO2核壳催化剂物化性质的影响。结果表明,预硫化对包覆状ZSM-5@t-ZrO2核壳催化剂晶相组成影响较小,但对表面酸碱性质影响较大。预硫化使核壳催化剂弱酸和中强酸强度增大,总酸量增至0.078mmol·g-1;弱碱和中强碱强度下降,总碱量降至0.067mmol·g-1。NH3/CO2-IR结合XPS分析表明了预硫化过程直接修饰了催化剂壳相t-ZrO2致使L酸增加而L碱下降。预硫化后形成的壳（t-ZrO2、L碱活性位）-核（ZSM-5、B酸活性位）特殊反应路径和基于复合固溶相界面形成的适宜L-B酸协同活性中心是催化剂硫醇化反应高活性的主要原因。以t-ZrO2、ZSM-5及ZSM-5/t-ZrO2物混催化剂为对比参考,研究了反应时间和温度对ZSM-5@t-ZrO2核壳催化剂积碳积硫量和物种的影响,借助TPO-MS、TG-IR、Raman、XRF、XPS、NH3/CO2-TPD、GC和GC-MS等表征手段揭示了积碳积硫量和物种的变化规律。结果表明,失活时t-ZrO2、ZSM-5、ZSM-5/t-ZrO2、ZSM-5@t-ZrO2积碳积硫量分别为28.39mg/gcatalyst、28.12mg/gcatalyst、25.96mg/gcatalyst和16.62mg/gcatalyst,积碳积硫形成速率分别为2.37mg/gcatalyst·h、3.52mg/gcatalyst·h、2.16mg/gcatalyst·h和0.83mg/gcatalyst·h,ZSM-5@t-ZrO2核壳催化剂具有最低积碳积硫量和最小积碳积硫形成速率。随反应温度升高,ZSM-5@t-ZrO2核壳催化剂积碳积硫形成速率逐渐增大。催化剂积碳积硫物种以多甲基苯、多甲基萘和含C-S、S-S键的化合物、环状单质硫为主。随反应时间增加,积碳积硫物种由中低温向高温物种转移;随反应温度升高,积碳物种由中低温物种向高温物种转移,积硫物种在低于370℃时呈现向高温物种转移趋势,但高于370℃时呈现向中低温物种转移趋势。与ZSM-5/t-ZrO2催化剂相比,ZSM-5@t-ZrO2催化剂的环状硫化物占比较高,大分子尺寸积硫物种更多,这与核壳结构催化剂特殊微-介孔体系有足够空间发生环化反应,并允许生成更多环状硫化物有关,同时构筑形成的微-介孔体系有助于减弱分子扩散限制,延缓催化剂积碳积硫失活速率,表现出优异的抗积碳积硫失活能力。
Abstract
jian yu ZSM-5@t-ZrO2he ke cui hua ji you yi cui hua xing neng ,cong xin xing jie gou cui hua ji she ji kai fa he gong ye cui hua ying yong jiao du chu fa ,wei jin yi bu jie shi gai cui hua ji yu liu hua zuo yong ji zhi he shi huo hang wei ,lun wen shou xian yan jiu yu liu hua tiao jian dui ZSM-5@t-ZrO2he ke cui hua ji wu hua xing zhi ji cui hua xing neng de ying xiang ,jie shi le yu liu hua zuo yong ji zhi ;yi t-ZrO2、ZSM-5ji ZSM-5/t-ZrO2wu li hun ge cui hua ji wei can kao dui bi ,yan jiu le fan ying tiao jian dui ZSM-5@t-ZrO2he ke cui hua ji ji tan ji liu liang he wu chong de ying xiang ,jie shi le he ke cui hua ji ji tan ji liu shi huo gui lv 。lun wen lv xian kao cha le bu tong yu liu hua shi jian dui ZSM-5@t-ZrO2he ke cui hua ji liu chun hua fan ying xing neng de ying xiang ,yu liu hua 3hjia chun zhuai hua lv 92.09%,jia liu chun shua ze xing 90.95%,yu wei yu liu hua cui hua ji xiang bi ,jia chun zhuai hua lv he jia liu chun shua ze xing fen bie di gao le 3.83%he 3.32%。jie zhu TEM、XRD、XPS、NH3/CO2-TPDhe NH3/CO2-IRdeng biao zheng shou duan ,yi ZSM-5/t-ZrO2wu hun cui hua ji wei dui bi can kao ,dui bi yan jiu le wei liu hua he yu liu hua 3hdui ZSM-5@t-ZrO2he ke cui hua ji wu hua xing zhi de ying xiang 。jie guo biao ming ,yu liu hua dui bao fu zhuang ZSM-5@t-ZrO2he ke cui hua ji jing xiang zu cheng ying xiang jiao xiao ,dan dui biao mian suan jian xing zhi ying xiang jiao da 。yu liu hua shi he ke cui hua ji ruo suan he zhong jiang suan jiang du zeng da ,zong suan liang zeng zhi 0.078mmol·g-1;ruo jian he zhong jiang jian jiang du xia jiang ,zong jian liang jiang zhi 0.067mmol·g-1。NH3/CO2-IRjie ge XPSfen xi biao ming le yu liu hua guo cheng zhi jie xiu shi le cui hua ji ke xiang t-ZrO2zhi shi Lsuan zeng jia er Ljian xia jiang 。yu liu hua hou xing cheng de ke （t-ZrO2、Ljian huo xing wei ）-he （ZSM-5、Bsuan huo xing wei ）te shu fan ying lu jing he ji yu fu ge gu rong xiang jie mian xing cheng de kuo yi L-Bsuan xie tong huo xing zhong xin shi cui hua ji liu chun hua fan ying gao huo xing de zhu yao yuan yin 。yi t-ZrO2、ZSM-5ji ZSM-5/t-ZrO2wu hun cui hua ji wei dui bi can kao ,yan jiu le fan ying shi jian he wen du dui ZSM-5@t-ZrO2he ke cui hua ji ji tan ji liu liang he wu chong de ying xiang ,jie zhu TPO-MS、TG-IR、Raman、XRF、XPS、NH3/CO2-TPD、GChe GC-MSdeng biao zheng shou duan jie shi le ji tan ji liu liang he wu chong de bian hua gui lv 。jie guo biao ming ,shi huo shi t-ZrO2、ZSM-5、ZSM-5/t-ZrO2、ZSM-5@t-ZrO2ji tan ji liu liang fen bie wei 28.39mg/gcatalyst、28.12mg/gcatalyst、25.96mg/gcatalysthe 16.62mg/gcatalyst,ji tan ji liu xing cheng su lv fen bie wei 2.37mg/gcatalyst·h、3.52mg/gcatalyst·h、2.16mg/gcatalyst·hhe 0.83mg/gcatalyst·h,ZSM-5@t-ZrO2he ke cui hua ji ju you zui di ji tan ji liu liang he zui xiao ji tan ji liu xing cheng su lv 。sui fan ying wen du sheng gao ,ZSM-5@t-ZrO2he ke cui hua ji ji tan ji liu xing cheng su lv zhu jian zeng da 。cui hua ji ji tan ji liu wu chong yi duo jia ji ben 、duo jia ji nai he han C-S、S-Sjian de hua ge wu 、huan zhuang chan zhi liu wei zhu 。sui fan ying shi jian zeng jia ,ji tan ji liu wu chong you zhong di wen xiang gao wen wu chong zhuai yi ;sui fan ying wen du sheng gao ,ji tan wu chong you zhong di wen wu chong xiang gao wen wu chong zhuai yi ,ji liu wu chong zai di yu 370℃shi cheng xian xiang gao wen wu chong zhuai yi qu shi ,dan gao yu 370℃shi cheng xian xiang zhong di wen wu chong zhuai yi qu shi 。yu ZSM-5/t-ZrO2cui hua ji xiang bi ,ZSM-5@t-ZrO2cui hua ji de huan zhuang liu hua wu zhan bi jiao gao ,da fen zi che cun ji liu wu chong geng duo ,zhe yu he ke jie gou cui hua ji te shu wei -jie kong ti ji you zu gou kong jian fa sheng huan hua fan ying ,bing yun hu sheng cheng geng duo huan zhuang liu hua wu you guan ,tong shi gou zhu xing cheng de wei -jie kong ti ji you zhu yu jian ruo fen zi kuo san xian zhi ,yan huan cui hua ji ji tan ji liu shi huo su lv ,biao xian chu you yi de kang ji tan ji liu shi huo neng li 。
论文参考文献
论文详细介绍
论文作者分别是来自贵州大学的刘飘，发表于刊物贵州大学2019-07-16论文，是一篇关于预硫化论文,积碳积硫量论文,积碳积硫物种论文,甲硫醇论文,贵州大学2019-07-16论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自贵州大学2019-07-16论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：预硫化论文; 积碳积硫量论文; 积碳积硫物种论文; 甲硫醇论文; 贵州大学2019-07-16论文;