本文主要研究内容
作者张永康(2019)在《基于CuZnOx和Cu-MOR催化剂构建的串联床层对合成气制乙醇的研究》一文中研究指出:乙醇作为重要的低碳醇,既可用作化工合成的基本原料,而且本身也是一种清洁能源,将煤基资源转化为乙醇有利于能源的清洁高效利用。目前,由合成气经串联催化间接制乙醇工艺受到研究者的广泛认可。其中,主要的工艺路线为合成气制甲醇、甲醇羰基化制乙酸甲酯及乙酸甲酯加氢获得乙醇,采用的催化剂分别为铜基(CO活化组分)、氢型丝光沸石(H-MOR,羰基化组分)以及铜基催化剂(加氢组分),但由于该路线涉及工艺过程较多,相关的报道较少,尤其对羰基化组分作用机理的研究仍不明确。本论文中作者通过三种催化剂构建的串联床层在一个反应器内实现了合成气到乙醇的转化,设计实验并结合不同的表征手段初步探究了羰基化组分中Cu物种的作用机理以及Br?nsted(B)酸再生现象。本论文的研究内容具体如下:1.CuZnOx与Cu-H-MOR三明治型床层的构建及催化合成气制乙醇反应性能研究采用共沉淀法及离子交换法分别制得CuZnOx及Cu-H-MOR催化剂,通过N2吸附-脱附、XRD、STEM、XPS、XAES、CO-TPD、FT-IR、NH3-TPD、UV-vis等表征手段,主要对Cu-H-MOR催化剂中铜物种以及B酸位点的变化情况进行了分析。在一个反应器内构建的CuZnOx|Cu-H-MOR|CuZnOx三明治型床层将CO活化、羰基化以及加氢过程在4.6MPa和200°C有效地偶联。通过考察不同浓度(0.05-0.5mol/L)硝酸铜溶液改性的H-MOR在该床层模式下对合成气制乙醇的催化性能,发现铜物种引入之后可明显降低DME的选择性并提高乙醇的选择性,其中通过0.1mol/L的硝酸铜溶液与H-MOR离子交换之后(即0.1CM)获得的乙醇选择性较高为15.62%,CO的转化率为7.73%。基于以上研究,进一步测试了CuZnOx|0.1CM|CuZnOx在不同还原温度下的催化性能,结合FT-IR、CO-TPD、XPS等表征结果作者认为羰基化组分中的Cu+物种对乙醇合成过程既有利也有弊,一方面其通过吸附并活化CO促进了羰基化过程,另一方面其与乙酰阳离子(中间体)的静电作用可能促进后者转化为乙烯酮进而转化为乙烷。表征结果表明离子交换过程中铜离子可能会优先交换八元环孔道以及侧袋孔口位置的B酸位点;在还原过程中还原温度不仅影响Cu物种的价态变化,同时也影响其在分子筛孔道中的分布;特别的,侧袋孔口位置不仅发生B酸位点的再生,而且可能发生Cu+离子与再生B酸位点的二次离子交换,随着还原温度的进一步增加B酸位点会二次再生。2.CuZnOx与Cu-Na-MOR三明治型床层催化合成气制乙醇反应性能研究采用共沉淀法及离子交换法分别制得CuZnOx及Cu-Na-MOR催化剂,通过N2吸附-脱附、XRD、NH3-TPD等表征手段,主要对Cu-Na-MOR催化剂中酸量的变化情况进行了分析。基于串联床层CuZnOx|Cu-Na-MOR|CuZnOx实现了合成气转化制乙醇的目的,通过测试不同浓度硝酸铜溶液处理的Na-MOR在串联模式下对合成气制乙醇的催化性能,最高乙醇选择性为12.11%,CO转化率为8.07%。结合表征结果初步确定了离子交换过程可再生钠型丝光沸石八元环孔道内的B酸位点。为研究第一、二床层活性组分的耦合方式对合成气转化制乙醇催化性能的影响,分别测试了串联、颗粒混合以及球磨等不同的催化剂耦合方式对反应结果的影响,结果发现耦合方式通过改变活性位点的接近距离对催化性能产生强烈的影响,活性位点之间的距离越近CO的转化率越高,乙醇的选择性越小,烷烃(尤其乙烷)的选择性急剧增加。
Abstract
yi chun zuo wei chong yao de di tan chun ,ji ke yong zuo hua gong ge cheng de ji ben yuan liao ,er ju ben shen ye shi yi chong qing jie neng yuan ,jiang mei ji zi yuan zhuai hua wei yi chun you li yu neng yuan de qing jie gao xiao li yong 。mu qian ,you ge cheng qi jing chuan lian cui hua jian jie zhi yi chun gong yi shou dao yan jiu zhe de an fan ren ke 。ji zhong ,zhu yao de gong yi lu xian wei ge cheng qi zhi jia chun 、jia chun tang ji hua zhi yi suan jia zhi ji yi suan jia zhi jia qing huo de yi chun ,cai yong de cui hua ji fen bie wei tong ji (COhuo hua zu fen )、qing xing si guang fei dan (H-MOR,tang ji hua zu fen )yi ji tong ji cui hua ji (jia qing zu fen ),dan you yu gai lu xian she ji gong yi guo cheng jiao duo ,xiang guan de bao dao jiao shao ,you ji dui tang ji hua zu fen zuo yong ji li de yan jiu reng bu ming que 。ben lun wen zhong zuo zhe tong guo san chong cui hua ji gou jian de chuan lian chuang ceng zai yi ge fan ying qi nei shi xian le ge cheng qi dao yi chun de zhuai hua ,she ji shi yan bing jie ge bu tong de biao zheng shou duan chu bu tan jiu le tang ji hua zu fen zhong Cuwu chong de zuo yong ji li yi ji Br?nsted(B)suan zai sheng xian xiang 。ben lun wen de yan jiu nei rong ju ti ru xia :1.CuZnOxyu Cu-H-MORsan ming zhi xing chuang ceng de gou jian ji cui hua ge cheng qi zhi yi chun fan ying xing neng yan jiu cai yong gong chen dian fa ji li zi jiao huan fa fen bie zhi de CuZnOxji Cu-H-MORcui hua ji ,tong guo N2xi fu -tuo fu 、XRD、STEM、XPS、XAES、CO-TPD、FT-IR、NH3-TPD、UV-visdeng biao zheng shou duan ,zhu yao dui Cu-H-MORcui hua ji zhong tong wu chong yi ji Bsuan wei dian de bian hua qing kuang jin hang le fen xi 。zai yi ge fan ying qi nei gou jian de CuZnOx|Cu-H-MOR|CuZnOxsan ming zhi xing chuang ceng jiang COhuo hua 、tang ji hua yi ji jia qing guo cheng zai 4.6MPahe 200°Cyou xiao de ou lian 。tong guo kao cha bu tong nong du (0.05-0.5mol/L)xiao suan tong rong ye gai xing de H-MORzai gai chuang ceng mo shi xia dui ge cheng qi zhi yi chun de cui hua xing neng ,fa xian tong wu chong yin ru zhi hou ke ming xian jiang di DMEde shua ze xing bing di gao yi chun de shua ze xing ,ji zhong tong guo 0.1mol/Lde xiao suan tong rong ye yu H-MORli zi jiao huan zhi hou (ji 0.1CM)huo de de yi chun shua ze xing jiao gao wei 15.62%,COde zhuai hua lv wei 7.73%。ji yu yi shang yan jiu ,jin yi bu ce shi le CuZnOx|0.1CM|CuZnOxzai bu tong hai yuan wen du xia de cui hua xing neng ,jie ge FT-IR、CO-TPD、XPSdeng biao zheng jie guo zuo zhe ren wei tang ji hua zu fen zhong de Cu+wu chong dui yi chun ge cheng guo cheng ji you li ye you bi ,yi fang mian ji tong guo xi fu bing huo hua COcu jin le tang ji hua guo cheng ,ling yi fang mian ji yu yi xian yang li zi (zhong jian ti )de jing dian zuo yong ke neng cu jin hou zhe zhuai hua wei yi xi tong jin er zhuai hua wei yi wan 。biao zheng jie guo biao ming li zi jiao huan guo cheng zhong tong li zi ke neng hui you xian jiao huan ba yuan huan kong dao yi ji ce dai kong kou wei zhi de Bsuan wei dian ;zai hai yuan guo cheng zhong hai yuan wen du bu jin ying xiang Cuwu chong de jia tai bian hua ,tong shi ye ying xiang ji zai fen zi shai kong dao zhong de fen bu ;te bie de ,ce dai kong kou wei zhi bu jin fa sheng Bsuan wei dian de zai sheng ,er ju ke neng fa sheng Cu+li zi yu zai sheng Bsuan wei dian de er ci li zi jiao huan ,sui zhao hai yuan wen du de jin yi bu zeng jia Bsuan wei dian hui er ci zai sheng 。2.CuZnOxyu Cu-Na-MORsan ming zhi xing chuang ceng cui hua ge cheng qi zhi yi chun fan ying xing neng yan jiu cai yong gong chen dian fa ji li zi jiao huan fa fen bie zhi de CuZnOxji Cu-Na-MORcui hua ji ,tong guo N2xi fu -tuo fu 、XRD、NH3-TPDdeng biao zheng shou duan ,zhu yao dui Cu-Na-MORcui hua ji zhong suan liang de bian hua qing kuang jin hang le fen xi 。ji yu chuan lian chuang ceng CuZnOx|Cu-Na-MOR|CuZnOxshi xian le ge cheng qi zhuai hua zhi yi chun de mu de ,tong guo ce shi bu tong nong du xiao suan tong rong ye chu li de Na-MORzai chuan lian mo shi xia dui ge cheng qi zhi yi chun de cui hua xing neng ,zui gao yi chun shua ze xing wei 12.11%,COzhuai hua lv wei 8.07%。jie ge biao zheng jie guo chu bu que ding le li zi jiao huan guo cheng ke zai sheng na xing si guang fei dan ba yuan huan kong dao nei de Bsuan wei dian 。wei yan jiu di yi 、er chuang ceng huo xing zu fen de ou ge fang shi dui ge cheng qi zhuai hua zhi yi chun cui hua xing neng de ying xiang ,fen bie ce shi le chuan lian 、ke li hun ge yi ji qiu mo deng bu tong de cui hua ji ou ge fang shi dui fan ying jie guo de ying xiang ,jie guo fa xian ou ge fang shi tong guo gai bian huo xing wei dian de jie jin ju li dui cui hua xing neng chan sheng jiang lie de ying xiang ,huo xing wei dian zhi jian de ju li yue jin COde zhuai hua lv yue gao ,yi chun de shua ze xing yue xiao ,wan ting (you ji yi wan )de shua ze xing ji ju zeng jia 。
论文参考文献
论文详细介绍
论文作者分别是来自太原理工大学的张永康,发表于刊物太原理工大学2019-07-26论文,是一篇关于合成气论文,乙醇论文,串联催化论文,物种论文,太原理工大学2019-07-26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,资料来自太原理工大学2019-07-26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:合成气论文; 乙醇论文; 串联催化论文; 物种论文; 太原理工大学2019-07-26论文;