本文主要研究内容
作者邸鑫（2019）在《负载型铼基催化剂制备及其双羧酸水相加氢性能》一文中研究指出：纤维素和半纤维素可以转化为多种平台分子,以这些平台分子作为原料生产化学品不仅可以减少石化原料制备精细化学品所需的额外功能化步骤,并且能够提供更加多样化的合成策略。丁二酸等双羧酸是生物平台化合物之一,能够代替现有的C4-C6平台分子,具有非常广阔的应用前景。铼基催化剂因其优异的加氢性能以及稳定性在双羧酸加氢领域极具应用价值。基于此,本论文以负载型铼基催化剂的制备为核心,考察金属载体相互作用、金属间协同作用等因素对双竣酸水相加氢的影响。并在此基础上深入研究双羧酸等反应物加氢反应机理,实现双羧酸的选择性转化。采用微波辅助热解法制备了单金属Re/C催化剂,以得到有效的双羧酸水相加氢体系。结果表明,该方法可以避免使用溶剂,并显著缩短合成时间。通过调变微波输入能量控制铼粒子尺寸,能够实现活性位数量的控制。与浸渍法制备催化剂相比,微波法制备催化剂具有更多的活性位,金属催化效率更高。在丁二酸水相加氢反应中Re/C催化剂可选择性促进四氢呋喃的生成,使其最终选择性达到80%。通过Re/C催化剂上丁二酸加氢反应网络的研究为后续工作奠定了基础。在单金属催化剂基础上,拓展微波法制备出粒子结构均匀的Re-M/C双金属催化剂(M=Ru、Pt和Rh),以深化丁二酸加氢反应研究,实现1,4-丁二醇的选择性制备。结果表明,Re-M金属间协同作用能够在保持高加氢活性的同时抑制催化剂的氢解性质,并且可以提高金属组分的还原效率和氢气活化能力从而增加反应活性。研究证实影响产物选择性的关键是中间产物γ-丁内酯的转化,Re-M金属间协同作用可以改变γ-丁内酯和氢气的活化状态促使其加氢开环生成1,4-丁二醇,且不同类型/强度的金属间协同作用对1,4-丁二醇动力学选择性的影响基本一致。但是Re-Rh/C和Re-Ru/C催化剂上较弱的相互作用无法完全抑制1,4-丁二醇氢解生成正丙醇,使其选择性低于于Re-Pt/C催化剂。此外,动力学研究证明低温更有利于γ-丁内酯加氢开环生成1,4-丁二醇,高温则会促进γ-丁内酯直接加氢脱水生成四氢呋喃。通过对反应机理的认识,控制反应温度可使1,4-丁二醇最终选择性达到80%。通过对不同碳链长度双羧酸加氢的研究,进一步理解中间产物对双羧酸加氢的调控机制。通过合成Re-Ir/C催化剂完善Re基双金属催化剂的研究,并结合反应机理实现不同双羧酸的选择性加氢。结果表明,Re-Ir/C催化剂活性位性质与其它双金属催化剂有所不同,Ir组分主要起到氢气活化的作用,而Re组分的功能主要是吸附双羧酸反应物以及辅助氢气活化。Re-Ir(1:1)催化剂上双竣酸吸附与氢气活化达到平衡,金属间协同作用对催化性能的改善最为明显。丁二酸、戊二酸以及己二酸加氢活性的差异主要来源于不同的加氢中间产物,随着碳链长度的增加环状中间产物内酯(γ-丁内酯等)的含量逐渐减少,链状中间产物端羟基羧酸(6-羟基己酸等)的含量逐渐增加。动力学研究证明金属间协同作用以及反应温度对选择性的影响只有在包含环状中间产物的反应中最为明显,而链状中间产物会增加二醇的转化优势,使其最终选择性达到90%。
Abstract
qian wei su he ban qian wei su ke yi zhuai hua wei duo chong ping tai fen zi ,yi zhe xie ping tai fen zi zuo wei yuan liao sheng chan hua xue pin bu jin ke yi jian shao dan hua yuan liao zhi bei jing xi hua xue pin suo xu de e wai gong neng hua bu zhou ,bing ju neng gou di gong geng jia duo yang hua de ge cheng ce lve 。ding er suan deng shuang suo suan shi sheng wu ping tai hua ge wu zhi yi ,neng gou dai ti xian you de C4-C6ping tai fen zi ,ju you fei chang an kuo de ying yong qian jing 。lai ji cui hua ji yin ji you yi de jia qing xing neng yi ji wen ding xing zai shuang suo suan jia qing ling yu ji ju ying yong jia zhi 。ji yu ci ,ben lun wen yi fu zai xing lai ji cui hua ji de zhi bei wei he xin ,kao cha jin shu zai ti xiang hu zuo yong 、jin shu jian xie tong zuo yong deng yin su dui shuang jun suan shui xiang jia qing de ying xiang 。bing zai ci ji chu shang shen ru yan jiu shuang suo suan deng fan ying wu jia qing fan ying ji li ,shi xian shuang suo suan de shua ze xing zhuai hua 。cai yong wei bo fu zhu re jie fa zhi bei le chan jin shu Re/Ccui hua ji ,yi de dao you xiao de shuang suo suan shui xiang jia qing ti ji 。jie guo biao ming ,gai fang fa ke yi bi mian shi yong rong ji ,bing xian zhe su duan ge cheng shi jian 。tong guo diao bian wei bo shu ru neng liang kong zhi lai li zi che cun ,neng gou shi xian huo xing wei shu liang de kong zhi 。yu jin zi fa zhi bei cui hua ji xiang bi ,wei bo fa zhi bei cui hua ji ju you geng duo de huo xing wei ,jin shu cui hua xiao lv geng gao 。zai ding er suan shui xiang jia qing fan ying zhong Re/Ccui hua ji ke shua ze xing cu jin si qing fu nan de sheng cheng ,shi ji zui zhong shua ze xing da dao 80%。tong guo Re/Ccui hua ji shang ding er suan jia qing fan ying wang lao de yan jiu wei hou xu gong zuo dian ding le ji chu 。zai chan jin shu cui hua ji ji chu shang ,ta zhan wei bo fa zhi bei chu li zi jie gou jun yun de Re-M/Cshuang jin shu cui hua ji (M=Ru、Pthe Rh),yi shen hua ding er suan jia qing fan ying yan jiu ,shi xian 1,4-ding er chun de shua ze xing zhi bei 。jie guo biao ming ,Re-Mjin shu jian xie tong zuo yong neng gou zai bao chi gao jia qing huo xing de tong shi yi zhi cui hua ji de qing jie xing zhi ,bing ju ke yi di gao jin shu zu fen de hai yuan xiao lv he qing qi huo hua neng li cong er zeng jia fan ying huo xing 。yan jiu zheng shi ying xiang chan wu shua ze xing de guan jian shi zhong jian chan wu γ-ding nei zhi de zhuai hua ,Re-Mjin shu jian xie tong zuo yong ke yi gai bian γ-ding nei zhi he qing qi de huo hua zhuang tai cu shi ji jia qing kai huan sheng cheng 1,4-ding er chun ,ju bu tong lei xing /jiang du de jin shu jian xie tong zuo yong dui 1,4-ding er chun dong li xue shua ze xing de ying xiang ji ben yi zhi 。dan shi Re-Rh/Che Re-Ru/Ccui hua ji shang jiao ruo de xiang hu zuo yong mo fa wan quan yi zhi 1,4-ding er chun qing jie sheng cheng zheng bing chun ,shi ji shua ze xing di yu yu Re-Pt/Ccui hua ji 。ci wai ,dong li xue yan jiu zheng ming di wen geng you li yu γ-ding nei zhi jia qing kai huan sheng cheng 1,4-ding er chun ,gao wen ze hui cu jin γ-ding nei zhi zhi jie jia qing tuo shui sheng cheng si qing fu nan 。tong guo dui fan ying ji li de ren shi ,kong zhi fan ying wen du ke shi 1,4-ding er chun zui zhong shua ze xing da dao 80%。tong guo dui bu tong tan lian chang du shuang suo suan jia qing de yan jiu ,jin yi bu li jie zhong jian chan wu dui shuang suo suan jia qing de diao kong ji zhi 。tong guo ge cheng Re-Ir/Ccui hua ji wan shan Reji shuang jin shu cui hua ji de yan jiu ,bing jie ge fan ying ji li shi xian bu tong shuang suo suan de shua ze xing jia qing 。jie guo biao ming ,Re-Ir/Ccui hua ji huo xing wei xing zhi yu ji ta shuang jin shu cui hua ji you suo bu tong ,Irzu fen zhu yao qi dao qing qi huo hua de zuo yong ,er Rezu fen de gong neng zhu yao shi xi fu shuang suo suan fan ying wu yi ji fu zhu qing qi huo hua 。Re-Ir(1:1)cui hua ji shang shuang jun suan xi fu yu qing qi huo hua da dao ping heng ,jin shu jian xie tong zuo yong dui cui hua xing neng de gai shan zui wei ming xian 。ding er suan 、wu er suan yi ji ji er suan jia qing huo xing de cha yi zhu yao lai yuan yu bu tong de jia qing zhong jian chan wu ,sui zhao tan lian chang du de zeng jia huan zhuang zhong jian chan wu nei zhi (γ-ding nei zhi deng )de han liang zhu jian jian shao ,lian zhuang zhong jian chan wu duan qiang ji suo suan (6-qiang ji ji suan deng )de han liang zhu jian zeng jia 。dong li xue yan jiu zheng ming jin shu jian xie tong zuo yong yi ji fan ying wen du dui shua ze xing de ying xiang zhi you zai bao han huan zhuang zhong jian chan wu de fan ying zhong zui wei ming xian ,er lian zhuang zhong jian chan wu hui zeng jia er chun de zhuai hua you shi ,shi ji zui zhong shua ze xing da dao 90%。
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论文作者分别是来自大连理工大学的邸鑫，发表于刊物大连理工大学2019-07-19论文，是一篇关于双羧酸加氢论文,铼基双金属催化剂论文,动力学研究论文,构效关系论文,大连理工大学2019-07-19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，资料来自大连理工大学2019-07-19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：双羧酸加氢论文; 铼基双金属催化剂论文; 动力学研究论文; 构效关系论文; 大连理工大学2019-07-19论文;