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中科院理论升级:"煤取代石油"的日子又近一步(图)

2017-07-10 16:58:51   中科院之声

2015年底第九套神华榆林

年产180万吨甲醇制取年产60万吨烯烃DMTO装置投产

至2015年底已经投产的九套DMTO装置

甲醇制烯烃国家工程实验室下属部分研究组

DMTO机理研究再升级

甲醇制烯烃国家工程实验室一直坚持应用研究与基础研究并重,不但在MTO过程工业化方面取得巨大成功,而且长期致力于该化学过程中的基础科学问题研究。虽然MTO过程稳态反应阶段的间接机理已形成广泛的共识,但MTO反应中从C1物种甲醇或者二甲醚生成第一个C-C键的反应一直是C1化学中极具挑战性和争议性的课题。由于转化发生在反应的最初始阶段,难以捕获中间物种,一直以来所提出的反应机理缺乏直接证据。

最近,大连化学物理研究所刘中民院士、魏迎旭研究员团队在甲醇制烯烃初始C-C键生成机理方面取得新进展,相关研究成果以热点文章形式发表在《德国应用化学》(Angewandte ChemieInternational Edition)杂志上(doi: 10.1002/anie.201703902),并被推荐为内封面文章。

刘中民院士

魏迎旭研究员

研究成果论文文章

本项工作中,研究人员通过在线监测最初始反应阶段,推测初始烯烃来源于催化剂表面C1吸附物种的直接转化;随后通过催化剂液氮淬冷和固体核磁表征,确定了催化剂上最初始反应阶段存在的表面C1吸附物种(甲醇和二甲醚)和C1活性物种(表面甲氧基和三甲基氧鎓离子);进一步通过原位固体核磁研究,在真实甲醇转化反应条件下,成功捕捉到二甲醚C-H键活化后生成的类亚甲氧基(methyleneoxyanalogue)物种,由此获取了C1物种活化生成第一个C-C键的直接证据;在此基础上提出了初始烯烃生成的反应路径—表面甲氧基/三甲基氧鎓离子协助甲醇/二甲醚活化转化的协同反应机理。

反应机理示意图

这是首次在MTO反应过程中原位观测到C1物种的初始活化和转化,这一发现将关联甲醇初始转化的直接机理和高效转化阶段的间接机理,建立甲醇转化反应完整的反应历程。此前在MTO反应稳定阶段烃池(HydrocarbonPool)机理的研究中,研究人员曾直接捕捉到最为重要的反应中间物种—苯基和环戊烯基碳正离子中间体,并确定了分子筛催化甲醇制烯烃的催化循环途径(J.Am.Chem.Soc.2012,134(2),836—839;Angew.Chem.Int.Ed.2013,52(44),11564-11568)。

分子筛催化甲醇制烯烃的催化循环途径

这些基础机理研究的工作,不但丰富了C1催化化学的基本理论,也对DMTO的工业应用具有重要的促进和支撑作用。

责任编辑:杨晓晨 CN067
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