Investigation of the direct catalytic conversion of methanol and ethanol to propylene

甲醇、乙醇直接催化转化制丙烯的研究

• 批准号: 498384863
• 负责人: Professor Dr. Jan J. Weigand
• 金额: --
• 依托单位: Professur für Anorganische Molekülchemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/498384863?language=en
• 关键词: Investigation; direct; catalytic; conversion; methanol

In the context of climate change, dropping ethanol price and rising demand and price for ethylene and propylene, the development of new sustainable on-purpose methods for conversion of ethylene, (bio-)ethanol and methanol to “green” propylene and other olefins is a major task for this decade. Compared to “green” ethylene by Braskem for polymers industry, new methods to produce propylene and follow-up products for PP, PEG etc. have attracted considerable attention.From the current state of catalytic direct and hydrocarbon pool conversion of alcohols on zeolites, two major economic questions arise: (i) For different process conditions and catalyst materials, which conversion routes promote the desired product formation of propylene from methanol or ethanol? (ii) Which catalyst properties promote the desired conversion routes to a selective production of propylene from methanol, ethanol or both in mixture?In a more scientific point of view, the following questions will be investigated more deeply: (iii) Which catalytic surface reaction steps and which interdependent kinetics are necessary for a selective propylene formation? (iv) From thermodynamics, which process routes are dominantly driven by enthalpy, which by entropy and which are re-directed by pore geometry and morphology?The work program is splitted into zeolite synthesis and characterization, catalytic testing and mechanistic evaluation experiments. Beside solid-state characterization of catalysts (XRD, NMR, IR, SEM, EDX, ICP-OES, TPD), catalytic testing in a continuous mode will be combined with sophisticated mechanistic studies of adsorption kinetics (e.g. Howarth kinetics) and detailed hydrocarbon product networks (intermediates). As a specialty, new interdepending mechanistic conclusions of static reaction chain networks will be investigated by new mixed isotope scrambling experiments with D6-ethanol and 13C-methanol and GC/MS analysis. Despite to current discussions, it should reveal a dynamic competition of different direct and pool formation routes to propylene, in contrast to total exclusion of certain routes. Furthermore, the experiments will reveal highly selective parameter fields with respective deactivation behavior of catalysts. The knowledge-based control of the conversion routes will enable to design suitable catalysts for industry.With respect to current price developments, there is already a need for MTP technologies (methanol-to-propylene) and there will be an economic need for ETP technologies (ethanol/ethylene-to-propylene) within the next 5-10 years. Furthermore, new investigations direct to a combined methanol and ethanol (or ethylene) conversion to olefins, such as propylene (METO), which show synergistic effects in product selectivity and catalyst deactivation. Such a selective process would be a scientific and economic breakthrough.

在气候变化、乙醇价格下降以及对乙烯和丙烯的需求和价格上升的背景下，开发新的可持续的专门用于将乙烯、(生物)乙醇和甲醇转化为“绿色”丙烯和其他烯烃的方法是本十年的一项主要任务。与Braskem用于聚合物工业的“绿色”乙烯相比，生产丙烯的新方法以及后续的PP、PEG等产品引起了人们的极大关注。从分子筛上醇类直接转化和碳氢化合物池转化的现状来看，存在两个主要的经济问题：(I)对于不同的工艺条件和催化剂材料，哪条转化路线促进了由甲醇或乙醇合成丙烯的预期产物？(Ii)哪些催化剂的性质促进了从甲醇、乙醇或两者的混合物中选择性地转化为丙烯的所需路线？从更科学的观点来看，将更深入地研究以下问题：(Iii)选择性地生成丙烯需要哪些催化表面反应步骤以及哪些相互依赖的动力学？(4)从热力学角度看，哪些工艺路线主要由热驱动，哪些工艺路线主要由熵驱动，哪些工艺路线受孔几何和形貌的影响？工作计划分为沸石合成与表征实验、催化测试实验和机理评价实验。除了催化剂的固态表征(X射线衍射、核磁共振、红外光谱、扫描电子显微镜、能谱分析、电感耦合等离子体发射光谱、TPD)外，连续模式的催化测试将与复杂的吸附动力学机理研究(例如，Howarth动力学)和详细的碳氢化合物产品网络(中间体)相结合。作为一个特长，静态反应链网络相互依赖的新的机理结论将通过与D6-乙醇和13C-甲醇的新的混合同位素扰乱实验和GC/MS分析来探索。尽管有目前的讨论，但它应该揭示出不同的直接和成池路线对丙烯的动态竞争，而不是完全排除某些路线。此外，实验还将揭示具有高度选择性的参量场和催化剂的失活行为。对转化路线的基于知识的控制将能够为工业设计合适的催化剂。就目前的价格发展而言，对MTP技术(甲醇到丙烯)的需求已经存在，在未来5-10年内对ETP技术(乙醇/乙烯到丙烯)将有经济上的需求。此外，新的研究指向甲醇和乙醇(或乙烯)联合转化为烯烃，如丙烯(METO)，这在产品选择性和催化剂失活方面显示出协同效应。这种有选择的过程将是一项科学和经济上的突破。