摘要
目前全球范围内出现气候变暖的趋势,解决该问题的核心是如何降低温室气体的产生及对大气的排放。从可持续发展和环境保护的角度出发,研究和开发化石能源的高效、洁净利用技术将成为降低温室气体排放的有效途径。其中,通过费托合成反应(简称F-T合成)获得清洁的液体燃料以减少化石能源直接燃烧带来的污染,是减少温室气体排放的有效手段之一。然而,如何提高F-T合成活性、减少尾气中CO_2和CH_4的产生以及降低反应过程中的能耗是未来F-T合成技术实现工业化生产亟待解决的问题。因此,设计和合成具有高活性、高选择性F-T合成催化剂就成为解决该问题的关键因素之一。
本文将配位聚合物潜在的功能催化优势应用到F-T合成领域当中,设计和合成具有规则空间构型的钴-铈异金属配位聚合物和钴配合物,把含活性钴(稀土助剂铈)的新型钴前驱体负载到γ-Al_2O_3载体上,制备空间有序排列的钴(稀土)催化材料,综合评价了该类催化剂对F-T合成的活性、甲烷及二氧化碳排放的影响。主要工作如下:
1.以吡啶-2,3-二羧酸(2,3-H_2pydc)、吡啶-2,6-二羧酸(2,6-H_2pydc)、吡啶-3,4-二羧酸(3,4-H_2pydc)为配体,采用常规水浴法和水热合成法,设计并合成了五种配合物;利用乙酰丙酮(acacH)配体合成了一例双聚体配合物。对所合成配合物的结构和性质进行了研究。
(1)以吡啶-2,3-二羧酸为配体得到了配合物[Co_2(2,3-Hpydc)_6](3-carboxypyridine)_2·6H_2O;[Co(H_2O)_6][Co(2,3-Hpydc)_3];[Co(2,3-Hpydc)_3]·3H_2O,均由氢键及π-π堆积形成了三维网状结构。配合物[Co_2(2,3-Hpydc)_6](3-carboxypyridine)_2·6H_2O在有机溶剂中具有较好的溶解性,本文选做F-T合成催化剂前驱体。
(2)以吡啶-2,6-二羧酸为配体得到Co、Ce空间排布规则有序的桥联配位聚合物{[Ce_2Co(2,6-pydc)_4(H_2O)_8](H_2O)_7)_n,其结构为一维Zigzag链式结构,并通过丰富的氢键连接成3D超分子配位聚合物。{[Ce_2CO(2,6-pydc)_4(H_2O)_8](H_2O)_7}_n溶于水,本文选做F-T合成催化剂前驱体。
(3)配合物Ce(acac)_3(acacH)_2具有双聚体结构,结构测试表明固态结构中acacH配体以少见的烯醇式中性配体形式与中心Ce(Ⅲ)离子配位,同时烯醇式acacH中的-OH不仅与配体上O形成了分子内氢键,还有一对分子间氢键将相邻的两个分子连接成环状二聚体。
(4)以吡啶-3,4-二羧酸为配体与Ce(Ⅲ)离子反应,得到二维带状链式结构的铈配位聚合物[Ce(3,4-pydc)_2]·H_2O,固体结构中同时存在氢键及π-π堆积作用。
2.选择了不同钴配合物作前驱体浸渍在γ-Al_2O_3载体上制备催化剂,利用所制备的催化剂考察了F-T合成性能,并结合比表面测试(BET)、X射线衍射(XRD)和程序升温还原(TPR)等技术对催化剂进行表征。结果表明:(1)含有机配体的钴(铈)配合物作为前驱体对氧化钴的分散程度大于以硝酸钴为前驱体的参比催化剂。(2)通过带有六元环的大分子配合物在载体中的孔结构表征,可以提供它在载体上的定位信息。
3.在组装的二氧化碳甲烷重整制合成气实验装置上进行了二氧化碳甲烷催化重整制合成气反应,模拟了F-T合成装置与二氧化碳甲烷催化重整装置耦合的生产模式,为进一步将F-T合成与二氧化碳甲烷催化重整装置耦合提供了有益的数据补充。
The global warming issues caused by greenhouse gas(GHG) emissions have been drawn great attention.Hence,many investigations have been focused on the decreasing of the rate of GHG emissions.Fischer Tropsch Synthesis(F-T Synthesis) is one of the efficient techniques to obtain clean liquid fuels and to control the GHG emissions from fossil-fuels burning.How to improve the F-T reaction activity, reduce exhaust of CO_2 and CH_4 as well as energy consumption in the process of F-T synthesis are urgent problems for future industrialization.A key solution for solving the problem is to develop the F-T synthesis catalyst with high activity and high selectivity.
In this paper,we constructed one Co(Ⅱ)-Ce(Ⅲ) polynuclear coordination polymer and a series of cobalt complexes with new space configuration.Two of the complexes were used as catalyst precursors for preparing alumina-supported catalysts for the F-T synthesis,and their catalytic performance were examined.The comprehensive evaluation of the catalysts such as F-T activity,selectivity of methane and carbon dioxide is presented and discussed.
Detailed results are summarized as follows:
1.Six coordination polymers have been obtained at room temperature or under hydrothermal conditions through assembling pyridine-2,3-dicarboxylic acid (2,3-H_2pydc),pyridine-2,6-dicarboxylic acid(2,6-H_2pydc),pyridine-3,4-dicarboxylic acid(3,4-H_2pydc) and acetylacetone(acacH) respectively with cobalt or cerium salt or both.Furthermore,the structural characteristics were investigated.
(1) Complex[Co_2(2,3-Hpydc)_6](3-carboxypyridine)_2·6H_2O;[Co(H_2O)_6][Co(2,3-Hpydc)_3]; [Co(2,3-Hpydc)_3]·3H_2O were synthesized with pyridine-2,3-dicarboxylic acid and cobalt salts,and their 3D network structure was formed by hydrogen bonds andπ-πinteractions.
(2) {[Ce_2Co(2,6-pydc)_4(H_2O)_8](H_2O)_7}_n contained 1D infinite polymeric zigzag chains which were formed through bridging ligands of pyridine-2,6-dicarboxylate.
(3) Complex Ce(acac)_3(acacH)_2 has a dimeric complex structure.The detailed analysis of crystal structure showed that the complex contained intramolecular H-bond and intermolecular H-bond formed through the neutral enol acetylacetone unidentate ligands.
(4) Complex[Ce(3,4-pydc)_2]·H_2O was synthesized by mixing cerium nitrates with pyridine-3,4-dicaboxylic acid solution under hydrothermal condition.It extended in an infinite belt along a-axis and H-bonding interactions also contributed to the 3D network.
2.A series of catalysts were prepared by impregnating different complex precursors onγ-Al_2O_3 support,and characterized by XRD,BET,and TPR techniques.The catalytic performance of these catalysts for F-T synthesis was tested,and their evaluation results are summarized as follows:
(1) Using cobalt complex or cobalt(Ⅱ)-cerium(Ⅲ) heteronuclear coordination polymer as catalyst precursors resulted in a significant increase of cobalt dispersion in comparison with reference catalyst made from cobalt nitrate.
(2) According to porous structure characteristics,the locating information of the macromolecular complexes with a six-member ring in the support could be estimated.
3.The reforming experiment was performed with an assembly device for reforming of methane from carbon dioxide to syngas,and a production mode was simulated by coupling of the F-T reaction device with carbon dioxide reforming unit.
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