渣油加氢脱硫催化剂改进研究进展
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- 英文论文题名：Progress in the improvement of residue hydrodesulfurization catalysts
- 论文作者：刘朔 ; 赵博 ; 曹东炜 ; 袁瑞 ; 赵瑞玉
- 英文论文作者：Shuo Liu ; Zhao ; Cao ; Yuan ; Zhao ; State Key Laboratory of Heavy Oil Processing ; Key Laboratory of Catalysis ; CNPC ; China University of Petroleum(Huadong)
- 年：2016
- 作者机构：中国石油大学重质油国家重点实验室CNPC催化重点实验室;
- 论文关键词：渣油加氢脱硫催化剂 ; 载体 ; 活性组分与载体间相互作用 ; 改进
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十二分会： 多孔功能材料
- 语种：中文
- 分类号：TE624.9
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十二分会 ; 多孔功能材料
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：278k
- 原文格式：D
- 会议级别：全国
摘要
目前渣油加氢脱硫催化剂面临着降低成本、提高活性的要求,其改进通常从载体改性、减弱活性组分与载体间相互作用力(MSI)两方面入手。由于渣油中分子大小分布较宽,理想的渣油加氢脱硫催化剂载体的孔径应呈梯度分布。针对此问题,目前增加载体中较大孔的比例的方法有水热处理、自组装~[1]、扩孔剂添加~[2]和烧结剂添加法~[3]。其中扩孔剂添加法因操作简单、扩孔效果明显而应用广泛,但扩孔后孔径过于弥散且机械强度降低,只有与其他方法配合~[4]才能得到合适的孔径。由于γ-A1_2O_3非惰性载体,其与mO(W)产生强相互作用,限制了活性组分的分散。因此近些年研究用来代替纯γ-A1_2O_3的材料有炭、SiO_2、TiO_2、复合氧化物如SiO_2–Al_2O_3、TiO_2–Al_2O_3、ZrO_2–Al_2O~[5]3等。目前部分商业催化剂中已添加Si/Ti/Zr等元素。常规浸渍过程中金属与载体间作用力太强,导致活性组分分布不均、催化活性高的II型活性相含量太少。目前用于减弱活性组分与载体间作用力的浸渍方法有添加助剂如氟、硼、磷~[6,7]等或添加络合剂如多元有机酸(如柠檬酸)、胺类和二醇类等~[8]。其中研究最多的是磷和柠檬酸,发现两者的添加能显著提高HDS活性。
The progress in the improvement of residue hydrodesulfurization catalysts is discussed,which focuses on two aspects,namely,the support(pore structure,type) and the interaction between metals and supports(MSI).Various pore-enlarging methods are used to improve the pore structures of supports.Then some new materials which replace alumina such as SiO_2,TiO_2 and composite oxides are studied for improving the activity of residue hydrodesulfurization.Finally the effects and mechanisms of secondary additives(phosphorus) and complexing agents(citric acid) to decrease MSI are discussed in detail,which shows that the two methods significantly enhance the activity of residue hydrodesulfurization catalysts.
The progress in the improvement of residue hydrodesulfurization catalysts is discussed,which focuses on two aspects,namely,the support(pore structure,type) and the interaction between metals and supports(MSI).Various pore-enlarging methods are used to improve the pore structures of supports.Then some new materials which replace alumina such as SiO_2,TiO_2 and composite oxides are studied for improving the activity of residue hydrodesulfurization.Finally the effects and mechanisms of secondary additives(phosphorus) and complexing agents(citric acid) to decrease MSI are discussed in detail,which shows that the two methods significantly enhance the activity of residue hydrodesulfurization catalysts.
引文
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[2]Wang,Y;Lan,X;Zhang,K;Chai,Y.Chem.Ind.Eng.Pro,2012,31(3):598.
[3]胡大为,杨清河,聂红,石亚华.石油炼制与化工,2004,(08):46.
[4]Zhang,C;Chai,Y;Wang,X;Li,G.Acta Petrolei Sinica(Petroleum Processing Section),2013,29(2):205.
[5]Badoga,S;Sharma,R.V;Dalai,A.K;Adjaye,J.Ind.Eng.Chem.Res,2014,53(49):18729.
[6]Maity,S.K;Flores,G.A;Ancheyta,J;Rana,M.S.Catal.Today,2008,130(2-4):374.
[7]Sun,M;Nicosia,D;Prins,R.Catal.Today,2003,86(1–4):173.
[8]黄婷婷,柴永明,商红岩,燕群.化工进展,2014,(04):914.