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Title:
半纤维素改性HZSM-5分子筛及其催化丁烯齐聚反应研究
Author: 李超
Degree Level: 硕士
Issued Date: 2017-05
Degree Grantor: 中国科学院大学
Place of Degree Grantor: 青岛
Supervisor: 半纤维素 ; 改性 ; HZSM-5 ; 丁烯齐聚
Keyword: 化学工程
Alternative Title: 化学工程
Major: 随着社会和经济的发展,石油资源日益枯竭,而工业生产、交通、军事、航空等方面对高品质液体燃料的需求却不断增加。开发非石油路线生产清洁燃料,对合理调整我国能源结构、生产环境友好型液体燃料具有重要的战略意义。以低碳烯烃为原料进行的齐聚反应,不仅是制备发动机燃料、增塑剂、润滑油、防冻剂等化学品的有效途径,更是制备高品质清洁液体燃料的一条重要途径。高效催化剂的开发是烯烃齐聚技术进步的关键因素,具备MFI型三维孔道结构和良好酸性的HZSM-5分子筛,因其适宜孔道的限域作用,在烯烃齐聚中表现出很好的抗积碳能力,且产物不易支链化,被认为是C3=、C4=烯烃齐聚制备高品质液体燃料最具前景的催化剂。 本论文以HZSM-5基分子筛为催化剂,创新性地选择生物质半纤维素对其进行改性,并在此基础上添加引发剂过硫酸铵和四甲基乙二胺,进一步探索其对HZSM-5分子筛晶化时间、酸性等影响。并且以丁烯齐聚为探针反应,考察半纤维素改性HZSM-5分子筛对低碳烯烃齐聚的催化能力,主要研究内容包括以下几个方面: 以生物质半纤维素为添加剂,使用水热法制备ZSM-5分子筛,利用半纤维素大分子碳骨架结构及表面丰富的羟基改善ZSM-5分子筛的形貌、织构特性及酸性等特征。考察不同含量半纤维素改性的HZSM-5分子筛,结果表明当半纤维素含量为1.6 wt. %时,改性分子筛的比表面积、介孔体积最大,酸性最强,催化丁烯齐聚表现出了明显的优势,反应140 h转化率仍维持在80%左右,且三聚、四聚产物最多,柴油组分的选择性最高。 为活化半纤维素表面丰富的羟基,使其产生羟基自由基以加速ZSM-5分子筛的晶化进程,在半纤维素改性的基础上,添加不同含量的过硫酸铵和四甲基乙二胺为引发剂,使其将半纤维素表面丰富的羟基活化为羟基自由基,以缩短ZSM-5分子筛的晶化时间。结果发现,该实验条件下引发剂的加入对分子筛结晶度和形貌的差异在短时间内有一定影响;与此同时,发现添加0.5 wt.%引发剂后的HZSM-5分子筛的酸性显著增强,出现了强酸,在丁烯齐聚反应评价时,催化性能进一步提高,反应前60 h的转化率维持在90 %,柴油选择性最高也稳定在90 %左右。
Abstract: With the development of economy and society, petroleum resource drying up, while more and more high quality liquid fules are needed from industrial production, transportation, military and aviation, etc. So, development of non-petroleum routes to produce clean fuels has important strategic significance for producing environmental friendly liquid fuels as well as adjusting energy structure in our country. The oligomerization reaction of light olefins is not only an effective way to produce motor fuel, plasticizer, lubricating oil, antifreeze and other chemicals, but also an important way to prepare high quality clean liquid fuels. Research and optimization of catalyst is the key to the progress of oligomerization technology. Owning the unique MFI three - dimensional channel structure, good acidic and suitable channel confined effect, HZSM-5 showed good resisrant to carbon deposition capability, and the products are not easy to be branched chain, so it is considered to be the most promising catalysts for C3= and C4= olefins oligomerization. In this work, HZSM-5 zeolite was studied as catalyst for olefin oligomerization. Biomass hemicellulose was used as additive to modify it, ammonium persulphate and tetramethylethylenediamine were added as initiator to explore the crystallization process and properties of HZSM-5 further. Butene oligomerization was tested to inspect the catalytic ability on light olifins oligomerization reaction of modified HZSM-5. The main bodies of the work included the following aspects: With hemicellulose as additive, ZSM-5 was prepared using hydrothermal method. The macromolecular carbon skeleton structure and the rich hydroxyl of hemicelluloses were used to improve the morphology, texture characteristics as well as acidity of HZSM-5. Preparation of the modified HZSM-5 with different content of hemicellulose, the results indicated that the HZSM-5 with 1.6 wt. % hemicellulose has the biggest BET surface and mesoporous volume, and the strongest acidity, and exhibited the best activity and stability on the butene oligomerization reaction, the conversion maintained about 80% after 140 h on stream. What’s more, it includes the highest selectivities of the trimer, tetramer and diesel component in the products. For activation the surface hydroxyl groups on the hemicellulose, ammonium persulphate and tetramethylethylenediamine were added as initiator on the basis of the hemicellulose to accelerate the crystallization ZSM-5. The results show, crystallinity and morphology of ZSM-5 can influnced by the initiator in a short time. The acidity of the modified HZSM-5 with 0.5 wt. % initiator enhanced obviously, catalytic ability on butene oligomerizaiton further improved, the conversion maintained above 90% for 60 h on stream, and the bset selectivity of diesel remained above 90%.
English Abstract: 中文
Language: 中文
Department: 热化学转化团队
Available Date: 2018-06
DOC Type: 学位论文
Content Type: 学位论文
URI: http://ir.qibebt.ac.cn/handle/337004/9974
Appears in Collections:热化学转化团队_学位论文

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description.institution: 中国科学院大学

Recommended Citation:
李超. 半纤维素改性HZSM-5分子筛及其催化丁烯齐聚反应研究[D]. 青岛. 中国科学院大学. 2017.
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