分子筛吸附剂在石化对二甲苯吸附分离装置中的应用研究
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摘要
随着材料科学的发展,性能优良的分子筛吸附剂的开发和应用范围不断拓展,并在能源、环境等重要领域发挥更大的作用。本文首先对分子筛吸附剂的发展历程、主要性能及测试方法和重要的应用领域,进行了系统总结。在此基础上,对天津石化芳烃车间二甲苯的吸附分离进行工业试验。研究结果表明,天津石化采用UOP公司新型ADS-27吸附剂,对二甲苯的纯度由99.70%提高到99.89%,收率由97.5%提高到99.0%,获得了先进的吸附剂操作数据和经验。此外,本文从工艺条件、控制系统、机械泄漏、吸附剂本身性能、床层压差等方面进行了全面、详实的分析、研究,确认吸附剂强度偏低和格栅局部损坏进而造成个别床层压差超高是根本原因。在不停车检修的情况下,采取反冲洗方案缓解了运行压力,使生产得以延续。在检修中,提出格栅修复、增加分配网、改变组件等可行的改进措施,应用到实践中,解决了实际生产难题,同时为吸附剂的工业应用提供了极其宝贵的经验。
With the development of material science, well-performed molecular sieve adsorbent has been under researching and its application area is widening with the time. It is playing more and more significant role in some important fields like energy and environment.
This thesis has summarized the history of the development of molecular sieve adsorbent, its nature and test method as well as major application area. Industrial trial has been conducted on the Adsorption & Separation System of PX Unit of Tianjin Petrochemical Aromatics Business. The research concludes that the purity of PX was improved from 99.70% to 99.89% and the yield from 97.5% to 99.0% with the application of new ADS-27 Adsorbent. Excellent operation data and experience has been obtained from the research.
In addition, the thesis has made thorough and elaborate analysis and study from the perspective of process condition, control system, mechanical leakage, adsorbent nature and differential pressure between beds. It comes to a conclusion that relevant weak strength of adsorbent and local damage of grids is the fundamental reason of super high differential pressure between particular beds. Back flushing program was carried out at non-stop condition in order to release the burden of operation and help to continue the production. During the overhaul period, feasible improvement measures, e.g., to repair grids, add distribution pipes and alternate BIA were brought forward and put into practice, which has helped in solving the serious practical problem and provided extremely precious experience for us in industrial application of adsorbent.
With the development of material science, well-performed molecular sieve adsorbent has been under researching and its application area is widening with the time. It is playing more and more significant role in some important fields like energy and environment.
This thesis has summarized the history of the development of molecular sieve adsorbent, its nature and test method as well as major application area. Industrial trial has been conducted on the Adsorption & Separation System of PX Unit of Tianjin Petrochemical Aromatics Business. The research concludes that the purity of PX was improved from 99.70% to 99.89% and the yield from 97.5% to 99.0% with the application of new ADS-27 Adsorbent. Excellent operation data and experience has been obtained from the research.
In addition, the thesis has made thorough and elaborate analysis and study from the perspective of process condition, control system, mechanical leakage, adsorbent nature and differential pressure between beds. It comes to a conclusion that relevant weak strength of adsorbent and local damage of grids is the fundamental reason of super high differential pressure between particular beds. Back flushing program was carried out at non-stop condition in order to release the burden of operation and help to continue the production. During the overhaul period, feasible improvement measures, e.g., to repair grids, add distribution pipes and alternate BIA were brought forward and put into practice, which has helped in solving the serious practical problem and provided extremely precious experience for us in industrial application of adsorbent.
引文
[1] 叶振华,化工吸附分离过程,北京:中国石化出版社,1992,13,
[2] 高滋、何鸣元、戴逸云,沸石催化与分离技术,北京:中国石化出版社,1999,5
[3] 徐如人、庞文琴等,分子筛与多孔材料化学,北京:科学出版社,2004,6~10
[4] 高滋、何鸣元、戴逸云,沸石催化与分离技术,北京:中国石化出版社,1999,23
[5] de van Mao R. React. Kinet. Catal. Letts.,1979,12:69
[6] Breck D W, Zeolite molecular sieves,New York:John wiley and sons, 1974,633
[7]冯孝庭,吸附分离技术,北京:化学工业出版社,2000,72
[8] UOP,Adsorbent Chamber Control System Equipment Instructions & Data Book
[9] UOP,Parex Process Unit General Operating Manual & Presentation Material
[10] 沈文霞,改性分子筛的表面酸性与苯烷基化反应活性的关系研究,无机化学学报,1998 年,(14):298
[11] 杨向萍,杨震,分子筛与多孔材料化学,北京:科学出版社
[12] 化工百科全书编辑部编,化工百科全书(8),北京:化学工业出版社,1994:223～232
[13] 牛春明,颜其洁,陈懿,甲醇选择性氧化 MoO3-TiO2 催化剂的研究,分子催化,1991,5(1):9
[14] 刘薇,徐亦德,用 FI-IR 技术研究 Mo/HZSM-5 分子筛的骨架结构, 催化学报, 1998,(4):339
[15] Meshram N R,Hegde S G,Kulkarni S B,Zeolites,1986,6:434
[16] 徐克勋主编,精细有机化工原料及中间体手册,北京:化学工业出版社,1998.1～204
[17] 魏文德,有机化工原料大全.北京:化学工业出版社,1999:224～227
[18] 姚宗君等,合成甲基异丁基酮的分子筛催化剂及制法[P],中国专利,ZL 91105 999,1993
[19] 胡颖、罗一斌等,骨架富硅分子筛 SRY 及其催化剂的研制,石油炼制与化工,1992
[20]上海试剂五厂,分子筛的应用与制备[M],上海:上海人民出版社,1976,24～26
[21] William H.Flank,Chappaqua,PROCESS FOR PREPARING MOLECULAR SIEVE BODIES[P],US Patent 4818508,1989
[22] 赵锡武,韩雪梅,王桂芝,无粘结剂分子筛制备[J],沈阳化工,1995,14 (4):25～27
[23] 李善安,柯跃珍,唐超等,无粘结剂球状A型分子筛制备方法[P].,ZL87105499,1988
[24] 陶彩娥,无粘结剂 3A分子筛吸附剂制备新技术[J],吉林石油化工,1990,(1):18～21
[25] 赵锡武,王桂芝,关伟宏等,高岭土合成无粘结剂 A 型分子筛的探索性研究[J],辽宁化工,1997,26(3):155～157
[26] 肖华军,袁修干,机载分子筛制氧技术发展的现状与动向 [J],航空科学技术,1997(1):26～28
[27] 孙兵,赵迎春,与侧管服配套的分子筛机载制氧系统方案设想[J],科技情报,1995(40):1～3
[28] 徐如人,庞文琴,屠昆岗,沸石分子筛的结构与合成[M],长春:吉林大学出版社,1987:98
[29] 张兆荣,索继栓,张小明,介孔硅基分子筛研究进展,化学进展,1999,2:11～20
[30] 陈小开,彭兵,柴立元,室内甲醛污染治理的研究进展[J],环境污染与防治(网络版),2005(9):1～6
[2] 高滋、何鸣元、戴逸云,沸石催化与分离技术,北京:中国石化出版社,1999,5
[3] 徐如人、庞文琴等,分子筛与多孔材料化学,北京:科学出版社,2004,6~10
[4] 高滋、何鸣元、戴逸云,沸石催化与分离技术,北京:中国石化出版社,1999,23
[5] de van Mao R. React. Kinet. Catal. Letts.,1979,12:69
[6] Breck D W, Zeolite molecular sieves,New York:John wiley and sons, 1974,633
[7]冯孝庭,吸附分离技术,北京:化学工业出版社,2000,72
[8] UOP,Adsorbent Chamber Control System Equipment Instructions & Data Book
[9] UOP,Parex Process Unit General Operating Manual & Presentation Material
[10] 沈文霞,改性分子筛的表面酸性与苯烷基化反应活性的关系研究,无机化学学报,1998 年,(14):298
[11] 杨向萍,杨震,分子筛与多孔材料化学,北京:科学出版社
[12] 化工百科全书编辑部编,化工百科全书(8),北京:化学工业出版社,1994:223～232
[13] 牛春明,颜其洁,陈懿,甲醇选择性氧化 MoO3-TiO2 催化剂的研究,分子催化,1991,5(1):9
[14] 刘薇,徐亦德,用 FI-IR 技术研究 Mo/HZSM-5 分子筛的骨架结构, 催化学报, 1998,(4):339
[15] Meshram N R,Hegde S G,Kulkarni S B,Zeolites,1986,6:434
[16] 徐克勋主编,精细有机化工原料及中间体手册,北京:化学工业出版社,1998.1～204
[17] 魏文德,有机化工原料大全.北京:化学工业出版社,1999:224～227
[18] 姚宗君等,合成甲基异丁基酮的分子筛催化剂及制法[P],中国专利,ZL 91105 999,1993
[19] 胡颖、罗一斌等,骨架富硅分子筛 SRY 及其催化剂的研制,石油炼制与化工,1992
[20]上海试剂五厂,分子筛的应用与制备[M],上海:上海人民出版社,1976,24～26
[21] William H.Flank,Chappaqua,PROCESS FOR PREPARING MOLECULAR SIEVE BODIES[P],US Patent 4818508,1989
[22] 赵锡武,韩雪梅,王桂芝,无粘结剂分子筛制备[J],沈阳化工,1995,14 (4):25～27
[23] 李善安,柯跃珍,唐超等,无粘结剂球状A型分子筛制备方法[P].,ZL87105499,1988
[24] 陶彩娥,无粘结剂 3A分子筛吸附剂制备新技术[J],吉林石油化工,1990,(1):18～21
[25] 赵锡武,王桂芝,关伟宏等,高岭土合成无粘结剂 A 型分子筛的探索性研究[J],辽宁化工,1997,26(3):155～157
[26] 肖华军,袁修干,机载分子筛制氧技术发展的现状与动向 [J],航空科学技术,1997(1):26～28
[27] 孙兵,赵迎春,与侧管服配套的分子筛机载制氧系统方案设想[J],科技情报,1995(40):1～3
[28] 徐如人,庞文琴,屠昆岗,沸石分子筛的结构与合成[M],长春:吉林大学出版社,1987:98
[29] 张兆荣,索继栓,张小明,介孔硅基分子筛研究进展,化学进展,1999,2:11～20
[30] 陈小开,彭兵,柴立元,室内甲醛污染治理的研究进展[J],环境污染与防治(网络版),2005(9):1～6