我国变压吸附制氧吸附剂及工艺研究进展
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摘要
新型吸附剂和变压吸附工艺开发是提高变压吸附装置性能的主要途径。本文综述了我国变压吸附制氧吸附剂改性及变压吸附制氧工艺研究进展,并指出目前存在问题:Li LSX型及Li+和其他离子的混合型吸附剂具有良好氧氮分离性能,但仍存在离子交换利用率低、成本高等问题;其他离子改性的吸附剂制备过程相对简单,但也有分离系数低或成本高等缺点;基于循环步骤改进的变压吸附制氧工艺优化研究大多以实验室规模制氧装置为主,未深入研究优化工艺的过程性能,难以有效地指导工业级制氧装置工艺优化;快速和双回流变压吸附制氧新工艺具有广阔发展前景,但相关研究欠深入;而多级和耦合变压吸附制氧工艺具有广阔应用前景,但存在流程复杂、能耗较高等缺点。指出未来制氧吸附剂和制氧工艺研究应进一步研究固相离子交换方法,提高LSX吸附剂Li+交换利用率,降低成本;开展优化工艺的过程性能研究,指导工业级制氧装置优化;加强快速变压吸附和双回流变压吸附制氧工艺研究,推动工程化应用。
Developing new adsorbents and PSA processes is an important way to improve performance of PSA devices. In this paper,progress of modified adsorbent and new processes of PSA producing oxygen are reviewed. Li-LSX or LSX exchanged with Li+ and other ions has ideal separation performance,but such adsorbents have problems of low ion exchange utilization and high cost. Preparation of other single or multi-ions modified adsorbents is relatively simple,but the disadvantages are low separation factor and high cost. Optimization process of modified PSA for oxygen production based on cycle step cannot provide guide for industrial oxygen devices because of laboratory scale data and less in-depth study. Rapid PSA and duplex PSA processes have broad development prospect for oxygen production,and should be paid enough attention. Moreover,multi-stage and coupled PSA processes have broad application prospect,but they have problems of complex process and high energy consumption.
Developing new adsorbents and PSA processes is an important way to improve performance of PSA devices. In this paper,progress of modified adsorbent and new processes of PSA producing oxygen are reviewed. Li-LSX or LSX exchanged with Li+ and other ions has ideal separation performance,but such adsorbents have problems of low ion exchange utilization and high cost. Preparation of other single or multi-ions modified adsorbents is relatively simple,but the disadvantages are low separation factor and high cost. Optimization process of modified PSA for oxygen production based on cycle step cannot provide guide for industrial oxygen devices because of laboratory scale data and less in-depth study. Rapid PSA and duplex PSA processes have broad development prospect for oxygen production,and should be paid enough attention. Moreover,multi-stage and coupled PSA processes have broad application prospect,but they have problems of complex process and high energy consumption.
引文
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[2]Whitley R D,Labuda M J,Wagner,G P,et al.Development of a high recovery O2 PVSA system[C]//2005 AICh E Annual Meeting and Fall Showcase,Conference Proceedings,2005:2470.
[3]Santos J C,Cruz P,Regala T,et al.High-purity oxygen production by pressure swing adsorption[J].Industrial and Engineering Chemistry Research,2007,46:591-599.
[4]Meng S,Jihong K,James A S,et al.Production of argon free oxygen by adsorptive air separation[J].AICh E Journal,2013,59(3):982-987.
[5]Yang Ralph T.吸附剂原理与应用[M].马丽萍,宁平,田森林译.北京:高等教育出版社,2010.
[6]周园园.制氧吸附剂的研制与节能型制氧工艺的计算模拟[D].天津:天津大学,2012.
[7]崔邑诚,张爱民,董家騄,等.Li-LSX沸石中阳离子分布于空分性能的研究[J].化工学报,2003,61(3):350-353.
[8]李宏愿,尹伟民,魏渝伟,等.高效空分制氧吸附剂Li LSX的组成和性能评价[J].石油学报:石油加工,2009,25(s1):106-108.
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[10]张永全,顾晓明,章小俊.高性能变压吸附5A分子筛及其制备方法:中国,1292831C[P].2007-01-03.
[11]李东林,苏为民.变压吸附专用高性能5A分子筛的制备方法:中国,101890332B[P].2012-07-18.
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[13]朱琳,张佳,乔世杰.固相离子交换法制备Li-Ca-LSX分子筛及其氮氧分离性能的研究[J].上海化工,2013,38(8):9-12.
[14]李宏愿,魏渝伟,庞玲玲,等.一种变压吸附空分制氧的分子筛吸附剂及其制备方法:中国,101708456A[P].2010-05-19.
[15]刘利爽,尹伟民,张帅等.一种含银分子筛吸附剂及其制备方法和应用:中国,102784617A[P].2012-11-21.
[16]陈宗蓬,赵宏炜,丁艳宾,等.一种X型沸石分离材料及其制备方法:中国,101733070A[P].2010-06-16.
[17]李杰,周理.变压吸附空分制氧的技术进展[J].化学工业与工程,2004,21(3):202-203.
[18]张小强.快速升高吸附塔压力的变压吸附装置:中国,201394410Y[P].2010-02-03.
[19]刘应书,刘文海,侯庆文,等.一种吸附器进气端均压的小型变压吸附制氧装置:中国,1748838A[P].2006-03-22.
[20]刘应书,刘文海,侯庆文,等.一种吸附器两端均压的微型变压吸附制氧装置:中国,1799988A[P].2006-07-12.
[21]卜令兵,刘应书,刘文海,等.微型变压吸附分离空气制氧均压过程[J].北京科技大学学报,2006,28(10):989-991.
[22]杨建,万康,李华飞.均压方式对微型变压吸附制氧装置的影响[J].化工生产与技术,2012,19(5):43-46.
[23]汤洪.变压吸附装置中均压设计的讨论[J].化工设计,2003,13(1):15-18.
[24]宋德华.用空气为原料制取氧气的方法:中国,1861246A[P].2006-11-15.
[25]耿云峰,姜贺,唐伟,等.一种真空变压吸附制氧系统及其控制方法:中国,103058144A[P].2013-04-24.
[26]周理,吕昌忠,边守军,等.非耦联吸附塔新变压吸附工艺的实验研究[J].化工学报,2003,54(5):639-641.
[27]郑新港.多孔介质变压吸附床内二维传输过程的研究[D].北京:北京科技大学,2011.
[28]李宁.变压吸附制氧装置:中国,1814543A[P].2006-08-09.
[29]郑才平.一种含有抽空置换步骤的变压吸附方法:中国,102172463A[P].2011-09-07.
[30]潘广通,潘东成,石军雄.一种用于变压吸附装置的并流泄压解吸装置:中国,201658930U[P].2010-12-01.
[31]赵华,刘应书.微型VPSA制氧流程反吹实验研究[J].低温工程,2005(6):45-49.
[32]张辉,刘应书,章新波.清洗工艺对变压吸附制氧的影响[J].低温与特气,2009,27(5):16-20.
[33]崔红社,刘应书,乐恺,等.一种变压吸附分子筛制氧装置:中国,1522788A[P].2004-08-25.
[34]刘应书,曹永正,林征宇,等.一种提高氧气回收率的间歇反吹方法:中国,101564636A[P].2009-10-28.
[35]刘应书,曹永正,刘文海,等.变压吸附制氧过程中不连续反吹对回收率的影响[J].北京科技大学学报,2010,32(5):663-666.
[36]Siew W C,Mayuresh V K,Shivaji S.Rapid pressure swing adsorption for reduction of bed size factor of a medical oxygen concentrator[J].Industrial and Engineering Chemistry Research,2011,50:8703-8710.
[37]龙春霞.制纯氧分子筛[J].广州化工,2010,38(11):67-68.
[38]GB/T 14604-2009电子工业用气体氧[S].北京:中国标准出版社,2009.
[39]宗航,刘应书,刘文海,等.微型单塔RPSA制氧工艺参数研究[J].低温与特气,2006,24(2):29-32.
[40]黄公连.单塔变压吸附空气分离的方法:中国,1470312A[P].2004-01-28.
[41]宗航,刘应书,刘文海,等.单吸附床微型真空变压吸附制氧实验研究[J].深冷技术,2006(6):24-28.
[42]蔚龙,李化治.两种PSA制纯氧工艺过程的探讨[J].低温与特气,2004,22(4):14-16.
[43]余谦虚.变压吸附流程制高浓度氧实验研究[D].北京:北京科技大学,2003.
[44]乐恺,余谦虚,刘应书,等.基于PLC的变压吸附制高纯氧系统[J].北京科技大学学报,2003,25(2):185-188.
[45]崔红社.两级变压吸附制高浓度氧实验研究与数值模拟[D].北京:北京科技大学,2004.
[46]朱孟府,王兴鹏,邓橙,等.医用氧变压吸附制备工艺研究进展[J].医疗卫生装备,2013,34(10):72-74.
[47]鲁东东,张正旺,银醇彪,等.双回流真空变压吸附空分模拟[J].现代化工,2014,34(4):152-157.
[48]李学平,肖瀚,黄传武.一种热解吸制氧装置:中国,201704061U[P].2010-05-12.
[49]张东辉,何东荣,胡智辉,等.从空气中富集氧气的方法:中国,101301999A[P].2008-11-12.
[50]张军,申春午,贺明星,等.带回吹加热罐的变压吸附制氧装置:中国,102311098B[P].2013-05-22.
[51]朱雪峰,杨维慎,丛铀,等.一种空气分离制氧气和氮气的方法:中国,101450792A[P].2009-06-10.
[52]Zhu Xuefeng,Sun Shumin,He Yufeng,et al.New concept on air separation[J].Journal of Membrane Science,2008,323:221-224.
[53]刘辉,刘安涟,刘飞,等.多循环常温空气分离系统和方法:中国,101961591B[P].2010-08-29.
[54]田原宇,巩志坚,乔英云,等.一种节能型空气分离工艺:中国,101441023A[P].2009-05-27.
[2]Whitley R D,Labuda M J,Wagner,G P,et al.Development of a high recovery O2 PVSA system[C]//2005 AICh E Annual Meeting and Fall Showcase,Conference Proceedings,2005:2470.
[3]Santos J C,Cruz P,Regala T,et al.High-purity oxygen production by pressure swing adsorption[J].Industrial and Engineering Chemistry Research,2007,46:591-599.
[4]Meng S,Jihong K,James A S,et al.Production of argon free oxygen by adsorptive air separation[J].AICh E Journal,2013,59(3):982-987.
[5]Yang Ralph T.吸附剂原理与应用[M].马丽萍,宁平,田森林译.北京:高等教育出版社,2010.
[6]周园园.制氧吸附剂的研制与节能型制氧工艺的计算模拟[D].天津:天津大学,2012.
[7]崔邑诚,张爱民,董家騄,等.Li-LSX沸石中阳离子分布于空分性能的研究[J].化工学报,2003,61(3):350-353.
[8]李宏愿,尹伟民,魏渝伟,等.高效空分制氧吸附剂Li LSX的组成和性能评价[J].石油学报:石油加工,2009,25(s1):106-108.
[9]庞玲玲,李宏愿,魏渝伟.一种Li LSX分子筛的制备方法:中国,101289196B[P].2010-06-30.
[10]张永全,顾晓明,章小俊.高性能变压吸附5A分子筛及其制备方法:中国,1292831C[P].2007-01-03.
[11]李东林,苏为民.变压吸附专用高性能5A分子筛的制备方法:中国,101890332B[P].2012-07-18.
[12]李志良,支建平,张玉林.起始物对Li+、Ca2+混合型低硅X型分子筛(LSX)制备及吸附性能的影响[J].无机材料学报,2008,23(5):975-980.
[13]朱琳,张佳,乔世杰.固相离子交换法制备Li-Ca-LSX分子筛及其氮氧分离性能的研究[J].上海化工,2013,38(8):9-12.
[14]李宏愿,魏渝伟,庞玲玲,等.一种变压吸附空分制氧的分子筛吸附剂及其制备方法:中国,101708456A[P].2010-05-19.
[15]刘利爽,尹伟民,张帅等.一种含银分子筛吸附剂及其制备方法和应用:中国,102784617A[P].2012-11-21.
[16]陈宗蓬,赵宏炜,丁艳宾,等.一种X型沸石分离材料及其制备方法:中国,101733070A[P].2010-06-16.
[17]李杰,周理.变压吸附空分制氧的技术进展[J].化学工业与工程,2004,21(3):202-203.
[18]张小强.快速升高吸附塔压力的变压吸附装置:中国,201394410Y[P].2010-02-03.
[19]刘应书,刘文海,侯庆文,等.一种吸附器进气端均压的小型变压吸附制氧装置:中国,1748838A[P].2006-03-22.
[20]刘应书,刘文海,侯庆文,等.一种吸附器两端均压的微型变压吸附制氧装置:中国,1799988A[P].2006-07-12.
[21]卜令兵,刘应书,刘文海,等.微型变压吸附分离空气制氧均压过程[J].北京科技大学学报,2006,28(10):989-991.
[22]杨建,万康,李华飞.均压方式对微型变压吸附制氧装置的影响[J].化工生产与技术,2012,19(5):43-46.
[23]汤洪.变压吸附装置中均压设计的讨论[J].化工设计,2003,13(1):15-18.
[24]宋德华.用空气为原料制取氧气的方法:中国,1861246A[P].2006-11-15.
[25]耿云峰,姜贺,唐伟,等.一种真空变压吸附制氧系统及其控制方法:中国,103058144A[P].2013-04-24.
[26]周理,吕昌忠,边守军,等.非耦联吸附塔新变压吸附工艺的实验研究[J].化工学报,2003,54(5):639-641.
[27]郑新港.多孔介质变压吸附床内二维传输过程的研究[D].北京:北京科技大学,2011.
[28]李宁.变压吸附制氧装置:中国,1814543A[P].2006-08-09.
[29]郑才平.一种含有抽空置换步骤的变压吸附方法:中国,102172463A[P].2011-09-07.
[30]潘广通,潘东成,石军雄.一种用于变压吸附装置的并流泄压解吸装置:中国,201658930U[P].2010-12-01.
[31]赵华,刘应书.微型VPSA制氧流程反吹实验研究[J].低温工程,2005(6):45-49.
[32]张辉,刘应书,章新波.清洗工艺对变压吸附制氧的影响[J].低温与特气,2009,27(5):16-20.
[33]崔红社,刘应书,乐恺,等.一种变压吸附分子筛制氧装置:中国,1522788A[P].2004-08-25.
[34]刘应书,曹永正,林征宇,等.一种提高氧气回收率的间歇反吹方法:中国,101564636A[P].2009-10-28.
[35]刘应书,曹永正,刘文海,等.变压吸附制氧过程中不连续反吹对回收率的影响[J].北京科技大学学报,2010,32(5):663-666.
[36]Siew W C,Mayuresh V K,Shivaji S.Rapid pressure swing adsorption for reduction of bed size factor of a medical oxygen concentrator[J].Industrial and Engineering Chemistry Research,2011,50:8703-8710.
[37]龙春霞.制纯氧分子筛[J].广州化工,2010,38(11):67-68.
[38]GB/T 14604-2009电子工业用气体氧[S].北京:中国标准出版社,2009.
[39]宗航,刘应书,刘文海,等.微型单塔RPSA制氧工艺参数研究[J].低温与特气,2006,24(2):29-32.
[40]黄公连.单塔变压吸附空气分离的方法:中国,1470312A[P].2004-01-28.
[41]宗航,刘应书,刘文海,等.单吸附床微型真空变压吸附制氧实验研究[J].深冷技术,2006(6):24-28.
[42]蔚龙,李化治.两种PSA制纯氧工艺过程的探讨[J].低温与特气,2004,22(4):14-16.
[43]余谦虚.变压吸附流程制高浓度氧实验研究[D].北京:北京科技大学,2003.
[44]乐恺,余谦虚,刘应书,等.基于PLC的变压吸附制高纯氧系统[J].北京科技大学学报,2003,25(2):185-188.
[45]崔红社.两级变压吸附制高浓度氧实验研究与数值模拟[D].北京:北京科技大学,2004.
[46]朱孟府,王兴鹏,邓橙,等.医用氧变压吸附制备工艺研究进展[J].医疗卫生装备,2013,34(10):72-74.
[47]鲁东东,张正旺,银醇彪,等.双回流真空变压吸附空分模拟[J].现代化工,2014,34(4):152-157.
[48]李学平,肖瀚,黄传武.一种热解吸制氧装置:中国,201704061U[P].2010-05-12.
[49]张东辉,何东荣,胡智辉,等.从空气中富集氧气的方法:中国,101301999A[P].2008-11-12.
[50]张军,申春午,贺明星,等.带回吹加热罐的变压吸附制氧装置:中国,102311098B[P].2013-05-22.
[51]朱雪峰,杨维慎,丛铀,等.一种空气分离制氧气和氮气的方法:中国,101450792A[P].2009-06-10.
[52]Zhu Xuefeng,Sun Shumin,He Yufeng,et al.New concept on air separation[J].Journal of Membrane Science,2008,323:221-224.
[53]刘辉,刘安涟,刘飞,等.多循环常温空气分离系统和方法:中国,101961591B[P].2010-08-29.
[54]田原宇,巩志坚,乔英云,等.一种节能型空气分离工艺:中国,101441023A[P].2009-05-27.