尿素水溶液全循环装置节能扩产改造
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摘要
本论文针对鲁南化肥厂的尿素水溶液全循环装置实际生产过程中存在氨和蒸汽耗量高的问题,主要对其存在的技术改造方案进行了对比,并对较优的节能改造方案进行了分析,为尿素系统的节能扩产改造提供了实际指导。本文较全面地综述了尿素工业的发展简况、尿素工业的当前技术状况、尿素水溶液全循环装置及工艺、尿素水溶液全循环发展方向及技术进展等,并分析了各种技术的优缺点,确定了采用的技术路线；对改造技术路线进行对比计算,确定了采用双高压节能工艺,并对尿素Ⅱ系统进行了节能扩产改造；对主要设备进行了物料衡算、热量衡算及系统分析,并进行了经济效益分析。通过改造合成高压圈和一段分解流程,形成了设备结构优化、流程独创的双高压工艺,使尿素消耗达到国内同类型装置的先进水平。另外,对后续单元消除系统瓶颈后,降低了氨耗,增强了系统操作的弹性、稳定性和安全性。经改造后的装置具有明显的经济效益和社会效益。
With view to these problems on the high consumptions of ammonia and steam in the actural operating process of urea/water solution recycling installation from Lu Nan Fertilizer Factory, this thesis mainly made a comparison on various projects for its technical innovation and also made an analysis on the optimum innovation projects, in order to provide actual guidances on saving energy and enlarging output for urea system. The thises summarized the development history of urea industry, the present technologies of urea industry, the urea/water solution recycling installation and its technical processes, the development trend and evolution of urea/water slolution recycling process, etc. The advantages and shortcomings of various technologies were also analyzed, consequently comfirming the adopted technical ruote. The innovation technical routes were calculated and compared. Therefore, a double high pressure technical process was comfirmed for saving energy. Simultaneously, the innovation on saving energy and enlarging output for ureaⅡsystem was carried out. The equilibrium calculations on feedings and heats, the analysis of system, and the anlysis of economical benefits were made. Through innovating high pressure circles and the first decomposition flow, an unique double high pressure technical process with the optimum structures of equipments was formed, resulting in the advanced installation. Besides, after resoving the subsequent system bottleneck, the comsumption of ammonia was decreased, and the operation flexibility, stability and security of the system were strengthened. The innovated installation had obviously economical and social benefits.
With view to these problems on the high consumptions of ammonia and steam in the actural operating process of urea/water solution recycling installation from Lu Nan Fertilizer Factory, this thesis mainly made a comparison on various projects for its technical innovation and also made an analysis on the optimum innovation projects, in order to provide actual guidances on saving energy and enlarging output for urea system. The thises summarized the development history of urea industry, the present technologies of urea industry, the urea/water solution recycling installation and its technical processes, the development trend and evolution of urea/water slolution recycling process, etc. The advantages and shortcomings of various technologies were also analyzed, consequently comfirming the adopted technical ruote. The innovation technical routes were calculated and compared. Therefore, a double high pressure technical process was comfirmed for saving energy. Simultaneously, the innovation on saving energy and enlarging output for ureaⅡsystem was carried out. The equilibrium calculations on feedings and heats, the analysis of system, and the anlysis of economical benefits were made. Through innovating high pressure circles and the first decomposition flow, an unique double high pressure technical process with the optimum structures of equipments was formed, resulting in the advanced installation. Besides, after resoving the subsequent system bottleneck, the comsumption of ammonia was decreased, and the operation flexibility, stability and security of the system were strengthened. The innovated installation had obviously economical and social benefits.
引文
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[6]Xianfeng Liu. Oxidation of organic substances in aqueous solutions over Ru catalysts by oxygen[J]. Advances in Environmental Research.2000,4(16):123-132.
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[8]汪家铭.尿素合成双塔高效组合技术及其应用[J].甘肃石油和化工.2007,1(2)：36-39.
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[10]索升富.尿素合成塔技改总结[J].化肥工业.1999,27(1)：54-55.
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[13]张巍.提高水溶液全循环尿素工艺二氧化碳转化率的重要途径[J].化工设计通讯.2003,29(3)：11-15.
[14]吕旭芒,赵兴.对尿素中压系统再改造的思考[J].山西化工.2000,20(3)：26-27.
[15]杨直,高超英,李海庆.全循环法尿素装置节能增产技术途径探讨[J].山西化工.1999,19(3)：28-29.
[16]李旭初.水溶液全循环尿素装置节能增产改造[J].小氮肥.2003,7(1)：1-3
[17]池树增,林海涛.水溶液全循环尿素装置节能增产改造[J].中氮肥.2003,6(1)：1-3.
[18]池树增.我公司专利技术在水溶液全循环尿素装置节能增产改造中的成功应用[J].2005,15(3)：1-4.
[19]宣凤琴.CO2气提法和NH3气提法尿素生产技术的比较[J].安徽化工.2001,17(4)：7-8.
[20]段思繁.尿素Ⅱ段吸收塔增设外冷器改造[J].云南化工.1999,17(3)：20-22.
[21]陈玉镇,汤立存.尿素合成塔塔板改造小结[J].河北化工.2003,4(5)：47-48
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[23]张廷奎.我厂尿素装置塔器改造数例[J].中氮肥.1997,5(6)：19-22.
[24]李业勤,尤爱诊.一段分解加热器节流结构的改进[J].化工设备设计.1999,36(4)：20-21.
[25]沈华民.等压相图在水溶液全循环法尿素工艺上的应用[J].中氮肥.1992,4(5)：25-36
[26]钱镜清.采用预分离-预精馏工艺流程改造水溶液全循环尿素装置的技术进展[J].中氮肥.2004,5(2)：1-5.
[27]石洪强.预分离-预精馏装置设计运行小结[J].小氮肥.2003,6(9)：14-15
[28]沈华民.工业尿素合成理论(三)[J].化肥工业.2010,31(1)：7-16.
[29]R G Nakamura, J F Breedceld, J M Prausnitz. Thermodynamic properties of gas mixtures containing common polar and nonpolar components[J]. Ind.Eng.Chem.Process Des Dev. 1976,15(4):557-559.
[30]袁一,胡德生.化工过程热力学分析法[M].北京：化学工业出版社.1985.
[31]李珊珊.尿素合成工艺的比较[J].科技情报开发与经济.2010,20(11)：215-216..
[32]沈华民.尿素合成的化工计算—热力学模型篇[J].小氮肥.2008,5(5)：1-6.
[33]胡列圻,魏柏益,沈华民.尿素生产中高温高压条件下NH3-CO2-H2O-NH2CONH2体系汽液平衡研究[J].化工学报.1990,41(6)：740-742
[34]Lemkowitz S M. Anempirical thermodynamic model for ammonia-urea-carbondioxide system at urea synthesis conditions[J]. Journal of Applied chemistry biotechnology.1973, 23(1):63
[35]Inoue, Kanai K, Otsuka E. Equilibrium of urea synthesis [J]. Bull Chem.Soc.Japan.1972, 45(5):1339-1345
[36]刘孝弟,刘志臣.尿素合成反应过程分析[J].化肥工业.2010,37(1)：17-25.
[37]中国寰球化学工程公司.氮肥工艺设计手册：尿素[M].北京：化学工业出版社.1988.
[38]Irazoqui H A. Simulation of a Urea Synthesis Reactor[J]. Ind.Eng.Chem.Res.1993,32(11): 45-47.
[39]钱镜清.水溶液全循环尿素装置增产节能的途径[J].氮肥与甲醇.2006,15(2)：17-19.
[40]史占飞,熊源泉,谢红银等.尿素、碳酸氢铵/添加剂同时脱硫脱硝试验研究[J].东南大学学报：自然科学版.2011,41(3)：591-596.
[41]Hongmi Xu, Gao Lin, Hanzhang Shi, et al. A new approach for Fe (Ⅲ) EDTA reduction in NOx scrubber solution using bio-electro reactor[J]. Bioresource Technology.2009,100(12): 2940-2944.
[42]周春琼,邓先和,徐伟等.乙二胺合钴/尿素湿法同时吸收S02和NO[J].化工学报.2006,57(3)：645-649.
[43]莫彩丽,刘亮.水碳比对尿素合成系统的影响[J].化工设计.2005,15(4)：25-26.
[44]蒋晓原,毛建新,陆维敏等.四氯化碳加氢制氯仿Pt—Pd/C催化剂的制备研究[J].石油化工.2000,29(7)：483-485.
[45]谢爽玲.尿素合成塔腐蚀情况及原因分析[J].辽宁化工.2004,33(3)：180-181.
[46]Xiangli Long, Wende Xiao, Weikang Yuan. Studies on removal of NO with ammoniac cobalt solution[J]. China Environmental Science.2002,22(6):511-514.
[47]Chaoping Cen, Guobang Gu. Simultaneous desulfurization and denitrification from flue gas by using urea/additive solution (Ⅱ):Absorption characteristics of SO2 and NOx in cleaning process[J]. Journal of South China University of Technology:Natural Science Edition.2004,32(2):14-17.
[48]辛志玲,张金龙,张大全等.高校液相吸收剂同时脱硫脱硝的实验研究[J].中国电机工程学报.2009,29(17)：76-82.
[49]谢红银,熊源泉,史占飞等.添加剂对尿素/氨溶液同时脱硝特性影响的试验研究[J].中国电机工程学报.2010,30(23)：51-55
[50]岑超平,古国榜.尿素/添加剂湿法烟气同时脱硫脱氮研究(Ⅰ)：吸收反应中尿素消耗的动力学方程[J].华南理工大学学报：自然科学版.2004,32(1)：37-40.
[2]钱镜清.水溶液全循环工艺尿素装置技术进展[J].小氮肥.1998,5(1)：5-8.
[3]唐文骞.国外尿素生产技术概况及进展[J].小氮肥设计技术.2000,21(3)：35-37.
[4]汪家铭.尿素合成双塔高效组合技术及其应用[J].氮肥技术.2006,12(6)：215-219.
[5]田文敏,李云龙.新技术在尿素装置改造中的应用[J].河南化工.1998,9(4)：37-38.
[6]Xianfeng Liu. Oxidation of organic substances in aqueous solutions over Ru catalysts by oxygen[J]. Advances in Environmental Research.2000,4(16):123-132.
[7]唐文骞.氨气提法和二氧化碳气提法尿素生产技术的新进展、比较及评价[J].化肥工业.1998,6(1)：4-10.
[8]汪家铭.尿素合成双塔高效组合技术及其应用[J].甘肃石油和化工.2007,1(2)：36-39.
[9]唐文骞.氨气提法和二氧化碳气提法尿素生产技术的新进展[J].化肥工业.1998,25(11)：10-19.
[10]索升富.尿素合成塔技改总结[J].化肥工业.1999,27(1)：54-55.
[11]田国柱.尿素装置节能改造[J].山西化工.2005,25(2)：78-79.
[12]翁绍柏.尿素系统节能降耗途径及探讨[C].第十五届全国尿素厂年会论文.2006,102-103.
[13]张巍.提高水溶液全循环尿素工艺二氧化碳转化率的重要途径[J].化工设计通讯.2003,29(3)：11-15.
[14]吕旭芒,赵兴.对尿素中压系统再改造的思考[J].山西化工.2000,20(3)：26-27.
[15]杨直,高超英,李海庆.全循环法尿素装置节能增产技术途径探讨[J].山西化工.1999,19(3)：28-29.
[16]李旭初.水溶液全循环尿素装置节能增产改造[J].小氮肥.2003,7(1)：1-3
[17]池树增,林海涛.水溶液全循环尿素装置节能增产改造[J].中氮肥.2003,6(1)：1-3.
[18]池树增.我公司专利技术在水溶液全循环尿素装置节能增产改造中的成功应用[J].2005,15(3)：1-4.
[19]宣凤琴.CO2气提法和NH3气提法尿素生产技术的比较[J].安徽化工.2001,17(4)：7-8.
[20]段思繁.尿素Ⅱ段吸收塔增设外冷器改造[J].云南化工.1999,17(3)：20-22.
[21]陈玉镇,汤立存.尿素合成塔塔板改造小结[J].河北化工.2003,4(5)：47-48
[22]冯文海,施树良,徐梁.尿素合成塔改造新技术[J].化工装备技术.1998,19(6)：21-24.
[23]张廷奎.我厂尿素装置塔器改造数例[J].中氮肥.1997,5(6)：19-22.
[24]李业勤,尤爱诊.一段分解加热器节流结构的改进[J].化工设备设计.1999,36(4)：20-21.
[25]沈华民.等压相图在水溶液全循环法尿素工艺上的应用[J].中氮肥.1992,4(5)：25-36
[26]钱镜清.采用预分离-预精馏工艺流程改造水溶液全循环尿素装置的技术进展[J].中氮肥.2004,5(2)：1-5.
[27]石洪强.预分离-预精馏装置设计运行小结[J].小氮肥.2003,6(9)：14-15
[28]沈华民.工业尿素合成理论(三)[J].化肥工业.2010,31(1)：7-16.
[29]R G Nakamura, J F Breedceld, J M Prausnitz. Thermodynamic properties of gas mixtures containing common polar and nonpolar components[J]. Ind.Eng.Chem.Process Des Dev. 1976,15(4):557-559.
[30]袁一,胡德生.化工过程热力学分析法[M].北京：化学工业出版社.1985.
[31]李珊珊.尿素合成工艺的比较[J].科技情报开发与经济.2010,20(11)：215-216..
[32]沈华民.尿素合成的化工计算—热力学模型篇[J].小氮肥.2008,5(5)：1-6.
[33]胡列圻,魏柏益,沈华民.尿素生产中高温高压条件下NH3-CO2-H2O-NH2CONH2体系汽液平衡研究[J].化工学报.1990,41(6)：740-742
[34]Lemkowitz S M. Anempirical thermodynamic model for ammonia-urea-carbondioxide system at urea synthesis conditions[J]. Journal of Applied chemistry biotechnology.1973, 23(1):63
[35]Inoue, Kanai K, Otsuka E. Equilibrium of urea synthesis [J]. Bull Chem.Soc.Japan.1972, 45(5):1339-1345
[36]刘孝弟,刘志臣.尿素合成反应过程分析[J].化肥工业.2010,37(1)：17-25.
[37]中国寰球化学工程公司.氮肥工艺设计手册：尿素[M].北京：化学工业出版社.1988.
[38]Irazoqui H A. Simulation of a Urea Synthesis Reactor[J]. Ind.Eng.Chem.Res.1993,32(11): 45-47.
[39]钱镜清.水溶液全循环尿素装置增产节能的途径[J].氮肥与甲醇.2006,15(2)：17-19.
[40]史占飞,熊源泉,谢红银等.尿素、碳酸氢铵/添加剂同时脱硫脱硝试验研究[J].东南大学学报：自然科学版.2011,41(3)：591-596.
[41]Hongmi Xu, Gao Lin, Hanzhang Shi, et al. A new approach for Fe (Ⅲ) EDTA reduction in NOx scrubber solution using bio-electro reactor[J]. Bioresource Technology.2009,100(12): 2940-2944.
[42]周春琼,邓先和,徐伟等.乙二胺合钴/尿素湿法同时吸收S02和NO[J].化工学报.2006,57(3)：645-649.
[43]莫彩丽,刘亮.水碳比对尿素合成系统的影响[J].化工设计.2005,15(4)：25-26.
[44]蒋晓原,毛建新,陆维敏等.四氯化碳加氢制氯仿Pt—Pd/C催化剂的制备研究[J].石油化工.2000,29(7)：483-485.
[45]谢爽玲.尿素合成塔腐蚀情况及原因分析[J].辽宁化工.2004,33(3)：180-181.
[46]Xiangli Long, Wende Xiao, Weikang Yuan. Studies on removal of NO with ammoniac cobalt solution[J]. China Environmental Science.2002,22(6):511-514.
[47]Chaoping Cen, Guobang Gu. Simultaneous desulfurization and denitrification from flue gas by using urea/additive solution (Ⅱ):Absorption characteristics of SO2 and NOx in cleaning process[J]. Journal of South China University of Technology:Natural Science Edition.2004,32(2):14-17.
[48]辛志玲,张金龙,张大全等.高校液相吸收剂同时脱硫脱硝的实验研究[J].中国电机工程学报.2009,29(17)：76-82.
[49]谢红银,熊源泉,史占飞等.添加剂对尿素/氨溶液同时脱硝特性影响的试验研究[J].中国电机工程学报.2010,30(23)：51-55
[50]岑超平,古国榜.尿素/添加剂湿法烟气同时脱硫脱氮研究(Ⅰ)：吸收反应中尿素消耗的动力学方程[J].华南理工大学学报：自然科学版.2004,32(1)：37-40.