圆筒式离心萃取器的程序设计及其在BuNENA后处理中的应用
|
摘要
本论文研究了含能化合物N-正丁基-2-硝酸乙基硝基胺(BuNENA)的小试生产工艺,针对BuNENA后处理中的水洗与碱洗过程,主要工作如下：
(1)首次开发了圆筒式离心萃取器结构参数的VB计算程序：(2)合成了BuNENA作为离心萃取器的待水洗有机相,并对产品结构进行了表征；(3)通过VB程序计算得出圆筒式离心萃取器各项参数。修正后的转鼓结构参数为澄清区长度3.94cm,转鼓内径2.07cm,轻相堰半径0.35cm,重相堰半径0.55-0.60cm；(4)以水与煤油进行了该萃取器的水力学实验,发现当转速在3000-4000r/min时,萃取器具有较好的水力学性能；(5)将圆筒式离心萃取器应用到BuNENA的连续运转试验中,确定了产品的水洗、碱洗工艺流程为七级错流水洗与碱洗,首先经过一次冰水洗,接着两次常温水洗,再经过三次碱洗,最后再经过水洗。原料液有机相的流量为75mL/min,水相流量都为60mL/min,整个过程运行稳定,收集到的有机相澄清无夹带,生产能力为1.5-2L／h,BuNENA的pH=4,收率达到88%。
Small-scale experimental production process of 2-(butyl-nitro-amino)ethyl nitrate (BuNENA) has been studied in this thesis. There are main works based on the washing and alkali washing process in the post-processing of BuNENA as follows:
(1)The VB calculating program for structure parameters of annular centrifugal extractors has been developed.
(2)Synthesize BuNENA as feed of organic phase, identify it by IR、MS、1H-NMR.
(3)Obtain structure parameters of annular centrifugal extractors through the VB calculating program. Modified structure parameters of annular centrifugal extractors are as follows:length of rotor is 3.94cm, diameter of rotor is 2.07cm, radius of light phase weir is 0.35cm, radius of heavy phase weir is 0.55-0.60cm.
(4)The hydraulic performance is studied in water-kerosene system. It shows that when the rotor's speed varies from 3000-4000r/min, annular centrifugal extractors are running stably at high level.
(5)Apply amended annular centrifugal extractors to continous-running experiment of BuNENA. There is seven-stage cross-flow centrifugal extractor battery in the post-processing of BuNENA as follows:single-stage washing with ice-water, two-stage washing, three-stage alkali washing, single-stage washing. When the flow rate of organic phase is 75mL/min and the flow rate of both water phase is 60mL/min, the whole process runs stable, the production capacity can reach 1.5～2L/h, collected organic phase is clear without any carryover as its pH is 4, the production rate can be up to 88%.
(1)首次开发了圆筒式离心萃取器结构参数的VB计算程序：(2)合成了BuNENA作为离心萃取器的待水洗有机相,并对产品结构进行了表征；(3)通过VB程序计算得出圆筒式离心萃取器各项参数。修正后的转鼓结构参数为澄清区长度3.94cm,转鼓内径2.07cm,轻相堰半径0.35cm,重相堰半径0.55-0.60cm；(4)以水与煤油进行了该萃取器的水力学实验,发现当转速在3000-4000r/min时,萃取器具有较好的水力学性能；(5)将圆筒式离心萃取器应用到BuNENA的连续运转试验中,确定了产品的水洗、碱洗工艺流程为七级错流水洗与碱洗,首先经过一次冰水洗,接着两次常温水洗,再经过三次碱洗,最后再经过水洗。原料液有机相的流量为75mL/min,水相流量都为60mL/min,整个过程运行稳定,收集到的有机相澄清无夹带,生产能力为1.5-2L／h,BuNENA的pH=4,收率达到88%。
Small-scale experimental production process of 2-(butyl-nitro-amino)ethyl nitrate (BuNENA) has been studied in this thesis. There are main works based on the washing and alkali washing process in the post-processing of BuNENA as follows:
(1)The VB calculating program for structure parameters of annular centrifugal extractors has been developed.
(2)Synthesize BuNENA as feed of organic phase, identify it by IR、MS、1H-NMR.
(3)Obtain structure parameters of annular centrifugal extractors through the VB calculating program. Modified structure parameters of annular centrifugal extractors are as follows:length of rotor is 3.94cm, diameter of rotor is 2.07cm, radius of light phase weir is 0.35cm, radius of heavy phase weir is 0.55-0.60cm.
(4)The hydraulic performance is studied in water-kerosene system. It shows that when the rotor's speed varies from 3000-4000r/min, annular centrifugal extractors are running stably at high level.
(5)Apply amended annular centrifugal extractors to continous-running experiment of BuNENA. There is seven-stage cross-flow centrifugal extractor battery in the post-processing of BuNENA as follows:single-stage washing with ice-water, two-stage washing, three-stage alkali washing, single-stage washing. When the flow rate of organic phase is 75mL/min and the flow rate of both water phase is 60mL/min, the whole process runs stable, the production capacity can reach 1.5～2L/h, collected organic phase is clear without any carryover as its pH is 4, the production rate can be up to 88%.
引文
[1]邰德荣,李光鸿,王仍陶.核燃料后处理研究进展[C].北京原子能出版社,1989
[2]Long J.T..核燃料处理工程[M].杨云鸿译.北京：原子能出版社,1980：621
[3]Bernard C, Michel P, Tarnero M. Experience with Centrifugal Extractors:Comparing with Other Types of Extractors[M]. Lodon:Society of Chemical Industry,1971:1282
[4]周嘉贞.10毫米微型环隙式离心萃取器[J].化学工程,1984,12(6)：25～29
[5]段五华等.φ70mm离心萃取器I机械性能和水力学特性[J].原子能科学技术,2001,35(1)：51～55
[6]段五华等.φ70mm离心萃取器II机械性能和水力学特性[J].原子能科学技术,2001,35(2)：174～178
[7]Wang J. C., et al. Application of Miniature Centrifugal Contactors for Treating High-level Liquid Waste[J]. Separation Science and Technology,2001,36(13):2983～2996
[8]刘秉仁等.分离法处理高放废液全流程热实验系统的建立与实验运行[J].核科学与工程,1997,17(4)：372-376
[9]Zhou J. Z., et al. Experimental and simulation study on the extraction of p-cresol using centrifugal extractors[J]. Chinese Journal of Chemical Engineering,2007,15(2):209～214
[10]包福毅等.离心萃取器在镍钴分离中的应用[J].有色金属,1995,47(1)：67～72
[11]段五华等.φ50mm核用离心萃取器的研制及其水力学性能[J].核科学与工程,2006,26(2)：97～102
[12]段五华等.三级串联的φ70mm核用离心萃取器性能[J].核科学与工程,2001,21(3)：282～287
[13]张德友等.新型离心萃取机的开发及其应用前景[J].过滤与分离,2008,18(3)：39～42
[14]赵百仁等.环隙式离心萃取器界面半径的测定与关联[J].化学工程,1997,25(2)：21～26
[15]陈崔龙等.实验室用小流量环隙式离心萃取器的设计[J].流体机械,2009,37(7)：24～27
[16]叶春林.圆筒式离心萃取器[M].北京：原子能出版社出版,1982
[17]周嘉贞.圆筒式离心萃取器的水力学计算[J].化学工程,1982,10(5)：50～56
[18]周嘉贞.环隙式离心萃取器的原理、性能和应用[J].化工机械,1984,11(5)：21～26
[19]李华,刘培龙.离心萃取机及其在三氯蔗糖生产中的应用[J].食品工业科技,2007,28(10)：192～194
[20]许金全等.用HL离心萃取器处理含对硝基酚废水的研究[J].坏境污染治理技术与设备,2006,7(10)：124～127
[21]Xu J. Q., et al. Extraction of phenol in wastewater with annular centrifugal contactors[J]. Journal of Hazardous Materials B,2006,31:98～102
[22]叶春林,汪兆泉.圆筒式离心萃取器在锆铪分离中的应用[J].有色金属,2004,2：34～36
[23]于文东等.用离心萃取器连续逆流提取氢化可的松的研究[J].精细化工,2001,18(10)：611～613
[24]段五华等.离心萃取器在咖啡因工业生产中的应用[J].化工进展,2005,24(4)：425～427
[25]Liu H. M., Wu Q. L.. Study on single-stage mass-transfer performance of centrifugal extractor(φ70) used in nuclear industry[J]. Journal of Nuclear and Radiochemistry,2001, 23(2):114～119
[26]张贵清等.从钨矿苏打浸出液中直接萃取钨的连续运转试验[J].中国钨业,2009,24(5)：49～52
[27]王胜,郭鹏成,赵燕春.离心萃取器在镍钴分离中的应用[J].湿法冶金,2008,27(1)：45～47
[28]Daniel S. P., et al. First demonstration of a centrifugal solvent extraction process for minor actinides from a concentrated spent fuel solution[J]. Separation and Purification Technology,2005,45:157～162
[29]Zhu J. Q., et al. Centrifugal extraction for separation of ethylbenzene and octane using 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid as extractant[J]. Separation and Purification Technology,2007,56:237～240
[30]Silver P. A, Stanley N. F.. BuNENA gun propellant[C]. JANNAF propulsion meeting, 1981,2:515
[31]Fong C. W. Temperature Sensitivity of Aircraft Cannon Propellants[J]. Journal of Ballistics,1982,6(4):1551～1534
[32]鲍冠苓,沈琼华,李遵来.羟乙基丁硝胺硝酸酯增塑剂的性能研究[J].兵工学报,1995,2：43～44
[33]陆安舫.新型含能增塑剂—硝氧乙基硝胺族化合物发展概况[J].含能材料,1998,6(1)：43～47
[34]陆安舫.含羟乙基丁硝胺硝酸酯发射药的研究[J].火炸药,1994,4：12-17
[35]Johnson R. A, et al. Stability and Performance Characteristics of NENA Materials and Formulations Proceedings for the ADPA Joint[C]. International Symposium on Energetic Materials Technology,1992
[36]沈琼华等.BuNENA增塑剂的合成与性能研究.204所内部资料,1990
[37]Shen Q. H., et al. Synthetic Study of the BuNENA[C].27th International Annual Conference of ICT,1996
[38]Kala P. C. Rao, et al. Studies on n-Butyl Nitroxyethylnitramine (n-BuNENA):Synthesis, Characterization and Propellant Evaluation. Propellants, Explosives, Pyrotechnics,2004, 29(2):93～98.
[39]Michael E. S., et al. Investigation of an N-Buty-N-(2-Nitroxyethyl) Nitramine(BuNENA) Process:Identification of Process Intermediates, By-Products and Reaction Pathways [J]. Propellants,Explosives,Pyrotechnics,2006,2(31):124～130
[40]Deshmukh S. S., et al. Residence time distribution and flow patterns in the single-phase annular region of annular centrifugal extractor[J]. Industrial & Engineering Chemistry Research,2009,48:37～46
[41]于文东等.E-44环氧树脂胶液的净化[J].化学工业与工程,2002,19(1)：26～31
[42]段五华,周秀珠,周嘉贞.微型离心萃取器在萃取工艺试验研究中的应用[J].现代化工,2004,24(7)：63～65
[43]Ralph A L.. Recent advances in centrifugal contactor design[J]. Separation Science and Technology,1988,23(12):1473～1487
[44]张春新,许涛.单级离心萃取机[P].CN:200977420Y,2007-11-21
[45]李慎文.用离心萃取器对粘性流体进行净化或萃取的方法和装置[P].CN：85100183A,1986-7-23
[46]杨宝光,王厚恒.单级圆筒式离心萃取器[P]. CN:1077137A,1993-10-13
[47]张进韬.圆筒式离心萃取器P]. CN:2283509Y,1998-6-10
[48]周嘉贞等.玻璃钢单台单级离心萃取器[P]CN:1069903A,1993-3-17
[49]李京莲,李慎文,李星文.一种用于化工操作的下传动式离心萃取器[P].CN：201006334Y,2008-1-16
[50]戴晖平.圆筒式离心萃取器的探讨[J].浙江化工,1992,42-45
[51]孙启才,金鼎五.离心机原理结构与设计计算[M].北京：机械工业出版社,1987
[52]陈崔龙等.实验室用小流量环隙式离心萃取器的设计[J].流体机械,2009,37(7)：24～27
[53]张圣麟,布天军,张庆东.圆筒式离心萃取器性能研究[J]河南化工,1993,9：19-23
[54]Kadam B. D., et al. Dispersed phase hpld-up, effective interfacial area and sauter mean drop diameter in annular centrifugal extractors[J]. Chemical Engineering Research and Design,2009,87:1379～1389
[55]Kadam B. D., et al. Hydrodynamic and mass transfer characteristics of annular centrifugal extractors[J]. Chemical Engineering Research and Design,2008,86:233～244
[56]许金全等.环隙式离心萃取器处理含酚废水的研究：I.单级实验[J].石油炼制与化工,1999,30(9)：48～51
[57]Duan W. H., et al. Development of a φ20mm annular centrifugal contactor for the hot test of the total TRPO process[J]. Progress in Nuclear Energy,2009,51:313～318
[2]Long J.T..核燃料处理工程[M].杨云鸿译.北京：原子能出版社,1980：621
[3]Bernard C, Michel P, Tarnero M. Experience with Centrifugal Extractors:Comparing with Other Types of Extractors[M]. Lodon:Society of Chemical Industry,1971:1282
[4]周嘉贞.10毫米微型环隙式离心萃取器[J].化学工程,1984,12(6)：25～29
[5]段五华等.φ70mm离心萃取器I机械性能和水力学特性[J].原子能科学技术,2001,35(1)：51～55
[6]段五华等.φ70mm离心萃取器II机械性能和水力学特性[J].原子能科学技术,2001,35(2)：174～178
[7]Wang J. C., et al. Application of Miniature Centrifugal Contactors for Treating High-level Liquid Waste[J]. Separation Science and Technology,2001,36(13):2983～2996
[8]刘秉仁等.分离法处理高放废液全流程热实验系统的建立与实验运行[J].核科学与工程,1997,17(4)：372-376
[9]Zhou J. Z., et al. Experimental and simulation study on the extraction of p-cresol using centrifugal extractors[J]. Chinese Journal of Chemical Engineering,2007,15(2):209～214
[10]包福毅等.离心萃取器在镍钴分离中的应用[J].有色金属,1995,47(1)：67～72
[11]段五华等.φ50mm核用离心萃取器的研制及其水力学性能[J].核科学与工程,2006,26(2)：97～102
[12]段五华等.三级串联的φ70mm核用离心萃取器性能[J].核科学与工程,2001,21(3)：282～287
[13]张德友等.新型离心萃取机的开发及其应用前景[J].过滤与分离,2008,18(3)：39～42
[14]赵百仁等.环隙式离心萃取器界面半径的测定与关联[J].化学工程,1997,25(2)：21～26
[15]陈崔龙等.实验室用小流量环隙式离心萃取器的设计[J].流体机械,2009,37(7)：24～27
[16]叶春林.圆筒式离心萃取器[M].北京：原子能出版社出版,1982
[17]周嘉贞.圆筒式离心萃取器的水力学计算[J].化学工程,1982,10(5)：50～56
[18]周嘉贞.环隙式离心萃取器的原理、性能和应用[J].化工机械,1984,11(5)：21～26
[19]李华,刘培龙.离心萃取机及其在三氯蔗糖生产中的应用[J].食品工业科技,2007,28(10)：192～194
[20]许金全等.用HL离心萃取器处理含对硝基酚废水的研究[J].坏境污染治理技术与设备,2006,7(10)：124～127
[21]Xu J. Q., et al. Extraction of phenol in wastewater with annular centrifugal contactors[J]. Journal of Hazardous Materials B,2006,31:98～102
[22]叶春林,汪兆泉.圆筒式离心萃取器在锆铪分离中的应用[J].有色金属,2004,2：34～36
[23]于文东等.用离心萃取器连续逆流提取氢化可的松的研究[J].精细化工,2001,18(10)：611～613
[24]段五华等.离心萃取器在咖啡因工业生产中的应用[J].化工进展,2005,24(4)：425～427
[25]Liu H. M., Wu Q. L.. Study on single-stage mass-transfer performance of centrifugal extractor(φ70) used in nuclear industry[J]. Journal of Nuclear and Radiochemistry,2001, 23(2):114～119
[26]张贵清等.从钨矿苏打浸出液中直接萃取钨的连续运转试验[J].中国钨业,2009,24(5)：49～52
[27]王胜,郭鹏成,赵燕春.离心萃取器在镍钴分离中的应用[J].湿法冶金,2008,27(1)：45～47
[28]Daniel S. P., et al. First demonstration of a centrifugal solvent extraction process for minor actinides from a concentrated spent fuel solution[J]. Separation and Purification Technology,2005,45:157～162
[29]Zhu J. Q., et al. Centrifugal extraction for separation of ethylbenzene and octane using 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid as extractant[J]. Separation and Purification Technology,2007,56:237～240
[30]Silver P. A, Stanley N. F.. BuNENA gun propellant[C]. JANNAF propulsion meeting, 1981,2:515
[31]Fong C. W. Temperature Sensitivity of Aircraft Cannon Propellants[J]. Journal of Ballistics,1982,6(4):1551～1534
[32]鲍冠苓,沈琼华,李遵来.羟乙基丁硝胺硝酸酯增塑剂的性能研究[J].兵工学报,1995,2：43～44
[33]陆安舫.新型含能增塑剂—硝氧乙基硝胺族化合物发展概况[J].含能材料,1998,6(1)：43～47
[34]陆安舫.含羟乙基丁硝胺硝酸酯发射药的研究[J].火炸药,1994,4：12-17
[35]Johnson R. A, et al. Stability and Performance Characteristics of NENA Materials and Formulations Proceedings for the ADPA Joint[C]. International Symposium on Energetic Materials Technology,1992
[36]沈琼华等.BuNENA增塑剂的合成与性能研究.204所内部资料,1990
[37]Shen Q. H., et al. Synthetic Study of the BuNENA[C].27th International Annual Conference of ICT,1996
[38]Kala P. C. Rao, et al. Studies on n-Butyl Nitroxyethylnitramine (n-BuNENA):Synthesis, Characterization and Propellant Evaluation. Propellants, Explosives, Pyrotechnics,2004, 29(2):93～98.
[39]Michael E. S., et al. Investigation of an N-Buty-N-(2-Nitroxyethyl) Nitramine(BuNENA) Process:Identification of Process Intermediates, By-Products and Reaction Pathways [J]. Propellants,Explosives,Pyrotechnics,2006,2(31):124～130
[40]Deshmukh S. S., et al. Residence time distribution and flow patterns in the single-phase annular region of annular centrifugal extractor[J]. Industrial & Engineering Chemistry Research,2009,48:37～46
[41]于文东等.E-44环氧树脂胶液的净化[J].化学工业与工程,2002,19(1)：26～31
[42]段五华,周秀珠,周嘉贞.微型离心萃取器在萃取工艺试验研究中的应用[J].现代化工,2004,24(7)：63～65
[43]Ralph A L.. Recent advances in centrifugal contactor design[J]. Separation Science and Technology,1988,23(12):1473～1487
[44]张春新,许涛.单级离心萃取机[P].CN:200977420Y,2007-11-21
[45]李慎文.用离心萃取器对粘性流体进行净化或萃取的方法和装置[P].CN：85100183A,1986-7-23
[46]杨宝光,王厚恒.单级圆筒式离心萃取器[P]. CN:1077137A,1993-10-13
[47]张进韬.圆筒式离心萃取器P]. CN:2283509Y,1998-6-10
[48]周嘉贞等.玻璃钢单台单级离心萃取器[P]CN:1069903A,1993-3-17
[49]李京莲,李慎文,李星文.一种用于化工操作的下传动式离心萃取器[P].CN：201006334Y,2008-1-16
[50]戴晖平.圆筒式离心萃取器的探讨[J].浙江化工,1992,42-45
[51]孙启才,金鼎五.离心机原理结构与设计计算[M].北京：机械工业出版社,1987
[52]陈崔龙等.实验室用小流量环隙式离心萃取器的设计[J].流体机械,2009,37(7)：24～27
[53]张圣麟,布天军,张庆东.圆筒式离心萃取器性能研究[J]河南化工,1993,9：19-23
[54]Kadam B. D., et al. Dispersed phase hpld-up, effective interfacial area and sauter mean drop diameter in annular centrifugal extractors[J]. Chemical Engineering Research and Design,2009,87:1379～1389
[55]Kadam B. D., et al. Hydrodynamic and mass transfer characteristics of annular centrifugal extractors[J]. Chemical Engineering Research and Design,2008,86:233～244
[56]许金全等.环隙式离心萃取器处理含酚废水的研究：I.单级实验[J].石油炼制与化工,1999,30(9)：48～51
[57]Duan W. H., et al. Development of a φ20mm annular centrifugal contactor for the hot test of the total TRPO process[J]. Progress in Nuclear Energy,2009,51:313～318