用于丙烯腈生产的C49MC催化剂性能和应用研究
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摘要
抚顺石油化工公司腈纶化工厂丙烯腈装置所使用的CTA-6催化剂,在更换初期两年内丙烯腈收率基本稳定在79%以上,在第三、四年时,收率下降1 %左右,且随着使用时间的延长,收率将会更低。因此,丙烯腈用催化剂的收率对装置的运行是至关重要的,选择丙烯腈收率高、性能好的催化剂可以提高丙烯腈产品的产量,降低物耗、能耗,提高经济效益。
针对国内丙烯装置的生产状况和催化剂使用情况进行调研,并对C49MC、CTA-6、MB-98催化剂的在性能上进行对比,优选出适合抚顺石油化工公司腈纶化工厂丙烯腈装置用的催化剂,围绕丙烯腈催化剂的性能研究和在8万吨/年丙烯腈生产装置的实际应用作为研究探索的方向。
通过对丙烯腈用催化剂的物理性能、丙烯腈收率、丙烯转化率、选择性、反应温度、反应配比、重时空速等方面的性能和操作条件进行比较,选用C49MC催化剂作为,抚顺石油化工公司丙烯腈用催化剂,从反应温度、压力、配比、重量时间空速(WWH)、收率、转化率、选择性等方面研究C49MC的性能和操作条件。通过实验,确定C49MC催化剂在8万吨/年丙烯腈装置上运行的最佳工艺条件,并在装置上应用,考核C49MC催化剂的物耗、能耗、产量、环保排放指标、产品质量及产品成本。
丙烯腈装置在换进口C49MC催化剂后,丙烯单耗达到较好水平;丙烯腈装置排放污水合格率100%,达到环保指标的要求;丙烯腈收率始终保持良好。更换新型催化剂在短期内就能收回成本,在其后的时间内,收率远远高于76%,所增效益是十分可观的。
The CTA-6 catalyst has been used in the production of acrylonitrile in the acrylic fiber plant of Fushun petrochemical company and the yield of acrylonitrile can reach to 79% above in the initial two years. Nevertheless, the yield of acrylonitrile can decrease about 1 % in the third and forth year, and will decline even much lower along with extension of using time. So the performance of catalyst has a great influence on the production of acrylonitrile. A kind of catalyst with higher catalytic activity can raise the yield of acrylic fiber products, lessen the use of material and energy, and improve the economic efficiency.
On the basis of investigation of the application of C49MC,CTA-6,MB-98 catalysts in the acrylonitrile production of acrylic fibers plants of Fushun petrochemical company, the optimum choice of the catalyst has been made considering the acrylonitrile production ability of 104 t/a.
By contrasting the performance of three catalysts under different operation conditions, the C49MC catalyst exhibited a best choice for the production of acrylonitrile in the acrylic fiber plant of Fushun petrochemical company. The effscts of the performance of C49MC catalyst on the reaction temperature,pressure,assignation ratio,WWH,yield,conversion and selectivity are studied in this paper.. The best operating condition of the C49MC catalyst is found out under the condition of the total yield of acrylonitrile of 80,000 t/a. And this optimum running condition has been used in the facilities, and the consumption of material and energy, the yield and product quality, the level of environmental protection and cost have also been evaluated.
The specific consumption of propylene declines to an ideal level due to use of the C49MC catalyst, and the waste water produced by the acrylic fibers plant accords with environment request.
Replacing new catalyst can recover cost in a short term. The yield can markedly exceed 76% in a long period, and the subsequent profit would be considerable.
针对国内丙烯装置的生产状况和催化剂使用情况进行调研,并对C49MC、CTA-6、MB-98催化剂的在性能上进行对比,优选出适合抚顺石油化工公司腈纶化工厂丙烯腈装置用的催化剂,围绕丙烯腈催化剂的性能研究和在8万吨/年丙烯腈生产装置的实际应用作为研究探索的方向。
通过对丙烯腈用催化剂的物理性能、丙烯腈收率、丙烯转化率、选择性、反应温度、反应配比、重时空速等方面的性能和操作条件进行比较,选用C49MC催化剂作为,抚顺石油化工公司丙烯腈用催化剂,从反应温度、压力、配比、重量时间空速(WWH)、收率、转化率、选择性等方面研究C49MC的性能和操作条件。通过实验,确定C49MC催化剂在8万吨/年丙烯腈装置上运行的最佳工艺条件,并在装置上应用,考核C49MC催化剂的物耗、能耗、产量、环保排放指标、产品质量及产品成本。
丙烯腈装置在换进口C49MC催化剂后,丙烯单耗达到较好水平;丙烯腈装置排放污水合格率100%,达到环保指标的要求;丙烯腈收率始终保持良好。更换新型催化剂在短期内就能收回成本,在其后的时间内,收率远远高于76%,所增效益是十分可观的。
The CTA-6 catalyst has been used in the production of acrylonitrile in the acrylic fiber plant of Fushun petrochemical company and the yield of acrylonitrile can reach to 79% above in the initial two years. Nevertheless, the yield of acrylonitrile can decrease about 1 % in the third and forth year, and will decline even much lower along with extension of using time. So the performance of catalyst has a great influence on the production of acrylonitrile. A kind of catalyst with higher catalytic activity can raise the yield of acrylic fiber products, lessen the use of material and energy, and improve the economic efficiency.
On the basis of investigation of the application of C49MC,CTA-6,MB-98 catalysts in the acrylonitrile production of acrylic fibers plants of Fushun petrochemical company, the optimum choice of the catalyst has been made considering the acrylonitrile production ability of 104 t/a.
By contrasting the performance of three catalysts under different operation conditions, the C49MC catalyst exhibited a best choice for the production of acrylonitrile in the acrylic fiber plant of Fushun petrochemical company. The effscts of the performance of C49MC catalyst on the reaction temperature,pressure,assignation ratio,WWH,yield,conversion and selectivity are studied in this paper.. The best operating condition of the C49MC catalyst is found out under the condition of the total yield of acrylonitrile of 80,000 t/a. And this optimum running condition has been used in the facilities, and the consumption of material and energy, the yield and product quality, the level of environmental protection and cost have also been evaluated.
The specific consumption of propylene declines to an ideal level due to use of the C49MC catalyst, and the waste water produced by the acrylic fibers plant accords with environment request.
Replacing new catalyst can recover cost in a short term. The yield can markedly exceed 76% in a long period, and the subsequent profit would be considerable.
引文
[1]全国丙烯腈行业年会文集.第六届,2005:1～53
[2]韩秀山,稽瑗,朱伟平.丙烯腈生产技术现状及发展趋势.化工生产与技术,2000,3(7):15～17
[3]顾政.丙烯腈催化剂的工业应用与发展.江苏化工,2005,33(03):55～58
[4]赵震,张惠民,徐春明等.丙烯氨氧化催化剂研究进展.黑龙江大学自然科学学报,2005,22(2):237～240
[5]王乐夫,吴国华,黄醒帆等.化学反应工程与工艺,1993,2:158
[6]Shelstad K A,Chong T C.Kinetics of the Ammoxidation of propylene over a bismuth-molybdate catalyst.Can J Chem.Eng,1969,47:597～602
[7]Burrington J D,Grasselli R K.Aspects of selective oxidation and ammoxidation mechanism over bismuth molybdate catalysts.J Catal,1979,59:79～99
[8]郭向明,吕春,刘超.优化尾氧含量指标与丙烯腈催化剂使用寿命.吉林化工学院学报,2004,21(04):15～18
[9]陈丰秋,魏小明,戴擎镰等.氧浓度振荡操作下丙烯氨氧化反应过程.化工学报,1999,50(6):845～850
[10]严仲明.丙烯腈催化剂活性衰减原因的分析及对策.石油化工,1999,28(7):469～473
[11]刘梅红,姜坪.丙烯氨氧化反应网络的确定.浙江工程学报,2003,20(2): 92～95
[12]詹晓力,陈丰秋.MO-Bi系丙烯氨氧化催化剂上氨分解反应动力学.石油化工,2001,30(7):524～527
[13]李劲之,尚振平,于衍善.丙烯腈生产中过氧化物超标原因分析及对策.化学工程师,2004,18(4):51～52
[14]李朔新,李德胜.丙烯腈装置高负荷回收率提高的措施.化学工程师,2006,20(10):39～42
[15]谢方友.丙烷氨氧化制丙烯腈催化剂设计进展.工业催化,2003,11(8):38～42
[16]金强.催化剂自动连续补加技术.石化技术与应用,2000,18(2):94～96
[17]张文钲.氨氧化催化剂研发进展.中国钼业,1994,86(03):267～285
[18]Adams C R,Voge H H,Morgan C.Z et al. Oxidation of butylenes and propylene over bismuth molybdate.J Catal,1964,3(4):379～386
[19]魏小明,詹晓力,陈丰秋.氧浓度振荡操作下的丙烯氨氧化反应动态动力学模型.高校化学工程学报,2002,16(6):38～642
[20]严忠明.催化剂流化高度与丙烯腈反应器的优化运行.石油化工,2002,31(2):118-120.
[21]俞坚,张虹,戴擎镰等.多组份钼铋催化剂上丙烯氨氧化反应Ⅰ.石油化工,1987,16(7):472～476
[22]俞坚,张虹,戴擎镰等.多组份钼铋催化剂上丙烯氨氧化反应Ⅱ.石油化工,1988,17(3):140～144
[23]罗保林,俞江平,范正等.丙烯氨氧化合成丙烯腈流化床反应器的数学拟合.化工冶金,1999,20(1):44-50
[24]Silveston P L,Forissier Michel.Influuence of composition on product yields and selectivity in partial oxidation of propylene over An antimony-tin oxide catalyst.Ind Eng Chem Proc Des Dev,1985,24:320～325
[25]陈欣,宋健.丙烯氨氧化催化剂的开发与研究.中国科学技术前言,2005(5):265～293.
[26]戴擎镰,俞坚,张虹.丙烯氨氧化制丙烯腈的反应网络与动力学模型.化学反应工程与工艺,1993,(9):345～352
[27]顾坚,魏靖,陈秋丰等.遗算法在丙烯氨氧化反应动力学参数估算中的应用.石油化工,1999,28(4):227～231
[28]魏飞,胡永琪,赖志平等.丙烯氨氧化循环流化床反应器数学模型.石油化工,1998,27(4):276～280
[29] Lankhuyzen S P,Florack P M,van der Baan H S.The catalytic ammoxidation of propylene over bismuth molybdate catalyst.J Catal,1976,42(1):20～28
[30]Wilson H D and Rinker G Robert . Concentration forcing in ammonia synthesis—1 Controlled cyclic operation.CHem Eng Sci,1982,37(3):343～355
[2]韩秀山,稽瑗,朱伟平.丙烯腈生产技术现状及发展趋势.化工生产与技术,2000,3(7):15～17
[3]顾政.丙烯腈催化剂的工业应用与发展.江苏化工,2005,33(03):55～58
[4]赵震,张惠民,徐春明等.丙烯氨氧化催化剂研究进展.黑龙江大学自然科学学报,2005,22(2):237～240
[5]王乐夫,吴国华,黄醒帆等.化学反应工程与工艺,1993,2:158
[6]Shelstad K A,Chong T C.Kinetics of the Ammoxidation of propylene over a bismuth-molybdate catalyst.Can J Chem.Eng,1969,47:597～602
[7]Burrington J D,Grasselli R K.Aspects of selective oxidation and ammoxidation mechanism over bismuth molybdate catalysts.J Catal,1979,59:79～99
[8]郭向明,吕春,刘超.优化尾氧含量指标与丙烯腈催化剂使用寿命.吉林化工学院学报,2004,21(04):15～18
[9]陈丰秋,魏小明,戴擎镰等.氧浓度振荡操作下丙烯氨氧化反应过程.化工学报,1999,50(6):845～850
[10]严仲明.丙烯腈催化剂活性衰减原因的分析及对策.石油化工,1999,28(7):469～473
[11]刘梅红,姜坪.丙烯氨氧化反应网络的确定.浙江工程学报,2003,20(2): 92～95
[12]詹晓力,陈丰秋.MO-Bi系丙烯氨氧化催化剂上氨分解反应动力学.石油化工,2001,30(7):524～527
[13]李劲之,尚振平,于衍善.丙烯腈生产中过氧化物超标原因分析及对策.化学工程师,2004,18(4):51～52
[14]李朔新,李德胜.丙烯腈装置高负荷回收率提高的措施.化学工程师,2006,20(10):39～42
[15]谢方友.丙烷氨氧化制丙烯腈催化剂设计进展.工业催化,2003,11(8):38～42
[16]金强.催化剂自动连续补加技术.石化技术与应用,2000,18(2):94～96
[17]张文钲.氨氧化催化剂研发进展.中国钼业,1994,86(03):267～285
[18]Adams C R,Voge H H,Morgan C.Z et al. Oxidation of butylenes and propylene over bismuth molybdate.J Catal,1964,3(4):379～386
[19]魏小明,詹晓力,陈丰秋.氧浓度振荡操作下的丙烯氨氧化反应动态动力学模型.高校化学工程学报,2002,16(6):38～642
[20]严忠明.催化剂流化高度与丙烯腈反应器的优化运行.石油化工,2002,31(2):118-120.
[21]俞坚,张虹,戴擎镰等.多组份钼铋催化剂上丙烯氨氧化反应Ⅰ.石油化工,1987,16(7):472～476
[22]俞坚,张虹,戴擎镰等.多组份钼铋催化剂上丙烯氨氧化反应Ⅱ.石油化工,1988,17(3):140～144
[23]罗保林,俞江平,范正等.丙烯氨氧化合成丙烯腈流化床反应器的数学拟合.化工冶金,1999,20(1):44-50
[24]Silveston P L,Forissier Michel.Influuence of composition on product yields and selectivity in partial oxidation of propylene over An antimony-tin oxide catalyst.Ind Eng Chem Proc Des Dev,1985,24:320～325
[25]陈欣,宋健.丙烯氨氧化催化剂的开发与研究.中国科学技术前言,2005(5):265～293.
[26]戴擎镰,俞坚,张虹.丙烯氨氧化制丙烯腈的反应网络与动力学模型.化学反应工程与工艺,1993,(9):345～352
[27]顾坚,魏靖,陈秋丰等.遗算法在丙烯氨氧化反应动力学参数估算中的应用.石油化工,1999,28(4):227～231
[28]魏飞,胡永琪,赖志平等.丙烯氨氧化循环流化床反应器数学模型.石油化工,1998,27(4):276～280
[29] Lankhuyzen S P,Florack P M,van der Baan H S.The catalytic ammoxidation of propylene over bismuth molybdate catalyst.J Catal,1976,42(1):20～28
[30]Wilson H D and Rinker G Robert . Concentration forcing in ammonia synthesis—1 Controlled cyclic operation.CHem Eng Sci,1982,37(3):343～355
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