MTBE运行周期短的原因及解决方案
摘要
MTBE是近二十年来发展最快的石油化工产品之一,广泛地应用于汽油产品的调和,目前虽然美国、日本、丹麦等国由于美国加州由于地下汽油罐泄漏,导致MTBE污染地下水源的问题,纷纷提出要禁止在汽油中添加MTBE,但是根据预测,在未来相当长的一段时期内,亚太和北欧等地区的MTBE需求量不但不会下降而且还有上升的趋势。
本文针对前郭石化公司年产2.0万吨/年MTBE装置在运行过程中出现的催化剂使用寿命短的问题,从反应器运行的宏观现象和使用后的催化剂分析数据两个方面,结合催化剂失活的原理、机理进行分析、对照,最终得出结论:前郭石化公司MTBE装置醚化催化剂的失活是一个扩散形失活,而不是平推流形的失活,影响催化剂使用寿命的主要原因在于原料碳四中的小分子胺、碱(钠离子)和水含量高所致。
在查出催化剂使用寿命短的原因后,针对这些原因,在装置上采取了对液化气进行水洗以洗去液化气中的小分子胺和碱(钠离子);对水洗后的液化气使用聚结器脱水和罐区沉降脱水,以脱除液化气中的游离水;对气体分馏装置的精馏塔的顶压、顶温、回流量、回流温度进行调整以达到进一步减少MTBE装置原料碳四中的水含量的目的。通过这些措施的实施,使催化剂的使用寿命增加了近一倍,连续使用时间达到16个月,基本与国内同类装置持平,效果非常明显。
MTBE is one of the petrochemical products most rapidly developed in the recent twenty years. It is widely used in the blending of gasoline. Even though the addition of MTBE in gasoline have been prohibited in many countries, including USA, Japan and Denmark, because the leakage of the underground oil tanks leads to the pollution of water sources. by estimation, but the demand of MTBE in the Asian-Pacific areas and North European areas will not decline, and get rise in a rather long period of time.
For the short lifetime of the catalyst in a 20,000 metric ton per year MTBE unit, combined the principle and mechanism of losing activity of catalyst with the analysis data of the non-active catalyst and the macroscopic pHenomena in the reactor running, the paper gave the reasons as follows:
First, the activity losing of etherification catalyst in the MTBE unit is a diffusing one, not the pushing one. Second, the main reason of the short lifetime of catalyst is the high content of small molecular amine, alkali or sodium ion and water in the raw material of C4 fraction.
To solve the above problems, several measures had been taken in the paper. These measures are, first, removing the small molecular amine and alkali or sodium ion by washing the LPG, second, separating the free water in the liquid gas by using the filter and tank sedimentation and third, decreasing the water content of material C4 fraction by adjusting the top pressure, top temperature, reflux amount and reflux temperature of the rectifying tower in gas fractionation unit. These measures double the use lifetime of the catalyst to 16 months in continuous process, reaching the high internal level with the same MTBE unit, significantly improving the catalyst lifetime in the MTBE plant.
本文针对前郭石化公司年产2.0万吨/年MTBE装置在运行过程中出现的催化剂使用寿命短的问题,从反应器运行的宏观现象和使用后的催化剂分析数据两个方面,结合催化剂失活的原理、机理进行分析、对照,最终得出结论:前郭石化公司MTBE装置醚化催化剂的失活是一个扩散形失活,而不是平推流形的失活,影响催化剂使用寿命的主要原因在于原料碳四中的小分子胺、碱(钠离子)和水含量高所致。
在查出催化剂使用寿命短的原因后,针对这些原因,在装置上采取了对液化气进行水洗以洗去液化气中的小分子胺和碱(钠离子);对水洗后的液化气使用聚结器脱水和罐区沉降脱水,以脱除液化气中的游离水;对气体分馏装置的精馏塔的顶压、顶温、回流量、回流温度进行调整以达到进一步减少MTBE装置原料碳四中的水含量的目的。通过这些措施的实施,使催化剂的使用寿命增加了近一倍,连续使用时间达到16个月,基本与国内同类装置持平,效果非常明显。
MTBE is one of the petrochemical products most rapidly developed in the recent twenty years. It is widely used in the blending of gasoline. Even though the addition of MTBE in gasoline have been prohibited in many countries, including USA, Japan and Denmark, because the leakage of the underground oil tanks leads to the pollution of water sources. by estimation, but the demand of MTBE in the Asian-Pacific areas and North European areas will not decline, and get rise in a rather long period of time.
For the short lifetime of the catalyst in a 20,000 metric ton per year MTBE unit, combined the principle and mechanism of losing activity of catalyst with the analysis data of the non-active catalyst and the macroscopic pHenomena in the reactor running, the paper gave the reasons as follows:
First, the activity losing of etherification catalyst in the MTBE unit is a diffusing one, not the pushing one. Second, the main reason of the short lifetime of catalyst is the high content of small molecular amine, alkali or sodium ion and water in the raw material of C4 fraction.
To solve the above problems, several measures had been taken in the paper. These measures are, first, removing the small molecular amine and alkali or sodium ion by washing the LPG, second, separating the free water in the liquid gas by using the filter and tank sedimentation and third, decreasing the water content of material C4 fraction by adjusting the top pressure, top temperature, reflux amount and reflux temperature of the rectifying tower in gas fractionation unit. These measures double the use lifetime of the catalyst to 16 months in continuous process, reaching the high internal level with the same MTBE unit, significantly improving the catalyst lifetime in the MTBE plant.
引文
[1]杨哲.MTBE等汽油含氧调合组分的发展趋势[J].石油炼制与化工,2002,33(7):44-48.
[2]高玉生,刘立群.甲基叔丁基醚市场分析[J].化学工业,2010,28(7):23-25.
[3]钱伯章,朱建芳.MTBE的使用现状和趋势[J].天然气与石油,2008(1):50-54.
[4]李大伟,项曙光,韩方煜.甲基叔丁基醚的生产工艺及应用进展[J].河北化工,2006,29(12):3-5.
[5]杨宗仁.MTBE生产技术知识问答[Z].MTBE技术协作组(内部资料2003年)
[6]孙晓轩,王晓东.禁用后的全球甲基叔丁基醚市场[J].化学工业,2008,(6):16-22.
[7] Xu Y,Long J,Shao X. A survey of novel processes to produce ultra low sulfur gasoline[J].China Petroleum Processing and Petrochemical Technology,2003,(2):19-23.
[8]李红艳,高锦伍,杨江,等.甲其叔丁基醚的遗传毒性研究[J].劳动医学,2001,18(6):341-343.
[9]李红艳.甲基叔丁基醚遗传毒性研究进展[J].南京铁道医学院学报.2000,19(1):70-72.
[10]贺性鹏,蔡亚平,贺栋梁.汽油添加剂甲基叔丁基醚对小鼠传毒性的作用[J].中国职业医学,2003,30(1):8-9.
[11]张维昊,徐小清,方涛,等.甲基叔丁基醚对生态与环境的影响[J].环境科学研究,2002,15(6):56-59.
[12]袁东,周伟,叶舜华.甲基叔丁基醚对大鼠血清生化指标及肾超微结构的影响[J].劳动医学,2001,18(5):265-268.
[13]袁东,叶舜华,周伟,黄关麟.无铅汽油新型添加剂甲基叔丁基醚的致突变性研究[J].中国公共卫生,2002,18(2):129-130.
[14]梁文,吴斐,冯建钢.MTBE装置催化剂失活原因分析及对策探讨[J].炼油技术与工程,2008,(1):18-21.
[15]刘冰,王承明,高培钧,等.甲基叔丁基醚作助溶剂合成生物柴油研究[J].现代商贸工业,2010,(2):297-299.
[16] Ma X.,Velu S,Kim J H. Deep desulfurization of gasoline by selective adsorption over solid adsorbents and impact of analytical methods onμg/g-level sulfur quantification for fuel cell applications[J].Applied catalysis B: Environmental,2005,56:137-147.
[17]牛治刚,周健.混相催化蒸馏法生产MTBE的技术及质量控制[J].化工技术与开发,2006,35(3):28-31.
[18]杨宗仁,郝兴仁.MTBE催化蒸馏技术开发[J].齐鲁石油化工,1997,11(1):21-24.
[19]张国玺,邓福利.MTBE装置甲醇萃取塔和精馏塔腐蚀原因分析及预防措施[J].科技创新导报,2009,(6):2.
[20] Song C. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel[J].Catalysis Today,2003,86:211-263.
[21]童兆春. MTBE装置催化剂失活原因分析及对策探讨[J].山东化工,2010,39(8):34-36.
[22]宗士权.大孔径阳离子交换树脂的研制与生产[C].2001年MTBE协作组年会会议论文集,MTBE协作组年会,昆明,2001年,淄博:MTBE协作组,2001:43-47.
[23]吴崇志,Wilbert Tsao.MTBE/TAME合成用催化剂树脂[C].2001年MTBE协作组年会会议论文集,MTBE协作组年会,昆明,2001年,淄博:MTBE协作组,2001:5-8.
[24]沙利,王传真,朱学军.炼油型MTBE装置混相床-催化蒸馏组合工艺设计[J].石油化工设计,2008,25(1):4-6.
[25] Lu R Q,Li J L,Liu C G.A theoretical study on effect of electronic and steric structures of thiophene derivatives for their deep desulfurization[J].J.of Molecular Catalysis (CHINA),2004,18 (3):229-233.
[26]刘国胜,谢涛.MTBE装置扩能改造技术路线的选择及分析[J].中外能源,2009,14(6):82-86.
[27]赵光辉,常玉红,牛明.MTBE的最新研究及替代产品的开发[J].四川化工与腐蚀控制,2003,6(1):29-33.
[28] Huang D,Wang Y J,Yang L M,et al. Chemical oxidation of dibenzothiophene with a directly combined amphiphilic catalyst for deep desulfurization[J].Industrial & Engineering Chemistry Research,2006,45:1880-1885.
[29]张莹莹.固定床+催化精馏MTBE精制塔冷却器生产过程工艺优化改进[J].黑龙江科技信息,2008,(31):46-47.
[30] Kabe T,Ishiharam A,Tajima H.Sulfur exchange on Co–Mo/Al2O3 hydrodesulfurization catalyst using radioisotope tracer[J].Catalysis Today,1996,31(5):197-202.
[2]高玉生,刘立群.甲基叔丁基醚市场分析[J].化学工业,2010,28(7):23-25.
[3]钱伯章,朱建芳.MTBE的使用现状和趋势[J].天然气与石油,2008(1):50-54.
[4]李大伟,项曙光,韩方煜.甲基叔丁基醚的生产工艺及应用进展[J].河北化工,2006,29(12):3-5.
[5]杨宗仁.MTBE生产技术知识问答[Z].MTBE技术协作组(内部资料2003年)
[6]孙晓轩,王晓东.禁用后的全球甲基叔丁基醚市场[J].化学工业,2008,(6):16-22.
[7] Xu Y,Long J,Shao X. A survey of novel processes to produce ultra low sulfur gasoline[J].China Petroleum Processing and Petrochemical Technology,2003,(2):19-23.
[8]李红艳,高锦伍,杨江,等.甲其叔丁基醚的遗传毒性研究[J].劳动医学,2001,18(6):341-343.
[9]李红艳.甲基叔丁基醚遗传毒性研究进展[J].南京铁道医学院学报.2000,19(1):70-72.
[10]贺性鹏,蔡亚平,贺栋梁.汽油添加剂甲基叔丁基醚对小鼠传毒性的作用[J].中国职业医学,2003,30(1):8-9.
[11]张维昊,徐小清,方涛,等.甲基叔丁基醚对生态与环境的影响[J].环境科学研究,2002,15(6):56-59.
[12]袁东,周伟,叶舜华.甲基叔丁基醚对大鼠血清生化指标及肾超微结构的影响[J].劳动医学,2001,18(5):265-268.
[13]袁东,叶舜华,周伟,黄关麟.无铅汽油新型添加剂甲基叔丁基醚的致突变性研究[J].中国公共卫生,2002,18(2):129-130.
[14]梁文,吴斐,冯建钢.MTBE装置催化剂失活原因分析及对策探讨[J].炼油技术与工程,2008,(1):18-21.
[15]刘冰,王承明,高培钧,等.甲基叔丁基醚作助溶剂合成生物柴油研究[J].现代商贸工业,2010,(2):297-299.
[16] Ma X.,Velu S,Kim J H. Deep desulfurization of gasoline by selective adsorption over solid adsorbents and impact of analytical methods onμg/g-level sulfur quantification for fuel cell applications[J].Applied catalysis B: Environmental,2005,56:137-147.
[17]牛治刚,周健.混相催化蒸馏法生产MTBE的技术及质量控制[J].化工技术与开发,2006,35(3):28-31.
[18]杨宗仁,郝兴仁.MTBE催化蒸馏技术开发[J].齐鲁石油化工,1997,11(1):21-24.
[19]张国玺,邓福利.MTBE装置甲醇萃取塔和精馏塔腐蚀原因分析及预防措施[J].科技创新导报,2009,(6):2.
[20] Song C. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel[J].Catalysis Today,2003,86:211-263.
[21]童兆春. MTBE装置催化剂失活原因分析及对策探讨[J].山东化工,2010,39(8):34-36.
[22]宗士权.大孔径阳离子交换树脂的研制与生产[C].2001年MTBE协作组年会会议论文集,MTBE协作组年会,昆明,2001年,淄博:MTBE协作组,2001:43-47.
[23]吴崇志,Wilbert Tsao.MTBE/TAME合成用催化剂树脂[C].2001年MTBE协作组年会会议论文集,MTBE协作组年会,昆明,2001年,淄博:MTBE协作组,2001:5-8.
[24]沙利,王传真,朱学军.炼油型MTBE装置混相床-催化蒸馏组合工艺设计[J].石油化工设计,2008,25(1):4-6.
[25] Lu R Q,Li J L,Liu C G.A theoretical study on effect of electronic and steric structures of thiophene derivatives for their deep desulfurization[J].J.of Molecular Catalysis (CHINA),2004,18 (3):229-233.
[26]刘国胜,谢涛.MTBE装置扩能改造技术路线的选择及分析[J].中外能源,2009,14(6):82-86.
[27]赵光辉,常玉红,牛明.MTBE的最新研究及替代产品的开发[J].四川化工与腐蚀控制,2003,6(1):29-33.
[28] Huang D,Wang Y J,Yang L M,et al. Chemical oxidation of dibenzothiophene with a directly combined amphiphilic catalyst for deep desulfurization[J].Industrial & Engineering Chemistry Research,2006,45:1880-1885.
[29]张莹莹.固定床+催化精馏MTBE精制塔冷却器生产过程工艺优化改进[J].黑龙江科技信息,2008,(31):46-47.
[30] Kabe T,Ishiharam A,Tajima H.Sulfur exchange on Co–Mo/Al2O3 hydrodesulfurization catalyst using radioisotope tracer[J].Catalysis Today,1996,31(5):197-202.