由对苯二甲酸残渣合成混合型增塑剂
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摘要
对苯二甲酸(TA)残渣是PTA装置在生产对苯二甲酸过程中排放出的一种含有少量醋酸钴、醋酸锰等催化剂的有机副产物,主要成份为苯甲酸,对甲基苯甲酸,间苯二甲酸,对苯二甲酸和其他杂质等,同时含有余量的水分。由于成份复杂,难于处理,长期以来一直由购买PTA残渣的客户与PTA残渣一起运离厂区,由其自行处理,主要手段就是掩埋,对掩埋地造成一定的环境污染,致使PTA残渣不能按原设计返回氧化单元,而PTA残渣以极低的价格销售,远远与其品质不相适应,对PTA装置的效益产生了一定的影响。
本研究通过对文献报道的各种TA残渣的综合利用及处理方法进行分析,对由TA残渣合成混合型增塑剂的过程进行了研究。研究表明,TA残渣与丁醇酯化,具有原料成本低,产物处理容易,可以生产高沸点溶剂、丁酯型增塑剂、二甘醇二苯甲酸酯增塑剂,残液可以用作低档增塑剂或加热炉燃料等特点,具有一定的实用价值和经济效益。
通过研究,提出了一种比较完善的TA残渣综合利用的工艺方案,并对其中的部分处理单元进行了放大试验,取得了较好的结果和小批量的试用产品。该工艺的开发成功使生产企业有望解决一直存在的困扰PTA装置的TA残渣的出路问题,从而使得PTA残渣可以按原设计返回氧化单元,由此,PTA装置可多产PTA产品1400吨/年以上,经济效益明显,同时也解决了TA残渣掩埋导致的环境污染。
Terephthalic acid(TA) residue is a byproduct composed of inorginatic and organic impurities from the unit of PX oxidation to synthesize terephthalic acid, and the main components of TA residue are benzoic acid, p-methyl benzoic acid, m-phthalic acid, terephthalic acid and other impurities. Because of the complexity in components of TA residue, it is difficult to treat, and combustion and burying are two general methods, but which leads to environmental pollution. For us, TA residue has been the tie-in product with PTA residue for a long time, so PTA residue can not be returned to PX oxidation unit, and be only sold at a lower price than its own value, therefore, the economic benefit of PTA uint is decreased.
This paper has analysed the synthetical utilization of TA residue, which were reported in some articles, and studied on the process of synthesizing mixed plasticizer with TA residue. The results show that the esterify reaction between TA residue and butanol has practicability and economic benefit. The esterify reaction also has several merits, such as low material cost, being apt to deal with product, producing high-boiling point solvent, butylether plasticizer, diglycol benzoic ether plasticizer,and the remnant solvent acted as low-end plasticizer or fuel of heater.
After the studies, a valuable synthsis process was exploited to utilize TA residue, and the pilot experiment of some units were studied, a better research achievement was obtained in batch production. This technique will enable corporation to solve the problem of TA residue, which worries PTA unit for a long time, and enable PTA to return to PX oxidation unit. So PTA unit can increase productivity more than 1400 t/a, and biggish benefit will be got also. At mean time, the environmental pollution, brought by burying TA residue, will be avoided.
本研究通过对文献报道的各种TA残渣的综合利用及处理方法进行分析,对由TA残渣合成混合型增塑剂的过程进行了研究。研究表明,TA残渣与丁醇酯化,具有原料成本低,产物处理容易,可以生产高沸点溶剂、丁酯型增塑剂、二甘醇二苯甲酸酯增塑剂,残液可以用作低档增塑剂或加热炉燃料等特点,具有一定的实用价值和经济效益。
通过研究,提出了一种比较完善的TA残渣综合利用的工艺方案,并对其中的部分处理单元进行了放大试验,取得了较好的结果和小批量的试用产品。该工艺的开发成功使生产企业有望解决一直存在的困扰PTA装置的TA残渣的出路问题,从而使得PTA残渣可以按原设计返回氧化单元,由此,PTA装置可多产PTA产品1400吨/年以上,经济效益明显,同时也解决了TA残渣掩埋导致的环境污染。
Terephthalic acid(TA) residue is a byproduct composed of inorginatic and organic impurities from the unit of PX oxidation to synthesize terephthalic acid, and the main components of TA residue are benzoic acid, p-methyl benzoic acid, m-phthalic acid, terephthalic acid and other impurities. Because of the complexity in components of TA residue, it is difficult to treat, and combustion and burying are two general methods, but which leads to environmental pollution. For us, TA residue has been the tie-in product with PTA residue for a long time, so PTA residue can not be returned to PX oxidation unit, and be only sold at a lower price than its own value, therefore, the economic benefit of PTA uint is decreased.
This paper has analysed the synthetical utilization of TA residue, which were reported in some articles, and studied on the process of synthesizing mixed plasticizer with TA residue. The results show that the esterify reaction between TA residue and butanol has practicability and economic benefit. The esterify reaction also has several merits, such as low material cost, being apt to deal with product, producing high-boiling point solvent, butylether plasticizer, diglycol benzoic ether plasticizer,and the remnant solvent acted as low-end plasticizer or fuel of heater.
After the studies, a valuable synthsis process was exploited to utilize TA residue, and the pilot experiment of some units were studied, a better research achievement was obtained in batch production. This technique will enable corporation to solve the problem of TA residue, which worries PTA unit for a long time, and enable PTA to return to PX oxidation unit. So PTA unit can increase productivity more than 1400 t/a, and biggish benefit will be got also. At mean time, the environmental pollution, brought by burying TA residue, will be avoided.
引文
[1]金葆桴,PTA生产过程中的氧化废渣处理,金山油化纤1997,(1):11-14
[2] Shigeyasu,Motoo,Yamazaki,etal,Method for recovering a liquid-phase oxidation catalyst for preparation of terephthalic acid,US3,956,175,1976-05-11
[3] Shigeyasu,Motoo,Ozaki,etal,Method of recovering heavy metal,bromides and hydrobromic acid catalysts for liquid-phase oxidation,US3,959,449,1976-05-25
[4] Holzhauer,Juergen K,Michalak,etal,Process for recovery of cobalt and manganese for oxidation residue incinerator ash,US4,786,621 1988-11-22
[5] Edwards,Robert C,Golson,etal,Process for the recovery of cobalt and manganese from oxidation residue incinerator ash, pyrolysis sand and pyrolysis char,US4,546,202,1985-08-08
[6] Royall,David John,Bartlett,etal,Production of aromatic carboxylic acids and recovery of Co/Mn catalyst from ash,US6,255,510,2001-07-3
[7]刘公召,隋智通,从PTA残渣中回收醋酸钴和醋酸锰的研究,矿产综合利用,2001,(3):41-43
[8]黄又明,简易法回收TA残渣中的钴、锰,合成技术及应用,1994,(4):24-26
[9]李殿卿,李林,刘大壮,葛巍,对苯二甲酸氧化残渣中钴、锰催化剂的回收方法,中国,发明专利,CN 1120893C,2003-09-10
[10]李殿卿,李林,刘大壮,葛巍,对苯二甲酸氧化残渣中钴、锰催化剂的回收方法,中国,发明专利,CN 1293260A,2001-05-02
[11]朱培玉,姚雪松,任珉,舒新华,从对苯二甲酸氧化残渣中回收苯甲酸的方法,中国,发明专利,CN 1332145A,2002-01-23
[12]黄莹,王秀兰,对苯二甲酸(TA)废渣的综合利用,1998,(2):31
[13]贾长英,李卫华,黄宪升,TA残渣中对苯二甲酸的分离提纯,1997,(4):21-26
[14]金葆桴,顾善康,何美琴,诸毓桐,工业对苯二甲酸残渣分离方法,中国,发明专利,CN 1034363A,1989-08-02
[15]何美琴,高健翼,童天中,等,一种利用对苯二甲酸粗制品残渣生产苯羧酸酯类的工业方法,中国,发明专利,CN 1490300A,2004-04-21
[16]贾长英, TA残渣制取混合型增塑剂,广西化工,1999,(1):54-57
[17]冯利民,张侦祥,对苯二甲酸残渣合成对苯二甲酸二异辛酯的研究,化学世界,1997,(11):606-608
[18]洪作伟,PTA残渣回收利用,金山油化纤,1989,(1):1-3
[19]邓诗峰,苏勇,李远,何美琴,混合单元苯羧酸二甘醇酯增塑剂的合成研究,江苏化工,1996,(6):19-21
[20]苏勇,邓诗峰,童天中,何美琴,改性分子筛催化剂合成混合单元苯羧酸二甘醇酯,辽宁化工,1996,(5):33-35
[21]张慧,曹善文,张伟江,相转移催化剂TA残渣中有机酸合成酯的研究,合成技术及应用,1998,(2):23-25
[22]张慧,曹善文,张伟江,BTEAC相转移催化TA残渣中芳香酸合成苄酯的研究,济南纺织化纤科技,2000,(2):17-19
[23] Wulff;Helmut;Hass等,Coating substances,美国专利,US4,186,227,1980-01-29
[24]李绍英,赵北征,王连仲,聚酯废料的再利用,河北轻化工学院学报,1996,(4):21-24
[25]展江宏,PTA装置中氧化残渣的分离利用,聚酯工业,2000,(2):24-28
[26]展江宏,用PTA废料和重芳烃制备防腐抗静电油罐涂料,石化技术与应用,2001,(1):12-14
[27]颜可顺,由氧化残渣制备的聚氨酯涂料及其制造方法,中国,发明专利,CN 1078738A,1993-11-24
[28]展江宏,潘以诚,王安江,单组分聚氨酯漆及其制备方法,中国,发明专利,CN1082077C,2002-04-03
[29]展江宏,潘以诚,王安江,单组分聚氨酯漆及其制备方法,中国,发明专利,CN1247214A,2000-03-15
[30] White,Alan W.,Pearcy,etal,Polyester compositions,US5,132,391,1992-07-21
[31] White,Alan W.,Pearcy,etal,Polyester compositions,US5,338,606,1994-08-16
[32] White,Alan W.,Pearcy,etal,Polyester compositions,US5,370,938,1994-12-06
[33] Strand,Marc Alan,Sublett,etal,Clarity copolyester,US5,688,899,1997-12-18
[34] JP06256747,(1994-09-13)
[35] Niinami,Yoshiharu,Polyester,adhesive,美国专利,US4096123,1978-06-20
[36]张敏,颜连学,丁龙福,由废对苯二甲酸生产对苯二甲酸二甲酯的新工艺,江苏化工,2001,(4)32-34
[37]周敬凯,药品包装铝箔用聚酯热熔粘合剂,中国胶粘剂,1995,(3):17-18
[38] Londrigan,Michael E,Reaction products of terephthalic acid residues and polycarboxylic acid-containing polyols and polymeric foams obtained therefrom,US4,652,591,1987-03-24
[39] Brennan,Michael E.,Aromatic polyols made from waste streams from themanufacture of terephthalic acids, alkylene glycols and dibasic acids,US4,444,918,1984-04-24
[40] Sakai,Hiroshi,Takeuchi,etal,Process for preparing soft transparent polyether polyester block copolymers,US4081494,1978-03-28
[41] Suenaga,Jun-ichi,Naito,etal,Thermotropic liquid crystal polyesters and a method for their production,US5,075,418,1991-12-24
[42]姚雪松,一种用对苯二甲酸氧化残渣制备活性炭的方法,中国,发明专利,CN 1508067A,2004-06-30
[43]袁乾,PTA装置残渣焚烧炉操作技术探讨,扬子石油化工,1993,(2):11-15
[44]沈福昌,精对苯二甲酸(PTA)残渣焚烧方法,中国,发明专利,CN 1356183A,2002-07-03精对苯二甲酸(PTA)残渣焚烧处理装置,中国,实用新型专利,CN 2503364Y,2002-07-31
[45]石万聪,盛承祥,增塑剂,北京:化学工业出版社,1989
[2] Shigeyasu,Motoo,Yamazaki,etal,Method for recovering a liquid-phase oxidation catalyst for preparation of terephthalic acid,US3,956,175,1976-05-11
[3] Shigeyasu,Motoo,Ozaki,etal,Method of recovering heavy metal,bromides and hydrobromic acid catalysts for liquid-phase oxidation,US3,959,449,1976-05-25
[4] Holzhauer,Juergen K,Michalak,etal,Process for recovery of cobalt and manganese for oxidation residue incinerator ash,US4,786,621 1988-11-22
[5] Edwards,Robert C,Golson,etal,Process for the recovery of cobalt and manganese from oxidation residue incinerator ash, pyrolysis sand and pyrolysis char,US4,546,202,1985-08-08
[6] Royall,David John,Bartlett,etal,Production of aromatic carboxylic acids and recovery of Co/Mn catalyst from ash,US6,255,510,2001-07-3
[7]刘公召,隋智通,从PTA残渣中回收醋酸钴和醋酸锰的研究,矿产综合利用,2001,(3):41-43
[8]黄又明,简易法回收TA残渣中的钴、锰,合成技术及应用,1994,(4):24-26
[9]李殿卿,李林,刘大壮,葛巍,对苯二甲酸氧化残渣中钴、锰催化剂的回收方法,中国,发明专利,CN 1120893C,2003-09-10
[10]李殿卿,李林,刘大壮,葛巍,对苯二甲酸氧化残渣中钴、锰催化剂的回收方法,中国,发明专利,CN 1293260A,2001-05-02
[11]朱培玉,姚雪松,任珉,舒新华,从对苯二甲酸氧化残渣中回收苯甲酸的方法,中国,发明专利,CN 1332145A,2002-01-23
[12]黄莹,王秀兰,对苯二甲酸(TA)废渣的综合利用,1998,(2):31
[13]贾长英,李卫华,黄宪升,TA残渣中对苯二甲酸的分离提纯,1997,(4):21-26
[14]金葆桴,顾善康,何美琴,诸毓桐,工业对苯二甲酸残渣分离方法,中国,发明专利,CN 1034363A,1989-08-02
[15]何美琴,高健翼,童天中,等,一种利用对苯二甲酸粗制品残渣生产苯羧酸酯类的工业方法,中国,发明专利,CN 1490300A,2004-04-21
[16]贾长英, TA残渣制取混合型增塑剂,广西化工,1999,(1):54-57
[17]冯利民,张侦祥,对苯二甲酸残渣合成对苯二甲酸二异辛酯的研究,化学世界,1997,(11):606-608
[18]洪作伟,PTA残渣回收利用,金山油化纤,1989,(1):1-3
[19]邓诗峰,苏勇,李远,何美琴,混合单元苯羧酸二甘醇酯增塑剂的合成研究,江苏化工,1996,(6):19-21
[20]苏勇,邓诗峰,童天中,何美琴,改性分子筛催化剂合成混合单元苯羧酸二甘醇酯,辽宁化工,1996,(5):33-35
[21]张慧,曹善文,张伟江,相转移催化剂TA残渣中有机酸合成酯的研究,合成技术及应用,1998,(2):23-25
[22]张慧,曹善文,张伟江,BTEAC相转移催化TA残渣中芳香酸合成苄酯的研究,济南纺织化纤科技,2000,(2):17-19
[23] Wulff;Helmut;Hass等,Coating substances,美国专利,US4,186,227,1980-01-29
[24]李绍英,赵北征,王连仲,聚酯废料的再利用,河北轻化工学院学报,1996,(4):21-24
[25]展江宏,PTA装置中氧化残渣的分离利用,聚酯工业,2000,(2):24-28
[26]展江宏,用PTA废料和重芳烃制备防腐抗静电油罐涂料,石化技术与应用,2001,(1):12-14
[27]颜可顺,由氧化残渣制备的聚氨酯涂料及其制造方法,中国,发明专利,CN 1078738A,1993-11-24
[28]展江宏,潘以诚,王安江,单组分聚氨酯漆及其制备方法,中国,发明专利,CN1082077C,2002-04-03
[29]展江宏,潘以诚,王安江,单组分聚氨酯漆及其制备方法,中国,发明专利,CN1247214A,2000-03-15
[30] White,Alan W.,Pearcy,etal,Polyester compositions,US5,132,391,1992-07-21
[31] White,Alan W.,Pearcy,etal,Polyester compositions,US5,338,606,1994-08-16
[32] White,Alan W.,Pearcy,etal,Polyester compositions,US5,370,938,1994-12-06
[33] Strand,Marc Alan,Sublett,etal,Clarity copolyester,US5,688,899,1997-12-18
[34] JP06256747,(1994-09-13)
[35] Niinami,Yoshiharu,Polyester,adhesive,美国专利,US4096123,1978-06-20
[36]张敏,颜连学,丁龙福,由废对苯二甲酸生产对苯二甲酸二甲酯的新工艺,江苏化工,2001,(4)32-34
[37]周敬凯,药品包装铝箔用聚酯热熔粘合剂,中国胶粘剂,1995,(3):17-18
[38] Londrigan,Michael E,Reaction products of terephthalic acid residues and polycarboxylic acid-containing polyols and polymeric foams obtained therefrom,US4,652,591,1987-03-24
[39] Brennan,Michael E.,Aromatic polyols made from waste streams from themanufacture of terephthalic acids, alkylene glycols and dibasic acids,US4,444,918,1984-04-24
[40] Sakai,Hiroshi,Takeuchi,etal,Process for preparing soft transparent polyether polyester block copolymers,US4081494,1978-03-28
[41] Suenaga,Jun-ichi,Naito,etal,Thermotropic liquid crystal polyesters and a method for their production,US5,075,418,1991-12-24
[42]姚雪松,一种用对苯二甲酸氧化残渣制备活性炭的方法,中国,发明专利,CN 1508067A,2004-06-30
[43]袁乾,PTA装置残渣焚烧炉操作技术探讨,扬子石油化工,1993,(2):11-15
[44]沈福昌,精对苯二甲酸(PTA)残渣焚烧方法,中国,发明专利,CN 1356183A,2002-07-03精对苯二甲酸(PTA)残渣焚烧处理装置,中国,实用新型专利,CN 2503364Y,2002-07-31
[45]石万聪,盛承祥,增塑剂,北京:化学工业出版社,1989