废旧轮胎热裂解与催化裂解行为研究
|
摘要
废旧轮胎催化裂解的研究是近年来人们一直关注和不断研究的一个重要课题,对于资源利用及环境保护具有重大意义。通过催化裂解的方式对废旧轮胎进行回收,国内外已进行了大量的研究,虽然已取得了很多成果,但目前在技术及经济上仍具有不可行性的特点。因此,对废旧轮胎催化裂解行为进行深入的研究,找出影响废旧轮胎催化裂解性能的重要因素,以提高裂解速率并获得更高质量的液体产品,是当前废旧轮胎催化裂解回收研究领域的重要课题。这一课题的解决,不仅具有理论意义,而且还具有应用价值。
本论文采用间歇釜式反应器,对废旧轮胎及轮胎组成中的几种主要的橡胶,包括天然橡胶(NR),聚丁二烯(BR)及丁苯橡胶(SBR)的热解和催化裂解行为进行了系统的研究,为通过催化裂解回收废旧轮胎提供坚实的理论基础。
首先研究了废旧轮胎的热解和催化裂解行为,得出在废旧轮胎的催化裂解中,润滑油的加入明显地提高了废旧轮胎催化降解的反应速率;并使催化裂解产物中液体收率增加,气体和固体产物收率减少;在废旧轮胎的催化裂解产物中,润滑油的加入使得液体产物中Cl、S和N的含量与废旧轮胎单独热解时相似;但轻组分含量明显提高,重组分含量减少。其中1,8-萜二烯组分的含量由7.54%(废旧轮胎/ZSM-5)提高到13.58%(废旧轮胎/ZSM-5/润滑油);在废旧轮胎催化裂解中单独使用催化剂ZSM-5分子筛或者单独使用润滑油,均不能显著提高废旧轮胎裂解效率。润滑油的加入增强了催化剂与废旧轮胎之间的相互作用,从而增强了其催化效果;不仅可以提高废旧轮胎裂解的反应速度,还可以增加其裂解产物中具有经济价值的化合物组分的含量。
Nowadays, waste tires have not only caused serious environmental problems but also a huge waste of resources. Among the different alternatives for tire recycling, such as retreating, reclaiming, incineration, grinding, biodegradation, etc., pyrolysis has been proposed as a viable recycling technology. However, owing to technical problems as well as economic and legal factors, the pyrolysis processes of tires have not been cost-effective up to now.
Large-scale tertiary recycling of waste tires will require efficient catalytic cracking methods. Therefore, the detailed knowledge of thermal and catalytic cracking mechanism is necessary. In this paper we systematically studied the behaviors of thermal and catalytic degradation of waste tires and the main rubber components of tires, including natural rubber (NR), polybutadiene rubber (BR) and styrene-butadiene rubber (SBR), in a batch reactor with stirring. The aims are to improve their catalytic degradation ability and at the same time control potential harmful products produced during catalytic degradation. Furthermore, it will be expected to provide a theoretical basis for recycling waste tires.
First, catalytic copyrolysis of waste tires over ZSM-5 zeolite with lubricant base oil (LBO) was investigated. By combining with LBO, the ZSM-5 catalyzed pyrolysis system of tires has a sharply enhanced degradation rate. Compared to the pyrolysis without LBO, the liquid yield is increased from 33.6 % to 48.0 %, while the gas and the residue yields are decreased. In the pyrolysis oils, the content of heavy components is decreased, and the content of light oils (n-C≤12) is increased from
本论文采用间歇釜式反应器,对废旧轮胎及轮胎组成中的几种主要的橡胶,包括天然橡胶(NR),聚丁二烯(BR)及丁苯橡胶(SBR)的热解和催化裂解行为进行了系统的研究,为通过催化裂解回收废旧轮胎提供坚实的理论基础。
首先研究了废旧轮胎的热解和催化裂解行为,得出在废旧轮胎的催化裂解中,润滑油的加入明显地提高了废旧轮胎催化降解的反应速率;并使催化裂解产物中液体收率增加,气体和固体产物收率减少;在废旧轮胎的催化裂解产物中,润滑油的加入使得液体产物中Cl、S和N的含量与废旧轮胎单独热解时相似;但轻组分含量明显提高,重组分含量减少。其中1,8-萜二烯组分的含量由7.54%(废旧轮胎/ZSM-5)提高到13.58%(废旧轮胎/ZSM-5/润滑油);在废旧轮胎催化裂解中单独使用催化剂ZSM-5分子筛或者单独使用润滑油,均不能显著提高废旧轮胎裂解效率。润滑油的加入增强了催化剂与废旧轮胎之间的相互作用,从而增强了其催化效果;不仅可以提高废旧轮胎裂解的反应速度,还可以增加其裂解产物中具有经济价值的化合物组分的含量。
Nowadays, waste tires have not only caused serious environmental problems but also a huge waste of resources. Among the different alternatives for tire recycling, such as retreating, reclaiming, incineration, grinding, biodegradation, etc., pyrolysis has been proposed as a viable recycling technology. However, owing to technical problems as well as economic and legal factors, the pyrolysis processes of tires have not been cost-effective up to now.
Large-scale tertiary recycling of waste tires will require efficient catalytic cracking methods. Therefore, the detailed knowledge of thermal and catalytic cracking mechanism is necessary. In this paper we systematically studied the behaviors of thermal and catalytic degradation of waste tires and the main rubber components of tires, including natural rubber (NR), polybutadiene rubber (BR) and styrene-butadiene rubber (SBR), in a batch reactor with stirring. The aims are to improve their catalytic degradation ability and at the same time control potential harmful products produced during catalytic degradation. Furthermore, it will be expected to provide a theoretical basis for recycling waste tires.
First, catalytic copyrolysis of waste tires over ZSM-5 zeolite with lubricant base oil (LBO) was investigated. By combining with LBO, the ZSM-5 catalyzed pyrolysis system of tires has a sharply enhanced degradation rate. Compared to the pyrolysis without LBO, the liquid yield is increased from 33.6 % to 48.0 %, while the gas and the residue yields are decreased. In the pyrolysis oils, the content of heavy components is decreased, and the content of light oils (n-C≤12) is increased from
引文
1、中国橡胶行业分析报告(2005 年 4 季度),中国行业分析报告.
2、袁俊霞,我国废旧轮胎的再循环利用,环境保护科学,2003,29(3):26-27,30.
3、吕百龄,废旧橡胶制品的回收利用,橡塑技术与装备,第 30 卷 第 7 期.
4、董诚春,废橡胶资源综合利用,北京:化学工业出版社,2003,378-381.
5、继红,橡胶再利用综述,师姐橡胶工业,2000,27(1):36-41.
6、B. Adhikari, D. De, S. Maiti, Progress in Polymer Science,2000,25(7) :909-948.
7、刘长柏,现代化工,1994,14(2):11-16.
8、汉堂,橡胶技术与装备,1996,22(3):19-24.
9、刘玉强,轮胎工业,2000,20(12):710-712.
10、P. Xu, Recycling of discraded tire.Environ Orotect Chem Ind 1998,18(2):79-81.
11、Editorial Staff, Recycling of rubber elastomer,Rubber.Industy,Taiwan ed.,1998,204:28-37
12、Y. Fang, M.S. Zhan, Y. Wang, The status of recycling of waste rubber,Materials and Desigh, 2001, 22(2):123-128.
13、刘登祥,刘世平译,丁苯橡胶加工技术,化学工业出版社,1983 年 6 月
14、刘玉强,废旧轮胎的回收利用,轮胎工业,2000,20.
15、张隐西,范茹良,废旧轮胎的总和利用,中国资源综合利用,2000,6.
16、袁俊霞,我国废旧轮胎的再循环利用,环境科学动态,2004 年,第一期
17、韩金永,阴广欣,刘建华等,废旧轮胎的回收利用,化工技术经济,2004,8.
18、邓海燕,废旧轮胎的几种综合利用途径,中国资源总和利用,2002,12.
19、刘银秀,潘志彦,钱小飞,废弃轮胎的热解回收技术,现代化工,2004,6.
20、魏清林,武玺,废旧轮胎的回收利用,山西建筑,2004,4.
21、Reprot on issues arising from transport and waste management-tire,The Environment Agency,U.K.1998.
22、IRSG preliminary statistics:http://www.rubber study.com/STATS.htm.
23、S. Chuck, Scrap Tire Problem Nearly Soved. Tire Business, 1995-2-20:17-8.
24、李水清,姚强,池涌,严建华,废轮胎小型和中型规模热解研究的试验方法,燃烧科学与技术,2004 年 2 月
25、蒋家羚,刘小龙,刘宝庆,废旧轮胎热解设备的开发,化工进展,2002 年第 9 期
26、王学锋,刘茜霞,废旧轮胎热解资源化研究新进展,开发与应用,2001 年 10 月
27、F. Murena, E. Garufi, R.B.F. Gioia, Hydrogenative pyrolysis of waster tires.Journal of Hazardous Materials,1996,50:79-98.
28、F. Toshitaka, T. Tetsuya, W. Noriaki, Supercritical estraction of used automotive tire with water. Journal of chemical engineering of Japan,1987,20(1):23-27.
29、Carbon Developent Crop.Gotshall WC,Quetty FC,et al.Methods to recycle scrap rubber advance.Chem.Eng.News,1977,55(25):5-6.
30、E.V. Anderson, Economics are bugaboo in scrap tire recycling. Chem.Eng.News,1972,50 (33): 8-10.
31、B. Benallal, C. Roy, H. Pakdel, et al., Characterization of pyrolytic light naphtha from vacuum pyrolysis of used tyres Comparison with petroleum naphtha.Fuel.1995,74(11): 1589- 1594.
32、R. Christian, J. Unsworth, Pilot Demonstration of Used Tires Vacuum Pyrolysis.Pyrolysis and Gasification.Elsevier Applied Science.London.1989,180-189.
33、C. Roy, A. Chaala, et al., The Vacuum Pyrolysis of Used Tires End-Uses for Oil and Carbon Black Products.Journal of Analytical and Applied Pyrolysis.1999,51:201-221.
34、李鑫,废轮胎硫化床热解特性研究,浙江大学博士学位论文,2003 年 1 月
35、J.W. Larsen, B. Chang, Scrap tires pyrolyzed in molten salts,Chem.Eng.News, 1976,54(21): 26-28.
36、陈凤珍,钱家麒,废轮胎裂解制区液体燃料和化学品,橡胶工业,1998 年第 45 卷
37、C. Chamber, J.W. Larse, W. Li, ea al., Polymer waste reclamation by pyrolysis in molten salts. Ind. Eng. Chem. Process Des.Dev.,1976,23(4):648-654.
38、J.W. Larsen, T. Lnoxville, Conversion of waste rubber to fuel and other useful products. USA,USP,1976-12-7.
39、R.C. Wingfield, J. Braslaw, R.L. Gealer, Use of zinc and copper salts to reduce sulfur and nitrogen impurities during the pyrolysis of plaatic and rubber waste to hydrocarbons. USA. USP4458095, 1984-07-03.
40、R.C. Wingfield, J. Braslaw, R.L. Gealer, Pyrolytic conversion of plastic and rubber waste to hydrocarbons with basic salt catalystis.USA, USP4515659, 1985-05-07.
41、N.Y. Chen, T.Y. Yan, Method for treatment of rubber and plastic waste.USA,1979-11-20.
42、 王文选,仲兆平,陈晓平,蓝计香,赵长遂,废轮胎热裂解技术,燃烧科学与技术,1999 年第 3 期
43、 颜丽红,再生炭黑的表面修饰及其在橡胶补强中的应用,浙江大学硕士学位论文,2004年 3 月
44、K.M. Murata, Nippon Kagaku Kaishi.1975 ;1 ;192-197.
45、M.F. Laresgoiti, B.M. Carballero, I.de Marco, A. Torres, M.A. Cabroero, M.J. Chomón., J Anal Appl Pyrolysis 2004; 71:917-34.
46、M.M. Barbooti, T.J. Mohamed, A.A. Hussain, F.O. Abas, J Anal Appl Pyrolysis 2004;72:165- 70.
47、A.M. Mastra, R. Murillo, M.S. Callén, T. García, C.E. Snape, Energ Fuel 2000;14; 739-744.
48、P.T. Williams, A.J. Brindle, Catalytic pyrolysis of tyres: influence of catalyst temperature. Fuel 2002; 81:2425-34.
49、P.T. Williams, A.J. Brindle, Aromatic chemicals from the catalytic pyrolysis of scrap tyres. J Anal Appl Pyrolysis 2003; 67:143-64.
50、P.T. Williams, A.J. Brindle, Fluidised bed catalytic pyrolysis of scrap tyres. Waste Manage Res 2002;20: 546-555.
51、J. Yanik, M.A. Uddin, Y. Sakata, Energ Fuel 2001;15;163-169.
52、S. Ucar, S. Karag?z, J.Yanik, M. Saglam, M. Yuksel, Copyrolysis of scrap tires with waste lubricant oil. Fuel Process Technol 2005; 87:53-8.
2、袁俊霞,我国废旧轮胎的再循环利用,环境保护科学,2003,29(3):26-27,30.
3、吕百龄,废旧橡胶制品的回收利用,橡塑技术与装备,第 30 卷 第 7 期.
4、董诚春,废橡胶资源综合利用,北京:化学工业出版社,2003,378-381.
5、继红,橡胶再利用综述,师姐橡胶工业,2000,27(1):36-41.
6、B. Adhikari, D. De, S. Maiti, Progress in Polymer Science,2000,25(7) :909-948.
7、刘长柏,现代化工,1994,14(2):11-16.
8、汉堂,橡胶技术与装备,1996,22(3):19-24.
9、刘玉强,轮胎工业,2000,20(12):710-712.
10、P. Xu, Recycling of discraded tire.Environ Orotect Chem Ind 1998,18(2):79-81.
11、Editorial Staff, Recycling of rubber elastomer,Rubber.Industy,Taiwan ed.,1998,204:28-37
12、Y. Fang, M.S. Zhan, Y. Wang, The status of recycling of waste rubber,Materials and Desigh, 2001, 22(2):123-128.
13、刘登祥,刘世平译,丁苯橡胶加工技术,化学工业出版社,1983 年 6 月
14、刘玉强,废旧轮胎的回收利用,轮胎工业,2000,20.
15、张隐西,范茹良,废旧轮胎的总和利用,中国资源综合利用,2000,6.
16、袁俊霞,我国废旧轮胎的再循环利用,环境科学动态,2004 年,第一期
17、韩金永,阴广欣,刘建华等,废旧轮胎的回收利用,化工技术经济,2004,8.
18、邓海燕,废旧轮胎的几种综合利用途径,中国资源总和利用,2002,12.
19、刘银秀,潘志彦,钱小飞,废弃轮胎的热解回收技术,现代化工,2004,6.
20、魏清林,武玺,废旧轮胎的回收利用,山西建筑,2004,4.
21、Reprot on issues arising from transport and waste management-tire,The Environment Agency,U.K.1998.
22、IRSG preliminary statistics:http://www.rubber study.com/STATS.htm.
23、S. Chuck, Scrap Tire Problem Nearly Soved. Tire Business, 1995-2-20:17-8.
24、李水清,姚强,池涌,严建华,废轮胎小型和中型规模热解研究的试验方法,燃烧科学与技术,2004 年 2 月
25、蒋家羚,刘小龙,刘宝庆,废旧轮胎热解设备的开发,化工进展,2002 年第 9 期
26、王学锋,刘茜霞,废旧轮胎热解资源化研究新进展,开发与应用,2001 年 10 月
27、F. Murena, E. Garufi, R.B.F. Gioia, Hydrogenative pyrolysis of waster tires.Journal of Hazardous Materials,1996,50:79-98.
28、F. Toshitaka, T. Tetsuya, W. Noriaki, Supercritical estraction of used automotive tire with water. Journal of chemical engineering of Japan,1987,20(1):23-27.
29、Carbon Developent Crop.Gotshall WC,Quetty FC,et al.Methods to recycle scrap rubber advance.Chem.Eng.News,1977,55(25):5-6.
30、E.V. Anderson, Economics are bugaboo in scrap tire recycling. Chem.Eng.News,1972,50 (33): 8-10.
31、B. Benallal, C. Roy, H. Pakdel, et al., Characterization of pyrolytic light naphtha from vacuum pyrolysis of used tyres Comparison with petroleum naphtha.Fuel.1995,74(11): 1589- 1594.
32、R. Christian, J. Unsworth, Pilot Demonstration of Used Tires Vacuum Pyrolysis.Pyrolysis and Gasification.Elsevier Applied Science.London.1989,180-189.
33、C. Roy, A. Chaala, et al., The Vacuum Pyrolysis of Used Tires End-Uses for Oil and Carbon Black Products.Journal of Analytical and Applied Pyrolysis.1999,51:201-221.
34、李鑫,废轮胎硫化床热解特性研究,浙江大学博士学位论文,2003 年 1 月
35、J.W. Larsen, B. Chang, Scrap tires pyrolyzed in molten salts,Chem.Eng.News, 1976,54(21): 26-28.
36、陈凤珍,钱家麒,废轮胎裂解制区液体燃料和化学品,橡胶工业,1998 年第 45 卷
37、C. Chamber, J.W. Larse, W. Li, ea al., Polymer waste reclamation by pyrolysis in molten salts. Ind. Eng. Chem. Process Des.Dev.,1976,23(4):648-654.
38、J.W. Larsen, T. Lnoxville, Conversion of waste rubber to fuel and other useful products. USA,USP,1976-12-7.
39、R.C. Wingfield, J. Braslaw, R.L. Gealer, Use of zinc and copper salts to reduce sulfur and nitrogen impurities during the pyrolysis of plaatic and rubber waste to hydrocarbons. USA. USP4458095, 1984-07-03.
40、R.C. Wingfield, J. Braslaw, R.L. Gealer, Pyrolytic conversion of plastic and rubber waste to hydrocarbons with basic salt catalystis.USA, USP4515659, 1985-05-07.
41、N.Y. Chen, T.Y. Yan, Method for treatment of rubber and plastic waste.USA,1979-11-20.
42、 王文选,仲兆平,陈晓平,蓝计香,赵长遂,废轮胎热裂解技术,燃烧科学与技术,1999 年第 3 期
43、 颜丽红,再生炭黑的表面修饰及其在橡胶补强中的应用,浙江大学硕士学位论文,2004年 3 月
44、K.M. Murata, Nippon Kagaku Kaishi.1975 ;1 ;192-197.
45、M.F. Laresgoiti, B.M. Carballero, I.de Marco, A. Torres, M.A. Cabroero, M.J. Chomón., J Anal Appl Pyrolysis 2004; 71:917-34.
46、M.M. Barbooti, T.J. Mohamed, A.A. Hussain, F.O. Abas, J Anal Appl Pyrolysis 2004;72:165- 70.
47、A.M. Mastra, R. Murillo, M.S. Callén, T. García, C.E. Snape, Energ Fuel 2000;14; 739-744.
48、P.T. Williams, A.J. Brindle, Catalytic pyrolysis of tyres: influence of catalyst temperature. Fuel 2002; 81:2425-34.
49、P.T. Williams, A.J. Brindle, Aromatic chemicals from the catalytic pyrolysis of scrap tyres. J Anal Appl Pyrolysis 2003; 67:143-64.
50、P.T. Williams, A.J. Brindle, Fluidised bed catalytic pyrolysis of scrap tyres. Waste Manage Res 2002;20: 546-555.
51、J. Yanik, M.A. Uddin, Y. Sakata, Energ Fuel 2001;15;163-169.
52、S. Ucar, S. Karag?z, J.Yanik, M. Saglam, M. Yuksel, Copyrolysis of scrap tires with waste lubricant oil. Fuel Process Technol 2005; 87:53-8.