工业有机废气热氧化技术研究进展

doi:10.16085/j.issn.1000-6613.2017-0382

摘要/Abstract

摘要： 研究开发节能、高效的有机废气处理技术对环境保护有重要意义。本文简要介绍了有机废气常见的处理技术，重点论述了蓄热式热氧化技术（RTO）和蓄热式催化氧化技术（RCO）用于处理工业有机废气的工作原理、适用条件。详细分析了关于蓄热式热氧化系统设计的关键技术问题，包括蓄热体的传热与流动阻力、催化剂的分类及各自的优缺点、催化剂的制备方法、换向系统的设计与选用、启动技术。蓄热式热氧化技术和蓄热式催化氧化技术在国内外都已有很多成功的实际运用案例，将来也将有更广阔的应用前景。由于企业有机废气的成分比较多元化、不稳定及企业间歇生产的特点，使得有机废气浓度和废气量都有间歇性变化，导致RTO系统运行不稳定，因此如何适应入口浓度的波动是需要进一步研究的问题。

关键词: 有机废气, 环境, 污染, 催化剂, 蓄热式热氧化, 蓄热式催化氧化

Abstract: The research on energy saving and high efficiency organic waste gas treatment technology is of great significance to environmental protection. The common treatment technologies of organic waste gas were introduced briefly in this paper,with emphatical discussion on the regenerative thermal oxidation technology(RTO)and regenerative catalytic oxidation(RCO)technology. The key technologies of regenerative thermal oxidation system design were analyzed,including the heat transfer coefficient and flow resistance of regenerator,the classification of catalysts and their respective advantages and disadvantages,the method of preparation of catalyst,design and selection of reversing system,the start-up technology and so on. Regenerative thermal oxidation technology and regenerative catalytic oxidation technology have been applied successfully at home and abroad. As a result of the instability resulted in the complexity of organic waste components and the intermittent operation of RTO system,how to adapt to the fluctuation of the inlet concentration is a problem that needs to be further studied.

Key words: organic waste gas, environment, pollution, catalyst, regenerative thermal oxidation, regenerative catalytic oxidation

中图分类号:

X701.7

王波, 马睿, 薛国程, 张龙. 工业有机废气热氧化技术研究进展[J]. 化工进展, 2017, 36(11): 4232-4242.

WANG Bo, MA Rui, XUE Guocheng, ZHANG Long. Research progress on thermal oxidation technology for industrial organic waste gas[J]. Chemical Industry and Engineering Progress, 2017, 36(11): 4232-4242.

参考文献

[1] 童喜润,党杰,杨明德,等. 蓄热催化氧化法处理挥发性有机物的研究进展[J]. 安徽化工,2004,30(1):40-43. TONG X R,DANG J,YANG M D,et al. Research development on the volatile organic compounds by the regenerative & catalytic oxidation[J]. Anhui Chemical Industry,2004,30(1):40-43.
[2] MILLS B. Abatement of VOCs[J]. Surface Coatings International,1998,81(5):223-229.
[3] 郭昊. 活性炭吸附回收VOCs的过程研究与工程设计[D]. 北京:中国林业科学研究院,2014. GUO H. Process study and engineering design of activated carbon adsorption and recovery of VOCs[D]. Beijing:Chinese Academy of Forestry Sciences,2014.
[4] 肖潇. 液体吸收法资源化处理工业甲苯废气的研究[D]. 北京:中国科学院大学,2015. XIAO X. Study on the treatment of toluene waste gas by liquid absorption[D]. Beijing:University of Chinese Academy of Sciences,2015.
[5] GUPTA V K,VERMA N. Removal of volatile organic compounds by cryogenic condensation followed by adsorption[J]. Chemical Engineering Science,2002,57(14):2679-2696.
[6] DEHGHANZADEH R,TORKIAN A,BINA B,et al. Biodegradation of styrene laden waste gas stream using a compost-based biofilter[J]. Chemosphere,2005,60(3):434-9.
[7] YAMAMOTO T. VOC decomposition by nonthermal plasma processing-a new approach[J]. Journal of Electrostatics,1997,42(1/2):227-238.
[8] 胡辉,李胜利,杨长河,等. 放电等离子体处理挥发性有机物的研究进展[J]. 高电压技术,2002,28(3):43-45. HU H,LI S L,YANG C H,et al. The progress on study of treatment of volatile organic compounds by discharge plasma[J]. High Voltage Engineering,2002,28(3):43-45.
[9] NAIR S A,PEMEN A J M,YAN K,et al. Tar removal from biomass-derived fuel gas by pulsed corona discharges[J]. Fuel Processing Technology,2003,84(1/2/3):161-173.
[10] 杨培法. 热氧化工艺在有机废气及废液处理中的应用[J]. 能源环境保护,2016,30(1):21-25. YANH P F. Application of thermal oxidation process in organic waste gas and waste liquid treatment[J]. Energy Environmental Protection,2016,30(1):21-25.
[11] 杨振华,马晓驰,蔡鹏山,等. 蓄热式热氧化器转化效率的研究[J]. 化工机械,2015(1):42-44. YANG Z H,MA X C,CAI P S,et al. Study of conversion rate of regenerative thermal oxidizer[J]. Chemical & Machinery,2015(1):42-44.
[12] 张建萍,项菲. 浅析蓄热式热力氧化技术处理挥发性有机废气[J].浙江化工,2014(3):36-39. ZHANG J P,XIANG F. The treatment of the volatile organic compound gas by the regenerative thermal oxidation technology[J]. Zhejiang Chemical Industry,2014(3):36-39.
[13] ZHANG J,ZHANG C,HE H. Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol[J]. Journal of Environmental Sciences,2015,35(9):69-75.
[14] 陈华栋,张翠亚,曹冠宇,等. 活性炭吸附器+蓄热式热氧化器集成设备的开发研究[J]. 化工机械,2016,43(1):55-58. CHEN H D,ZHANG C Y,CAO G Y,et al. Developmental research of device integrating activated carbon adsorber with regenerative thermal oxidizer[J]. Chemical Machinery,2016,43(1):55-58.
[15] 罗晓,杜玮,谢安国. 蓄热体结构分析及其内部气体流动特性的数值研究[J]. 节能技术,2012,30(3):239-244. LUO X,DU W,XIE A G. Numerical research of structural analysis and innerflow characteristics in honeycomb regenerator of different shapes[J]. Energy Conservation Technology,2012(3):239-244.
[16] 范蕾,马青波. 高温燃烧技术中蓄热体研究[J]. 河南机电高等专科学校学报,2010,18(3):31-33. FAN L,MA Q B. Study of regenerator in high temperature air combustion[J]. Journal of Henan Mechanical and Electrical Engineering College,2010,18(3):31-33.
[17] 张振兴,刘永启,高振强,等. 陶瓷蓄热体的流动与传热特性模拟研究[J]. 内燃机与动力装置,2010(2):18-22. ZHANG Z X,LIU Y Q,GAO Z Q,et al. Simulation study on flow and heat transfer in ceramic regenerator[J]. Internal Combustion Engine & Powerplant,2010(2):18-22.
[18] 中国建筑材料联合会. 蜂窝陶瓷蓄热体:JC/T 2135-2012[S]. 北京:中国建材工业出版社,2013. China Building Materials Federation. Honeycomb ceramic regenerator:JC/T 2135-2012[S]. Beijing:China Building Materials Industry Press,2013.
[19] 宋婧,曾令可,刘艳春,等. 陶瓷蓄热体的研究现状及应用[J]. 中国陶瓷,2007,43(6):7-10. SONG J,ZENG L K,LIU Y C,et al. Research and application of ceramic heat storage materials[J]. China Ceramics,2007,43(6):7-10.
[20] 牟宝杰. 蜂窝陶瓷蓄热体阻力特性和传热特性实验研究[D]. 淄博:山东理工大学,2011. MOU B J. Experimental research on honeycomb ceramic regenerator fluid dynamic and thermal performance[D]. Zibo:Shandong University of Technology,2011.
[21] 张志诚. 蜂窝陶瓷蓄热体综合性能实验台监控系统开发与研究[D]. 淄博:山东理工大学,2011. ZHANG Z C. Research and development of monitoring and control system on honeycomb ceramic performance test[D]. Zibo:Shandong University of Technology,2011.
[22] 郑志伟,仇性启,祁风雷,等. 蜂窝陶瓷蓄热体传热和阻力特性实验研究[J]. 石油化工设备,2013,42(1):9-13. ZHENG Z W,QIU X Q,QI F L,et al. Experimental study of heat transfer and resistance characteristics on honeycomb ceramic regenerator[J]. Petro-Chemical Equipment,2013,42(1):9-13.
[23] 高阳,雍海泉,徐志鹏,等. 蜂窝陶瓷蓄热体传热与阻力特性的热态实验研究[J]. 冶金能源,2008,27(5):25-27. GAO Y,YONG H Q,XU Z P,et al. Thermal state experiment research on the heat transfer and resistance characters of honeycomb ceramic regenerator[J]. Energy for Metallurgical Industry,2008,27(5):25-27.
[24] 欧阳德刚,肖坤伟,周明石,等. 蜂窝陶瓷辐射体非稳态传热特性研究[J]. 钢铁研究,1997(2):44-49. OUYANG D G,XIAO K W,ZHOU M S,et al. Study on unsteady heat transfer characteristics honeycomb ceramic heat radiator[J]. Research on Iron & Steel,1997(2):44-49.
[25] KLEIN H,EIGENBERGERB G. Approximate solutions for metallic regenerative heat exchangers[J]. International Journal of Heat & Mass Transfer,2001,44(18):3553-3563.
[26] 艾元方,梅炽,黄国栋,等. 薄壁蓄热器最大相对温度和最佳切换时间[J]. 热能动力工程,2006,21(4):362-365. AI Y F,MEI Z,HUANG G D,et al. Maximal relative temperature and optimum switching-over time for a thin-wall heat accumulator[J]. Journal of Engineering for Thermal Energy and Power,2006,21(4):362-365.
[27] 陈新进,王庆顺,孙伟. 基于Fluent的蓄热体传热过程的数值模拟[J]. 机械工程师,2015(4):71-73. CHEN X J. WANG Q S,SUN W. Numerical simulation of heat transfer process regenerator based on Fluent[J]. Mechanical Engineer,2015(4):71-73.
[28] 刘光临,诸葛伟林,王玺堂,等. 蓄热式燃烧系统动态运行特性研究[J]. 武汉科技大学学报(自然科学版),2004,27(2):145-147. LIU G L,ZHUGE W L,WANG X T,et al. Research on dynamic operation characteristics of the regenerative combustion system[J]. Journal of Wuhan University of Science and Technology(Natural Science Edition),2004,27(2):145-147.
[29] 张振兴. 基于均匀多孔介质模型的氧化床阻力特性数值研究[D]. 淄博:山东理工大学,2010. ZHANG Z X. Resistance investigation of the oxidation bed based on homogeneous porous media mode[D]. Zibo:Shandong University of Technology,2010.
[30] SPIVEY J J. Complete catalytic oxidation of volatile organics[J]. Ind. Eng. Chem. Res,1989,26(11):2165-2180.
[31] TIAN Z Y,NGAMOU P H T,VANNIER V,et al. Catalytic oxidation of VOCs over mixed Co-Mn oxides[J]. Applied Catalysis B:Environmental,2012,117(3):125-134.
[32] BECKER L,FORSTER H. Oxidative decomposition of benzene and its methyl derivatives catalyzed by copper and palladium ion-exchanged Y-type zeolites[J]. Applied Catalysis B:Environmental,1998,17(1/2):43-49.
[33] ZAITAN H,MANERO M H,VALDES H. Application of high silica zeolite ZSM-5 in a hybrid treatment process based on sequential adsorption and ozonation for VOCs elimination[J]. Journal of Environmental Sciences,2016,41(3):59-68.
[34] 张鹏. CuO-CeO₂/Al₂O₃催化剂的制备及催化氧化甲苯和二甲苯的研究[D]. 哈尔滨:哈尔滨工业大学,2008. ZHANG P. Study on preparation and property of CuO-CeO₂/Al₂O₃ catalyst in the catalytic oxidation of toluene and xylene[D]. Harbin:Harbin Institute of Technology,2008.
[35] CASTAÑO M H,MOLINA R,MORENO S. Cooperative effect of the Co-Mn mixed oxides for the catalytic oxidation of VOCs:Influence of the synthesis method[J]. Applied Catalysis A:General,2015,492(29):48-59.
[36] 孙敬方,葛成艳,姚小江,等. 固相浸渍法制备NiO/CeO₂催化剂及其在CO氧化反应中的应用[J]. 物理化学学报,2013,29(11):2451-2458. SUN J F,GE C Y,YAO X J,et al. Preparation of NiO/CeO₂ catalysts by solid state impregnation and their application in CO oxidation[J]. Journal of Physical Chemistry,2013,29(11):2451-2458.
[37] YUAN G,MENG F,JI K,et al. Slurry phase methanation of carbon monoxide over nanosized Ni-Al₂O₃ catalysts prepared by microwave-assisted solution combustion[J]. Applied Catalysis A:General,2016,510:74-83.
[38] 李朝晖,戴伟,傅吉全. 微乳液法制备纳米催化剂的应用研究进展[J]. 化工进展,2008,27(4):499-502. LI C H,DAI W,FU J Q. Advances in preparation of nano-catalyst by micro-emulsification[J]. Chemical Industry and Engineering Progress,2008,27(4):499-502.
[39] JUNG S C,PARK Y K,JUNG H Y,et al. Effects of calcination and support on supported manganese catalysts for the catalytic oxidation of toluene as a model of VOCs[J]. Research on Chemical Intermediates,2015,42(1):1-15.
[40] 赵志军. 延长蜂窝式催化剂的使用寿命[C]//全国电厂燃煤节能减排升级改造解决方案经验交流会,浙江,2015:181-186. ZHAO Z J. Extend the life of the honeycomb catalyst[C]//Experience of exchanging and improving the solution of energy-saving and emission-reduction of coal-fired power plant in China,Zhejiang,2015:181-186.
[41] 李艳芳,刘夏丹,于宏. 旋转式四通换向阀在蓄热式燃烧系统中的应用[J]. 工业加热,2001(3):52-53. LI Y F,LIU X D,YU H. Application of revolving four-direction-connected valve in regenerative combustion system[J]. Industrial Heating,2001(3):52-53.
[42] PENNINGTON R L,LISZEWSKI M. Get more from your regenerative thermal oxidizer[J]. Chemical Engineering,1999,106(5):137-142.
[43] 萧琦,姜泽毅,张欣欣. 多室蓄热式有机废气焚烧炉工程应用研究[J]. 环境工程,2011,29(2):69-72. XIAO Q,JIANG Z Y,ZHANG X X. Engineering application research of multiple-chamber RTO[J]. Environmental Engineering,2011,29(2):69-72.
[44] SALOMONS S,HAYES R E,POIRIER M,et al. Flow reversal reactor for the catalytic combustion of lean methane mixtures[J]. Catalysis Today,2003,83(1/2/3/4):59-69.
[45] 刘慧,李亚冰,陈文仲. 蓄热式燃烧最佳换向时间的计算[J]. 东北大学学报(自然科学版),2012,33(2):243-246. LIU H,LI Y B,CHEN W Z. Calculation of best switching time of heat accumulating combustion[J]. Journal of Northeastern University(Natural Science),2012,33(2):243-246.
[46] 张先珍,戴德彦. 换向时间对蓄热式燃烧的影响[J]. 冶金能源,2005,24(4):30-32. ZHANG X Z,DAI D Y. The switching time's effects on the regenerative combustion[J]. Energy for Metallurgical Industry,2005,24(4):30-32.
[47] 张欣茹,姜泽毅,张欣欣,等. 新型档位蓄热器的开发与研究[J]. 工业加热,2005,34(5):26-28. ZHANG X R,JIANG Z Y,ZHANG X X,et al. Development and investigation on a new rotary-switching regenerator[J]. Industrial Heating,2005,34(5):26-28.
[48] RAFIDI N,BLASIAK W. Heat transfer characteristics of HiTAC heating furnace using regenerative burners[J]. Applied Thermal Engineering,2006,26(16):2027-2034.
[49] 张建军,冯自平,宋文吉,等. 连续式蓄热燃烧技术的研究[J]. 四川冶金,2010,32(6):19-24. ZHANG J J,FENG Z P,SONG W J,et al. Investigation of high temperature air combustion of self-regenerator[J]. Sichuan Metallurgy,2010,32(6):19-24.
[50] 胡志伦,臧占稳. 煤矿乏风氧化装置加热启动系统的研究[J]. 科技与企业,2014(19):181-182. HU Z L,ZANG Z W. Research on heat-starting system for VAM oxidation equipment[J]. Science & Technology and Enterprises,2014(19):181-182.
[51] 李冬梅,任伟娜,李圣强,等. 立式乏风氧化装置的开发与应用[J].能源与节能,2013(10):5-6. LI D M,REN W N,LI S Q,et al. Development and application of vertical vam oxidation device[J]. Energy and Energy Conservation,2013(10):5-6.
[52] 李勇. 基于PLC的低浓度瓦斯预掺混输送监控系统的设计[J]. 山东工业技术,2015(9):58-58. LI Y. Design of monitoring and control system for low concentration gas pre mixing transportation based on PLC[J]. Shandong Industrial Technology,2015(9):58-58.
[53] BARRESI A A,GIANCARLO BALDI A,FISSORE D. Forced unsteady-state reactors as efficient devices for integrated processes:case histories and new perspectives[J]. Industrial & Engineering Chemistry Research,2007,46(25):8693-8700.
[54] 滕富华,顾震宇,项敏,等. 蓄热式热氧化炉处理医化废气[J]. 中国环保产业,2015(4):4-7. TENG F H,GU Z Y,XIANG M,et al. Medical and chemical exhaust gas treated by heat oxidation oven with heat-storage type[J]. China Environmental Protection Industry,2015(4):4-7.
[55] 喻昌军. 蓄热式热氧化炉(RTO)处理医化废气的运行管理与优化[J]. 现代制造,2013(23):54-57. YU C J. Operation management and optimization of regenerative thermal oxidizer for treatment of medical waste gas[J]. Maschinen Markt,2013(23):54-57.
[56] 简力,孙昆. 蓄热式氧化炉在处理SBS生产废气中的应用[J]. 节能技术,2014,32(2):185-189. JIAN L,SUN K. The application of regenerative thermal oxidizer in dealing with the waste gas in SBS production[J]. Energy Conservation Technology,2014,32(2):185-189.
[57] 李海柱,贡祥磊,甘霖. 蓄热式氧化焚烧炉(RTO)在羧基丁苯胶乳生产线上的应用[J]. 山东化工,2013,42(9):90-92. LI H Z,GONG X L,GAN L. Application of regenerative thermal oxidizer in XSBRL production line[J]. Shandong Chemical Industry,2013,42(9):90-92.
[58] 蔡鹏山,马晓驰,杨振华,等. 顺酐行业中蓄热式热氧化器的应用[J]. 化工机械,2013,40(5):676-678. CAI P S,MA X C,YANG Z H,et al. Application of regenerative thermal oxidizer in the maleic anhydride industry[J]. Chemical Engineering & Machinery,2013,40(5):676-678.
[59] 王钢强. 蓄热催化氧化法在涂装烘房废气处理中的应用[J]. 中国环保产业,2015(8):16-18. WANG G Q. Application of regenerative catalytic oxidation in exhaust gas treatment of besmearing-baking house[J]. China Environmental Protection Industry,2015(8):16-18.
[60] 陈义良,李汶冬,李继文,等. 蓄热催化氧化技术在处理丁苯橡胶尾气中的应用[J]. 化工科技,2015(1):59-62. CHEN Y L,LI W D,LI J W,et al. The application of catalytic oxidation in treating the exhaust gas for SBR production[J]. Science and Technology in Chemical Industry,2015(1):59-62.