Review of waste refrigerant destruction methods

doi:10.11949/0438-1157.20201566

Abstract

Abstract:

Some refrigerants have begun to be replaced due to their strong greenhouse effects. The waste refrigerants should be degraded. China is the main producer and consumer of refrigerants, so there will be a huge demand for destruction of waste refrigerants in the coming decades. This paper presents a review of the main destruction technology for waste refrigerant destruction, including the summary and analysis for the combustion method, plasma method, and catalysis method. Further research trends of waste refrigerant destruction are also discussed in this paper.

Key words: waste refrigerant, pyrolysis, catalysis, photocatalysis, catalyst

摘要：

部分人工合成制冷剂由于存在环保问题，目前正按照环保公约进行淘汰。淘汰后的废弃制冷剂需要进行降解销毁，我国是目前国际上主要的制冷剂生产和消费国，因此面临着巨大的废弃制冷剂销毁压力。总结归纳了废弃制冷剂目前主要的降解方法，包括焚烧热解法、等离子法、催化分解法等技术路线的研究进展，并对未来可能的发展方向进行思考与讨论。

关键词: 废弃制冷剂, 热解, 催化, 光催化, 催化剂

CLC Number:

TK 123

DAI Xiaoye, AN Qingsong, XU Yunting, SHI Lin. Review of waste refrigerant destruction methods[J]. CIESC Journal, 2021, 72(S1): 1-6.

戴晓业, 安青松, 许云婷, 史琳. 废弃制冷剂降解方法研究现状及思考[J]. 化工学报, 2021, 72(S1): 1-6.

Figures/Tables 3

References 35

1	张朝晖, 陈敬良, 高钰, 等. 《蒙特利尔议定书》基加利修正案对制冷空调行业的影响分析[J]. 制冷与空调, 2017, 17(1): 1-7, 15.
	Zhang Z H, Chen J L, Gao Y, et al. Analysis on the influence of Kigali Amendment to Montreal Protocol to refrigeration and air-conditioning industry [J]. Refrigeration and Air-Conditioning, 2017, 17(1): 1-7, 15.
2	中国制冷空调行业制冷剂替代政策及进展[R]. 北京: 环境保护部环境保护对外合作中心, 2018.
	Policy and progress of refrigerant substitution in air-conditioning industry [R]. Beijing: Foreign Economic Cooperation Office, Ministry of Ecology and Environment, 2018.
3	Country programme data and prospects for implementation [R]. Montreal: United Nations Environment Programme, 2017.
4	张贺然, 于可利, 邱金凤, 等. 美国、欧盟、日本的制冷剂回收处置现状[J]. 资源再生, 2018, (11): 48-51.
	Zhang H R, Yu K L, Qiu J F, et al. Current status of refrigerant recovery and disposal in the United States, the European Union, and Japan [J]. Resource Recycling, 2018, (11): 48-51.
5	Report of the fifteenth meeting of the Parties to the Montreal Protocol on substances that deplete the ozone layer [R]. Nairobi: United Nations Environment Programme, 2003.
6	Tokuhashi K, Urano Y, Horiguchi S, et al. Incineration of CFC-12 by burner methods [J]. Combustion Science and Technology, 1990, 72(1/2/3): 117-129.
7	Ueno H, Iwasaki Y, Tatsuichi S, et al. Destruction of chlorofluorocarbons in a cement kiln [J]. Journal of the Air & Waste Management Association, 1997, 47(11): 1220-1223.
8	Lemieux P M, Ryan J V, Bass C, et al. Emissions of trace products of incomplete combustion from a pilot-scale incinerator secondary combustion chamber [J]. Journal of the Air & Waste Management Association, 1996, 46(4): 309-316.
9	Wang L C, Wang I C, Chang J E, et al. Emission of polycyclic aromatic hydrocarbons (PAHs) from the liquid injection incineration of petrochemical industrial wastewater [J]. Journal of Hazardous Materials, 2007, 148(1/2): 296-302.
10	Tsang W, Burgess D R, Babushok V. On the incinerability of highly fluorinated organic compounds [J]. Combustion Science and Technology, 1998, 139(1): 385-402.
11	Lamb C, Dellinger B, Wagner M, et al. Incinerability of halons and HCFCs: theoretical calculations of DRE and czone-depleting or global-warming gases [J]. Environmental Engineering Science, 2010, 27: 7.
12	International ozone depleting substances (ODS) destruction in the US & Abroad [R]. Fairfax: ICF International, 2018.
13	万小春, 胡建信, 张剑波. 氟利昂替代品降解产物TFA对生态环境的影响评价[J]. 环境科学研究, 2001, 14(2): 26-29.
	Wan X C, Hu J X, Zhang J B. Evaluation of environment impact of trifluoroacetates from the degradation of CFC substitutes [J]. Research of Environmental Sciences, 2001, 14(2): 26-29.
14	毕晓妹, 刘志莲, 张炉青, 等. 含氟有机化合物的转产与降解研究进展[J]. 有机氟工业, 2011, (1): 42-46, 52.
	Bi X M, Liu Z L, Zhang L Q, et al. Degradation research progress of fluorinated organic compounds [J]. Organo-Fluorine Industry, 2011, (1): 42-46, 52.
15	Ogata A, Kim H H, Futamura S, et al. Effects of catalysts and additives on fluorocarbon removal with surface discharge plasma [J]. Applied Catalysis B: Environmental, 2004, 53(3): 175-180.
16	Ren G Q, Jia L J, Zhao G Q, et al. Catalytic decomposition of dichlorodifluoromethane (CFC-12) over MgO/ZrO₂ solid base catalyst [J]. Catalysis Letters, 2019, 149(2): 507-512.
17	Han T U, Yoo B S, Kim Y M, et al. Catalytic conversion of 1,1,1,2-tetrafluoroethane (HFC-134a) [J]. Korean Journal of Chemical Engineering, 2018, 35(8): 1611-1619.
18	Iizuka A, Ishizaki H, Mizukoshi A, et al. Simultaneous decomposition and fixation of F-gases using waste concrete [J]. Industrial & Engineering Chemistry Research, 2011, 50(21): 11808-11814.
19	Wang F, Zhang W X, Liang Y, et al. Pd/Al_F3 catalysts for catalytic dehydrofluorination of 1,1,1,3,3-pentafluoropropane [J]. Chemical Research in Chinese Universities, 2015, 31(6): 1003-1006.
20	Mao W, Bai Y B, Jia Z H, et al. Highly efficient gas-phase dehydrofluorination of 1,1,1,3,3-pentafluoropropane to 1,3,3,3-tetrafluoropropene over mesoporous nano-aluminum fluoride prepared from a polyol mediated sol-gel process [J]. Applied Catalysis A: General, 2018, 564: 147-156.
21	Wang H L, Han W F, Li X L, et al. Solution combustion synthesis of Cr₂O₃ nanoparticles and the catalytic performance for dehydrofluorination of 1,1,1,3,3-pentafluoropropane to 1,3,3,3-tetrafluoropropene [J]. Molecules, 2019, 24(2): 361.
22	Luo J W, Song J D, Jia W Z, et al. Catalytic dehydrofluorination of 1,1,1,3,3-pentafluoropropane to 1,3,3,3-tetrafluoropropene over fluorinated NiO/Cr₂O₃ catalysts [J]. Applied Surface Science, 2018, 433: 904-913.
23	Jia W Z, Liu M, Lang X W, et al. Catalytic dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene over a modified NiO/Al₂O₃ catalyst [J]. Catalysis Science & Technology, 2015, 5(6): 3103-3107.
24	Lim S, Kim M S, Choi J W, et al. Catalytic dehydrofluorination of 1,1,1,2,3-pentafluoropropane (HFC-245eb) to 2,3,3,3-tetrafluoropropene (HFO-1234yf) using in situ fluorinated chromium oxyfluoride catalyst [J]. Catalysis Today, 2017, 293/294: 42-48.
25	Zheng X, Xiao Q, Zhang Y, et al. Deactivation of Pd/C catalysts in the hydrodechlorination of the chlorofluorocarbons CFC-115 and CFC-12 [J]. Catalysis Today, 2011, 175(1): 615-618.
26	Mori T, Yasuoka T, Morikawa Y. Hydrodechlorination of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) over supported ruthenium and other noble metal catalysts [J]. Catalysis Today, 2004, 88(3/4): 111-120.
27	Legawiec-Jarzyna M, Śrębowata A, Juszczyk W, et al. Hydrodechlorination of dichlorodifluoromethane (CFC-12) on Pd-Pt/Al₂O₃ catalysts [J]. Catalysis Today, 2004, 88(3/4): 93-101.
28	Bonarowska M, Malinowski A, Juszczyk W, et al. Hydrodechlorination of CCl₂F₂ (CFC-12) over silica-supported palladium-gold catalysts [J]. Applied Catalysis B: Environmental, 2001, 30(1/2): 187-193.
29	Winkelmann K, Calhoun R L, Mills G. Chain photoreduction of CCl₃F in TiO₂ suspensions: enhancement induced by O₂ [J]. The Journal of Physical Chemistry A, 2006, 110(51): 13827-13835.
30	Tennakone K, Wijayantha K G U. Photocatalysis of CFC degradation by titanium dioxide [J]. Applied Catalysis B: Environmental, 2005, 57(1): 9-12.
31	Sangchakr B, Hisanaga T, Tanaka K. Photocatalytic degradation of 1,1-difluoroethane (HFC-152a) [J]. Chemosphere, 1998, 36(9): 1985-1992.
32	Yin L F. Photocatalytic degradation of hydrofluorocarbon under visible light irradiation [J]. Applied Mechanics and Materials, 2014, 651/652/653: 1357-1360.
33	Kutsuna S, Takeuchi K, Ibusuki T. Adsorption and reaction of trichlorofluoromethane on various particles [J]. Journal of Atmospheric Chemistry, 1992, 14(1/2/3/4): 1-10.
34	王丽敏, 王利清, 张一弛, 等. 光热协同催化技术在能源领域的应用[J]. 化工进展, 2017, 36(7): 2457-2463.
	Wang L M, Wang L Q, Zhang Y C, et al. Photothermal synergistic catalytic technology in energy field [J]. Chemical Industry and Engineering Progress, 2017, 36(7): 2457-2463.
35	Zhang Y W, Xu C Y, Chen J C, et al. A novel photo-thermochemical cycle for the dissociation of CO₂ using solar energy [J]. Applied Energy, 2015, 156: 223-229.

国别	设施数量	使用的技术	销毁能力/(t/a)
美国	11	回转窑法/等离子体法/固定炉单元等	318
捷克	1	回转窑法	40
芬兰	1	回转窑法	545
德国	7	焚烧法、反应炉裂解法、多孔反应堆法	1600
匈牙利	5	回转窑法、液体喷射焚烧法	88
英国	2	高温焚烧法	—
日本	80	水泥窑/弃物焚烧法/液体喷射焚烧法、微波等离子体法、气相催化脱卤法、过热蒸汽反应堆法、固相碱性反应堆法	2636

国别	设施数量	使用的技术	销毁能力/(t/a)
美国	11	回转窑法/等离子体法/固定炉单元等	318
捷克	1	回转窑法	40
芬兰	1	回转窑法	545
德国	7	焚烧法、反应炉裂解法、多孔反应堆法	1600
匈牙利	5	回转窑法、液体喷射焚烧法	88
英国	2	高温焚烧法	—
日本	80	水泥窑/弃物焚烧法/液体喷射焚烧法、微波等离子体法、气相催化脱卤法、过热蒸汽反应堆法、固相碱性反应堆法	2636

文献	时间	催化剂	反应物	产物	反应温度/℃	最高转化率/%
[19]	2015	湿润浸渍法制备的系列Pd/AlF₃	HFC-245fa	HFO-1234ze	300	79.5
[20]	2018	溶胶-凝胶法合成的介孔纳米氟化铝	HFC-245fa	HFO-1234ze	280	57
[21]	2019	Cr₂O₃纳米颗粒	HFC-245fa	HFO-1234ze	500	—
[22]	2018	氟化NiO/Cr₂O₃	HFC-245fa	HFO-1234ze	450	89
[22]	2018	Cr₂O₃	HFC-245fa	HFO-1234ze	450	68
[23]	2015	NiAlF	HFC134	FEP（氟化乙烯）	430	20.1
[24]	2017	Cr₂O₃	HFC-245eb	HFO-1234y	350	80.1

文献	时间	催化剂	反应物	产物	反应温度/℃	最高转化率/%
[19]	2015	湿润浸渍法制备的系列Pd/AlF₃	HFC-245fa	HFO-1234ze	300	79.5
[20]	2018	溶胶-凝胶法合成的介孔纳米氟化铝	HFC-245fa	HFO-1234ze	280	57
[21]	2019	Cr₂O₃纳米颗粒	HFC-245fa	HFO-1234ze	500	—
[22]	2018	氟化NiO/Cr₂O₃	HFC-245fa	HFO-1234ze	450	89
[22]	2018	Cr₂O₃	HFC-245fa	HFO-1234ze	450	68
[23]	2015	NiAlF	HFC134	FEP（氟化乙烯）	430	20.1
[24]	2017	Cr₂O₃	HFC-245eb	HFO-1234y	350	80.1

文献	时间	反应物	产物	催化剂	条件	结论
[29]	2006	CFC-11	CHCl₂F和Cl^-	TiO₂悬浊液	常温	转化率29%
[30]	2005	CFC-12	CO₂, HF, Cl₂等	无	常温	CFC吸收波长200～260 nm
[30]	2005	CFC-12	CO₂, HF, Cl₂等	TiO₂颗粒	常温	吸收波长范围扩大至365～366 nm, 404～408 nm, 577～579 nm
[31]	1998	HFC-152a	CH₃CF₂O, O₂等	无	185 nm光	可直接发生分解
				TiO₂颗粒	254 nm光	分解率与无催化剂185 nm光解相同
				TiO₂颗粒	185 nm光	分解率约为无催化剂185 nm光解速率2倍
[32]	2014	部分HFCs	—	Bi₂O₃	常温	Bi₂O₃光催化效率比直接光解效率高