废弃制冷剂R134a的光催化降解

doi:10.16085/j.issn.1000-6613.2022-1035

化工进展 ›› 2023, Vol. 42 ›› Issue (4): 2109-2114.DOI: 10.16085/j.issn.1000-6613.2022-1035

废弃制冷剂R134a的光催化降解

杨状¹(), 李闰华¹, 强增寿¹, 王雅君¹(), 姚文清²()

^1.中国石油大学(北京)新能源与材料学院，北京 102249
^2.清华大学化学系，北京 100084

收稿日期:2022-06-06 修回日期:2022-09-20 出版日期:2023-04-25 发布日期:2023-05-08
通讯作者: 王雅君,姚文清
作者简介:杨状（1993—），男，博士研究生，研究方向为光催化、纳米材料合成。E-mail：2019310616@student.cup.edu.cn。
基金资助:
国家重点研发计划(2019YFC1904500);国家自然科学基金(52270115);中国石油大学（北京）科学基金(2462019QNXZ05);重质油国家重点实验室自主项目

Photocatalytic degradation of waste refrigerant R134a

YANG Zhuang¹(), LI Runhua¹, QIANG Zengshou¹, WANG Yajun¹(), YAO Wenqing²()

^1.School of New Energy and Materials, China University of Petroleum (Beijing), Beijing 102249, China
^2.Department of Chemistry, Tsinghua University, Beijing 100084, China

Received:2022-06-06 Revised:2022-09-20 Online:2023-04-25 Published:2023-05-08
Contact: WANG Yajun, YAO Wenqing

摘要/Abstract

摘要：

根据《蒙特利尔破坏臭氧层物质管制议定书》要求，废弃制冷剂由于其温室效应及生态危害，将被逐步淘汰和销毁。目前还没有高效低成本处理废弃制冷剂的方法，本文提出光催化处理废弃制冷剂新策略。制备了BiPO₄/GA气凝胶，材料兼具了石墨烯优异的吸附能力与BiPO₄高效的光催化能力，可实现污染物的迅速吸附与彻底矿化。以原位红外光谱为评价手段，在线监测了光催化降解典型制冷剂四氟乙烷（CH₂FCF₃，R134a）的进程，包括R134a的瞬间吸附、R134a大量被光催化降解时C—F键的断裂、R134a被彻底降解的过程。明确了光催化降解R134a的最终产物为HF和CO₂。结果表明，在BiPO₄/GA气凝胶光催化作用下，R134a可被彻底矿化分解。研究结果将为降解废弃制冷剂提供有效途径，原位红外光谱的应用也将为废弃制冷剂的分解过程提供可靠的监测手段。

关键词: 光催化, 催化剂, 磷酸铋, 石墨烯, 吸附, 制冷剂, 反应

Abstract:

According to "Montreal Protocol on Substances that Deplete the Ozone Layer", waste refrigerants will be phased out and destroyed due to their greenhouse effect and ecological hazards. At present, there is no efficient and low-cost method to treat waste refrigerant. We propose a new strategy for the photocatalytic treatment of waste refrigerant. BiPO₄/GA aerogels were prepared, which showed excellent adsorption capacity of graphene and efficient photocatalytic capacity of BiPO₄. The rapid adsorption and complete mineralization of pollutants were realized. The process of photocatalytic degradation of typical refrigerant tetrafluoroethane (CH₂FCF₃, R134a) was monitored online by in situ infrared spectroscopy. The process of bond breaking and complete degradation of R134a was analyzed. It was clear that the final product of photocatalytic degradation of R134a was HF and CO₂. The results showed that R134a could be completely mineralized and decomposed under the photocatalysis of BiPO₄/GA aerogel. The research provided an effective way to degrade waste refrigerants, and the application of in-situ infrared spectra would also be a reliable method for monitoring the decomposition process of waste refrigerants.

Key words: photocatalysis, catalyst, BiPO₄, graphene, adsorption, refrigerant, reaction

中图分类号:

X511

杨状, 李闰华, 强增寿, 王雅君, 姚文清. 废弃制冷剂R134a的光催化降解[J]. 化工进展, 2023, 42(4): 2109-2114.

YANG Zhuang, LI Runhua, QIANG Zengshou, WANG Yajun, YAO Wenqing. Photocatalytic degradation of waste refrigerant R134a[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2109-2114.

图/表 6

图1 BiPO4/GA气凝胶的扫描电子显微镜图像

图2 BiPO4/GA气凝胶的X射线衍射谱图

图3 BiPO4/GA气凝胶的傅里叶变换红外光谱图

图4 BiPO4/GA气凝胶的紫外-可见吸收光谱图

图5 R134a光催化随时间变化的原位傅里叶变换红外光谱图

图6 光催化降解体积分数2%的R134a随时间变化的原位傅里叶变换红外光谱图

参考文献 15

1	MOLINA M J, ROWLAND F S. Stratospheric sink for chlorofluoromethanes: chlorine atom-catalysed destruction of ozone[J]. Nature, 1974, 249(5460): 810-812.
2	MOLINA M J, ROWLAND F S. Qzone depletion: 20 years after alarm[J]. Chemical & Engineering News, 1974, 72(33): 8-13.
3	史琳, 安青松, 戴晓业, 等. 论我国受控制冷剂销毁的紧迫性及潜在新技术开发的重要性[J]. 制冷与空调, 2021, 21(7): 61-66.
	SHI Lin, AN Qingsong, DAI Xiaoye, et al. Discussion on the urgency of phase out refrigerants destruction work and the importance of new technology development[J]. Refrigeration and Air-conditioning, 2021, 21(7): 61-66.
4	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 Zhaohui, CHEN Jingliang, GAO Yu, et al. Analysis on theinfluence of Kigali Amendment to Montreal Protocol to refrigeration and air-conditioning industry[J]. Refrigeration and Air-Conditioning, 2017, 17(1): 1-7， 15.
5	OHM T I, CHAE J S, ZHANG Meng yu, et al. Effect of burner types and steam injection methods on thermal destruction of waste refrigerants (HFC-134a)[J]. Process Safety and Environmental Protection, 2019, 121: 62-68.
6	TARALUNGA M, MIJOIN J, MAGNOUX P. Catalytic destruction of chlorinated POPs—Catalytic oxidation of chlorobenzene over PtHFAU catalysts[J]. Applied Catalysis B: Environmental, 2005, 60(3/4): 163-171.
7	ZHANG Kai, WANG Jun, JIANG Wenjun, et al. Self-assembled perylene diimide based supramolecular heterojunction with Bi₂WO₆ for efficient visible-light-driven photocatalysis[J]. Applied Catalysis B: Environmental, 2018, 232: 175-181.
8	WANG Yajun, QIANG Zengshou, ZHU Wei, et al. BiPO₄ nanorod/graphene composite heterojunctions for photocatalytic degradation of tetracycline hydrochloride[J]. ACS Applied Nano Materials, 2021, 4(9): 8680-8689.
9	WEI Zhen, LIU Yanfang, WANG Jun, et al. Controlled synthesis of a highly dispersed BiPO₄ photocatalyst with surface oxygen vacancies[J]. Nanoscale, 2015, 7(33): 13943-13950.
10	KOUTAVARAPU R, TAMTAM M R, MYLA C R, et al. Enhanced solar-light-driven photocatalytic properties of novel Z-scheme binary BiPO₄ nanorods anchored onto NiFe₂O₄ nanoplates: Efficient removal of toxic organic pollutants[J]. Journal of Environmental Sciences, 2021, 102: 326-340.
11	ZHU Xin, WANG Yuting, GUO Yang, et al. Environmental-friendly synthesis of heterojunction photocatalysts g-C₃N₄/BiPO₄ with enhanced photocatalytic performance[J]. Applied Surface Science, 2021, 544: 148872.
12	ZHAO Xiaohan, WANG Xiaohong, SUN Zhuo, et al. Efficient visible-light photocatalytic performance of CdS/BiPO₄ nanoparticles fabricated by solvothermal method[J]. Optik, 2020, 208: 164543.
13	WANG Yajun, WANG Fengmei, HE Jun. Controlled fabrication and photocatalytic properties of a three-dimensional ZnO nanowire/reduced graphene oxide/CdS heterostructure on carbon cloth[J]. Nanoscale, 2013, 5(22): 11291-11297.
14	KUMAR S, KARFA P, MAJHI K C, et al. Photocatalytic, fluorescent BiPO₄@Graphene oxide based magnetic molecularly imprinted polymer for detection, removal and degradation of ciprofloxacin[J]. Materials Science and Engineering: C, 2020, 111: 110777.
15	唐诗卉, 姚文清, 谭瑞琴. 氧化石墨烯氧化程度对磷酸铋/石墨烯复合气凝胶光催化活性的影响[J]. 环境化学, 2019, 38(7): 1656-1665.
	TANG Shihui, YAO Wenqing, TAN Ruiqin. Effect of oxidation degree of graphene oxide on photocatalytic activity of bismuth phosphate/graphene composite aerogel[J]. Environmental Chemistry, 2019, 38(7): 1656-1665.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[6]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[7]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[8]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[9]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[10]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[11]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[12]	孙玉玉, 蔡鑫磊, 汤吉海, 黄晶晶, 黄益平, 刘杰. 反应精馏合成甲基丙烯酸甲酯工艺优化及节能[J]. 化工进展, 2023, 42(S1): 56-63.
[13]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[14]	盛维武, 程永攀, 陈强, 李小婷, 魏嘉, 李琳鸽, 陈险峰. 微气泡和微液滴双强化脱硫反应器操作分析[J]. 化工进展, 2023, 42(S1): 142-147.
[15]	黄益平, 李婷, 郑龙云, 戚傲, 陈政霖, 史天昊, 张新宇, 郭凯, 胡猛, 倪泽雨, 刘辉, 夏苗, 主凯, 刘春江. 三级环流反应器中气液流动与传质规律[J]. 化工进展, 2023, 42(S1): 175-188.

废弃制冷剂R134a的光催化降解

Photocatalytic degradation of waste refrigerant R134a

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 15

相关文章 15

编辑推荐

Metrics

本文评价