脉冲气液两相放电等离子体耦合Fe改性的TiO2催化剂降解废水中的4-氯酚

doi:10.16085/j.issn.1000-6613.2020-2573

摘要/Abstract

摘要：

为了提高酚类废水的降解效果，本文以4-氯酚为处理对象建立了多针-板式高压脉冲气液两相放电等离子体催化体系。实验制备了系列催化剂并进行了表征分析，考察了各因素对4-氯酚降解的影响，并分析了降解过程总有机碳（TOC）、中间产物及其浓度变化。结果表明，催化剂焙烧温度及投加量对降解率有很大影响；4-氯酚浓度为150mg/L时，在电极间距10mm、脉冲电压26kV、脉冲频率70Hz、曝气量4L/min条件下，添加0.05g焙烧温度为500℃的Fe-TiO₂催化剂与放电等离子体耦合降解效果最好。中间产物对苯酚、对苯醌、4-氯邻苯二酚在放电过程中浓度随着放电时间的延长先增大后减小，最后都趋于零。催化剂表征显示脉冲放电可以改变催化剂的晶形和结构，且掺杂Fe改性的Fe-TiO₂催化性能较好，能进一步提升4-氯酚的降解率。

关键词: 脉冲放电, 废水, 降解, 矿化率, 环境

Abstract:

In order to improve the degradation of phenols in wastewater, a multi-needle plate catalysis system with high voltage pulsed gas-liquid two-phase discharge plasma was established for the removal of 4-chlorophenol. A series of catalysts were prepared and characterized, and the effects of various factors on 4-chlorophenol degradation were investigated by analysis of TOC, intermediate products and their concentrations in the degradation process. The results showed that catalyst roasting temperature and dosage had a great influence on the degradation rate of 4-chlorophenol. When the concentration of 4-chlorophenol was 150mg/L, under the conditions of electrode spacing 10mm, pulse voltage 26kV, pulse frequency 70Hz, aeration 4L/min, the discharge plasma with the Fe-TiO₂ catalyst of 0.05g calcinated at 500℃ gave the best degradation effect. The concentrations of byproducts such as p-phenol, p-benzoquinone and 4-chlorocatechol increased firstly and then decreased gradually and eventually disappeared with the increase of discharge time. Characterization results showed that the pulse discharge changed the crystal form and structure of the catalyst, and the Fe-TiO₂ modified with Fe had good catalytic performance, which further improved the degradation rate of 4-chlorophenol.

Key words: pulse discharge, waste water, degradation, mineralization rate, environment

中图分类号:

X703.1

董冰岩, 李贞栋, 王佩祥, 罗婷, 邹颖, 涂文娟. 脉冲气液两相放电等离子体耦合Fe改性的TiO₂催化剂降解废水中的4-氯酚[J]. 化工进展, 2021, 40(12): 6721-6728.

DONG Bingyan, LI Zhendong, WANG Peixiang, LUO Ting, ZOU Ying, TU Wenjuan. 4-Chlorophenol containing wastewater joint treated by pulsed discharge plasma in gas-liquid two phase and Fe-modified TiO₂catalyst[J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6721-6728.

图/表 13

图1 实验装置系统图

图2 多针-板式放电反应器装置示意图

图3 不同焙烧温度下Fe-TiO2催化剂的SEM图

图4 不同焙烧温度下Fe-TiO2催化剂的XRD图

图5 焙烧温度对4-氯酚降解率的影响

图6 催化剂投加量对4-氯酚降解率的影响

图7 4-氯酚降解率随放电时间的变化规律

图8 耦合TiO2催化剂中间产物浓度随放电时间的变化规律

图9 耦合Fe-TiO2催化剂中间产物浓度随放电时间的变化规律

图10 耦合TiO2催化剂溶液的TOC和矿化率随放电时间的变化规律

图11 耦合Fe-TiO2催化剂溶液的TOC和矿化率随放电时间的变化规律

图12 不同反应体系的反应速率

表1 不同反应体系的4-氯酚反应速度常数

不同反应体系

k_cp/min^-1

R²

放电90min的

降解率/%

参考文献 31

1	王韬, 李鑫钢, 杜启云. 含酚废水治理技术研究进展[J].化工进展, 2008, 27(2)：231-235.
	WANG Tao, LI Xingang, DU Qiyun. Research progress of phenol-containing waste water disposal technique[J]. Chemical Industry and Engineering Progress, 2008, 27(2):231-235.
2	OLIVEIRA A S, BAEZA J A, SAENZ DE MIERA B, et al. Aqueous phase reforming coupled to catalytic wet air oxidation for the removal and valorisation of phenolic compounds in wastewater[J]. Journal of Environmental Management, 2020, 274: 111199.
3	ZHANG Meng, ZHANG Zhi, LIU Shaocong, et al. Ultrasound-assisted electrochemical treatment for phenolic wastewater[J]. Ultrasonics Sonochemistry, 2020, 65: 105058.
4	HUONG D T, NGUYEN V T, HA X L, et al. Enhanced degradation of phenolic compounds in coal gasification wastewater by methods of microelectrolysis Fe-C and anaerobic-anoxic-oxic moving bed biofilm reactor (A2O-MBBR) [J]. Processes, 2020, 8(10): 1258.
5	SU Yanyu, LIU Shuai, ZHAO Chunfeng, et al. Needle electrode design of pulsed high voltage discharge reactor for performance enhancement of 4-chlorophenol degradation in highly conductive solution[J]. Chemosphere, 2020, 266: 129203.
6	DUAN Zhihui, ZHANG Wanhui, LU Muwen, et al. Magnetic Fe₃O₄/activated carbon for combined adsorption and Fenton oxidation of 4-chlorophenol[J]. Carbon, 2020, 167: 351-63.
7	LIU Chang, MIN Yuan, ZHANG Aiyong,et al. Electrochemical treatment of phenol-containing wastewater by facet-tailored TiO₂: efficiency, characteristics and mechanisms[J]. Water Research, 2019, 165: 114980.
8	李和平, 于达仁, 孙文廷, 等. 大气压放电等离子体研究进展综述[J]. 高电压技术, 2016, 42(12): 3697-3727.
	LI Heping, YU Daren, SUN Wenting, et al. State-of-the-art of at-mospheric discharge plasmas[J]. High Voltage Engineering, 2016, 42(12): 3697-3727.
9	王方铮, 李杰, 吴彦, 等. 高压脉冲放电等离子体溶液中苯酚的降解[J]. 高电压技术, 2007(2): 124-127.
	WANG Fangzheng, LI Jie, WU Yan, et al. Degradation of phenol in aqueous solution by high voltage pulsed discharge plasma[J]. High Voltage Engineering, 2007(2): 124-127.
10	董冰岩, 邓苇, 孙宇, 等. 高压脉冲放电协同纳米催化剂降解苯酚废水[J]. 高电压技术, 2017, 43(8): 2645-2652.
	DONG Bingyan, DENG Wei, SUN Yu, et al. Phenol wastewater treatment by high voltage pulse discharge combined with nanometer catalyst[J]. High Voltage Engineering, 2017, 43(8): 2645-2652.
11	程爱华, 马万超, 徐哲. 等离子体改性海绵铁活化过硫酸盐处理含酚废水[J]. 化工进展, 2020, 39(2): 798-804.
	CHENG Aihua, MA Wanchao, XU Zhe. Treatment of phenol wastewater with persulfate activated by plasmamodified sponge iron[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 798-804.
12	MA S, KIM K, CHUN S, et al. Plasma-assisted advanced oxidation process by a multi-hole dielectric barrier discharge in water and its application to wastewater treatment[J]. Chemosphere, 2020, 243: 125377.
13	ZAIDY S S H, VACCHI F I, UMBUZEIRO G A, et al. Approach to waterless dyeing of textile substrates-use of atmospheric plasma[J]. Industrial Engineering Chemistry Research, 2019, 58(40): 18478-18487.
14	SUN B, SATO M, CLEMENTS J SID. Optical study of active species produced by a pulsed streamer corona discharge in water[J]. Journal of Electrostatics, 1997, 39(3): 189-202.
15	JOSE J, RAMANUJAM S, PHILIP L. Applicability of pulsed corona discharge treatment for the degradation of chloroform[J]. Chemical Engineering Journal, 2019, 360: 1341-1354.
16	SINGH R K, PHILIP L, RAMANUJAM S. Rapid degradation, mineralization and detoxification of pharmaceutically active compounds in aqueous solution during pulsed corona discharge treatment[J]. Water Research, 2017, 121: 20-36.
17	孙明, 金宏力, 杨颜颜, 等. 脉冲放电等离子体协同二氧化钛降解偶氮类染料废水[J]. 高电压技术, 2015, 41(9): 2862-2867.
	SUN Ming, JIN Hongli, YANG Yanyan, et al. Degradation of azo dye wastewater using pulsed discharge plasma with TiO₂[J]. High Voltage Engineering, 2015, 41(9): 2862-2867.
18	ZHU Bin, ZHANG Luyao, YAN Yan, et al. Enhancing toluene removal in a plasma photocatalytic system through a black TiO₂ photocatalyst[J]. Plasma Science and Plasma Technology, 2019, 21(11): 115503.
19	MOHAMMADI P, GHORBANI-SHAHNA F, BAHRAMI A, et al. Plasma-photocatalytic degradation of gaseous toluene using SrTiO₃/rGO as an efficient heterojunction for by-products abatement and synergistic effects[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2020, 394: 112460.
20	董冰岩, 张鹏, 聂亚林, 等. 针-板式高压脉冲气液两相放电降解废水中的苯酚[J]. 化工进展, 2016, 35(1): 314-319.
	DONG Bingyan, ZHANG Peng, NIE Yalin, et al. Phenol wastewater treatment by needle-plate pulsed high voltage discharge in gas-liquid two phase[J]. Chemical Industry and Engineering Progress, 2016, 35(1): 314-319.
21	董冰岩, 王慧, 张雨路. 高压脉冲放电降解4-氯酚废水的实验研究[J]. 化学工程, 2019, 47(2): 12-17.
	DONG Bingyan, WANG Hui, ZHANG Yulu. Degradation of 4-chlorophenol wastewater by high voltage pulse discharge[J]. Chemical Engineering(China), 2019, 47(2): 12-17.
22	彭晓春, 陈新庚, 黄鹄, 等. n-TiO₂光催化机理及其在环境保护中的应用研究进展[J]. 环境工程学报, 2002, 3(3): 1-6.
	PENG Xiaochun. CHEN Xingeng, HUANG Hu,et al. The light catalytic mechanism of n-TiO2 and its application in the environmental protection[J].Chinese Journal of Environmental Engineering, 2002, 3(3): 1-6.
23	董冰岩, 施志勇, 何俊文, 等. 脉冲放电等离子体耦合Mn/TiO₂分子筛、Fe/TiO₂分子筛、Cu/TiO₂分子筛催化剂降解甲醛[J]. 化工进展, 2015, 34(9): 3337-3344.
	DONG Bingyan, SHI Zhiyong, HE Junwen, et al. Research of pulse discharge plasma combined with Mn/TiO₂-molecular、Fe/TiO₂-molecular、Cu/TiO₂-molecular sieve catalysts decomposition of formaldehyde[J]. Chemical Industry and Engineering Progress, 2015, 34(9): 3337-3344.
24	闫鹏飞, 王建强, 江欣, 等. 掺铁TiO₂纳米晶的制备及光催化性能研究[J]. 材料科学与工艺, 2002, 10(1): 28-31.
	YAN Pengfei, WANG Jianqiang, JIANG Xin, et al. Preparation and photocatalytic properties of iron-doped TiO₂ nanocrystal[J]. Materials Science and Technology, 2002, 10(1): 28-31.
25	KOMARAIAH D, RADHA E, SIVAKUMAR J, et al. Structural optical properties and photocatalytic activity of Fe³⁺ doped TiO₂ thin films deposited by sol-gel spin coating[J]. Surfaces and Interfaces, 2019, 17.
26	JRABA A, ANNA Z, ELALOUI E. Effects of Sr²⁺, Fe³⁺ and Al³⁺ doping on the properties of TiO₂ prepared using the sol-gel method[J]. Comptes Rendus Chimie, 2019, 22(9/10): 648-658.
27	HARIFI T, MONTAZER M. Fe³⁺: Ag/TiO₂ nanocomposite: synthesis, characterization and photocatalytic activity under UV and visible light irradiation[J]. Applied Catalysis A: General, 2014, 473: 104-115.
28	CUI Tao, SHEN Chenyang, XU Anlin, et al. Use of a novel coupled-oxidation tubular reactor (COTR)/NTP-DBD catalytic plasma in a synergistic electro-catalysis system for odorous mercaptans degradation[J]. Chemosphere, 2019, 216: 533-544.
29	GUO He, JIANG Nan, LI Jie, et al. Synergistic degradation of bisphenol A by pulsed discharge plasma with granular activated carbon: effect of operating parameters, synergistic mechanism and possible degradation pathway[J]. Vacuum, 2018, 156: 402-410.
30	HAO XiaoLong, ZHOU MingHua, XIN Qing, et al. Pulsed discharge plasma induced Fenton-like reactions for the enhancement of the degradation of 4-chlorophenol in water[J]. Chemosphere, 2007, 66(11): 2185-2192.
31	LI Shanping, WANG Xiaoping, LIU Lijun, et al. Enhanced degradation of perfluorooctanoic acid using dielectric barrier discharge with La/Ce-doped TiO₂[J]. Environmental Science and Pollution Research, 2017, 24(18): 15794-15803.

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脉冲气液两相放电等离子体耦合Fe改性的TiO₂催化剂降解废水中的4-氯酚

4-Chlorophenol containing wastewater joint treated by pulsed discharge plasma in gas-liquid two phase and Fe-modified TiO₂catalyst

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