Treatment of refractory organics sulfonated phenolic resin with ferrate

doi:10.16085/j.issn.1000-6613.2022-1485

Abstract

Abstract:

The refractory organic matter sulfonated phenolic resin (SMP) was treated with ferrate. The influences of various factors on the COD_Cr removal rate of SMP were studied. The optimal conditions were determined. When the initial concentration of SMP was 0.05% (mass ratio), the ferrate was 1.2g/L, the pH=13 and the reaction time was 2h, the COD_Cr removal rate of SMP was 79.4%. The amount of ferrate had a great influence on the COD_Cr removal rate. Different concentrations of SMP should choose different ferrate dosage. The removal rate of SMP was still dominated by oxidation and flocculation accounted for a low proportion of the total removal rate. Combined with UV-Vis, GPC and GC -MS analysis, it can be concluded that the sulphomethyl structure of SMP was completely degraded, and the macromolecular backbone of SMP was broken to generate substances with a molecular weight of about 1300 with a benzene ring. When the backbone was degraded to a certain degree, the benzene ring began to be oxidized and the ring-opening reaction occurred to form small molecular organic hydrocarbons, which were eventually oxidized to CO₂ and H₂O.

Key words: ferrate, sulfonated phenolic resin, waste water, degradation, chromatography

摘要：

采用高铁酸盐处理难降解有机物磺化酚醛树脂（SMP），研究了各影响因素对SMP的COD_Cr去除率的影响，确定了最佳条件，当SMP初始浓度为0.05%（质量分数）时，高铁酸盐投量为1.2g/L、反应体系pH为13、反应2h，SMP的COD_Cr去除率为79.4%。高铁酸盐的投量对SMP的COD_Cr去除率有很大的影响，不同浓度的SMP应当选择不同的高铁酸盐投量。絮凝作用对SMP的去除效果占总去除率一定比例，但SMP的去除仍以氧化作用为主。结合紫外-可见分光光度法（UV-Vis）、凝胶渗透色谱（GPC）和气相色谱-质谱联用（GC-MS）分析可以断定SMP分子结构中磺甲基结构基本完全降解，SMP的大分子主链发生断裂生成分子量为1300左右的带有苯环结构的物质，当主链降解到一定程度后，苯环结构开始被氧化发生开环反应，生成烃类小分子有机物，最终氧化成 CO₂ 和 H₂O。

关键词: 高铁酸盐, 磺化酚醛树脂, 废水, 降解, 色谱

CLC Number:

X741

YANG Hongmei, GAO Tao, YU Tao, QU Chengtun, GAO Jiapeng. Treatment of refractory organics sulfonated phenolic resin with ferrate[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3302-3308.

杨红梅, 高涛, 鱼涛, 屈撑囤, 高家朋. 高铁酸盐处理难降解有机物磺化酚醛树脂[J]. 化工进展, 2023, 42(6): 3302-3308.

Figures/Tables 12

References 25

1	张擎翰, 蒋文举. 钻井废水处理技术研究进展[J]. 四川化工, 2011, 14(1): 45-48.
	ZHANG Qinghan, JIANG Wenju. The development of drilling wastewater treatment technology[J]. Sichuan Chemical Industry, 2011, 14(1): 45-48.
2	彭娟华, 莫正平, 李旭东. Fenton试剂预处理提高钻井废水可生化性[J]. 应用与环境生物学报, 2008, 14(2): 265-269.
	PENG Juanhua, MO Zhengping, LI Xudong. Improvement of biodegradability of drilling wastewater pretreated by Fenton’s reagent[J]. Chinese Journal of Applied & Environmental Biology, 2008, 14(2): 265-269.
3	WANG Yanming, YANG Min, ZHANG Jing, et al. Improvement of biodegradability of oil field drilling wastewater using ozone[J]. Ozone: Science & Engineering, 2004, 26(3): 309-315.
4	张红岩, 吕荣湖, 郭绍辉. 混凝-臭氧氧化法处理三磺泥浆体系钻井废水[J]. 过程工程学报, 2007, 7(4): 718-722.
	ZHANG Hongyan, Ronghu LYU, GUO Shaohui. Treatment of drilling wastewater correlated with three-sulfonated mud system by coagulation-ozone oxidation process[J]. The Chinese Journal of Process Engineering, 2007, 7(4): 718-722.
5	李凡修, 崔淑红, 薛发生. 用二级絮凝强化技术处理钻井污水研究[J]. 油气田环境保护, 2006, 16(1): 18-20, 60.
	LI Fanxiu, CUI Shuhong, XUE Fasheng. Drilling sewage disposal by using two-step enhanced chemical flocculation technology[J]. Environmental Protection of Oil & Gas Fields, 2006, 16(1): 18-20, 60.
6	梁宏, 陈英燕, 彭红, 等. 软锰矿粒子电极的制备及其对SMP的催化降解[J]. 环境工程学报, 2019, 13(8): 1822-1830.
	LIANG Hong, CHEN Yingyan, PENG Hong, et al. Preparation of pyrolusite particle electrode and its catalytic degradation of SMP[J]. Chinese Journal of Environmental Engineering, 2019, 13(8): 1822-1830.
7	肖惠文, 梁宏, 庞凯, 等. 软锰矿粒子电极处理SMP模拟废水实验研究[J]. 四川理工学院学报(自然科学版), 2016, 29(1): 12-16.
	XIAO Huiwen, LIANG Hong, PANG Kai, et al. Experiment study on treating SMP simulation sewage by using pyrolusite particle electrode[J]. Journal of Sichuan University of Science & Engineering (Natural Science Edition), 2016, 29(1): 12-16.
8	FENG Mingbao, CIZMAS Leslie, WANG Zunyao, et al. Synergistic effect of aqueous removal of fluoroquinolones by a combined use of peroxymonosulfate and ferrate(‍Ⅵ)[J]. Chemosphere, 2017, 177: 144-148.
9	SHARMA Virender K. Ferrate(Ⅵ) and ferrate(Ⅴ) oxidation of organic compounds: kinetics and mechanism[J]. Coordination Chemistry Reviews, 2013, 257(2): 495-510.
10	Mihee LIM, KIM Myoung Jin. Removal of natural organic matter from river water using potassium ferrate(‍Ⅵ)[J]. Water, Air, and Soil Pollution, 2009, 200(1/2/3/4): 181-189.
11	方智煌, 刘祥, 余阳, 等. 高铁酸盐对水中H₂受体拮抗剂的降解特性[J]. 化工进展, 2021, 40(8): 4647-4655.
	FANG Zhihuang, LIU Xiang, YU Yang, et al. Performance and properties of H₂-receptor antagonist degradation by ferrate[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4647-4655.
12	ZHANG Kejia, LUO Zhang, ZHANG Tuqiao, et al. Degradation effect of sulfa antibiotics by potassium ferrate combined with ultrasound[Fe(Ⅵ)-US][J]. BioMed Research International, 2015, 2015: 169215.
13	ZHOU Zhengwei, JIANG Jiaqian. Reaction kinetics and oxidation products formation in the degradation of ciprofloxacin and ibuprofen by ferrate(Ⅵ)[J]. Chemosphere, 2015, 119: S95-S100.
14	顾国亮, 杨文忠. 高铁酸钾的制备方法及应用[J]. 工业水处理, 2006, 26(3): 59-61.
	GU Guoliang, YANG Wenzhong. Preparation and application of potassium ferrate[J]. Industrial Water Treatment, 2006, 26(3): 59-61.
15	ANQUANDAH George A K, SHARMA Virender K, PANDITI Venkata R, et al. Ferrate(Ⅵ) oxidation of propranolol: kinetics and products[J]. Chemosphere, 2013, 91(1): 105-109.
16	SHARMA Virender K. Potassium ferrate(‍Ⅵ): an environmentally friendly oxidant[J]. Advances in Environmental Research, 2002, 6(2): 143-156.
17	JIANG Jiaqian, LLOYD Barry. Progress in the development and use of ferrate(Ⅵ) salt as an oxidant and coagulant for water and wastewater treatment[J]. Water Research, 2002, 36(6): 1397-1408.
18	LI C, LI X Z, GRAHAM N. A study of the preparation and reactivity of potassium ferrate[J]. Chemosphere, 2005, 61(4): 537-543.
19	GRAHAM Nigel, JIANG Chengchun, LI Xiangzhong, et al. The influence of pH on the degradation of phenol and chlorophenols by potassium ferrate[J]. Chemosphere, 2004, 56(10): 949-956.
20	SHARMA Virender K, ZBORIL Radek, VARMA Rajender S. Ferrates: greener oxidants with multimodal action in water treatment technologies[J]. Accounts of Chemical Research, 2015, 48(2): 182-191.
21	MA Jun, LIU Wei. Effectiveness and mechanism of potassium ferrate(Ⅵ) preoxidation for algae removal by coagulation[J]. Water Research, 2002, 36(4): 871-878.
22	李洪枚, 王鼎九, 马福洪, 等. 高铁酸钾氧化处理含苯胺黑药废水试验研究[J]. 湿法冶金, 2020, 39(1): 74-79.
	LI Hongmei, WANG Dingjiu, MA Fuhong, et al. Treatment of simulated beneficiation wastewater containing dianilinodithiophosphoric acid using potassium ferrate[J]. Hydrometallurgy of China, 2020, 39(1): 74-79.
23	YANG Tao, WANG Lu, LIU Yulei, et al. Ferrate oxidation of bisphenol F and removal of oxidation products with ferrate resulted particles[J]. Chemical Engineering Journal, 2020, 383: 123167.
24	WANG Bing, XIONG Xingaoyuan, SHUI Yiyu, et al. A systematic study of enhanced ozone mass transfer for ultrasonic-assisted PTFE hollow fiber membrane aeration process[J]. Chemical Engineering Journal, 2019, 357: 678-688.
25	LIANG Hong, QIU Yang, ZHAO Liying, et al. Investigation of a novel pyrolusite particle electrode effects in the chlorine-containing wastewater[J]. Water Science and Technology， 2018, 78(7): 1427-1437.

样品	M_n	M_w	M_z	M_w/M_n
SMP处理后	1.26×10³	1.33×10³	1.41×10³	1.06
SMP处理前	4.65×10⁴	6.03×10⁴	7.79×10⁴	1.29

样品	M_n	M_w	M_z	M_w/M_n
SMP处理后	1.26×10³	1.33×10³	1.41×10³	1.06
SMP处理前	4.65×10⁴	6.03×10⁴	7.79×10⁴	1.29

编号	停留时间/min	质量分数/%
1	0.592	1.53
2	0.708	24.89
3	1.258	15.96
4	1.342	27.72
5	1.667	0.61
6	12.067	0.84
7	12.950	2.97
8	14.375	0.32
9	14.625	24.17
10	28.250	0.98

编号	停留时间/min	质量分数/%
1	0.592	1.53
2	0.708	24.89
3	1.258	15.96
4	1.342	27.72
5	1.667	0.61
6	12.067	0.84
7	12.950	2.97
8	14.375	0.32
9	14.625	24.17
10	28.250	0.98

[1]	XU Chunshu, YAO Qingda, LIANG Yongxian, ZHOU Hualong. Research progress on functionalization strategies of covalent organic frame materials and its adsorption properties for Hg(Ⅱ) and Cr(Ⅵ) [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 461-478.
[2]	GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.
[3]	WANG Chen, BAI Haoliang, KANG Xue. Performance study of high power UV-LED heat dissipation and nano-TiO₂ photocatalytic acid red 26 coupling system [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4905-4916.
[4]	CHU Tiantian, LIU Runzhu, DU Gaohua, MA Jiahao, ZHANG Xiao’a, WANG Chengzhong, ZHANG Junying. Preparation and chemical degradability of organoguanidine-catalyzed dehydrogenation type RTV silicone rubbers [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3664-3673.
[5]	XU Wei, LI Kaijun, SONG Linye, ZHANG Xinghui, YAO Shunhua. Research progress of photocatalysis and co-electrochemical degradation of VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3520-3531.
[6]	GONG Pengcheng, YAN Qun, CHEN Jinfu, WEN Junyu, SU Xiaojie. Properties and mechanism of eriochrome black T degradation by carbon nanotube-cobalt ferrite composites activated persulfate [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3572-3581.
[7]	WU Fengzhen, LIU Zhiwei, XIE Wenjie, YOU Yating, LAI Rouqiong, CHEN Yandan, LIN Guanfeng, LU Beili. Preparation of biomass derived Fe/N co-doped porous carbon and its application for catalytic degradation of Rhodamine B via peroxymonosulfate activation [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3292-3301.
[8]	CAI Juyan, SU Qiong, WANG Yanbin, WANG Hongling, LIANG Junxi, WANG Zhongxu, GUO Li, ZHAO Libin. Research progress on biodegradable foaming materials [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1457-1470.
[9]	LIU Dan, FAN Yunjie, WANG Huimin, YAN Zheng, LI Pengfei, LI Jiacheng, CAO Xuebo. High value-added functional porous carbon materials from waste PET and their applications [J]. Chemical Industry and Engineering Progress, 2023, 42(2): 969-984.
[10]	ZHANG Han, ZHANG Xiaojing, MA Bingbing, NAI Can, LIU Shuoshuo, MA Yongpeng, SONG Yali. Feasibility of starting anammox process with municipal waste sludge as seed sludge [J]. Chemical Industry and Engineering Progress, 2023, 42(2): 1080-1088.
[11]	DUO Jia, YAO Guodong, WANG Yingji, ZENG Xu, JIN Binbin. Effects on the photo-degradation of norfloxacin using modified Au-TiO₂ [J]. Chemical Industry and Engineering Progress, 2023, 42(2): 624-630.
[12]	ZHANG Pingping, DING Shuhai, GAO Jingjing, ZHAO Min, YU Haixiang, LIU Yuehong, GU Lin. Carbon quantum dots modified semiconductor composite photocatalysts for degradation of organic pollutants in water [J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5487-5500.
[13]	ZHANG Yingjie, LU Jiayue, WANG Fanggang. Synthesis of a new MCER and its performance in removing Cu(Ⅱ) from water [J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5558-5566.
[14]	LIU Haicheng, MENG Wushuang, HUANG Zhe, YOU Yu, HUA Ruiqi, CAO Mengru. Preparation of WO₃/BiOCl_0.7I_0.3 photocatalyst and its photocatalytic degradation mechanism [J]. Chemical Industry and Engineering Progress, 2023, 42(1): 255-264.
[15]	SUN Mengwei, LIU Zhuang, XIE Rui, JU Xiaojie, WANG Wei, CHU Liangyin. Preparation of Lanthanum ion intercalated MoS₂ membrane for treating dyeing wastewater with high brine [J]. Chemical Industry and Engineering Progress, 2023, 42(1): 346-353.