升温速率对污泥-赤泥炭活化过一硫酸盐的影响

doi:10.19965/j.cnki.iwt.2022-0676

摘要/Abstract

摘要：

将污泥-赤泥复配热解制备催化剂可实现大宗固废的资源化利用。活性位点对活性物种的生成具有重要作用。升温速率可调控污泥-赤泥炭基催化剂（RSDBC）表面活性位点的组成，影响过一硫酸盐（PMS）体系中活性物种的生成。使用10 ℃/min的热解升温速率制备的RSDBC活化PMS，在120 min内磺胺甲唑（SMX）的降解率可达99.6%。通过N₂吸附脱附、扫描电子显微镜（SEM）和X射线光电子能谱（XPS）等手段对RSDBC进行表征。结果表明，当升温速率在5~10 ℃/min范围内增大时，比表面积、Fe（Ⅱ）、C=O、吡啶氮和吡咯氮含量均增大。此外，机理探究表明Fe（Ⅱ）、C=O、吡啶氮和吡咯氮可同时促进羟基自由基（·OH）、硫酸根自由基（SO₄^·-）和单线态氧（¹O₂）这3种活性物种的生成，有利于SMX的降解。RSDBC-10/PMS体系中¹O₂为主要的活性物种。

关键词: 污泥-赤泥炭, 热解, 过一硫酸盐, 催化, 降解

Abstract:

Conversion of sewage sludge and red mud into catalysts is an effective strategy for resource utilization of solid waste. The active sites play an important role in the generation of active oxidants. Additionally，the heating rate can regulate the active site composition on the surface of the sewage sludge-red mud catalyst carbon-based catalysts（RSDBC），which affects the production of active oxidants in the peroxymonosulfate（PMS） system. It was found that the degradation efficiency of sulfanilamide（SMX） could reach 99.6% within 120 min when PMS was activated using RSDBC prepared at a temperature rise rate of 10 ℃/min. The RSDBC was characterized by N₂ adsorption-desorption，scanning electron microscopy（SEM） and X-ray photoelectron spectroscopy（XPS）. Research found that the specific surface area，Fe（Ⅱ），C=O，pyridinic N，and pyrrolic N contents increased as the heating rate increased from 5 ℃/min to 10 ℃/min. Furthermore，the mechanistic investigation showed that Fe（Ⅱ），C=O，pyridinic N，and pyrrolic N could simultaneously promote the production of hydroxyl radicals（·OH），sulfate radicals（SO₄^·-） and single oxygen（¹O₂），facilitating the degradation of SMX. ¹O₂ was the main active oxidant in the RSDBC-10/PMS system.

Key words: sewage sludge-red mud char, pyrolysis, peroxymonosulfate, catalysis, degradation

中图分类号:

X703.1

甄志禄, 梁澜, 孙国文, 李宁. 升温速率对污泥-赤泥炭活化过一硫酸盐的影响[J]. 工业水处理, 2023, 43(5): 60-68.

Zhilu ZHEN, Lan LIANG, Guowen SUN, Ning LI. Effect of heating rate on activation of peroxymonosulfate by sewage sludge-red mud char[J]. Industrial Water Treatment, 2023, 43(5): 60-68.

https://www.iwt.cn/CN/Y2023/V43/I5/60

图/表 15

表1 HPLC测定SMX浓度方法

Table 1 The method for determination of SMX concentration via HPLC

时间/min	流速/（mL·min^-1）	A/%	B/%
0	0.5	75	25
1	0.5	75	25
10	0.5	30	70
15	0.5	30	70
15.1	0.5	75	25
20	0.5	75	25

图1 不同热解升温速率下RSDBC的XRD

Fig. 1 XRD patterns of RSDBC under different pyrolysis heating rates

图2 不同热解升温速率下RSDBC的拉曼光谱

Fig. 2 Raman spectra of RSDBC under different pyrolysis heating rates

表2 不同热解升温速率下RSDBC的比表面积和孔分布特性

Table 2 The specific surface area and pore distribution characteristics of RSDBC under different pyrolysis heating rates

样品	比表面积/（m²·g^-1）	总孔体积/（cm³·g^-1）	平均孔径/nm
RSDBC-5	57.77	0.11	7.96
RSDBC-10	65.88	0.13	8.23
RSDBC-20	47.03	0.12	10.89

图3 RSDBC-5、RSDBC-10和RSDBC-20的SEM

Fig. 3 SEM images of RSDBC-5，RSDBC-10 and RSDBC-20

图4 不同热解升温速率下RSDBC的红外光谱

Fig. 4 FTIR spectra of RSDBC under different pyrolysis heating rates

图5 不同热解升温速率下RSDBC和SDBC-10的XPS全谱

Fig. 5 XPS survey of RSDBC under different pyrolysis heating rates and SDBC-10

表3 不同热解升温速率下RSDBC和SDBC-10中元素的原子分数

Table 3 Relative mass fraction of different elements in RSDBC under different pyrolysis and SDBC-10

样品	C原子分数/%	O原子分数/%	N原子分数/%	Fe原子分数/%
SDBC-10	51.15	40.45	4.28	4.12
RSDBC-5	51.93	41.46	2.92	3.69
RSDBC-10	44.60	46.68	4.00	4.70
RSDBC-20	50.30	42.83	2.65	4.22

表4 不同热解升温速率下RSDBC和SDBC-10中C活性位点的相对质量分数

Table 4 Relative mass fraction of different C active sites in RSDBC under different pyrolysis and SDBC-10

样品	C—C/C=C相对质量分数/%	C—N/C—O相对质量分数/%	C=O相对质量分数/%
SDBC-10	22.49	21.72	6.94
RSDBC-5	26.66	15.76	9.51
RSDBC-10	21.35	11.08	12.17
RSDBC-20	27.18	13.97	9.15

表5 不同热解升温速率下RSDBC和SDBC-10中吡啶氮、吡咯氮、石墨氮的相对质量分数

Table 5 Relative mass fraction of pyridinic N，pyrrolic N and graphitic N in RSDBC under different pyrolysis and SDBC-10

样品	吡啶氮相对质量分数/%	吡咯氮相对质量分数/%	石墨氮相对质量分数/%
SDBC-10	1.46	0.36	2.46
RSDBC-5	0.74	0.29	1.87
RSDBC-10	1.41	0.80	1.76
RSDBC-20	0.72	0.35	1.58

表6 不同热解升温速率下RSDBC和SDBC-10中Fe（Ⅱ）和Fe（Ⅲ）的相对质量分数

Table 6 Relative mass fraction of Fe（Ⅱ） and Fe（Ⅲ） in RSDBC under different pyrolysis and SDBC-10

样品	Fe（Ⅱ）相对质量分数/%	Fe（Ⅲ）相对质量分数/%
SDBC-10	1.29	1.77
RSDBC-5	1.22	2.37
RSDBC-10	2.39	1.89
RSDBC-20	1.86	2.03

图6 不同升温速率下RSDBC和SDBC-10活化PMS降解SMX

Fig. 6 SMX degradation by PMS activation with RSDBC under different pyrolysis heating rates and SDBC-10

图7 不同RSDBC/PMS和SDBC-10/PMS体系中SMX的一级动力学常数

Fig. 7 pseudo-first-order kinetic constant in different RSDBC/PMS systems and SDBC-10/PMS system

图8 向3种PMS体系中加入不同猝灭剂后SMX的降解动力学分析

Fig. 8 SMX degradation kinetics with different quenchers in three PMS systems

表7 不同热解升温速率下RSDBC表面活性位点与活性氧化物种释放之间的相关性系数

Table 7 The correlation coefficients between the active oxidants and active sites on RSDBC surface under different pyrolysis heating rates

活性位点	活性氧化物种
活性位点	SO₄^·-	·OH	¹O₂
Fe（Ⅱ）	+0.64	+0.53	+0.75
Fe（Ⅲ）	-0.46	-0.36	-0.58
C—C/C=C	-0.99	-0.99	-0.98
C—N/C—O	-0.81	-0.72	-0.90
C=O	+0.99	+0.99	+0.97
吡啶氮	+0.99	+0.98	+0.99
吡咯氮	+0.97	+0.92	+0.99
石墨氮	+0.04	+0.09	0

参考文献 32

1	WANG Jia， LIAO Zhuwei， IFTHIKAR J，et al. Treatment of refractory contaminants by sludge-derived biochar/persulfate system via both adsorption and advanced oxidation process［J］. Chemosphere，2017，185：754-763． doi:10.1016/j.chemosphere.2017.07.084
2	DIAO Zenghui， DONG Fuxin， YAN Liu，et al. Synergistic oxidation of Bisphenol A in a heterogeneous ultrasound-enhanced sludge biochar catalyst/persulfate process：Reactivity and mechanism［J］. Journal of Hazardous Materials，2020，384：121385． doi:10.1016/j.jhazmat.2019.121385
3	JAWAD A， ZHAN Kun， WANG Haibin，et al. Tuning of persulfate activation from a free radical to a nonradical pathway through the incorporation of non-redox magnesium oxide［J］. Environmental Science & Technology，2020，54（4）：2476-2488． doi:10.1021/acs.est.9b04696
4	WANG Jia， GONG Qing，ALI J，et al. pH-dependent transformation products and residual toxicity evaluation of sulfamethoxazole degradation through non-radical oxygen species involved process［J］. Chemical Engineering Journal，2020，390：124512． doi:10.1016/j.cej.2020.124512
5	MUKIZA E， ZHANG Lingling， LIU Xiaoming，et al. Utilization of red mud in road base and subgrade materials：A review［J］. Resources，Conservation and Recycling，2019，141：187-199． doi:10.1016/j.resconrec.2018.10.031
6	WANG Jia， SHEN Min， WANG Hailong，et al. Red mud modified sludge biochar for the activation of peroxymonosulfate：Singlet oxygen dominated mechanism and toxicity prediction［J］. Science of the Total Environment，2020，740：140388． doi:10.1016/j.scitotenv.2020.140388
7	WANG Yanshan， SONG Yingjin， LI Ning，et al. Tunable active sites on biogas digestate derived biochar for sulfanilamide degradation by peroxymonosulfate activation［J］. Journal of Hazardous Materials，2022，421：126794． doi:10.1016/j.jhazmat.2021.126794
8	ZHAO Bin， O’CONNOR D， ZHANG Junli，et al. Effect of pyrolysis temperature，heating rate，and residence time on rapeseed stem derived biochar［J］. Journal of Cleaner Production，2018，174：977-987． doi:10.1016/j.jclepro.2017.11.013
9	DUAN Xiaoguang， SU Chao， MIAO Jie，et al. Insights into perovskite-catalyzed peroxymonosulfate activation：Maneuverable cobalt sites for promoted evolution of sulfate radicals［J］. Applied Catalysis B：Environmental，2018，220：626-634． doi:10.1016/j.apcatb.2017.08.088
10	LIANG Chenju， SU H W. Identification of sulfate and hydroxyl radicals in thermally activated persulfate［J］. Industrial & Engineering Chemistry Research，2009，48（11）：5558-5562． doi:10.1021/ie9002848
11	REN Wei， CHENG Cheng， SHAO Penghui，et al. Origins of electron-transfer regime in persulfate-based nonradical oxidation processes［J］. Environmental Science & Technology，2022，56（1）：78-97． doi:10.1021/acs.est.1c05374
12	WANG Ronghua， WANG Yan， XU Chaohe，et al. Facile one-step hydrazine-assisted solvothermal synthesis of nitrogen-doped reduced graphene oxide：Reduction effect and mechanisms［J］. RSC Advances，2013，3（4）：1194-1200． doi:10.1039/c2ra21825a
13	CHEN Xiao， OH W D， HU Zhongting，et al. Enhancing sulfacetamide degradation by peroxymonosulfate activation with N-doped graphene produced through delicately-controlled nitrogen functionalization via tweaking thermal annealing processes［J］. Applied Catalysis B：Environmental，2018，225：243-257． doi:10.1016/j.apcatb.2017.11.071
14	ZHU Xiefei， LI Kai， ZHANG Liqiang，et al. Comparative study on the evolution of physicochemical characteristics of biochar produced from bio-oil distillation residue under different induction atmosphere［J］. Energy Conversion and Management，2018，157：288-293． doi:10.1016/j.enconman.2017.12.010
15	LEE J W， KIDDER M， EVANS B R，et al. Characterization of biochars produced from cornstovers for soil amendment［J］. Environmental Science & Technology，2010，44（20）：7970-7974． doi:10.1021/es101337x
16	ANGIN D. Effect of pyrolysis temperature and heating rate on biochar obtained from pyrolysis of safflower seed press cake［J］. Bioresource Technology，2013，128：593-597． doi:10.1016/j.biortech.2012.10.150
17	WANG Shizong， WANG Jianlong. Activation of peroxymonosulfate by sludge-derived biochar for the degradation of triclosan in water and wastewater［J］. Chemical Engineering Journal，2019，356：350-358． doi:10.1016/j.cej.2018.09.062
18	YU Jiangfang， TANG Lin， PANG Ya，et al. Magnetic nitrogen-doped sludge-derived biochar catalysts for persulfate activation：Internal electron transfer mechanism［J］. Chemical Engineering Journal，2019，364：146-159． doi:10.1016/j.cej.2019.01.163
19	孙晨. 改性生物炭对于水中重金属与有机污染物去除的性能与机理［D］. 杭州：浙江大学，2021．
	SUN Chen. Modified biochars for heavy metal and organic pollutant removal：Performance and mechanism［D］. Hangzhou：Zhejiang University，2021．
20	MIAN M M， LIU Guijian， ZHOU Huihui. Preparation of N-doped biochar from sewage sludge and melamine for peroxymonosulfate activation：N-functionality and catalytic mechanisms［J］. Science of the Total Environment，2020，744：140862． doi:10.1016/j.scitotenv.2020.140862
21	LIANG Lan， CHEN Guanyi， LI Ning，et al. Active sites decoration on sewage sludge-red mud complex biochar for persulfate activation to degrade sulfanilamide［J］. Journal of Colloid and Interface Science，2022，608：1983-1998． doi:10.1016/j.jcis.2021.10.150
22	MENG Hong， NIE Chunyang， LI Wenlang，et al. Insight into the effect of lignocellulosic biomass source on the performance of biochar as persulfate activator for aqueous organic pollutants remediation：Epicarp and mesocarp of citrus peels as examples［J］. Journal of Hazardous Materials，2020，399：123043． doi:10.1016/j.jhazmat.2020.123043
23	HU Wanrong， XIE Yi， LU Shan，et al. One-step synthesis of nitrogen-doped sludge carbon as a bifunctional material for the adsorption and catalytic oxidation of organic pollutants［J］. Science of the Total Environment，2019，680：51-60． doi:10.1016/j.scitotenv.2019.05.098
24	MIAO Jie， GENG Wei， ALVAREZ P J J，et al. 2D N-doped porous carbon derived from polydopamine-coated graphitic carbon nitride for efficient nonradical activation of peroxymonosulfate［J］. Environmental Science & Technology，2020，54（13）：8473-8481． doi:10.1021/acs.est.0c03207
25	YIN Renli， GUO Wanqian， WANG Huazhe，et al. Singlet oxygen-dominated peroxydisulfate activation by sludge-derived biochar for sulfamethoxazole degradation through a nonradical oxidation pathway：Performance and mechanism［J］. Chemical Engineering Journal，2019，357：589-599． doi:10.1016/j.cej.2018.09.184
26	LU Jian， ZHOU Yi， LEI Juying，et al. Fe₃O₄/graphene aerogels：A stable and efficient persulfate activator for the rapid degradation of malachite green［J］. Chemosphere，2020，251：126402． doi:10.1016/j.chemosphere.2020.126402
27	潘萌娇，孙姣，贺强，等. 热解终温和加热速率对棉杆热解生物炭的影响研究［J］. 河北工业大学学报，2014，43（5）：60-66．
	PAN Mengjiao， SUN Jiao， HE Qiang，et al. The effect of pyrolysis temperature and heating rate on biochar obtained from pyrolysis of cotton stalk［J］. Journal of Hebei University of Technology，2014，43（5）：60-66．
28	王格格，李刚，陆江银，等. 热解工艺对污泥制备生物炭物理结构的影响［J］. 环境工程学报，2016，10（12）：7289-7293． doi:10.12030/j.cjee.201507124
	WANG Gege， LI Gang， LU Jiangyin，et al. Effect of pyrolysis process on physical structure of biochar［J］. Chinese Journal of Environmental Engineering，2016，10（12）：7289-7293． doi:10.12030/j.cjee.201507124
29	国家市场监督管理总局. 生活饮用水卫生标准［S］．
30	国家环境保护总局. 污水综合排放标准［S］．
31	ZHOU Xinquan， LUO Chunguang， LUO Mengyi，et al. Understanding the synergetic effect from foreign metals in bimetallic oxides for PMS activation：A common strategy to increase the stoichiometric efficiency of oxidants［J］. Chemical Engineering Journal，2020，381：122587． doi:10.1016/j.cej.2019.122587
32	GUAN Chaoting， JIANG Jin， LUO Congwei，et al. Oxidation of bromophenols by carbon nanotube activated peroxymonosulfate （PMS） and formation of brominated products：Comparison to peroxydisulfate（PDS）［J］. Chemical Engineering Journal，2018，337：40-50． doi:10.1016/j.cej.2017.12.083

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