热解时间对污泥生物炭活化过硫酸盐的影响研究

doi:10.11949/0438-1157.20211848

摘要/Abstract

摘要：

污泥热解制备生物炭是一种污泥有效处理处置与资源化利用方法。通过控制热解时间，调控污泥生物炭表面的活性位点，改变过一硫酸盐(PMS)体系中的活性物种组成，可实现环丙沙星(CIP)的高效降解。研究发现，热解温度为700℃、热解时间为120 min时，污泥生物炭具有较高的PMS活化性能，对CIP的去除率近90%。机理探究表明，¹O₂在体系中发挥主要作用。C $? ?????$ O、吡咯氮和—OH位点有利于¹O₂产生，C—O、吡啶氮、晶格氧和Fe位点促进^?OH和SO₄^?-释放，石墨氮可促进PMS活化产生SO₄^?-。

关键词: 热解, 污泥, 生物炭, 过硫酸盐

Abstract:

Biochar production by sewage sludge pyrolysis is an effective approach for sludge treatment and resource utilization. By controlling the pyrolysis time, regulating the active sites on the surface of sludge biochar, and changing the composition of active species in the peroxymonosulfate (PMS) system, the efficient degradation of ciprofloxacin (CIP) can be achieved. Research found that the sludge-derived biochar exhibited high PMS activation performance, achieving nearly 90% removal of CIP at pyrolysis time of 120 min and pyrolysis temperature of 700℃. The mechanism exploration showed that ¹O₂ played a major role in the system. The C $? ?????$ O, pyrrolic N and —OH sites might accelerate the production of ¹O₂. Besides, C—O, pyridine N, lattice oxygen and Fe sites promoted the release of ^?OH and SO₄^?-. Graphite N played a positive role in PMS activation to produce SO₄^?-.

Key words: pyrolysis, sludge, biochar, peroxymonosulfate

中图分类号:

X 52

陈冠益, 童图军, 李瑞, 王燕杉, 颜蓓蓓, 李宁, 侯立安. 热解时间对污泥生物炭活化过硫酸盐的影响研究[J]. 化工学报, 2022, 73(5): 2111-2119.

Guanyi CHEN, Tujun TONG, Rui LI, Yanshan WANG, Beibei YAN, Ning LI, Li'an HOU. Influence of pyrolysis time on sludge-derived biochar performance for peroxymonosulfate activation[J]. CIESC Journal, 2022, 73(5): 2111-2119.

图/表 9

表1 UHPLC-MS/MS流动相配比

Table 1 UHPLC-MS/MS parameters

时间/min	流速/(ml/min)	A/%(体积)	B/%(体积)
0	0.3	93	7
1	0.3	93	7
20	0.3	50	50
25	0.3	93	7
30	0.3	93	7

图1 不同热解时间下污泥生物炭的XPS全谱

Fig.1 XPS survey spectra of SSB prepared at different pyrolysis time

表2 不同热解时间下污泥生物炭表面活性位点相对含量

Table 2 Relative amount of functional active sites in SSB prepared at different pyrolysis time

位点	含量/%
位点	30 min	120 min	180 min	300 min
C—C/C $? ?????$ C	29.5	29.2	29.9	29.0
C—O	13.0	12.8	12.1	11.3
C—N	4.6	7.6	7.8	6.5
C $? ?????$ O	4.6	3.5	5.1	4.1
吡啶氮	1.1	1.1	0.9	0.8
吡咯氮	1.3	0.3	0.8	1.1
石墨氮	1.3	2.9	2.1	2.1
氧化氮	1.3	0.7	0.5	0.5
晶格氧	11.1	10.3	9.9	9.7
—OH	14.0	14.3	14.4	14.5
C $? ?????$ O	14.8	13.8	13.0	17.1
Fe(0)	0.1	0.1	0.1	0.1
Fe(Ⅱ)	1.3	1.5	1.6	1.6
Fe(Ⅲ)	2.0	1.9	1.8	1.6

表2 不同热解时间下污泥生物炭表面活性位点相对含量

Table 2 Relative amount of functional active sites in SSB prepared at different pyrolysis time

位点	含量/%
位点	30 min	120 min	180 min	300 min
C—C/C $? ?????$ C	29.5	29.2	29.9	29.0
C—O	13.0	12.8	12.1	11.3
C—N	4.6	7.6	7.8	6.5
C $? ?????$ O	4.6	3.5	5.1	4.1
吡啶氮	1.1	1.1	0.9	0.8
吡咯氮	1.3	0.3	0.8	1.1
石墨氮	1.3	2.9	2.1	2.1
氧化氮	1.3	0.7	0.5	0.5
晶格氧	11.1	10.3	9.9	9.7
—OH	14.0	14.3	14.4	14.5
C $? ?????$ O	14.8	13.8	13.0	17.1
Fe(0)	0.1	0.1	0.1	0.1
Fe(Ⅱ)	1.3	1.5	1.6	1.6
Fe(Ⅲ)	2.0	1.9	1.8	1.6

图2 在不同热解时间下制备污泥生物炭活化PMS对CIP的去除率

Fig.2 CIP removal efficiency in PMS systems with SSB prepared with different pyrolysis time

图3 SSB-120/PMS体系中?OH和SO4?-（a），1O2（b）在5、10和30 min的ESR谱图及有无SSB-120条件下1O2在PMS体系中的强度（c）

Fig.3 ESR spectra of ?OH and SO4?- (a), 1O2 (b) in 5, 10 and 30 min in SSB-120/PMS system and 1O2 in 5 min with/without SSB-120 in PMS system (c)

图4 不同热解时间制备的SSB在甲醇[(a),(d)]，叔丁醇[(b),(e)]和L-组氨酸[(c),(f)]捕捉剂作用下活化PMS降解CIP的性能和氧化反应速率常数

Fig.4 CIP degradation efficiency and reaction rate constant during oxidation process catalyzed by SSB prepared under different pyrolysis time with methanol [(a),(d)], TBA [(b),(e)] and L-histidine [(c),(f)]

图5 不同热解时间制备的SSB活化PMS体系ROS贡献度

Fig.5 Contribution of ROSs in PMS systems with SSB prepared under different pyrolysis time

图6 污泥生物炭表面位点与PMS体系中ROSs贡献度之间的相关性

Fig.6 Correlation coefficients between the active sites of SSB and contribution of ROSs in PMS systems

图7 CIP降解路径

Fig.7 Degradation pathway of CIP

参考文献 30

1	Antoniou M G, Cruz A A, Dionysiou D D. Degradation of microcystin-LR using sulfate radicals generated through photolysis, thermolysis and e^- transfer mechanisms[J]. Applied Catalysis B: Environmental, 2010, 96(3/4): 290-298.
2	Ouyang D, Chen Y, Yan J C, et al. Activation mechanism of peroxymonosulfate by biochar for catalytic degradation of 1, 4-dioxane: important role of biochar defect structures[J]. Chemical Engineering Journal, 2019, 370: 614-624.
3	Yang Z, Wang Z W, Liang G W, et al. Catalyst bridging-mediated electron transfer for nonradical degradation of bisphenol A via natural manganese ore-cornstalk biochar composite activated peroxymonosulfate[J]. Chemical Engineering Journal, 2021, 426: 131777.
4	Ghanbari F, Moradi M. Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: review[J]. Chemical Engineering Journal, 2017, 310: 41-62.
5	Gao Y, Wang Q, Ji G Z, et al. Degradation of antibiotic pollutants by persulfate activated with various carbon materials[J]. Chemical Engineering Journal, 2022, 429: 132387.
6	Xing J, Xu G R, Li G B. Comparison of pyrolysis process, various fractions and potential soil applications between sewage sludge-based biochars and lignocellulose-based biochars[J]. Ecotoxicology and Environmental Safety, 2021, 208: 111756.
7	Wang X P, Gu L, Zhou P, et al. Pyrolytic temperature dependent conversion of sewage sludge to carbon catalyst and their performance in persulfate degradation of 2-naphthol[J]. Chemical Engineering Journal, 2017, 324: 203-215.
8	Yu J F, Tang L, Pang Y, et al. Hierarchical porous biochar from shrimp shell for persulfate activation: a two-electron transfer path and key impact factors[J]. Applied Catalysis B: Environmental, 2020, 260: 118160.
9	李辉, 吴晓芙, 蒋龙波, 等. 城市污泥脱水干化技术进展[J]. 环境工程, 2014, 32(11): 102-107, 101.
	Li H, Wu X F, Jiang L B, et al. Progress on the dewatering and drying technology of municipal sludge[J]. Environmental Engineering, 2014, 32(11): 102-107, 101.
10	向晓黎, 党富民, 罗力力, 等. 城市污水污泥成分测定及资源化利用途径可行性研究: 以新疆石河子市为例[J]. 农产品加工, 2015(6): 51-53, 57.
	Xiang X L, Dang F M, Luo L L, et al. Composition determined and feasibility study on resource utilization way of sewage sludge: taking Shihezi city for example[J]. Farm Products Processing, 2015(6): 51-53, 57.
11	Bai X, Zhang Y C, Shi J, et al. A new application pattern for sludge-derived biochar adsorbent: ideal persulfate activator for the high-efficiency mineralization of pollutants[J]. Journal of Hazardous Materials, 2021, 419: 126343.
12	Liu C, Chen L W, Ding D H, et al. From rice straw to magnetically recoverable nitrogen doped biochar: efficient activation of peroxymonosulfate for the degradation of metolachlor[J]. Applied Catalysis B: Environmental, 2019, 254: 312-320.
13	Zang T C, Wang H, Liu Y H, et al. Fe-doped biochar derived from waste sludge for degradation of rhodamine B via enhancing activation of peroxymonosulfate[J]. Chemosphere, 2020, 261: 127616.
14	Graat P C J, Somers M A J. Simultaneous determination of composition and thickness of thin iron-oxide films from XPS Fe 2p spectra[J]. Applied Surface Science, 1996, 100/101: 36-40.
15	Keller P, Strehblow H H. XPS investigations of electrochemically formed passive layers on Fe/Cr-alloys in 0.5 M H₂SO₄ [J]. Corrosion Science, 2004, 46(8): 1939-1952.
16	Li X W, Liu X T, Lin C Y, et al. Catalytic oxidation of contaminants by Fe⁰ activated peroxymonosulfate process: Fe(Ⅳ) involvement, degradation intermediates and toxicity evaluation[J]. Chemical Engineering Journal, 2020, 382: 123013.
17	Fang G D, Liu C, Gao J, et al. Manipulation of persistent free radicals in biochar to activate persulfate for contaminant degradation[J]. Environmental Science & Technology, 2015, 49(9): 5645-5653.
18	Yu Y, Li N, Lu X K, et al. Co/N co-doped carbonized wood sponge with 3D porous framework for efficient peroxymonosulfate activation: performance and internal mechanism[J]. Journal of Hazardous Materials, 2022, 421: 126735.
19	Chen X, Zhou J, Yang H W, et al. PMS activation by magnetic cobalt-N-doped carbon composite for ultra-efficient degradation of refractory organic pollutant: mechanisms and identification of intermediates[J]. Chemosphere, 2022, 287: 132074.
20	Kohantorabi M, Giannakis S, Moussavi G, et al. An innovative, highly stable Ag/ZIF-67@GO nanocomposite with exceptional peroxymonosulfate (PMS) activation efficacy, for the destruction of chemical and microbiological contaminants under visible light[J]. Journal of Hazardous Materials, 2021, 413: 125308.
21	Wang L H, Xu H D, Jiang N, et al. Trace cupric species triggered decomposition of peroxymonosulfate and degradation of organic pollutants: Cu(Ⅲ) being the primary and selective intermediate oxidant[J]. Environmental Science & Technology, 2020, 54(7): 4686-4694.
22	Wang Y B, Cao D, Zhao X. Heterogeneous degradation of refractory pollutants by peroxymonosulfate activated by CoO _x -doped ordered mesoporous carbon[J]. Chemical Engineering Journal, 2017, 328: 1112-1121.
23	Rodgers M A J. The relaxation of O₂(¹Δ_g) in condensed systems[J]. Journal of Photochemistry, 1984, 25(2/3/4): 127-129.
24	Yun E T, Lee J H, Kim J, et al. Identifying the nonradical mechanism in the peroxymonosulfate activation process: singlet oxygenation versus mediated electron transfer[J]. Environmental Science & Technology, 2018, 52(12): 7032-7042.
25	Wang S Z, Wang J L. Synergistic effect of PMS activation by Fe⁰@Fe₃O₄ anchored on N, S, O co-doped carbon composite for degradation of sulfamethoxazole[J]. Chemical Engineering Journal, 2022, 427: 131960.
26	Zhou Y B, Zhang Y L, Hu X M. Novel zero-valent Co-Fe encapsulated in nitrogen-doped porous carbon nanocomposites derived from CoFe₂O₄@ZIF-67 for boosting 4-chlorophenol removal via coupling peroxymonosulfate[J]. Journal of Colloid and Interface Science, 2020, 575: 206-219.
27	Li J, Wan Y J, Li Y J, et al. Surface Fe(Ⅲ)/Fe(Ⅱ) cycle promoted the degradation of atrazine by peroxymonosulfate activation in the presence of hydroxylamine[J]. Applied Catalysis B: Environmental, 2019, 256: 117782.
28	Dai H W, Zhou W J, Wang W. Co/N co-doped carbonaceous polyhedron as efficient peroxymonosulfate activator for degradation of organic pollutants: role of cobalt[J]. Chemical Engineering Journal, 2021, 417: 127921.
29	Chen X, Oh W D, Hu Z T, 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.
30	Yang S S, Duan X D, Liu J Q, et al. Efficient peroxymonosulfate activation and bisphenol A degradation derived from mineral-carbon materials: key role of double mineral-templates[J]. Applied Catalysis B: Environmental, 2020, 267: 118701.

[1]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[2]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[3]	刘春雨, 周桓宇, 马跃, 岳长涛. CaO调质含油污泥干燥特性及数学模型[J]. 化工学报, 2023, 74(7): 3018-3027.
[4]	屈园浩, 邓文义, 谢晓丹, 苏亚欣. 活性炭/石墨辅助污泥电渗脱水研究[J]. 化工学报, 2023, 74(7): 3038-3050.
[5]	杨峥豪, 何臻, 常玉龙, 靳紫恒, 江霞. 生物质快速热解下行式流化床反应器研究进展[J]. 化工学报, 2023, 74(6): 2249-2263.
[6]	陈宇豪, 陈晓平, 马吉亮, 梁财. 市政污泥回转窑焚烧气态污染物排放特性研究[J]. 化工学报, 2023, 74(5): 2170-2178.
[7]	张兰河, 赖青燚, 王铁铮, 关潇卓, 张明爽, 程欣, 徐小惠, 贾艳萍. H₂O₂对SBR脱氮效率和污泥性能的影响[J]. 化工学报, 2023, 74(5): 2186-2196.
[8]	李瑞康, 何盈盈, 卢维鹏, 王园园, 丁皓东, 骆勇名. 电化学强化钴基阴极活化过一硫酸盐的研究[J]. 化工学报, 2023, 74(5): 2207-2216.
[9]	衣思敏, 马亚丽, 刘伟强, 张金帅, 岳岩, 郑强, 贾松岩, 李雪. 微晶菱镁矿蒸氨及水化动力学研究[J]. 化工学报, 2023, 74(4): 1578-1586.
[10]	闫新龙, 黄志刚, 胡清勋, 张新, 胡晓燕. Cu/Co掺杂多孔炭活化过硫酸盐降解水中硝基酚研究[J]. 化工学报, 2023, 74(3): 1102-1112.
[11]	徐银, 蔡洁, 陈露, 彭宇, 刘夫珍, 张晖. 异相可见光催化耦合过硫酸盐活化技术在水污染控制中的研究进展[J]. 化工学报, 2023, 74(3): 995-1009.
[12]	陈瑞哲, 程磊磊, 顾菁, 袁浩然, 陈勇. 纤维增强树脂复合材料化学回收技术研究进展[J]. 化工学报, 2023, 74(3): 981-994.
[13]	张娜, 潘鹤林, 牛波, 张亚运, 龙东辉. 酚醛树脂热裂解反应机理的密度泛函理论研究[J]. 化工学报, 2023, 74(2): 843-860.
[14]	姜家豪, 黄笑乐, 任纪云, 朱正荣, 邓磊, 车得福. 生物炭吸附溶液中Pb²⁺的定性及定量研究[J]. 化工学报, 2023, 74(2): 830-842.
[15]	郝泽光, 张乾, 高增林, 张宏文, 彭泽宇, 杨凯, 梁丽彤, 黄伟. 生物质与催化裂化油浆共热解协同作用研究[J]. 化工学报, 2022, 73(9): 4070-4078.