Influence of pyrolysis time on sludge-derived biochar performance for peroxymonosulfate activation

doi:10.11949/0438-1157.20211848

Abstract

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

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

CLC Number:

X 52

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.

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.

Figures/Tables 9

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

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

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

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

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

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)

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)]

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

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

Fig.7 Degradation pathway of CIP

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