Tetracycline adsorption properties of sludge-based biochar ball-milled co-modified by phosphomolybdic acid-Fe3O4

doi:10.16085/j.issn.1000-6613.2024-0062

Chemical Industry and Engineering Progress ›› 2025, Vol. 44 ›› Issue (1): 583-595.DOI: 10.16085/j.issn.1000-6613.2024-0062

• Resources and environmental engineering • Previous Articles Next Articles

Tetracycline adsorption properties of sludge-based biochar ball-milled co-modified by phosphomolybdic acid-Fe₃O₄

ZHAO Liyang¹(), LI Qian¹, HE Peixi¹, PAN Honghui¹^,²(), LIU Yan¹, LIU Xixiang¹^,²()

^1.Research Center for Soil and Groundwater Environment, Guangxi Colleges and Universities Key Laboratory of Environmental-friendly Materials and New Technology for Carbon Neutralization, Guangxi Key Laboratory of Advanced Structural Materials and Carbon Neutralization, School of Materials and Environment, Guangxi Minzu University, Nanning 530006, Guangxi, China
^2.Guangxi Research Institute of Chemical Industry Co. , Ltd. , Nanning 530001, Guangxi, China

Received:2024-01-09 Revised:2024-03-04 Online:2025-02-13 Published:2025-01-15
Contact: PAN Honghui, LIU Xixiang

磷钼酸-Fe₃O₄球磨共改性污泥基生物炭对四环素的吸附特性

赵丽阳¹(), 李倩¹, 何佩熹¹, 潘鸿辉¹^,²(), 刘艳¹, 刘细祥¹^,²()

^1.广西民族大学材料与环境学院，广西先进结构材料与碳中和重点实验室，广西高校环境友好材料及碳中和新技术重点实验室，土壤与地下水环境研究中心，广西南宁 530006
^2.广西化工研究院有限公司，广西南宁 530001

通讯作者: 潘鸿辉,刘细祥
作者简介:赵丽阳（1996—），女，硕士研究生，研究方向为污泥生物炭制备及应用。E-mail: 240946929@qq.com。
基金资助:
国家自然科学基金(41967030);广西科技基地和人才专项(桂科AD23026173);广西自然科学基金(2020GXNSFAA159170);广西民族大学相思湖青年学者创新团队（2022）;广西民族大学人才启动项目(2022KJQD29);大学生创新创业训练(202310608026)

Abstract

Abstract:

Using residual sludge as raw material, original biochar (BC), ball-milled sludge biochar (FBC), phosphomolybdic acid-modified biochar (PBC), and phosphomolybdic acid-Fe₃O₄ ball-milled co-modified biochar (PFBC) were prepared at a pyrolysis temperature of 200℃ through phosphomolybdic acid (PMA) modification and ball milling method for Fe₃O₄ loading. These adsorbents were employed for the adsorption of tetracycline (TC) from water. The results demonstrated that PFBC exhibited a larger specific surface area and pore volume, and smaller particle size. The co-modification can significantly enhance the surface oxygen functional groups. The spectra of XRD and XPS both indicated that PFBC was successfully loaded with Fe₃O₄. The PFBC achieved a TC removal efficiency of up to 88.7% under optimum conditions with an initial TC concentration of 30mg/L, a PFBC dosage of 0.25g/L, and a pH of 7. The adsorption of TC onto PFBC fitted well with the Langmuir adsorption isotherm and pseudo-second-order kinetic models, which indicated that the adsorption process was a mono molecular layer chemisorption. The saturation adsorption capacity reached 500.0mg/g at 25℃. Even after five recycle run, a removal efficiency of over 63.3% for TC could still be achieved by PFBC from the solution. Its saturation magnetization intensity reached 18.1emu/g, allowing for effective recovery by means of a magnetic apparatus. The mechanisms involved in TC adsorption onto PFBC include pore filling, π-π interactions, electrostatic attraction, and chelation. In conclusion, this study provides a new strategy for the application of modified sludge biochar in antibiotic wastewater treatment.

Key words: sludge biochar, ball milling, co-modification, tetracycline, adsorption

摘要：

以剩余污泥为原料，在200℃的热解温度下，通过磷钼酸（PMA）改性和球磨法负载Fe₃O₄，分别制备原始生物炭（BC）、球磨污泥生物炭（FBC）、磷钼酸改性生物炭（PBC）、磷钼酸-Fe₃O₄球磨共改性生物炭（PFBC），用以吸附水体中的四环素（TC）。结果表明，PFBC具有更大的比表面积、孔体积和更小的粒径，共改性后表面含氧官能团含量明显增强，XRD和XPS表征结果表明PFBC成功负载Fe₃O₄。TC初始浓度为30mg/L、PFBC投加量为0.25g/L、pH=7时，PFBC对TC的去除率可达到88.7%。PFBC对TC的吸附可以很好地用Langmuir吸附等温线和准二级吸附动力学模型拟合，表明吸附过程为单分子层的化学吸附，饱和吸附容量在25℃达到500.0mg/g。在重复利用5次后，PFBC仍能去除溶液中63.3%的TC，其饱和磁化强度达18.1emu/g，可在外加磁场作用下简易回收。PFBC对TC的吸附包括孔隙填充、π-π交互作用、静电吸引、络合作用。本研究为改性污泥生物炭在废水抗生素治理中的应用提供了一种新策略。

关键词: 污泥生物炭, 球磨, 共改性, 四环素, 吸附

CLC Number:

X705

ZHAO Liyang, LI Qian, HE Peixi, PAN Honghui, LIU Yan, LIU Xixiang. Tetracycline adsorption properties of sludge-based biochar ball-milled co-modified by phosphomolybdic acid-Fe₃O₄[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 583-595.

赵丽阳, 李倩, 何佩熹, 潘鸿辉, 刘艳, 刘细祥. 磷钼酸-Fe₃O₄球磨共改性污泥基生物炭对四环素的吸附特性[J]. 化工进展, 2025, 44(1): 583-595.

Figures/Tables 18

样品	参数	O	Si	P	Ca	Fe	Mo
BC	质量分数/%	64	31.2	1.6	0.3	0.9	2
	原子分数/%	76.9	21.3	1	0.3	0.1	0.4
PBC	质量分数/%	52.5	20.8	7.3	1.6	5.9	11.9
	原子分数/%	72.5	16.3	5.2	0.9	2.4	2.7
PFBC	质量分数/%	41.5	8.3	2.8	0.9	38	8.5
	原子分数/%	68.8	7.8	2.4	0.5	18.1	2.4

样品	比表面积 /m²·g^-1	孔体积 /m³·g^-1	平均孔径 /nm	平均粒度
BC	18.3	0.05	28.6	68.5μm
FBC	42.2	0.06	14.4	418.5nm
PBC	40.2	0.14	19.7	111.9μm
PFBC	57.2	0.15	14.6	440.6nm

PBC

PFBC

13.4

10.1

2.0

2.2

24.8

19.7

1.2

1.8

5.9

2.6

1.6

17.5

0.15

0.22

1.85

1.95

1.94

2.13

结合能/eV	特征峰	占比/%
结合能/eV	特征峰	BC	PBC	PFBC
284.8	C—C	60.6	58.5	43.5
286.1	C—OH	19.2	19.5	19.5
286.8	C—O—C	7.2	8.8	14.2
287.8 288.7	C $\overset{}{̿}$ O	6.0	6.4	7.9
287.8 288.7	O—C $\overset{}{̿}$ O	7.0	6.8	14.9
530.9	Fe—O	42.3	40.1	44.0
531.8	C—O	32.2	35.3	26.8
533.1	C $\overset{}{̿}$ O	25.5	24.6	29.2
711.1/724.1	Fe(Ⅱ)	59.6	60.2	63.6
713.5/726.5	Fe(Ⅲ)	40.4	39.8	36.4

结合能/eV	特征峰	占比/%
结合能/eV	特征峰	BC	PBC	PFBC
284.8	C—C	60.6	58.5	43.5
286.1	C—OH	19.2	19.5	19.5
286.8	C—O—C	7.2	8.8	14.2
287.8 288.7	C $\overset{}{̿}$ O	6.0	6.4	7.9
287.8 288.7	O—C $\overset{}{̿}$ O	7.0	6.8	14.9
530.9	Fe—O	42.3	40.1	44.0
531.8	C—O	32.2	35.3	26.8
533.1	C $\overset{}{̿}$ O	25.5	24.6	29.2
711.1/724.1	Fe(Ⅱ)	59.6	60.2	63.6
713.5/726.5	Fe(Ⅲ)	40.4	39.8	36.4

拟合模型	参数	10mg/L	30mg/L	50mg/L
实验吸附量	q_e/mg·g^-1	38.2	112.4	167.7
准一级动力学模型	q_e/mg·g^-1	23.3	88.9	121.5
	k₁/h^-1	0.279	0.220	0.149
	R²	0.973	0.985	0.960
准二级动力学模型	q_m/mg·g^-1	38.5	116.3	166.7
	k₂/g·mg^-1·h^-1	0.047	0.008	0.003
	R²	0.999	0.995	0.990

拟合模型	参数	25℃	35℃	45℃
实验吸附量	q_max/mg·g^-1	491.3	548.5	644.2
Langmuir等温线	q_max/mg·g^-1	500.0	555.6	666.7
	K_L/L·mg^-1	0.035	0.035	0.021
	R²	0.999	0.999	0.996
Freundlich等温线	K_F/mg·g^-1·(L·mg^-1)^1/ⁿ	86.05	73.19	80.39
	1/n	0.307	0.316	0.340
	R²	0.923	0.952	0.974

原料	改性方法	饱和吸附量/mg·g^-1			参考文献
原料	改性方法	25℃	35℃	45℃	参考文献
污泥	H₃PO₄·12MoO₃+球磨	500.0	555.6	666.7	本文
污泥	NaOH+壳聚糖+NH₄Fe(SO₄)₂·12H₂O+(NH₄)₂Fe(SO₄)₂·6H₂O	184.3	199.3	240.3	[44]
污泥	KOH+FeCl₂+FeCl₃	140.7	141.6	139.8	[5]
污泥	ZnCl₂+壳聚糖+FeSO₄·7H₂O+Na₂S·9H₂O	183.0	199.4	223.9	[45]
污泥	ZnCl₂+FeSO₄·7H₂O+Na₂S·9H₂O	174.1	154.6	—	[46]
造纸污泥	未改性	125.2	—	—	[43]
花生壳	CaCl₂	72.3	—	—	[47]
橘子皮	MnCl₂+FeCl₃·6H₂O+FeCl₂·4H₂O	167.5	—	—	[48]
秸秆	KOH	307.8	379.5	491.2	[49]
秸秆	MnCl₂	736.0	876.0	—	[50]
木质纤维素	HCl	1078.9	1901.4	—	[51]

样品	比表面积/m²·g^-1	总孔容/m³·g^-1	平均孔径/nm
PFBC	57.2	0.15	14.6
PFBC-TC	6.0	0.04	17.5

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