Adsorption Characterization of Atrazine in Aqueous Medium on Goethite Biochar Composites

doi:10.16258/j.cnki.1674-5906.2021.10.013

Ecology and Environment ›› 2021, Vol. 30 ›› Issue (10): 2067-2075.DOI: 10.16258/j.cnki.1674-5906.2021.10.013

• Research Articles • Previous Articles Next Articles

Adsorption Characterization of Atrazine in Aqueous Medium on Goethite Biochar Composites

CONG Xin(), LI Yao, WANG Yu, ZHENG Li

College of Environmental Science and Engineering, Liaoning Engineering Technology University, Fuxin 123000, China

Received:2021-09-18 Online:2021-10-18 Published:2021-12-21

生物炭基针铁矿复合材料对水中莠去津吸附特性研究

丛鑫(), 李瑶, 王宇, 郑力

辽宁工程技术大学环境科学与工程学院,辽宁阜新 123000

作者简介:丛鑫（1976年生）,女,教授,博士,研究方向为土壤环境化学和生态修复。E-mail: congxin1800@163.com
基金资助:
国家重点研发计划项目(2019YFC1803800);辽宁工程技术大学学科创新团队资助项目(LNTU20TD-24)

Abstract

Abstract:

Cow dung and rice straw were chosen as raw materials to prepare biochar at 300 ℃ and 500 ℃, respectively. Meanwhile, goethite biochar composites were prepared through co-precipitation of the iron metal ions onto biochar to study the adsorption characterization of atrazine in aqueous medium on biochars and goethite biochar composites. The results of scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis showed that the surface roughness of the composites increased, and the peaks at 2θ=21.2°, 33.4°, 36.6° and 47.6° could be agreed well with the standard othorhombic phase of goethite, which suggested goethite biochar composites were successfully prepared. The study of adsorption kinetics and isotherms showed that the adsorption process of atrazine on biochars was in accordance with quasi-second-order kinetic equations, and the isothermal adsorption process was well fitted to Freundlich model (r²: 0.92-0.996). At 25 ℃, The adsorption capacities of atrazine on the goethite-loaded cow dung biochar prepared at 300 and 500 ℃ was 1.59 and 2.99 times, and the adsorption capacities on the goethite-loaded rice straw biochar was 2.02 and 1.73 times than those of the original biochar, respectively. The analysis of specific surface area and pore structure showed that the specific surface areas of biochar composites were 4.41-20.8 times than those of the original biochar materials. Mesoporous was the main pore structure of the prepared biochar materials. Thermodynamic analysis showed that the adsorption process of atrazine on biochar was spontaneous and endothermic. The biochar prepared from rice straw had better adsorption capacity for atrazine than that prepared from cow dung. The adsorption properties of atrazine on biochars showed that goethite biochar composites had better adsorption capacity for atrazine than the original biochar did. With the increase of preparation temperature, the adsorption capacities of atrazine on biochars increased slightly. The results have certain theoretical significance for the application of biochars and goethite biochar composites in the treatment of wastewater containing atrazine residues.

Key words: goethite biochar composites, atrazine, adsorption characteristics, cow dung biochar, rice straw biochar

摘要：

以牛粪和水稻秸秆为原料,分别在300 ℃和500 ℃条件下制备生物炭,同时通过共沉淀方法制备生物炭基针铁矿复合材料,研究生物炭及生物炭基复合材料对水中莠去津吸附特征。SEM和XRD分析结果表明,复合材料表面粗糙程度增加,2θ在21.2°、33.4°、36.6°、47.6°处出现针铁矿的特征衍射峰,生物炭基针铁矿复合材料制备成功。通过对吸附动力学和等温吸附平衡分析发现,生物炭对莠去津的吸附行为更符合准二级动力学方程,等温吸附过程符合Freundlich模型（r²为0.925—0.996）。在25 ℃条件下,莠去津在300 ℃和500 ℃条件下制备的针铁矿负载牛粪生物炭上的吸附量分别是原生物炭上吸附量的1.59倍和2.99倍,在针铁矿负载水稻秸秆生物炭上的吸附量分别是原生物炭上吸附量的2.02倍和1.73倍。比表面积和孔结构数据显示,生物炭基复合材料的比表面积是原生物炭材料的4.41—20.8倍,制备生物炭材料的孔结构以中孔为主。莠去津在生物炭上的吸附大体表现为吸热的自发过程。对不同材料制备的生物炭及与生物炭基复合材料吸附性能进行对比,结果表明水稻秸秆制备的生物炭对莠去津的吸附性能优于牛粪制备的生物炭,生物炭基针铁矿复合材料对莠去津的吸附效果优于原生物炭。随制备温度的升高,相同材料生物炭对莠去津吸附性能略有增加。研究结果可为生物炭及生物炭基针铁矿复合材料去除水中莠去津的应用提供理论依据。

关键词: 生物炭基针铁矿, 莠去津, 吸附性能, 牛粪生物炭, 水稻秸秆生物炭

CLC Number:

CONG Xin, LI Yao, WANG Yu, ZHENG Li. Adsorption Characterization of Atrazine in Aqueous Medium on Goethite Biochar Composites[J]. Ecology and Environment, 2021, 30(10): 2067-2075.

丛鑫, 李瑶, 王宇, 郑力. 生物炭基针铁矿复合材料对水中莠去津吸附特性研究[J]. 生态环境学报, 2021, 30(10): 2067-2075.

Figures/Tables 8

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生物炭种类 Types of biochar	元素原子百分比 Atomic percentage of element/%				比表面积 Specific surface area/ (m²∙g^-1)	孔结构分析 Pore structure analysis
生物炭种类 Types of biochar	C	O	Fe	S	比表面积 Specific surface area/ (m²∙g^-1)	最可几孔径 Mode pore size/nm	平均孔径 Mean pore size/nm	总孔体积 Total pore volume/(cm³∙g^-1)
N300	69.28	30.21	0.43	0.08	1.995	3.452	9.055	0.0079
N500	73.45	26.48	0.03	0.03	4.437	3.726	14.78	0.0785
J300	89.74	10.22	0.01	0.04	16.11	3.048	4.575	0.0412
J500	50.02	49.48	0.18	0.32	36.06	3.779	11.91	0.0435
GN300	66.28	30.65	2.84	0.22	35.43	3.396	15.83	0.1309
GN500	90.44	8.79	0.66	0.11	92.13	3.398	15.88	0.2086
GJ300	84.57	13.8	1.63	0	154.2	3.402	13.61	0.5416
GJ500	71.35	27.62	0.95	0.08	159.1	3.403	16.39	0.6321

生物炭种类 Types of biochar	元素原子百分比 Atomic percentage of element/%				比表面积 Specific surface area/ (m²∙g^-1)	孔结构分析 Pore structure analysis
生物炭种类 Types of biochar	C	O	Fe	S	比表面积 Specific surface area/ (m²∙g^-1)	最可几孔径 Mode pore size/nm	平均孔径 Mean pore size/nm	总孔体积 Total pore volume/(cm³∙g^-1)
N300	69.28	30.21	0.43	0.08	1.995	3.452	9.055	0.0079
N500	73.45	26.48	0.03	0.03	4.437	3.726	14.78	0.0785
J300	89.74	10.22	0.01	0.04	16.11	3.048	4.575	0.0412
J500	50.02	49.48	0.18	0.32	36.06	3.779	11.91	0.0435
GN300	66.28	30.65	2.84	0.22	35.43	3.396	15.83	0.1309
GN500	90.44	8.79	0.66	0.11	92.13	3.398	15.88	0.2086
GJ300	84.57	13.8	1.63	0	154.2	3.402	13.61	0.5416
GJ500	71.35	27.62	0.95	0.08	159.1	3.403	16.39	0.6321

生物炭类型 Types of biochar	准一级动力学方程 Pseudo first-order kinetic equation			准二级动力学方程 Pseudo second-order kinetic equation			双常数方程 Double-constant equation
生物炭类型 Types of biochar	q_e/(mg∙g^-1)	k₁/h^-1	r²	q_e/(mg∙g^-1)	k₂/(g∙mg^-1∙h^-1)	r²	lna	K_s/(mg∙g^-1∙h^-1)	r²
N300	0.612	0.157	0.962	0.694	0.703	0.990	-1.445	0.313	0.989
N500	0.452	0.211	0.898	0.528	0.513	0.995	-1.347	0.201	0.972
J300	4.973	0.659	0.883	5.573	0.222	0.998	1.126	0.178	0.966
J500	4.454	0.232	0.823	5.125	0.202	0.996	1.067	0.163	0.986
GN300	1.323	0.158	0.978	1.468	0.331	0.992	-0.775	0.344	0.975
GN500	1.529	0.186	0.990	1.677	0.318	0.994	-0.612	0.339	0.968
GJ300	10.82	0.474	0.866	12.21	0.122	0.998	2.095	0.116	0.992
GJ500	8.097	0.237	0.729	9.274	0.112	0.997	1.617	0.178	0.967

生物炭类型 Types of biochar	准一级动力学方程 Pseudo first-order kinetic equation			准二级动力学方程 Pseudo second-order kinetic equation			双常数方程 Double-constant equation
生物炭类型 Types of biochar	q_e/(mg∙g^-1)	k₁/h^-1	r²	q_e/(mg∙g^-1)	k₂/(g∙mg^-1∙h^-1)	r²	lna	K_s/(mg∙g^-1∙h^-1)	r²
N300	0.612	0.157	0.962	0.694	0.703	0.990	-1.445	0.313	0.989
N500	0.452	0.211	0.898	0.528	0.513	0.995	-1.347	0.201	0.972
J300	4.973	0.659	0.883	5.573	0.222	0.998	1.126	0.178	0.966
J500	4.454	0.232	0.823	5.125	0.202	0.996	1.067	0.163	0.986
GN300	1.323	0.158	0.978	1.468	0.331	0.992	-0.775	0.344	0.975
GN500	1.529	0.186	0.990	1.677	0.318	0.994	-0.612	0.339	0.968
GJ300	10.82	0.474	0.866	12.21	0.122	0.998	2.095	0.116	0.992
GJ500	8.097	0.237	0.729	9.274	0.112	0.997	1.617	0.178	0.967

生物炭类型 Types of biochars	温度 Temperature/K	Freundlich Model		$\lg {{q}_{\text{e}}}=\lg {{k}_{\text{f}}}+\frac{1}{\text{n}}\lg {{\rho }_{\text{e}}}$		Langmuir Model	$\frac{1}{{{q}_{\text{e}}}}=\frac{1}{{{Q}_{\text{max}}}}+\frac{1}{{{Q}_{\max }}b}\cdot \frac{1}{{{\rho }_{\text{e}}}}$
生物炭类型 Types of biochars	温度 Temperature/K	n	K_F	r²	K_oc/(L·g^-1）	Q_max/(mg·L^-1）	b	r²
N300	298.15	0.869	0.091	0.991	0.498	8.355	0.009	0.992
	308.15	0.858	0.107	0.995	0.687	8.853	0.009	0.991
	318.15	0.853	0.143	0.995	0.920	10.96	0.010	0.991
N500	298.15	0.650	0.089	0.995	0.673	1.324	0.046	0.988
	308.15	0.584	0.132	0.987	1.033	1.362	0.065	0.977
	318.15	0.544	0.193	0.982	1.492	1.584	0.084	0.973
J300	298.15	0.393	2.090	0.958	12.17	7.823	0.266	0.951
	308.15	0.356	2.677	0.987	15.06	8.379	0.385	0.888
	318.15	0.348	3.505	0.937	19.29	10.11	0.462	0.923
J500	298.15	0.327	2.190	0.925	23.22	6.197	0.462	0.939
	308.15	0.364	2.726	0.940	27.85	8.785	0.363	0.881
	318.15	0.297	3.821	0.937	37.29	9.351	0.682	0.880
GN300	298.15	0.677	0.208	0.995	1.448	3.363	0.045	0.998
	308.15	0.716	0.126	0.996	0.852	2.924	0.030	0.990
	318.15	0.651	0.119	0.992	0.890	1.732	0.048	0.981
GN500	298.15	0.705	0.229	0.989	1.449	4.397	0.038	0.993
	308.15	0.691	0.249	0.993	1.588	4.576	0.038	0.997
	318.15	0.696	0.262	0.992	1.846	5.252	0.034	0.981
GJ300	298.15	0.371	4.378	0.991	21.48	15.42	0.253	0.959
	308.15	0.429	3.228	0.993	17.60	14.20	0.200	0.980
	318.15	0.483	2.278	0.985	12.76	13.04	0.134	0.968
GJ500	298.15	0.413	2.918	0.976	29.57	11.80	0.234	0.984
	308.15	0.414	3.095	0.980	31.00	12.52	0.232	0.954
	318.15	0.374	3.716	0.994	36.04	13.19	0.254	0.924

Adsorption Characterization of Atrazine in Aqueous Medium on Goethite Biochar Composites

生物炭基针铁矿复合材料对水中莠去津吸附特性研究

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References 36

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Types of biochars	Temperature/ K	ΔG⁰/ (kJ∙mol^-1)	ΔH⁰/ (kJ∙mol^-1)	ΔS⁰/ (kJ∙mol^-1∙K^-1)	Types of biochars	Temperature/ K	ΔG⁰/ (kJ∙mol^-1)	ΔH⁰/ (kJ∙mol^-1)	ΔS⁰/ (kJ∙mol^-1∙K^-1)
N300	298.15	-11.15	18.26	0.098	GN300	298.15	-13.23	-22.01	-0.03
	308.15	-11.97				308.15	-12.31
	318.15	-13.12				318.15	-12.65
N500	298.15	-11.13	30.58	0.140	GN500	298.15	-13.47	5.35	0.06
	308.15	-12.51				308.15	-14.07
	318.15	-13.92				318.15	-14.73
J300	298.15	-18.95	20.37	0.132	GJ300	298.15	-20.78	-25.73	-0.02
	308.15	-20.22				308.15	-20.70
	318.15	-21.59				318.15	-20.45
J500	298.15	-19.07	21.89	0.137	GJ500	298.15	-19.78	9.48	0.10
	308.15	-20.27				308.15	-20.59
	318.15	-21.82				318.15	-21.74

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