镁浸渍生物炭吸附氨氮和磷：制备优化和吸附机理

doi:10.11949/0438-1157.20190802

化工学报 ›› 2020, Vol. 71 ›› Issue (4): 1683-1695.DOI: 10.11949/0438-1157.20190802

镁浸渍生物炭吸附氨氮和磷：制备优化和吸附机理

李安玉^1,²(),李双莉^1,²,余碧戈^1,²,马爱英^1,²,周鑫兰^1,²,谢建慧^1,²,蒋艳红^1,²,邓华^1,²()

^1.广西师范大学珍稀濒危动植物生态与环境保护教育部重点实验室，广西桂林 541004
^2.岩溶生态与环境变化研究广西高校重点实验室，广西桂林 541004

收稿日期:2019-07-11 修回日期:2019-10-14 出版日期:2020-04-05 发布日期:2020-04-05
通讯作者: 邓华
作者简介:李安玉（1994—），男，硕士研究生，lianyu@stu.gxnu.edu.cn
基金资助:
广西师范大学珍稀濒危动植物生态与环境保护教育部重点实验室基金项目(ERESEP2019Z07);国家自然科学基金项目(41301343);岩溶生态与环境变化研究广西高校重点实验室基金项目(YRHJ15Z009)

Adsorption of ammonia nitrogen and phosphorus by magnesium impregnated biochar: preparation optimization and adsorption mechanism

Anyu LI^1,²(),Shuangli LI^1,²,Bige YU^1,²,Aiying MA^1,²,Xinlan ZHOU^1,²,Jianhui XIE^1,²,Yanhong JIANG^1,²,Hua DENG^1,²()

^1.Key Laboratory of Ecology of Rare and Endangered Species and Environmental Protection (Guangxi Normal University）, Ministry of Education, Guangxi Normal University, Guilin 541004, Guangxi, China
^2.Key Laboratory of Karst Ecology and Environment Change of Guangxi Department of Education, Guilin 541004, Guangxi, China

Received:2019-07-11 Revised:2019-10-14 Online:2020-04-05 Published:2020-04-05
Contact: Hua DENG

摘要/Abstract

摘要：

利用废弃的木薯杆制备了载镁的生物炭吸附剂。以氨氮、磷为目标污染物，采用控制变量法研究了不同镁盐改性、MgCl₂浓度、碳化温度、固液比和碳化时间对氨氮、磷吸附性能的影响，制备最具吸附性能的载镁木薯秆基生物炭（Mg-BC），进行批量吸附氨氮和磷实验。利用等温模型（Langmuir和Freundlich模型）和动力学模型（准一级动力学、准二级动力学和颗粒内扩散模型）探究其吸附特性，在其吸附特性研究的基础上，运用FTIR、XRD、SEM-EDS、XPS等表征手段对其吸附机理进行探讨。结果表明，Mg-BC对氨氮和磷的吸附过程均符合Freundlich模型和准二级动力学模型，为多分子层的化学吸附，理论饱和吸附量分别为43.48 mg·g^-1和96.00 mg·g^-1。结合表征结果推测，Mg-BC吸附氨氮、磷主要通过官能团作用、络合沉淀和离子交换等多过程协同完成。

关键词: 负载镁, 生物炭, 木薯秸秆, 吸附, 吸附剂, 吸附机制

Abstract:

Magnesium-loaded biochar adsorbent was prepared from waste cassava stalks. The effects of modification of different magnesium salts, MgCl₂ concentration, carbonization temperature, solid-liquid ratio and carbonization time on the adsorption of ammonia-nitrogen and phosphorus were studied using the controlled variable method. Samples of magnesium-loaded cassava stalk-based biochar (Mg-BC) using the process with the best adsorption performance were prepared and batch adsorption experiments for ammonia-nitrogen and phosphorus were carried out. The adsorption characteristics were studied using isothermal models (Langmuir and Freundlich model) and kinetic models (quasi-first-order kinetics, quasi-second-order kinetics and intra-particle diffusion model). The adsorption mechanism was also studied using FTIR, XRD, SEM-EDS and XPS. The results show that the adsorption process of ammonia-nitrogen and phosphorus by Mg-BC conforms to the Freundlich model and quasi-second-order kinetic model, and is multilayer chemisorption. The theoretical saturated adsorption capacities were 43.48 mg·g^-1 and 96.00 mg·g^-1for ammonia-nitrogen and phosphorus respectively. Combined with the characterization results, it is speculated that magnesium-titanium-based biochar (Mg-BC) adsorbs ammonia nitrogen and phosphorus mainly through functional groups, complex precipitation and ion exchange and other processes.

Key words: Mg-loading, biochar, cassava straw, adsorption, sorbent, adsorption mechanism

中图分类号:

X 53

李安玉, 李双莉, 余碧戈, 马爱英, 周鑫兰, 谢建慧, 蒋艳红, 邓华. 镁浸渍生物炭吸附氨氮和磷：制备优化和吸附机理[J]. 化工学报, 2020, 71(4): 1683-1695.

Anyu LI, Shuangli LI, Bige YU, Aiying MA, Xinlan ZHOU, Jianhui XIE, Yanhong JIANG, Hua DENG. Adsorption of ammonia nitrogen and phosphorus by magnesium impregnated biochar: preparation optimization and adsorption mechanism[J]. CIESC Journal, 2020, 71(4): 1683-1695.

图/表 15

图1 单因素控制变量实验

Fig.1 Single factor control variable experiment

图2 Mg-BC在不同pH下对氨氮和磷的吸附效果比较

Fig.2 Comparison of adsorption effects of Mg-BC on ammonia nitrogen and phosphorus at different pH

图3 Mg-BC对氨氮、磷的吸附等温曲线

Fig.3 Adsorption isotherm curves of Mg-BC for ammonia nitrogen and phosphorus

表1 Mg-BC吸附氨氮、磷的等温模型拟合参数

Table 1 Isothermal model fitting parameters of Mg-BC adsorption of ammonia nitrogen and phosphorus

Mg-BC

Langmuir model

Freundlich model

K_L/

(L·mg^-1)

Q_m/

(mg·g^-1)

R²

R²

图4 Mg-BC对氨氮、磷的吸附动力学曲线

Fig.4 Adsorption kinetics of Mg-BC on ammonia nitrogen and phosphorus

表2 Mg-BC吸附氨氮、磷的等温动力学拟合参数

Table 2 Isothermal kinetic parameters of adsorption of ammonia nitrogen and phosphorus by Mg-BC

Mg-BC	Quasi-first-order kinetic			Quasi-second-order kinetic			Intraparticle diffusion
Mg-BC	Q_e/(mg·g^-1)	K₁/min^-1	R²	K₂/(g·(mg·min)^-1)	Q_e/(mg·g^-1)	R²	C/(mg·g^-1)	K₃/(mg·g^-1·min^-0.5)	R²
氨氮	53.89	0.2806	0.9572	0.0022	44.84	0.9979	13.22	2.14	0.8111
磷	19.71	0.0229	0.7174	0.0009	68.97	0.9887	13.02	3.88	0.7537

图5 Mg-BC的物理性质

Fig.5 Physical properties of Mg-BC

表3 Mg-BC的物理性质参数

Table 3 Physical property parameters of Mg-BC

Biochar	BET/(m²·g^-1)	Total pore volume/(cm³·g^-1)	Average aperture/nm	Biochar magnesium content /(g·kg^-1)
Mg-BC	10.33	0.0406	15.71	113.21
BC	4.10	0.0196	9.60	—
Biochar	C/%	H/%	N/%	O/%
Mg-BC	47.13	7.81	0.66	22.41
BC	57.55	8.29	0.24	28.24
Biochar	O/C	H/C	(O+N)/C	(O+H)/C
Mg-BC	0.48	0.17	0.49	0.64
BC	0.49	0.14	0.50	0.63

图6 Mg-BC吸附氨氮、磷前后的FTIR谱图

Fig.6 FTIR spectra of Mg-BC before and after adsorption of ammonia nitrogen and phosphorus

图7 Mg-BC吸附氨氮、磷前后的SEM-EDS对比

Fig.6 Comparison of SEM-EDS before and after adsorption of ammonia nitrogen and phosphorus by Mg-BC

图8 Mg-BC吸附氮、磷前后的XRD谱图

Fig.8 XRD patterns of Mg-BC before and after adsorption of nitrogen and phosphorus

图9 Mg-BC吸附氨氮、磷前后的XPS光谱图

Fig.9 XPS spectra of Mg-BC before and after adsorption of ammonia nitrogen and phosphorus

表4 Mg-BC吸附氨氮、磷前后的XPS全谱图原子占比

Table 4 Atomic ratio of XPS full spectrum before and after Mg-BC adsorption of ammonia nitrogen and phosphorus

Sample	Atomic/%
Sample	P 2p	C 1s	N 1s	O 1s	Mg 1s
Mg-BC	0.35	73.05	1.68	20.72	4.21
Mg-BC+N/P	1.05	78.82	2.28	16.48	1.37

表5 Mg-BC吸附氨氮、磷前后解卷积P 2p、N 1s、C 1s和O 1s的峰拟合参数

Table 5 Peak fitting parameters of deconvoluted P 2p, N 1s, C 1s and O 1s before and after Mg-BC adsorption of ammonia nitrogen and phosphorus

峰	样品	BE/eV	基团	Atomic/%
P 2p	Mg-BC+N/P	135.28	P—O/P—OH/PO	100
N 1s	Mg-BC+N/P	398.39	C—N	20.36
		399.58	C—H₂	62.74
		400.48	C—O—NH₂	16.90
C 1s	Mg-BC	284.98	C—C	61.21
		285.98	C—O—H/C—O—C	31.59
		287.28	CO	7.20
	Mg-BC+N/P	285.08	C—C	84.87
	Mg-BC+N/P	286.08	CO	15.13
O 1s	Mg-BC	531.68	Mg—O—Mg	62.13
	Mg-BC	533.08	Mg—O—P	37.87
	Mg-BC+N/P	531.68	Mg—O—Mg	65.89
		532.98	Mg—O—P/PO	29.79
		533.58	P—OH	4.38

图10 Mg-BC可能的吸附机制

Fig.10 Possible adsorption mechanism of Mg-BC

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镁浸渍生物炭吸附氨氮和磷：制备优化和吸附机理

Adsorption of ammonia nitrogen and phosphorus by magnesium impregnated biochar: preparation optimization and adsorption mechanism

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