镁改性生物炭吸附水和畜禽养殖废水中氮磷的研究

doi:10.19965/j.cnki.iwt.2022-0965

摘要/Abstract

摘要：

畜禽养殖废水中含高浓度的氮、磷污染物，随意排放容易导致水体富营养化。以松木生物炭为原料，氯化镁为改性剂，制备镁改性松木生物炭（MgBC），采用SEM-EDS、XRD、FT-IR和BET对改性前后的材料进行表征。在确定适宜溶液pH的基础上，研究了MgBC对氮和磷的吸附动力学和吸附等温线，并进一步探究MgBC对实际畜禽养殖废水中氮、磷、COD的去除效果。结果表明，在中性条件下，改性剂浓度为2 mol/L时制备的MgBC对氮和磷的吸附效果较好，对氮和磷的理论平衡吸附量分别为24.70 mg/g和97.52 mg/g；准二级动力学模型可以更好地描述镁改性松木生物炭在模拟废水中的吸附过程，Langmuir方程的拟合程度更高；对实际畜禽养殖废水中氮、磷、COD的去除率分别为10.04%、74.82%、37.91%。

关键词: 松木生物炭, 镁改性, 氮磷吸附, 畜禽养殖废水

Abstract:

The uncontrolled discharge of high concentrations of nitrogen and phosphorus in livestock and poultry wastewater will easily lead to eutrophication of surface waters. A type of magnesium-modified pine biochar （MgBC） was prepared by using pine biochar as raw material and magnesium chloride as modifier. The materials before and after modification were characterized by SEM-EDS，XRD，FT-IR and BET. After the appropriate pH was determined，the adsorption kinetics and adsorption isotherms of MgBC on nitrogen and phosphorus were studied，and the removal performance of MgBC on nitrogen，phosphorus and COD in actual livestock and poultry breeding wastewater was further explored. The results showed that under neutral conditions，the MgBC prepared with 2 mol/L MgCl₂ as modifier exhibited better adsorption effect on nitrogen and phosphorus，and the theoretical equilibrium adsorption capacities for nitrogen and phosphorus were 24.70 mg/g and 97.52 mg/g，respectively. The pseudo-second-order kinetic model could better describe the adsorption process of magnesium-modified pine biochar in simulated wastewater，and the Langmuir equation fitted the adsorption isotherm better. In addition，the removal rates of nitrogen，phosphorus and COD in the actual livestock and poultry breeding wastewater were 10.04%，74.82% and 37.91%.

Key words: pine biochar, magnesium modification, nitrogen and phosphorus adsorption, livestock and poultry breeding wastewater

中图分类号:

X703.1

唐鑫磊, 邢涛, 夏金雨, 周正伟. 镁改性生物炭吸附水和畜禽养殖废水中氮磷的研究[J]. 工业水处理, 2023, 43(9): 144-152.

Xinlei TANG, Tao XING, Jinyu XIA, Zhengwei ZHOU. Adsorption of nitrogen and phosphorus in water and livestock and poultry wastewater by magnesium-modified biochar[J]. Industrial Water Treatment, 2023, 43(9): 144-152.

https://www.iwt.cn/CN/Y2023/V43/I9/144

图/表 14

图1 MgCl₂浓度对镁改性生物炭吸附氮和磷的影响

Fig. 1 Influence of MgCl₂ on the adsorption of nitrogen and phosphorus by modified biochar

图2 BC和MgBC的SEM、EDS

Fig.2 SEM，EDS images of BC and MgBC

图3 改性前后生物炭材料的XRD

Fig. 3 XRD of BC and MgBC

图4 改性前后松木生物炭的FT-IR光谱

Fig. 4 FT-IR of BC and MgBC

图5 MgBC的N₂吸附脱附曲线

Fig. 5 N₂ adsorption-desorption curve of MgBC

表1 MgBC的表面结构特征

Table 1 The surface structural characteristics of the MgBC

样品	比表面积/（m²·g^-1）	孔容/（cm³·g^-1）	平均孔径/nm
BC	1.39	0.004 0	11.47
MgBC	388.26	0.175 9	1.81

图6 溶液pH对MgBC吸附磷酸盐和氨氮性能的影响

Fig. 6 Effect of solution pH on nitrogen and phosphorus adsorption by MgBC

图7 MgBC吸附氮、磷拟合吸附动力学模型

Fig.7 Nitrogen and phosphorus adsorption by the MgBC and the adsorption data fitted by the kinetic models

表2 MgBC的吸附动力学模型拟合参数

Table 2 Kinetic constants of nitrogen and phosphorus adsorption by MgBC

吸附质

准一级动力学模型

准二级动力学模型

Q _cal/

（g·mg^-1）

k ₁/h^-1

R ²

q _e/

（g·mg^-1）

k ₂/

（g·mg^-1·h^-1）

图8 MgBC吸附氮、磷拟合吸附等温线

Fig.8 Adsorption isotherms of nitrogen and phosphorus by MgBC

表3 MgBC的吸附等温线模型拟合参数

Table 3 Adsorption isotherm constants of nitrogen and phosphorus adsorption by MgBC

吸附质	Langmuir			Freundlich
吸附质	q _m/（mg·g^-1）	K _L/（L·mg^-1）	R ²	K _F	1/n	R ²
氨氮	24.70	0.008	0.989	0.66	0.608	0.974
磷酸盐	97.52	0.015	0.965	3.96	0.586	0.934

图9 pH对MgBC处理畜禽养殖废水中污染物的影响

Fig. 9 Effect of pH on the treatment of pollutants in livestock and poultry breeding wastewater by MgBC

图10 MgBC投加量对畜禽养殖废水中污染物的去除效果

Fig. 10 Effect of MgBC dosage on the removal of pollutants from livestock and poultry breeding wastewater

表4 MgBC与其他吸附剂材料对比

Table 4 Comparison of capacity between MgBC with other adsorbent materials

吸附剂	理论最大吸附量/（mg·g^-1）		去除率/%
吸附剂	氨氮	总磷	氨氮	总磷	COD
La-HM^〔28〕	—	11.63~21.71	—	—	—
生物质半焦^〔29〕	—	—	7.10	31.00	12.30
改性赤泥^〔30〕	6.10	1.08	39.89	37.49	85.56
B400^〔31〕	—	18.21	—	—	—
La-RHBC₉ ^〔32〕	—	45.62	—	—	—
La-201^〔33〕	—	57.4	—	—	—
Z-P^〔34〕	13.56	—	—	—	—
NaCl改性沸石^〔35〕	13.21	—	—	—	—
HBC^〔36〕	—	—	20.94	20.67	17.09
CFC^〔37〕	—	70.90	—	—	—
本研究MgBC	24.70	97.52	10.04	74.85	37.91

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