农膜-秸秆生物质炭对亚甲基蓝的吸附性能

doi:10.19965/j.cnki.iwt.2024-0168

摘要/Abstract

摘要：

为了研究农膜掺杂对秸秆生物质炭材料结构和吸附性能的影响，以聚乙烯农膜和玉米秸秆为原料，无水碳酸钾为改性剂，制备了石墨化生物质炭SPS600-B，通过SEM、TEM、BET、XRD、元素分析等对材料进行了表征，考察了其吸附亚甲基蓝（MB）的性能和机理。研究结果表明SPS600-B高度石墨化，表面具有很多不穿透介孔以及碳微球结构，比表面积达到了821.96 m²/g。在25 ℃、pH=7时，0.2 g/L SPS600-B对100 mg/L MB的去除率为93.2%，吸附容量为466.2 mg/g，经过5次解吸附循环利用，去除率仍可达79.4%。吸附机理研究表明：吸附过程符合准二级动力学模型和Langmuir模型，以化学吸附为主。吸附过程受到包括孔吸附作用、π-π电子作用、静电引力作用和氢键作用等的共同影响，吸附行为属于自发的吸热反应。

关键词: 农膜, 秸秆, 生物质炭, 亚甲基蓝, 吸附

Abstract:

In order to explore the effect of agricultural film doping on the structure and adsorption properties of straw biochar materials, the graphitized biochar of SPS600-B was prepared using waste corn straw mixed with polyethylene agricultural film as raw materials and anhydrous potassium carbonate as modifier. The material was characterized by SEM, TEM, BET, XRD and elemental analysis. The adsorption performance and mechanism for methylene blue(MB) by SPS600-B were investigated. The results showed that SPS600-B was highly graphitized with many non-penetrating pore and carbon microsphere structures on its surface, and the specific surface area was 821.96 m²/g. At 25 ℃ and pH=7, the removal rate of 100 mg/L MB by 0.2 g/L SPS600-B reached 93.2%, and the adsorption capacity was 466.2 mg/g. After 5 cycles of adsorption-desorption recycling, the removal rate of MB could still reach 79.4%. The adsorption mechanism revealed that the adsorption process conformed to the quasi-second-order kinetic model and Langmuir model, which was dominated by chemisorption. The adsorption process was affected by pore adsorption, electrostatic attraction, π-π electron interaction and hydrogen bonding. The adsorption behaviour was a spontaneous adsorption reaction.

Key words: straw, agricultural film, biochar, methylene blue, adsorption

中图分类号:

X703

王庆元, 张彦平, 李一兵, 李芬. 农膜-秸秆生物质炭对亚甲基蓝的吸附性能[J]. 工业水处理, 2025, 45(3): 110-120.

Qingyuan WANG, Yanping ZHANG, Yibing LI, Fen LI. Adsorption of methylene blue by biochar prepared using straw mixed with agricultural film[J]. Industrial Water Treatment, 2025, 45(3): 110-120.

https://www.iwt.cn/CN/Y2025/V45/I3/110

图/表 17

图1 生物质炭的SEM（×20 000倍）以及TEM

Fig.1 SEM（×20 000） and TEM of biochar

表1 SPS600和SPS600-B样品的结构参数

Table 1 Structure parameters of SPS600 and SPS600-B

样品	比表面积/（m²·g^-1）	总孔容/（cm³·g^-1）	平均孔径/nm
SPS600	9.72	0.048 8	17.441 5
SPS600-B	821.96	0.202 4	6.306 7

图2 SPS600和SPS600-B的氮气吸附脱附等温曲线及孔径分布曲线

Fig.2 Adsorption and desorption isotherms and pore size distribution curves of SPS600 and SPS600-B

表2 SPS600和SPS600-B的元素分析以及元素质量比

Table 2 Elemental analysis and elemental mass ratio of SPS600 and SPS600-B

样品	C/%	H/%	N/%	O/%	H/C	O/C	（O+N）/C
SPS600	37.84	1.82	0.28	55.51	0.049	1.46	1.47
SPS600-B	48.78	2.21	0.11	44.9	0.045	0.92	0.92

图3 SPS600和SPS600-B的红外光谱

Fig.3 Infrared spectra of SPS600 and SPS600-B

图4 SPS600和SPS600-B的XRD

Fig.4 XRD of SPS600 and SPS600-B

图5 SPS600-B投加量对吸附MB效果的影响

Fig.5 Effect of SPS600-B dosage on adsorption of MB

图6 MB初始质量浓度对吸附MB的影响

Fig.6 Effect of MB initial mass concentration on adsorption of MB

图7 SPS600-B吸附MB的效果及Zeta电位随pH的变化情况

Fig.7 MB adsorption effect and Zeta potential change of SPS600-B with pH

图8 SPS600-B去除MB的可重复利用性

Fig.8 Reusability of SPS600-B for MB removal

图9 SPS600-B吸附MB的动力学特性

Fig.9 Adsorption kinetics of SPS600-B for MB

表3 SPS600-B吸附MB的动力学特性参数

Table 3 Adsorption kinetics parameters of SPS600-B for MB

准一级反应动力学模型			准二级反应动力学模型			颗粒内扩散模型
q _e/（mg·g^-1）	k ₁	R ²	q _e/（mg·g^-1）	k ₂	R ²	K _d1	C ₁	R ²	K _d2	C ₂	R ²	K _d3	C ₃	R ²
429.82	0.025 3	0.937	454.32	0.002 1	0.997	67.45	13.92	0.982	15.47	298.59	0.936	1.75	443.57	0.909

图10 SPS600-B吸附MB的等温拟合曲线

Fig.10 Adsorption isothermal fitting curre of MB by SPS600-B

表4 SPS600-B吸附MB的等温模型参数

Table 4 Isothermal adsorption characteristics of MB by SPS600-B

Langmuir			Freundlich
K _L	q _m/（mg·g^-1）	R ²	K _F	1/n	R ²
0.001 99	465.51	0.998 9	0.174	0.161	0.969

表5 吸附热力学参数

Table 5 Thermodynamic parameters of adsorption

温度/K	ΔG ⁰/（kJ·mol^-1）	ΔH ⁰/（kJ·mol^-1）	ΔS ⁰/（kJ·mol^-1·K^-1）
298	-11.38	45.93	0.192
308	-13.3
318	-15.23

表6 SPS600-B与其他基于玉米秸秆的吸附剂对MB的吸附能力对比

Table 6 Comparison of the adsorption capacity of SPS600-B and other corn stover-based adsorbents for MB

原材料	改性方法	比表面积/（m²·g^-1）	吸附容量/（mg·g^-1）	参考文献
玉米秸秆	KOH	82.11	222.93	〔28〕
玉米秸秆	H₃PO₄	820.00	330.50	〔29〕
玉米秸秆/污泥	ZnCl₂	769.00	152.80	〔30〕
玉米秸秆	ZnCl₂/微波活化	131.46	236.57	〔31〕
玉米秸秆/农膜	无水K₂CO₃	821.96	466.2	本研究

图11 吸附机理

Fig.11 Adsorption mechanism diagram

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