富Ca香菇菌渣基生物炭对含磷废水处理性能的研究

doi:10.11949/0438-1157.20220916

摘要/Abstract

摘要：

为了寻求食用菌菌渣合理的资源化利用途径和开发绿色、高效的除磷吸附剂，以香菇菌渣(mushroom residue， MR)为原料，将其在800、900和1000℃下碳化制备生物炭后用于含磷废水的处理(MR-800C、MR-900C和MR-1000C)。理化特性分析显示，该生物炭富含K、Na、Ca和Mg等矿物质，尤其是Ca，其含量高达4328.43~4919.38 mmol/kg。Ca在生物炭中主要以CaCO₃的形式存在，随着热解温度升高，部分被分解为CaO。另外，生物炭还具有较高的pH_pzc（11.86~12.04）、发达的孔隙结构(比表面积为167.56~223.80 m²/g)和丰富的表面官能团(如C $̿$ O、C $̿$ C、C—O、Ca—O等)。在磷的吸附过程中，生物炭对磷的吸附量服从MR-800C< MR-900C< MR-1000C，且均可被Langmuir吸附等温线模型和准二级动力学模型很好拟合，即该吸附过程为化学作用主导的单层吸附。MR-800C、MR-900C和MR-1000C对磷的理论最大吸附量分别为104.17、121.95和128.21 mg/g。静电作用、孔填塞、配位作用及CaO所引起的沉淀作用［形成CaHPO₄和Ca₅(PO₄)₃（OH）］在该过程中起着重要作用。结果表明，食用菌菌渣可被开发作为低廉、高效的除磷吸附材料。

关键词: 食用菌菌渣, Ca, 生物炭, 磷, 吸附

Abstract:

In order to seek a reasonable way for the utilization of edible fungi residue and develop a green and high-efficient adsorbent for the treatment of phosphorus-containing wastewater, mushroom residue (MR) was employed as a raw material to prepare biochars under 800, 900 and 1000℃, and the adsorption capability of the biochars was investigated. It is found that the biochars are abundant in minerals, such as K, Na, Ca and Mg. Particularly, the content of Ca in the biochars are 4328.43—4919.38 mmol/kg and the Ca existed in biochars are mainly in the form of CaCO₃. The increase of pyrolysis temperature results in the decomposition of part of CaCO₃ into CaO. Moreover, the biochars possess relatively higher pH_pzc of 11.86—12.04, developed pore structure with a specific surface area of 167.56—223.80 m²/g and abundant surface functional groups, such as C $̿$ O, C $̿$ C, C—O, Ca—O, as well. The adsorption of phosphate onto the biochars is in the order of MR-800C< MR-900C< MR-1000C and the adsorption processes can be well fitted by Langmuir model and pseudo-second-order model, indicating that the adsorption of phosphate using the bicohars are dominated by a chemical and homogeneous monolayer adsorption process. The theoretical maximum adsorption capacity of MR-800C, MR-900C and MR-1000C calculated from the Langmuir model are 104.17, 121.95 and 128.21 mg/g. Electrostatic interaction, complexation, and precipitation caused by CaO in the forms of CaHPO₄and Ca₅(PO₄)₃(OH) are responsible for the adsorption of phosphate using the biochars. The results of this study indicate that edible fungus residue can be developed as an inexpensive and efficient adsorption material for phosphorus removal.

Key words: edible fungi residue, Ca, biochar, phosphate, adsorption

中图分类号:

X 712

秦坤, 李佳乐, 王章鸿, 张会岩. 富Ca香菇菌渣基生物炭对含磷废水处理性能的研究[J]. 化工学报, 2022, 73(11): 5263-5274.

Kun QIN, Jiale LI, Zhanghong WANG, Huiyan ZHANG. Biochars derived from Ca-rich mushroom residue for phosphorus-containing wastewater treatment[J]. CIESC Journal, 2022, 73(11): 5263-5274.

图/表 16

图1 生物炭的SEM图像

Fig.1 SEM images of biochars

表1 生物炭的工业分析及矿物组分分析

Table 1 Proximate analysis and minerals of biochars

项目	MR-800C	MR-900C	MR-1000C
pH	11.98	11.95	11.83
pH_pzc	11.86	12.04	11.88
水分/%	1.17	1.07	1.04
灰分/%	55.03	54.82	60.34
可燃分/%	43.80	44.11	38.62
K/(mmol/kg)	762.34	650.87	738.43
Na/(mmol/kg)	136.44	145.56	167.98
Ca/(mmol/kg)	4328.43	4576.84	4919.38
Mg/(mmol/kg)	488.46	495.87	496.76
Fe/(mmol/kg)	123.24	138.43	164.87
Ni/(mmol/kg)	11.45	10.76	12.65
Pb/(mmol/kg)	0.65	0.95	0.84
Cd/(mmol/kg)	0.12	0.42	0.46

图2 生物炭的XRD谱图

Fig.2 XRD patterns of biochars

图3 生物炭的FT-IR谱图

Fig.3 FT-IR spectra of biochars

图4 生物炭的吸附-脱附曲线及孔径分布

Fig.4 Adsorption-desorption curves and pore size distribution of biochars

图5 磷溶液初始浓度对生物炭吸附量(a)及去除率(b)的影响

Fig.5 Effect of phosphate initial concentration on the adsorption capacity (a) and removal rate (b) of biochars

图6 吸附时间对生物炭吸附磷的影响

Fig.6 Effect of adsorption time on the adsorption of phosphate by biochars

图7 吸附温度对生物炭吸附磷的影响

Fig.7 Effect of adsorption temperature on the adsorption of phosphate by biochars

图8 溶液pH对生物炭吸附磷的影响

Fig.8 Effect of solution pH on the adsorption of phosphate by biochars

图9 吸附等温线线性拟合

Fig.9 Linear fitting for adsorption data using adsorption isotherm models

表 2 吸附等温线参数

Table 2 Isotherm parameters of phosphate adsorption by biochars derived from adsorption isotherm models

样品	Langmuir模型			Freundlich模型
样品	Q_m/(mg/g)	K_L/(L/mg)	R²	K_f/(mg^(1-ⁿ⁾·L ⁿ /g)	n	R²
MR-800C	104.17	0.01	0.926	25.73	5.55	0.840
MR-900C	121.95	0.01	0.903	34.42	6.74	0.792
MR-1000C	128.21	0.01	0.891	37.39	6.98	0.803

图10 吸附动力学模型线性拟合

Fig.10 Linear fitting of experimental data using adsorption kinetic models

表 3 吸附动力学参数

Table 3 Kinetic parameters of phosphate adsorption by biochars fitting with adsorption kinetic models

样品	q_e,exp/(mg/g)	准一级动力学模型			准二级动力学模型
样品	q_e,exp/(mg/g)	k₁/(1/h)	q_e/(mg/g)	R²	k₂/(g/(mg·h))	q_e/(mg/g)	R²
MR-800C	40.58	8.31	2.04	0.237	145.08	39.81	0.998
MR-900C	48.90	9.90	2.01	0.524	5.70	49.16	0.996
MR-1000C	48.69	9.06	1.99	0.509	64.80	49.38	0.997

表4 吸附热力学参数

Table 4 Thermodynamic parameters of phosphate adsorption by biochars

样品	ΔG⁰/(kJ/mol)				ΔH⁰/（kJ/mol）	ΔS⁰/(J/(mol·K))
样品	288 K	298 K	308 K	318 K	ΔH⁰/（kJ/mol）	ΔS⁰/(J/(mol·K))
MR-800C	-5.1	-5.54	-6.34	-6.65	10.58	54.42
MR-900C	-5.77	-6.47	-7.16	-7.61	12.16	62.42
MR-1000C	-5.9	-6.46	-7.09	-7.67	11.18	59.27

图11 MR-1000C吸附磷前后的FT-IR光谱

Fig.11 FT-IR spectra of MR-1000C before and after phosphate adsorption

图12 MR-1000C对磷吸附前后的XPS谱图

Fig.12 XPS spectra of MR-1000C before and after adsorption

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