改性无烟煤材料的制备及其对磷的吸附回收性能

武越; 赵婷; 金彦任; 薛燕; 张凌旋; 李达; 乔晋如; 黄杨

doi:10.12153/j.issn.1674-991X.20210349

改性无烟煤材料的制备及其对磷的吸附回收性能

doi: 10.12153/j.issn.1674-991X.20210349

武越^1,,
赵婷¹,
金彦任¹,
薛燕¹,
张凌旋¹,
李达¹,
乔晋如¹,
黄杨^2, ,

1.
山西新华防化装备研究院有限公司
2.
成都信息工程大学资源环境学院

基金项目: 国家自然科学基金青年基金项目(51708050)

详细信息

作者简介:
武越（1992—），男，工程师，硕士，主要从事吸附材料的开发与改性研究，1508235620@qq.com

通讯作者:
黄杨（1990—），女，副教授，博士，主要从事吸附机理研究，huangyang@cuit.edu.cn

中图分类号: X703
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- 被引次数: 0
出版历程
- 收稿日期: 2021-07-21

Preparation of modified anthracites and research on their adsorption and recovery performance on phosphorus

1.
Shanxi Xinhua Chemical Defense Equipment Research Institute Co., Ltd.
2.
College of Resources and Environment, Chengdu University of Information Technology

摘要

摘要:
为了实现污水中磷的回收与资源化利用，提出采用Fe-Al-Zr改性的无烟煤材料吸附-回收磷的方法。该吸附剂对磷的总吸附量为13.022 mg/g，吸附机理主要包括静电作用、配体交换和表面沉积等；微孔提供主要的吸附位点，决定了磷的吸附容量。该吸附剂可循环使用4个周期，直至磷的吸附率低于50%。在碱性条件下，通过投加一定量的CaCl₂〔Ca∶P（摩尔比）=2∶1〕，磷能够以羟基磷灰石（HAP）的形式脱附和被回收。
- Fe-Al-Zr改性 /
- 无烟煤 /
- 吸附机理 /
- 磷回收 /
- 羟基磷灰石（HAP）
Abstract:
To recover and reutilize phosphorus from wastewater, a methodological framework for phosphorous removal and recovery using Fe-Al-Zr modified anthracite materials was proposed. The adsorbent presented a total adsorption capacity of 13.022 mg/g and the adsorption mechanism mainly included electrostatic forces, ligands exchange and surface deposition and so on. Micropores provided the major adsorption sites for phosphorous, and determined the adsorption capacity of phosphorous. The modified adsorbents could be repeatedly used in four operation cycles until the adsorption rate decreased below 50%. The phosphorous could be desorbed and recovered in the form of hydroxyapatite (HAP) by adding a certain amount of CaCl₂ (n(Ca)∶n(P)=2∶1) under alkaline conditions.
- Fe-Al-Zr modification /
- anthracite /
- adsorption mechanism /
- phosphorus recovery /
- hydroxyapatite (HAP)

HTML全文

图 1 原始无烟煤和Fe-Al-Zr改性无烟煤的SEM图像以及Fe-Al-Zr改性无烟煤的EDS谱图

Figure 1. SEM image of original anthracite and Fe-Al-Zr modified anthracite, and EDS mapping of Fe-Al-Zr modified anthracite

下载: 全尺寸图片幻灯片

图 2 原始无烟煤以及Fe-Al-Zr改性无烟煤吸附磷前后的XRD

Figure 2. XRD curve of origin anthracites and Fe-Al-Zr modified anthracites before and after adsorption

下载: 全尺寸图片幻灯片

图 3 原始无烟煤和Fe-Al-Zr改性无烟煤的投加量对磷去除率的影响

Figure 3. Effect of original and Fe-Al-Zr modified anthracites dosage on adsorption rate of phosphorus

下载: 全尺寸图片幻灯片

图 4 Fe-Al-Zr改性无烟煤对磷的吸附动力学曲线拟合

Figure 4. Adsorption dynamics of phosphorus onto Fe-Al-Zr modified anthracites

下载: 全尺寸图片幻灯片

图 5 Fe-Al-Zr改性无烟煤在不同吸附时间的孔径分布曲线

Figure 5. Pore size distribution of Fe-Al-Zr modified anthracites at different time in the adsorption process

下载: 全尺寸图片幻灯片

图 6 CaCl₂的投加量和溶液pH对磷回收率的影响

Figure 6. Effect of CaCl₂ dosage and pH on the recovery efficiency of phosphorous

下载: 全尺寸图片幻灯片

表 1 无烟煤改性过程中药剂投加量的正交设计

Table 1. Orthogonal design of the dosage of reagent in the anthracite modification process

药剂投加量(mmol/g，以无烟煤计)				磷的去除率/%
FeSO₄·7H₂O	FeCl₃·6H₂O	Cl₂OZr·8H₂O	Al(NO₃)₃·9H₂O	磷的去除率/%
1	2	2	2	71.35
1	2	4	4	93.37
2	4	4	4	68.79
2	4	4	2	63.87

下载: 导出CSV

表 2 Fe-Al-Zr改性无烟煤吸附磷的动力学与等温吸附模型拟合参数

Table 2. Fitting parameters of kinetic models and isotherm parameters for the adsorption of phosphorus onto Fe-Al-Zr modified anthracites

模型	模型参数	拟合值
伪一级动力学模型 ${q_t}{\text{ = } }{q_{\rm{e} } }(1 - { {\rm{e} }^{ - {K_1}t} })$	K₁/(min⁻¹)	0.008 6
	q_e/(mg/g)	3.256
	R²	0.975 1
伪二级动力学模型 $\dfrac{t}{ { {q_t} } } = \dfrac{1}{ { {K_2}q_{\rm{e}}^2} } + \dfrac{t}{ { {q_{\rm{e}}} } }$	K₂/〔g/(mg·min)〕	0.006 0
	q_e/(mg/g)	5.656
	R²	0.998 8
Langmuir模型 ${q_{\rm{e}}} = \dfrac{ { {q_{\rm{m}}}{K_{\rm{L}}}{C_{\rm{e}}} } }{ {1 + {K_{\rm{L}}}{C_{\rm{e}}} } }$	q_m/(mg/g)	12.853 0
	K_L (L/mg)	2.350
	R²	0.998 3
Freundlich模型 ${q_{\rm{e}}} = {K_{\rm{F}}}{C_{\rm{e}}}^{1/n}$	K_F/〔(mg/g)/(mg/L)^1/n〕	6.373 0
	1/n	2.378
	R²	0.918 2

下载: 导出CSV

表 3 Fe-Al-Zr改性无烟煤吸附磷的颗粒内扩散模型拟合参数

Table 3. Fitting parameters of intraparticle diffusion model for the adsorption of phosphorus onto Fe-Al-Zr modified anthracites

模型	参数	第一阶段	第二阶段
$ {q}_{t}={K}_{i}{t}^{1/2}+C $	K_i/〔mg/(g·min^−1/2)〕	0.188	0.009
	C/(mg/g)	2.012	5.138
	R²	0.978 7	0.648 1

下载: 导出CSV

表 4 不同吸附剂除磷性能的比较

Table 4. Comparison of phosphorous adsorption of different adsorbent

吸附剂	吸附量/（mg/g）	数据来源
硅改性花生壳生物炭	2.79	文献[23]
污泥生物炭	9.615	文献[24]
磁性水滑石/生物炭复合材料	9.50	文献[25]
微孔碳＠粉煤灰复合材料	8.375	文献[26]
Fe-Al-Zr改性无烟煤	13.022	本研究

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表 5 Fe-Al-Zr改性无烟煤在4个循环周期中对磷的吸附量和去除率

Table 5. Adsorption amount and removal efficiency of Fe-Al-Zr modified anthracites in the four operation cycles

项目	第1次循环			第2次循环		第3次循环		第4次循环
项目	第1次吸附	第2次吸附	第3次吸附	第1次吸附	第2次吸附	第1次吸附	第2次吸附	第1次吸附
吸附量/(mg/g)	6.289	4.181	2.552	4.915	2.139	3.645	1.309	2.778
去除率/%	96.42	76.53	44.12	76.53	35.28	60.93	22.48	48.03

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