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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参考文献(27)

[1]	桑倩倩, 王芳君, 赵元添, 等.铁硫改性生物炭去除水中的磷[J]. 环境科学,2021,42(5):2313-2323. SANG Q Q, WANG F J, ZHAO Y T, et al. Application of iron and sulfate-modified biochar in phosphorus removal from water[J]. Environmental Science,2021,42(5):2313-2323.
[2]	崔荣国, 张艳飞, 郭娟, 等.资源全球配置下的中国磷矿发展策略[J]. 中国工程科学,2019,21(1):128-132. CUI R G, ZHANG Y F, GUO J, et al. Development strategy of phosphate rock in China under global allocation of resources[J]. Engineering Science,2019,21(1):128-132.
[3]	SHEPHERD J G, SOHI S P, HEAL K V. Optimising the recovery and re-use of phosphorus from wastewater effluent for sustainable fertiliser development[J]. Water Research,2016,94:155-165. doi: 10.1016/j.watres.2016.02.038
[4]	LIU T, CHEN X, WANG X, et al. Highly effective wastewater phosphorus removal by phosphorus accumulating organism combined with magnetic sorbent MFC@La(OH)₃[J]. Chemical Engineering Journal,2018,335:443-449. doi: 10.1016/j.cej.2017.10.117
[5]	赵鹏, 李红艳, 崔建国, 等.载铝活性炭纤维的制备及其脱氮除磷性能[J]. 工业水处理,2020,40(11):79-83. ZHAO P, LI H Y, CUI J G, et al. Preparation of aluminum-loaded activated carbon fiber and its nitrogen and phosphorus removal performance[J]. Industrial Water Treatment,2020,40(11):79-83.
[6]	OGINNI O, YAKABOYLU G A, SINGH K, et al. Phosphorus adsorption behaviors of MgO modified biochars derived from waste woody biomass resources[J]. Journal of Environmental Chemical Engineering,2020,8(2):103723. doi: 10.1016/j.jece.2020.103723
[7]	王春丽, 吴俊奇, 宋永会, 等.活化赤泥颗粒吸附除磷的效能与机制研究[J]. 环境工程技术学报,2015,5(2):143-148. doi: 10.3969/j.issn.1674-991X.2015.02.021 WANG C L, WU J Q, SONG Y H, et al. Research on performance and mechanisms of activated red mud particles on adsorbing and removing phosphorus[J]. Journal of Environmental Engineering Technology,2015,5(2):143-148. doi: 10.3969/j.issn.1674-991X.2015.02.021
[8]	何一帆, 聂小保, 余志, 等.低磷污水的HAP诱导结晶磷回收[J]. 环境科学学报,2021,41(2):566-573. HE Y F, NIE X B, YU Z, et al. Phosphorus recovery from wastewater with low phosphorus concentration by HAP induced crystallization[J]. Acta Scientiae Circumstantiae,2021,41(2):566-573.
[9]	胡怡, 宋永会, 钱锋, 等.赤泥诱导磷酸钙结晶法回收废水中的磷[J]. 环境工程技术学报,2014,4(1):60-66. doi: 10.3969/j.issn.1674-991X.2014.01.011 HU Y, SONG Y H, QIAN F, et al. Phosphorus recovery from wastewater by red mud-seeded crystallization of calcium phosphate[J]. Journal of Environmental Engineering Technology,2014,4(1):60-66. doi: 10.3969/j.issn.1674-991X.2014.01.011
[10]	LEI Y, SAAKES M, van der WEIJDEN R D, et al. Electrochemically mediated calcium phosphate precipitation from phosphonates: implications on phosphorus recovery from non-orthophosphate[J]. Water Research,2020,169:115206. doi: 10.1016/j.watres.2019.115206
[11]	HE J, ZHOU Q H, GUO J S, et al. Incredulity on assumptions for the simplified Bohart-Adams model: 17a-ethinylestradiol separation in lab-scale anthracite columns[J]. Journal of Hazardous Materials,2020,384:121501. doi: 10.1016/j.jhazmat.2019.121501
[12]	PAI C W, LEONG D, CHEN C Y, et al. Occurrences of pharmaceuticals and personal care products in the drinking water of Taiwan and their removal in conventional water treatment processes[J]. Chemosphere,2020,256:127002. doi: 10.1016/j.chemosphere.2020.127002
[13]	MOHAMED E A, SELIM A Q, AHMED S A, et al. H₂O₂-activated anthracite impregnated with chitosan as a novel composite for Cr(Ⅵ) and methyl orange adsorption in single-compound and binary systems: modeling and mechanism interpretation[J]. Chemical Engineering Journal,2020,380:122445. doi: 10.1016/j.cej.2019.122445
[14]	常会庆, 王浩, 徐晓峰.无烟煤活性炭对酸碱性不同染料废水的吸附研究[J]. 水土保持学报,2014,28(2):276-280. CHANG H Q, WANG H, XU X F. Adsorption studies of acid and base dyes wastewater on anthracite activated carbon[J]. Journal of Soil and Water Conservation,2014,28(2):276-280.
[15]	简志强, 周高婷, 龚斌, 等.微米零价铁去除磷酸盐效果与机理研究[J]. 环境工程技术学报,2021,11(5):927-934. doi: 10.12153/j.issn.1674-991X.20210027 JIAN Z Q, ZHOU G T, GONG B, et al. Study on the efficacy of micron zero-valent iron on phosphate removal and its mechanism[J]. Journal of Environmental Engineering Technology,2021,11(5):927-934. doi: 10.12153/j.issn.1674-991X.20210027
[16]	FENG J W, JIANG L, YUAN B X, et al. Enhanced removal of aqueous phosphorus by Zr–Fe-, Mn–Fe-, and Mn–Zr–Fe-modified natural zeolites: comparison studies and adsorption mechanism[J]. Environmental Engineering Science,2020,37(8):572-584. doi: 10.1089/ees.2019.0490
[17]	LIN X C, XIE Y L, LU H J, et al. Facile preparation of dual La-Zr modified magnetite adsorbents for efficient and selective phosphorus recovery[J]. Chemical Engineering Journal,2021,413:127530. doi: 10.1016/j.cej.2020.127530
[18]	HE J, GUO J S, ZHOU Q H, et al. Adsorption characteristics of nitrite on natural filter medium: Kinetic, equilibrium, and site energy distribution studies[J]. Ecotoxicology and Environmental Safety,2019,169:435-441. doi: 10.1016/j.ecoenv.2018.11.039
[19]	WANG M, YU X L, YANG C L, et al. Removal of fluoride from aqueous solution by Mg-Al-Zr triple-metal composite[J]. Chemical Engineering Journal,2017,322:246-253. doi: 10.1016/j.cej.2017.03.155
[20]	MACÍAS-GARCÍA A, GÓMEZ CORZO M, ALFARO DOMÍNGUEZ M, et al. Study of the adsorption and electroadsorption process of Cu(Ⅱ) ions within thermally and chemically modified activated carbon[J]. Journal of Hazardous Materials,2017,328:46-55. doi: 10.1016/j.jhazmat.2016.11.036
[21]	刘赫尊, 陈亮, 张海丰, 等.改性海绵铁深度除磷及其再生磷回收方法[J]. 环境科学学报,2020,40(1):147-154. LIU H Z, CHEN L, ZHANG H F, et al. Phosphorus removal and recovery based on modified sponge iron[J]. Acta Scientiae Circumstantiae,2020,40(1):147-154.
[22]	LI Y G, LI Q Q, WU C X, et al. The inappropriate application of the regression Langmuir Q_m for adsorption capacity comparison[J]. Science of the Total Environment,2020,699:134222. doi: 10.1016/j.scitotenv.2019.134222
[23]	赵敏, 张小平, 王梁嵘. 2021. 硅改性花生壳生物炭对水中磷的吸附特性[J/OL]. 环境科学, 2021. doi: 10.13227/j.hjkx.202103012. ZHAO M, ZHANG X P, WANG L R. Characteristics of phosphorous adsorption in aqueous solution by Si-modified peanut shell biochar[J/OL]. Environmental Science, 2021. doi: 10.13227/j.hjkx.202103012.
[24]	梁宁, 莫福金, 周街荣, 等.污泥生物炭制备及其对磷的吸附性能研究[J]. 无机盐工业,2021,53(6):174-179. LIANG N, MO F J, ZHOU J R, et al. Study on preparation of sludge biochar and its adsorption performance for phosphorus[J]. Inorganic Chemicals Industry,2021,53(6):174-179.
[25]	肖作义, 肖宇, 肖明慧, 等.磁性水滑石/生物炭复合材料的制备及其对水溶液中磷的吸附性能[J]. 环境污染与防治,2020,42(9):1090-1095. doi: 10.15985/j.cnki.1001-3865.2020.09.005 XIAO Z Y, XIAO Y, XIAO M H, et al. Preparation of magnetic hydrotalcite/biochar composite and its adsorption performance for phosphorus in aqueous solution[J]. Environmental Pollution & Control,2020,42(9):1090-1095. doi: 10.15985/j.cnki.1001-3865.2020.09.005
[26]	张晓, 陈晨, 程婷, 等.微孔碳@粉煤灰颗粒复合材料合成及其吸附磷应用[J]. 有色金属工程,2020,10(9):134-144. doi: 10.3969/j.issn.2095-1744.2020.09.020 ZHANG X, CHEN C, CHENG T, et al. Synthesis of micro-porous Carbon@Fly ash particle composite material and its application to phosphorus adsorption[J]. Nonferrous Metals Engineering,2020,10(9):134-144. doi: 10.3969/j.issn.2095-1744.2020.09.020
[27]	YE J E, CONG X N, ZHANG P Y, et al. Interaction between phosphate and acid-activated neutralized red mud during adsorption process[J]. Applied Surface Science,2015,356:128-134. □ doi: 10.1016/j.apsusc.2015.08.053