海藻酸钠-氢氧化镧改性Y型分子筛颗粒除氟研究

doi:10.11962/1006-4990.2020-0059

摘要/Abstract

摘要：

为解决除氟吸附剂分离困难、有效成分流失等问题,以海藻酸钠（SA）与氢氧化镧改性Y型分子筛（LHMS）为原料,采用滴球法制备了SA@LHMS颗粒吸附剂,并采用模拟废水对其进行了除氟研究。通过正交实验确定了吸附剂最佳制备条件,并通过间歇吸附实验测试了吸附剂投加量、pH、共存离子等因素对吸附的影响,探究了吸附速率、吸附等温线等吸附性能。结果表明,SA@LHMS吸附速率曲线符合拟二级反应速率方程;吸附等温线符合Ⅱ型等温线,为多分子层吸附;初始pH（3~12）对吸附效果没有显著影响;高浓度共存阴离子（50 mg/L）对吸附过程有一定抑制;1 mol/L和2 mol/L氢氧化钠溶液对SA@LHMS再生效果较好,经3次再生仍然保留较高的吸附能力。SA@LHMS颗粒表面和截面形态以及吸附前后颗粒的表面形态差异明显;吸附前后颗粒表面能谱（EDS）分析以及红外光谱（FT-IR）分析结果显示,吸附过程中溶液中的氟离子（F^-）与颗粒表面及内部的羟基（—OH）发生配体交换。

关键词: 海藻酸钠, 颗粒吸附剂, 除氟, 氢氧化镧, Y型分子筛

Abstract:

In order to solve the problem of the separation of defluorinated adsorbents and the loss of effective components,SA@LHMS adsorbents were prepared with sodium alginate（SA） and lanthanum hydroxide modified Y zeolite （LHMS） as raw materials.The optimum preparation conditions of adsorbent were determined by orthogonal experiment.The effect of factors,such as dosage of adsorbent,pH and co-existing ions etc.,was tested by batch adsorption experiment,and the adsorption performance of adsorption rate and adsorption isotherm was researched.The results showed that the adsorption rate curve of the SA@LHMS conformed to the second-order reaction rate equation.Adsorption isotherm conformed to the type Ⅱ isotherm,multilayer physical adsorption.The initial pH （3~12） had no significant effect on the adsorption effect.High concentration of co-existing anions （50 mg/L） inhibited the adsorption process.The regeneration effect of 1 mol/L and 2 mol/L NaOH solution on SA@LHMS was better,and SA@LHMS still retained a high adsorption capacity after three regeneration.The surface and cross section morphology of SA @LHMS as well as the surface morphology before and after adsorption were significantly different.EDS component analysis and FT-IR spectrum analysis before and after adsorption showed that ligand exchange occur-curred between F^- and —OH on the surface and inside of particles during adsorption.

Key words: sodium alginate, particle adsorbent, defluorination, lanthanum hydroxide, Y zeolite

中图分类号:

TQ133.3

卞晓彤,邱兆富,杨骥,严瑞琪,吕树光. 海藻酸钠-氢氧化镧改性Y型分子筛颗粒除氟研究[J]. 无机盐工业, 2020, 52(12): 86-91.

Bian Xiaotong,Qiu Zhaofu,Yang Ji,Yan Ruiqi,Lü Shuguang. Study on fluoride removal by modified Y zeolite particles with sodium alginate-lanthanum hydroxide[J]. Inorganic Chemicals Industry, 2020, 52(12): 86-91.

图/表 13

表1

图1

表2

图2

图3

表3

图4

图5

图6

图7

图8

图9

图10

参考文献 25

[1]	Cui Y, Zhang B, Ma J, et al. Dopamine receptor D2 gene polymorphism,urine fluoride,and intelligence impairment of children in China:A school-based cross-sectional study[J]. Ecotoxicology and Environmental Safety, 2018,165:270-277.
[2]	WHO. WHO guidelines approved by the guidelines review committee[M]. Guidelines for Drinking-Water Quality:Fourth Edition Incorporating the First Addendum.Geneva;World Health Organization Copyright(c) World Health Organization 2017. 2017.
[3]	Zhang L, Huang D. Probabilistic risk assessment of Chinese residents’ exposure to fluoride in improved drinking water in endemic fluorosis areas[J]. Environmental Pollution, 2017,222:118-125.
[4]	Wang M. Distribution,health risk assessment,and anthropogenic sources of fluoride in farmland soils in phosphate industrial area,southwest China[J]. Environmental Pollution, 2019,249:423-433.
[5]	Wu C, Wu X, Qian C, et al. Hydrogeochemistry and groundwater quality assessment of high fluoride levels in the Yanchi endorheic region,northwest China[J]. Applied Geochemistry, 2018,98:404-417.
[6]	Zhou G, Lu Y, Chen L, et al. Low-to-moderate fluoride exposure,relative mitochondrial DNA levels,and dental fluorosis in Chinese children[J]. Environment International, 2019,127:70-77.
[7]	Aldaco R. Calcium fluoride recovery from fluoride wastewater in a fluidized bed reactor[J]. Water Research, 2007,41(4):810-818.
[8]	窦若岸, 陈彬彬, 罗生乔, 等. 化学沉淀法处理高浓度含氟废水的研究[J]. 有机氟工业, 2016(2):9-11,27.
[9]	余锋. 含氟废水的处理[J]. 无机盐工业, 2001,33(6):31-32.
[10]	Maliyekkal S M, Sharma A K, Philip L. Manganese-oxide-coated alumina:A promising sorbent for defluoridation of water[J]. Water Research, 2006,40(19):3497-3506.
[11]	Meenakshi S, Viswanathan N. Identification of selective ion-exch-ange resin for fluoride sorption[J]. Journal of Colloid and Interface Science, 2007,308(2):438-450.
[12]	Lu N C, Liu J C. Removal of phosphate and fluoride from waste-water by a hybrid precipitation-microfiltration process[J]. Separa-tion and Purification Technology, 2010,74(3):329-335.
[13]	张小东, 赵飞燕, 王永旺, 等. 废水除氟技术研究现状[J]. 无机盐工业, 2019,51(12):6-9,19.
[14]	Jagtap S, Yenkie M K. Fluoride in drinking water and defluoridation of water[J]. Chemical Reviews, 2012,112(4):2454-2466.
[15]	Dong S, Wang Y. Characterization and adsorption properties of a lanthanum-loaded magnetic cationic hydrogel composite for fluo-ride removal[J]. Water Research, 2016,88:852-860.
[16]	Nabbou N, Belhachemi M. Removal of fluoride from groundwater using natural clay(kaolinite):Optimization of adsorption conditions[J]. Comptes Rendus Chimie, 2019,22(2):105-112.
[17]	Kang D, Yu X, Ge M, et al. Insights into adsorption mechanism for fluoride on cactus-like amorphous alumina oxide microspheres[J]. Chemical Engineering Journal, 2018,345:252-259.
[18]	Dou X, Zhang Y, Wang H, et al. Performance of granular zirconi-um-iron oxide in the removal of fluoride from drinking water[J]. Water Research, 2011,45(12):3571-3578.
[19]	Chaudhary M, Maiti A. Defluoridation by highly efficient calcium hydroxide nanorods from synthetic and industrial wastewater[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2019,561:79-88.
[20]	Raghav S, Nehra S, Kumar D. Biopolymer scaffold of pectin and alginate for the application of health hazardous fluoride removal studies by equilibrium adsorption,kinetics and thermodynamics[J]. Journal of Molecular Liquids, 2019,284:203-214.
[21]	Nagaraj A, Sadasivuni K K, Rajan M. Investigation of lanthanum impregnated cellulose,derived from biomass,as an adsorbent for the removal of fluoride from drinking water[J]. Carbohydrate Polymers, 2017,176:402-410.
[22]	Zúñiga-Muro N M, Bonilla-Petriciolet A, Mendoza-Castillo D I, et al. Fluoride adsorption properties of cerium-containing bone char[J]. Journal of Fluorine Chemistry, 2017,197:63-73.
[23]	Yuan L. Development of lanthanum hydroxide loaded on molecular sieve adsorbent and mechanistic study for phosphate removal[J]. Journal of Alloys and Compounds, 2018,768:953-961.
[24]	Ertugay M F, Certel M. Moisture sorption isotherms of cereals at different temperatures[J]. Die Nahrung, 2000,44:107-109.
[25]	Vilar V J P, Botelho C M S. Influence of pH,ionic strength and temperature on lead biosorption by Gelidium and agar extraction algal waste[J]. Process Biochemistry, 2005,40(10):3267-3275.

水平	因素
水平	SA质量分数/%	CaCl₂ 质量分数/%	交联时间/ h	LHMS包埋量/（g·L^-1）
1	1	2	12	60
2	2	3	24	80
3	3	4	36	100

实验编号	因素水平				F^-去除率/%
实验编号	A	B	C	D	F^-去除率/%
1	1	1	1	1	85.5
2	1	2	2	2	79.7
3	1	3	3	3	84.5
4	2	1	2	2	87.9
5	2	2	3	3	80.2
6	2	3	1	1	75.4
7	3	1	3	3	57.2
8	3	2	1	1	59.6
9	3	3	2	2	59.1
k₁	83.2	76.9	73.5	73.5
k₂	81.2	73.2	75.6	75.6
k₃	58.6	73.0	74.0	74.0
R	24.6	3.9	2.1	2.1

拟一级动力学模型	q_e	k₁	R²	备注
log（q_e-q_t）=log q_e-（k₁/2.303）t	0.457	0.002	0.627 6	—
拟二级动力学模型	q_e	k₂	R²	备注
t/q_t=1/k₂q_e²+（1/q_e）t	0.454	0.040	0.999 4	—
Weber-Morris动力学模型	k_ip	C	R²	备注
q_t=k_ipt^1/2+C	0.043	-0.065	0.994 7	阶段1
	0.007	0.237	0.967 3	阶段2
	0.000	0.439	0.320 4	阶段3

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会