Performance of Granular Lanthanum Oxycarbonate in Removing Fluorine from Water

doi:10.19894/j.issn.1000-0518.230319

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (2): 297-307.DOI: 10.19894/j.issn.1000-0518.230319

• Full Papers • Previous Articles

Performance of Granular Lanthanum Oxycarbonate in Removing Fluorine from Water

Tao ZHANG¹, Si-Ying LI¹, Jun-Le LI¹, Si-Yu SHAO¹, Chuan-Dong WU²^,³, Mei LING¹, Dong-Wei LYU¹, Wei WANG²()

^1.School of Environment，Harbin Institute of Technology，Harbin 150090，China
^2.Harbin Institute of Technology National Engineering Research Center of Urban Water Resources Co. ，Ltd. ，Harbin 150090，China
^3.Guangdong Yuehai Water Investment Co. ，Ltd. ，Shenzhen 518021，China

Received:2023-10-13 Accepted:2024-01-18 Published:2024-02-01 Online:2024-03-05
Contact: Wei WANG
About author:wangweirs@hit.edu.cn
Supported by:
the National Natural Science Foundation of China(51678181)

Abstract

Abstract:

To address the issue of low adsorption capacity for fluoride ions in traditional adsorbents， granular lanthanum oxycarbonate （La₂O₂CO₃） materials are prepared by activating lanthanum oxide （La₂O₃）. La₂O₂CO₃ exhibits strong adsorption performance for fluoride ions and effectively removes fluoride over a wide pH range of 3.0 to 10.0， achieving a fluoride ion removal rate of 94.5% to 98.0%. The adsorption behavior of La₂O₂CO₃ for fluoride ions follows the Langmuir model and is characterized as an endothermic process. At 25 ℃， it reaches a saturated adsorption capacity of 22.47 mg/g， which is approximately five times higher than that of traditional La₂O₃materials. The adsorption kinetics adhere to a pseudo-second-order kinetic model， primarily involving chemical adsorption. La₂O₂CO₃ can be regenerated using a sodium hydroxide solution， with a desorption rate of 90.3% achieved at a sodium hydroxide concentration of 1.0 mol/L， enabling the reuse of the adsorbent.

Key words: Lanthanum oxycarbonate, Adsorbent, Defluorination in water, Thermodynamics, Kinetics, Regeneration

CLC Number:

O643

Tao ZHANG, Si-Ying LI, Jun-Le LI, Si-Yu SHAO, Chuan-Dong WU, Mei LING, Dong-Wei LYU, Wei WANG. Performance of Granular Lanthanum Oxycarbonate in Removing Fluorine from Water[J]. Chinese Journal of Applied Chemistry, 2024, 41(2): 297-307.

Figures/Tables 15

Fig.1 （A） SEM image and （B） XRD diagram of adsorption material

Fig.2 N2 adsorption/desorption isotherms of adsorption material

Fig.3 （A） SEM image of La2O2CO3 material after adsorption and （B） MIR diagram of La2O2CO3 before and after adsorption

Fig.4 The effect of mass concentration of adsorbent on the defluorination effect of La2O2CO3

Table 1 Kinetic models for the adsorption of fluoride ions on La2O2CO3 material （25 ℃）

Kinetic model	ρ（fluoride ions）/（mg·L^-1）	Formula	R²
	5	y=-0.00063x+0.4763	0.882 5
Quasi-first-order kinetic model	10	y=-0.00138x+1.8514	0.826 0
	20	y=-0.00058x+2.5190	0.990 4
	5	y=0.2073x+17.1663	0.996 9
Quasi-second-order kinetic model	10	y=0.0973x+18.8842	0.993 2
	20	y=0.0609x+29.2919	0.942 4

Fig.5 Quasi-second-order kinetic curve fitting of La2O2CO3

Table 2 Fitting parameters of adsorption contour line temperature and related subjects of La2O2CO3 at different temperatures

T/K	Langmuir			Freundlich
T/K	q_m/（mg·g^-1）	b/（L·mg^-1）	R²	K_f/（mg·g^-1）	n	R²
298.15	22.47	2.38	0.991	13.79	7.13	0.862
308.15	24.81	2.87	0.992	16.62	7.20	0.780
313.15	27.64	3.00	0.997	18.35	6.84	0.828

Fig.6 Langmuir adsorption contour line temperature and related subjects fitting of La2O2CO3

Table 3 Comparison of adsorption capacity of different fluoride removal agents

Fluoride removal agent	Adsorption capacity/（mg·g^-1）	Ref.
Aluminum hydroxide	18.90	［18］
Manganese-oxide-coated alumina	7.56	［19］
Neodymium-modified chitosan	22.38	［20］
Activated alumina	16.34	［21］
Granular ceramic adsorption	12.12	［22］
Granular zirconium-iron oxide	9.80	［23］
Meso-structured zirconium phosphate	4.27	［24］
Granular lanthanum oxycarbonate	27.64	This study
Lanthanum oxide	2.50	［13］
Lanthanum hydroxide	11.9	［25］

Fig.7 Adsorption thermodynamic fitting of La2O2CO3

Table 4 Thermodynamic data of La2O2CO3 adsorption of fluoride ions

T/K	ΔG₀/（kJ·mol^-1）	ΔS₀/（kJ·mol^-1·K^-1）	ΔH₀/（kJ·mol^-1）
298.15	-2.155 7
308.15	-2.705 1	48.299 4	12.229
313.15	-2.862 7

Fig.8 The effect of pH value on adsorption and fluoride removal ratio

Fig.9 The effect of coexisting anions on fluoride removal ratio

Fig.10 Effect of different concentrations of sodium hydroxide solution on the defluorination rate of La2O2CO3 during the regeneration process

Fig.11 The fluoride removal efficiency of La2O2CO3 in actual well water

References 30

1	JAGTAP S， YENKIE M K， LABHSETWAR N， et al. Fluoride in drinking water and defluoridation of water［J］. Chem Rev， 2012， 112（4）： 2454-2466.
2	ORGANIZATION W H. Guidelines for drinking-water quality［M］. World Health Organization， 2004.
3	NUR T， LOGANATHAN P， NGUYEN T C， et al. Batch and column adsorption and desorption of fluoride using hydrous ferric oxide： solution chemistry and modeling［J］. Chem Eng J， 2014， 247： 93-102.
4	GARCIA-SANCHEZ J J， SOLACHE-RIOS M， MARTINEZ-MIRANDA V， et al. Removal of fluoride ions from drinking water and fluoride solutions by aluminum modified iron oxides in a column system［J］. J Colloid Interface Sci， 2013， 407： 410-415.
5	DEATH C， COULSON G， KIERDORF U， et al. Chronic excess fluoride uptake contributes to degenerative joint disease （DJD）： evidence from six marsupial species［J］. Ecotoxicol Environ Saf， 2018， 162： 383-390.
6	刘航，彭稳，陆继长，等. 吸附法处理含氟水体的研究进展［J］. 水处理技术， 2017， 43（9）： 13-18.
	LIU H， PENG W， LU J C， et al. Research progress on adsorption method for treating fluoride-containing water［J］. Technol Water Treat， 2017， 43（9）： 13-18.
7	赵瑨云，胡家朋，刘瑞来，等. La-金属有机骨架化合物的制备及其除氟性能研究［J］. 化学通报， 2021， 84（1）： 75-80.
	ZHAO J Y， HU J P， LIU R L， et al. Preparation of La-metal organic framework compounds and study on their fluorine removal performance［J］. Chemistry， 2021， 84（1）： 75-80.
8	唐瑾，陈志莉. 金属基吸附剂除氟研究进展［J］. 水处理技术， 2019， 45（11）： 14-18， 34.
	TANG J， CHEN Z L. Research progress on metal-based adsorbents for fluoride removal［J］. Technol Water Treat， 2019， 45（11）： 14-18， 34.
9	赵迎新，宋倩，马同宇，等. 改性/新型氟吸附材料的研究进展［J］. 工业水处理， 2018， 38（5）： 9-14.
	ZHAO Y X， SONG Q， MA T Y， et al. Research progress on modified/new fluorine adsorption materials［J］. Ind Water Treat， 2018， 38（5）： 9-14.
10	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］. Carbohydr Polym， 2017， 176： 402-410.
11	张小磊，李尚明，李红艳，等. 负载镧镁改性活性氧化铝的除氟性能［J］. 环境工程学报， 2016， 10（8）： 4189-4195.
	ZHANG X L， LI S M， LI H Y， et al. Fluorine removal performance of loaded lanthanum and magnesium modified activated alumina［J］. Chin J Environ Eng， 2016， 10（8）： 4189-4195.
12	王莉莉，杨宏伟，祝万鹏，等. 粒径对水合氧化镧除氟效果的影响［J］. 环境科学研究， 2009， 22（1）： 103-107.
	WANG L L， YANG H W， ZHU W P， et al. Effect of particle size on the defluoridation effect of hydrated lanthanum oxide［J］. Res Environ Sci， 2009， 22（1）： 103-107.
13	RAO C R N， KARTHIKEYAN J. Removal of fluoride from water by adsorption onto lanthanum oxide［J］. Water Air Soil Pollut， 2012， 223（3）： 1101-1114.
14	卞晓彤，邱兆富，杨骥，等. 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 X T， QIU Z F， YANG J， et al. Research on fluoride removal by sodium alginate-lanthanum hydroxide modified Y-type molecular sieve particles［J］. Inorg Chem Ind， 2020， 52（12）： 86-91.
15	谢燕华，刘国明，杨汝馨，等. Fe（Ⅲ）-La（Ⅲ）/壳聚糖复合材料对地下水中氟的吸附性能研究［J］. 水处理技术， 2014， 40（10）： 42-46.
	XIE Y H， LIU G M， YANG R X， et al. Study on the adsorption performance of Fe（Ⅲ）-La（Ⅲ）/chitosan composite materials for fluorine in groundwater［J］. Technol Water Treat， 2014， 40（10）： 42-46.
16	CHOUDHARY G， YADAV M， SAINI B， et al. Effect of calcination temperature on hydroxyapatite in fluoride removal from groundwater： process optimization and kinetic study［J］. Desalination， 2024， 574： 117268.
17	WANG L， CHEN S， DING G， et al. Efficient defluoridation of water by employing hybrid nanosized cerium oxides embedded within cross-linked cellulose foam［J］. Sep Purif Technol， 2024， 336： 126236.
18	赵娜. 铁铝复合纳米材料的制备及其吸附氟离子的研究［D］. 长沙：中南大学， 2012.
	ZHAO N. Preparation of iron-aluminum composite nanomaterials and research on their adsorption of fluoride ions［D］. Changsha： Central South University， 2012.
19	MALIYEKKAL S M， SHARMA A K， PHILIP L. Manganese-oxide-coated alumina： a promising sorbent for defluoridation of water［J］. Water Res， 2006， 40（19）： 3497-3506.
20	YAO R， MENG F， ZHANG L， et al. Defluoridation of water using neodymium-modified chitosan［J］. J Hazard Mater， 2009， 165（1/3）： 454-460.
21	KU Y， CHIOU H M. The adsorption of fluoride ion from aqueous solution by activated alumina［J］. Water Air Soil Pollut， 2002， 133（1/4）： 349-360.
22	CHEN N， ZHANG Z， FENG C， et al. Fluoride removal from water by granular ceramic adsorption［J］. J Colloid Interface Sci， 2010， 348（2）： 579-584.
23	DOU X， ZHANG Y， WANG H， et al. Performance of granular zirconium-iron oxide in the removal of fluoride from drinking water［J］. Water Res， 2011， 45（12）： 3571-3578.
24	SWAIN S K， PATNAIK T， SINGH V K， et al. Kinetics， equilibrium and thermodynamic aspects of removal of fluoride from drinking water using meso-structured zirconium phosphate［J］. Chem Eng J， 2011， 171（3）： 1218-1226.
25	IRUSTA S， CORNAGLIA L M， LOMBARDO E A. Effects of rhodium and platinum on the reactivity of lanthanum phases［J］. Mater Chem Phys， 2004， 86（2/3）： 440-447.
26	OU J H， WANG C C， VERPOORT F， et al. Development of innovative and green adsorbents for in situ cleanup of fluoride-polluted groundwater： mechanisms and field-scale studies［J］.Chemosphere， 2024， 350：141035.
27	贾瑞娟，王钰翠，常春，等. Fe/Cu纳米复合材料对罗丹明B的吸附性能研究［J］. 郑州大学学报（工学版）， 2020， 41（5）： 31-36.
	JIA R J， WANG Y C， CHANG C， et al. Study on the adsorption performance of Fe/Cu nanocomposites on rhodamine B［J］. Zhengzhou Univ （Eng Sci）， 2020， 41（5）： 31-36.
28	GHIASI M， MALEKZADEH A. Synthesis， characterization and photocatalytic properties of lanthanum oxy-carbonate， lanthanum oxide and lanthanum hydroxide nanoparticles［J］. Superlattices Microstruct， 2015， 77： 295-304.
29	ZHI Y， PATERSON A R， CALL D F， et al. Mechanisms of orthophosphate removal from water by lanthanum carbonate and other lanthanum-containing materials［J］. Sci Total Environ， 2022， 820： 153153.
30	韩润平，房丽燕，李小钰，等. 聚乙烯亚胺负载四氧化三铁对刚果红的吸附性能［J］. 郑州大学学报（工学版）， 2019， 40（2）： 59-65.
	HAN R P， FANG L Y， LI X Y， et al. Adsorption performance of Congo red by polyethyleneimine-supported ferric tetroxide［J］. J Zhengzhou Univ （Eng Sci）， 2019， 40（2）： 59-65.

[1]	Lu-Fei WANG, Meng-Meng ZHEN, Bo-Xiong SHEN. Research Progress of Controlling Lithium-Sulfur Batteries by Electrocatalysts under Lean Electrolyte Conditions [J]. Chinese Journal of Applied Chemistry, 2023, 40(2): 188-209.
[2]	Jing YAO, Ming-Ming DAI. Preparation and Properties of Reclaimed Rubber Based on Passenger Car Tire Tread Powder [J]. Chinese Journal of Applied Chemistry, 2023, 40(1): 52-58.
[3]	Qin-Qin TIAN, Jia ZHANG, Zhi CHEN, Wei HE, Sheng-Yong ZHANG. Progress in Synthesis， Detection and Clinical Application of Posaconazole [J]. Chinese Journal of Applied Chemistry, 2022, 39(8): 1177-1189.
[4]	Yue-Hua ZHAO, Da-Peng WANG. Coadsorption Kinetics of Amino‑Functionalized Graphene Oxide and Fatty Acids at the Water/Oil Interface [J]. Chinese Journal of Applied Chemistry, 2022, 39(8): 1274-1284.
[5]	Li-Zhi SUN, Hao LYU, Xiao-Wen MIN, Ben LIU. Mesoporous Palladium⁃Boron Alloy Nanocatalysts： Synthesis and Performance in Methanol Oxidation Electrocatalysis [J]. Chinese Journal of Applied Chemistry, 2022, 39(4): 673-684.
[6]	ZHOU Wen, TONG Shan-Shan. Research Progress on Novel Adsorbent Materials for Separation and Enrichment of Noble Metals [J]. Chinese Journal of Applied Chemistry, 2021, 38(8): 897-910.
[7]	GAO Song-Hong, YANG Di, LI Zhong-Qi, ZHENG Fei, JEON You-Jin, DAI Yu-Lin. Rapid Resolution Liquid Chromatography with Tandem Mass Spectrometry on Pharmacokinetics of Type 2 Diabetic Rats with Oral Administration of Sijunzitang Decoration [J]. Chinese Journal of Applied Chemistry, 2021, 38(3): 0-0.
[8]	GAO Song-Hong, YANG Di, LI Zhong-Qi, ZHENG Fei, JEON You-Jin, DAI Yu-Lin. Rapid Resolution Liquid Chromatography with Tandem Mass Spectrometry on Pharmacokinetics of Type 2 Diabetic Rats with Oral Administration of Sijunzitang Decoration [J]. Chinese Journal of Applied Chemistry, 2021, 38(3): 315-322.
[9]	SHE Yun-Ting, YANG Chang-Yu, LI De-Liang, CHANG Zhi-Xian. Reactive Extraction of Amphoteric Organics from the Dilute Solutions [J]. Chinese Journal of Applied Chemistry, 2021, 38(1): 24-35.
[10]	HE Yufang, YAN Pinping, HUANG Baoquan, LUO Fubin, LI Hongzhou, QIAN Qingrong, CHEN Qinghua. Thermal Conductivity and Crystallization Behavior of Polyethylene Glycol/Boron Nitride Phase Change Composites [J]. Chinese Journal of Applied Chemistry, 2020, 37(6): 650-657.
[11]	GUO Xiaoyan, CHENG Xiaoqi, ZHANG Liangliang, HUANG Yiping, XU Gewen, BAO Junjie. Preparation and Properties of Sulfonic Waterborne Polyurethane Hydrogels with Sodium N,N-Bis (2-hydroxyethyl)-2-aminoethane Sulfonate as Chain Extender [J]. Chinese Journal of Applied Chemistry, 2019, 36(6): 631-640.
[12]	LI Jingping, YANG Shihai, LIU Yang, BO Wenbo. Preparation of Attapulgite Clay Supported Nano TiO₂-Fe₃O₄ Adsorbent and Removal of Cr(Ⅵ) [J]. Chinese Journal of Applied Chemistry, 2019, 36(3): 324-334.
[13]	ZHOU Fengzhen, LI Wenqiu, WANG Wenjing, GUO Huiling. Influencing Factors of Lanthanum Adsorption by Ca-Montmorillonite and Its Application [J]. Chinese Journal of Applied Chemistry, 2019, 36(12): 1413-1421.
[14]	HONG Dongyang, ZHOU Jinsong, ZHOU Qixin. Effect of Hydrogen Sulfur on the Removal of Elemental Mercury with Activated Carbon [J]. Chinese Journal of Applied Chemistry, 2019, 36(10): 1194-1201.
[15]	YANG Xian, MIN Lingli, ZHU Yinglin, CAO Liuxuan, XIE Yanbo, HOU Xu. Recent Research Progress on Nanopores and Nanochannels Based Electrokinetical Energy Conversion Systems [J]. Chinese Journal of Applied Chemistry, 2018, 35(6): 613-624.

Performance of Granular Lanthanum Oxycarbonate in Removing Fluorine from Water

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 15

References 30

Related Articles 15

Recommended Articles

Metrics

Comments