Preparation of mesoporous silica/sodium alginate composites and its removal performance of radioactive Sr2+

doi:10.19965/j.cnki.iwt.2024-0099

Abstract

Abstract:

The extensive use of nuclear energy has brought new challenges to nuclear wastewater treatment, and it is urgent to develop absorptive materials with promising applications. The mesoporous silica(HMSS, MCM-41, SBA-15)/sodium alginate(SA) composites were constructed by embedding method, and the effects of raw material ratio, pH, adsorption time, initial concentration, adsorbent dosage, and competing ions on the Sr²⁺ adsorption performance of composite materials were explored. The composite materials before and after adsorption were characterized by fourier transform spectroscopy(FT-IR), scanning electron microscopy(SEM) and energy dispersive spectroscopy(EDS). The results showed that under the conditions of T=298 K, pH=7.0, t=240 min, the saturated adsorption capacities of HMSS/SA(1∶3), MCM-41/SA(1∶3) and SBA-15/SA(1∶3) for Sr²⁺ could reach 49.67, 40.54 mg/g and 34.90 mg/g, respectively. The adsorption process was consistent with the Langmuir isotherm model and the pseudo-second-order reaction kinetics model, indicating that chemical adsorption characterized by monolayer adsorption was primarily involved. In the presence of competing ions Na⁺, K⁺, Ca²⁺ and Mg²⁺, the inhibitory strength followed Na⁺≈K⁺<Mg²⁺<Ca²⁺, and still a high selectivity for Sr²⁺ in Cs⁺ and Sr²⁺ systems. In addition, HMSS/SA(1∶3), MCM-41/SA(1∶3) and SBA-15/SA(1∶3) had good recycling performance.

Key words: mesoporous silica, strontium, radioactive wastewater, adsorption

摘要：

核能的广泛使用给废水处理带来了新的挑战，亟待开发具有应用前景的吸附材料处理含放射性元素废水。通过包埋法构建介孔硅（HMSS、MCM-41、SBA-15）/海藻酸钠（SA）复合材料，探究原料配比、溶液pH、吸附时间、初始Sr²⁺质量浓度、吸附剂投加量、竞争离子对复合材料吸附Sr²⁺性能的影响。通过傅里叶变换红外光谱仪（FT-IR）、扫描电子显微镜（SEM）以及能谱仪（EDS）对吸附前后的复合材料进行表征分析。结果表明：在T=298 K、pH=7.0、t=240 min的条件下，HMSS/SA（1∶3）、MCM-41/SA（1∶3）、SBA-15/SA（1∶3）对Sr²⁺的平衡吸附容量分别达到49.67、40.54、34.90 mg/g。吸附过程符合Langmuir等温模型和准二级反应动力学模型，吸附过程是以单层吸附为主的化学吸附。在竞争离子Na⁺、K⁺、Ca²⁺、Mg²⁺存在的情况下，对Sr²⁺吸附抑制程度遵循Na⁺≈K⁺<Mg²⁺<Ca²⁺，并在Cs⁺、Sr²⁺共存体系中，对Sr²⁺仍拥有较高的选择性。此外，HMSS/SA（1∶3）、MCM-41/SA（1∶3）和SBA-15/SA（1∶3）拥有良好的循环使用性能。

关键词: 介孔硅, 锶, 放射性废水, 吸附

CLC Number:

X703

Wei JIANG, Xiaodie CAI, Xinyu WEN, Sili CHEN, Jinsong WANG, Zhengke ZHANG. Preparation of mesoporous silica/sodium alginate composites and its removal performance of radioactive Sr²⁺[J]. Industrial Water Treatment, 2025, 45(3): 90-98.

江惟, 蔡萧蝶, 文昕宇, 陈思莉, 王劲松, 张政科. 介孔硅/海藻酸钠复合材料的制备及其对放射性Sr²⁺的去除[J]. 工业水处理, 2025, 45(3): 90-98.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2024-0099

https://www.iwt.cn/EN/Y2025/V45/I3/90

Figures/Tables 12

Fig.1 FT-IR of HMSS，SA，HMSS/SA，MCM-41/SA and SBA-15/SA

Fig.2 SEM images of SA，and SEM images of HMSS/SA，MCM-41/SA，SBA-15/SA before and after Sr²⁺adsorption

Fig.3 EDS of HMSS/SA，MCM-41/SA，SBA-15/SA before and after Sr²⁺ adsorption

Fig.4 Effect of raw material ratio on adsorption of composite material

Fig.5 Effect of pH on adsorption of composite material

Fig.6 Effect of adsorption time on adsorption properties of composite materials and fitting of reaction kinetics model

Table 1 Adsorption kinetic fitting parameters

复合材料	准一级反应动力学			准二级反应动力学
复合材料	q _e/（mg·g^-1）	k ₁/min^-1	R ²	q _e/（mg·g^-1）	k ₂/（g·mg^-1·min^-1）	R ²
HMSS/SA	24.22	0.096 5	0.981 6	25.64	0.006 6	0.996 4
MCM-41/SA	20.03	0.038 5	0.976 2	22.12	0.002 3	0.994 1
SBA-15/SA	18.50	0.039 5	0.974 8	20.39	0.002 6	0.991 1

Fig.7 Effect of Sr²⁺ initial mass concentration on adsorption properties of composites and Langmuir，Freundlich adsorption isotherm

Table 2 Parameters of adsorption isothermal models

复合材料	Langmuir			Freundlich
复合材料	q _e/（mg·g^-1）	K _L/（L·mg^-1）	R ²	n	K _F/（L^1/ ⁿ ·mg^1-1/ ⁿ ·g^-1）	R ²
HMSS/SA	49.67	0.015 2	0.991 9	5.210 1	0.351 6	0.967 5
MCM-41/SA	40.54	0.015 4	0.986 0	4.048 1	0.360 6	0.972 0
SBA-15/SA	34.90	0.020 3	0.988 3	4.669 0	0.317 8	0.972 9

Fig.8 Effect of dosage on adsorption

Fig.9 Effect of competing ions on adsorption

Fig.10 Recycling performance

References 37

1	俞誉福. 萃取色层法测定食品中⁹⁰锶［J］. 环境科学，1978，3：8-13.
	YU Yufu. Determination of 90 strontium in food by extraction chromatography［J］. Environmental Science，1978，3：8-13.
2	CHEN Kai， KANG Yanshang， ZHAO Yue，et al. Cucurbit［6］uril-based supramolecular assemblies：Possible application in radioactive cesium cation capture［J］. Journal of the American Chemical Society，2014，136（48）：16744-16747. doi:10.1021/ja5098836
3	FIGUEIREDO B R， CARDOSO S P， PORTUGAL I，et al. Inorganic ion exchangers for cesium removal from radioactive wastewater［J］. Separation & Purification Reviews，2018，47（4）：306-336. doi:10.1080/15422119.2017.1392974
4	FISKUM S K， PEASE L F， PETERSON R A. Review of ion exchange technologies for cesium removal from caustic tank waste［J］. Solvent Extraction and Ion Exchange，2020，38（6）：573-611. doi:10.1080/07366299.2020.1780688
5	WANG Rong， CHU Yingying， CHEN Mengjun. Adsorption kinetics of ¹³⁷Cs⁺/⁹⁰Sr²⁺ on Ca-bentonite［J］. Water Environment Research，2017，89（9）：791-797. doi:10.2175/106143017x14902968254593
6	WANG Jianlong， ZHUANG Shuting. Removal of cesium ions from aqueous solutions using various separation technologies［J］. Reviews in Environmental Science and Bio/Technology，2019，18（2）：231-269. doi:10.1007/s11157-019-09499-9
7	ZHANG Huagui， KIM Y K， HUNTER T N，et al. Organically modified clay with potassium copper hexacyanoferrate for enhanced Cs⁺ adsorption capacity and selective recovery by flotation［J］. Journal of Materials Chemistry A，2017，5（29）：15130-15143. doi:10.1039/c7ta03873a
8	KRESGE C T， LEONOWICZ M E， ROTH W J，et al. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism［J］. Nature，1992，359：710-712. doi:10.1038/359710a0
9	YUE Qin， LI Jialuo， LUO Wei，et al. An interface coassembly in biliquid phase：Toward core-shell magnetic mesoporous silica microspheres with tunable pore size［J］. Journal of the American Chemical Society，2015，137（41）：13282-13289. doi:10.1021/jacs.5b05619
10	GÉRARDIN C， REBOUL J， BONNE M，et al. Ecodesign of ordered mesoporous silica materials［J］. Chemical Society Reviews，2013，42（9）：4217-4255. doi:10.1039/c3cs35451b
11	GUO Yige， LIU Dongfang， ZHAO Ying，et al. Synthesis of chitosan-functionalized MCM-41-A and its performance in Pb（Ⅱ） removal from synthetic water［J］. Journal of the Institute of Chemical Engineers，2017，71：537-545. doi:10.1016/j.jtice.2016.12.033
12	SCHRODEN R C， AL-DAOUS M， SOKOLOV S，et al. Hybrid macroporous materials for heavy metal ion adsorption［J］. Journal of Materials Chemistry，2002，12（11）：3261-3267. doi:10.1039/b204065b
13	IDRIS S A， HARVEY S R， GIBSON L T. Selective extraction of mercury（Ⅱ） from water samples using mercapto functionalised-MCM-41 and regeneration of the sorbent using microwave digestion［J］. Journal of Hazardous Materials，2011，193：171-176. doi:10.1016/j.jhazmat.2011.07.037
14	VIDYA K， GUPTA N M， SELVAM P. Influence of pH on the sorption behaviour of uranyl ions in mesoporous MCM-41 and MCM-48 molecular sieves［J］. Materials Research Bulletin，2004，39（13）：2035-2048. doi:10.1016/j.materresbull.2004.07.013
15	ZHANG Ning， LIU Shujuan， JIANG Ling，et al. Adsorption of strontium from aqueous solution by silica mesoporous SBA-15［J］. Journal of Radioanalytical and Nuclear Chemistry，2015，303（3）：1671-1677. doi:10.1007/s10967-014-3681-1
16	赵联芳，丁奎元，于雪晴. 海藻酸钠-活性炭固定化藻菌球的制备及其对碱性橙Ⅱ的降解［J］. 中国环境科学，2024，44（2）：781-792.
	ZHAO Lianfang， DING Kuiyuan， YU Xueqing. Preparation of sodium alginate-activated carbon immobilized algal-bacteria and its effect on basic orangeⅡ degradation［J］. China Environmental Science，2024，44（2）：781-792.
17	BOUKOUSSA B， MOKHTAR A， GUERDAOUI A EL，et al. Adsorption behavior of cationic dye on mesoporous silica SBA-15 carried by calcium alginate beads：Experimental and molecular dynamics study［J］. Journal of Molecular Liquids，2021，333：115976. doi:10.1016/j.molliq.2021.115976
18	HACHEMAOUI M， MOKHTAR A， MEKKI A，et al. Composites beads based on Fe₃O₄@MCM-41 and calcium alginate for enhanced catalytic reduction of organic dyes［J］. International Journal of Biological Macromolecules，2020，164：468-479. doi:10.1016/j.ijbiomac.2020.07.128
19	LI Wenjiang， SHA Xiaoxiang， DONG Wenjun，et al. Synthesis of stable hollow silica microspheres with mesoporous shell in nonionic W/O emulsion［J］. Chemical Communications，2002，20：2434-2435. doi:10.1039/b206020e
20	HO Y S. Citation review of Lagergren kinetic rate equation on adsorption reactions［J］. Scientometrics，2004，59（1）：171-177. doi:10.1023/b:scie.0000013305.99473.cf
21	HO Y S， MCKAY G. Pseudo-second order model for sorption processes［J］. Process Biochemistry，1999，34（5）：451-465. doi:10.1016/s0032-9592(98)00112-5
22	HONEYMAN B D， SANTSCHI P H. Metals in aquatic systems［J］. Environmental Science & Technology，1988，22（8）：862-871. doi:10.1021/es00173a002
23	ALSHHAB A， YILMAZ E. Sodium alginate/poly（4-vinylpyridine） polyelectrolyte multilayer films：Preparation，characterization and ciprofloxacin HCl release［J］. International Journal of Biological Macromolecules，2020，147：809-820. doi:10.1016/j.ijbiomac.2019.10.058
24	LI Xiancai， LU Tianren， WANG Ying，et al. Study on the controllable synthesis of SH-MCM-41 mesoporous materials and their adsorption properties of the La³⁺，Gd³⁺ and Yb³⁺ ［J］. Chinese Chemical Letters，2019，30（12）：2318-2322. doi:10.1016/j.cclet.2019.05.056
25	GHAREKHANI H， OLAD A， MIRMOHSENI A，et al. Superabsorbent hydrogel made of NaAlg-g-poly（AA-co-AAm） and rice husk ash：Synthesis，characterization，and swelling kinetic studies［J］. Carbohydrate Polymers，2017，168：1-13. doi:10.1016/j.carbpol.2017.03.047
26	GANJI S， MUTYALA S， NEELI C K P，et al. Selective hydrogenation of the CC bond of α，β-unsaturated carbonyl compounds over PdNPs-SBA-15 in a water medium［J］. RSC Advances，2013，3（29）：11533-11538. doi:10.1039/c3ra41966e
27	DING Xue， YU Xi chang， SUN Hai xia. Preparation and characterization of MCM-41 mesoporous silica functionalized with sulfonic acid groups［J］. Advanced Materials Research，2013，781/782/783/784：215-218. doi:10.4028/www.scientific.net/amr.781-784.215
28	BAJPAI S K， SHARMA S. Investigation of swelling/degradation behaviour of alginate beads crosslinked with Ca²⁺ and Ba²⁺ ions［J］. Reactive and Functional Polymers，2004，59（2）：129-140. doi:10.1016/j.reactfunctpolym.2004.01.002
29	HONG H J， KIM B G， HONG J，et al. Enhanced Sr adsorption performance of MnO₂-alginate beads in seawater and evaluation of its mechanism［J］. Chemical Engineering Journal，2017，319：163-169. doi:10.1016/j.cej.2017.02.132
30	郑佳豪，江惟，陈思莉，等. 复合材料MnO₂/MCM-41对放射性废水中Sr²⁺的去除［J］. 工业水处理，2024，44（2）：105-111.
	ZHENG Jiahao， JIANG Wei， CHEN Sili，et al. Removal of Sr²⁺ from radioactive wastewater by the composite MnO₂/MCM-41［J］. Industrial Water Treatment，2024，44（2）：105-111.
31	杜志辉，贾铭椿，王晓伟，等. 聚丙烯腈基钛酸钾球形复合吸附剂的制备及其对Sr²⁺的吸附性能研究［J］. 原子能科学技术，2019，53（8）：1359-1366.
	DU Zhihui， JIA Mingchun， WANG Xiaowei，et al. Preparation of polyacrylonitrile-potassium titanate spherical composite adsorbents and their adsorption properties for Sr²⁺ ［J］. Atomic Energy Science and Technology，2019，53（8）：1359-1366.
32	AWUAL M R， YAITA T， MIYAZAKI Y，et al. A reliable hybrid adsorbent for efficient radioactive cesium accumulation from contaminated wastewater［J］. Scientific Reports，2016，6：19937. doi:10.1038/srep19937
33	KHANDAKER S， TOYOHARA Y， SAHA G C，et al. Development of synthetic zeolites from bio-slag for cesium adsorption：Kinetic，isotherm and thermodynamic studies［J］. Journal of Water Process Engineering，2020，33：101055. doi:10.1016/j.jwpe.2019.101055
34	DING Dahu， LEI Zhongfang， YANG Yingnan，et al. Selective removal of cesium from aqueous solutions with nickel（Ⅱ） hexacyanoferrate（Ⅲ） functionalized agricultural residue-walnut shell［J］. Journal of Hazardous Materials，2014，270：187-195. doi:10.1016/j.jhazmat.2014.01.056
35	YOO J M， PARK S S， YAN Yongzhu，et al. Crown-ether-modified SBA-15 for the adsorption of Cr（Ⅵ） and Zn（Ⅱ） from water［J］. Materials，2021，14（17）：5060. doi:10.3390/ma14175060
36	NAEIMI S， FAGHIHIAN H. Performance of novel adsorbent prepared by magnetic metal-organic framework（MOF） modified by potassium nickel hexacyanoferrate for removal of Cs⁺ from aqueous solution［J］. Separation and Purification Technology，2017，175：255-265. doi:10.1016/j.seppur.2016.11.028
37	HONG H J，RYU J， PARK I S，et al. Investigation of the strontium〔Sr（Ⅱ）〕 adsorption of an alginate microsphere as a low-cost adsorbent for removal and recovery from seawater［J］. Journal of Environmental Management，2016，165：263-270. doi:10.1016/j.jenvman.2015.09.040

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Preparation of mesoporous silica/sodium alginate composites and its removal performance of radioactive Sr²⁺

介孔硅/海藻酸钠复合材料的制备及其对放射性Sr²⁺的去除

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