Preparation of amino modified styrene-divinylbenzene resin and its adsorption of rhenium

doi:10.11949/0438-1157.20191459

Abstract

Abstract:

The ion exchange method is widely used in the hydrometallurgical industry because it is suitable for the separation and enrichment of low-concentration substances. The synthesis and application of new high-efficiency adsorption materials have become the development trend in this field. In view of the current situation that the associated scarce rhenium minerals in uranium mine need to recover synchronously, the preparation of amino modified styrene-divinylbenzene resin (LSC-Re) was used to recover rhenium in this work. The effect of aqueous acidity, initial concentration, adsorption time and adsorption temperature on the adsorption performance were systematically investigated by static and dynamic adsorption desorption experiments. The results show that 6 h is sufficient up to equilibrium for the LSC-Re anion exchange resin at room temperature, and the acidity has little effect on the adsorption. The LSC-Re anion exchange resin exhibited higher affinity toward Re (Ⅳ) than U(Ⅵ) at pH 1.5, the maximum value of separation factor β_{Re(Ⅳ)/U(Ⅵ)} is 41.68. The saturated adsorption capacity of resins could reach 129.3 mg·g^-1 at present conditions. The adsorption mechanism is in accordance with Langmuir adsorption isotherm model and quasi-second-order kinetic model, and the adsorption process is a spontaneous endothermic from the perspective of thermodynamics and kinetics. The dynamic saturated adsorption capacity could reach 76.17 g·L^-1 and the saturation ratio could reach 2.35 by controlling the solution flow rate to 0.5 ml·min^-1 in the dynamic adsorption experiment. The 8 resin bed volumes can be desorbed completely by 1 mol·L^-1NH₃·H₂O, the enrichment factor is close to 70 times, which means that the LSC-Re anion exchange resin has good industrial application prospects in recovery Re (Ⅳ).

Key words: rhenium, separation and enrichment, LSC-Re resin, kinetics, adsorption, desorption

摘要：

离子交换法因适于低浓度物质的分离富集而被广泛应用于湿法冶金行业，新型高效吸附材料的合成与应用成为该领域的发展趋势。针对铀矿中伴生铼这一稀缺资源需要同步回收的现状，根据新近研发的氨基改性苯乙烯阴离子交换树脂(LSC-Re)，通过静态和动态吸附解吸试验，系统考察了溶液酸度、初始浓度、吸附时间、吸附温度等因素对吸附性能的影响，结果表明：在室温(25℃)下，铼溶液初始浓度为100 mg·L^-1，该树脂6 h达到吸附平衡，酸度对该树脂吸附铼的影响不大，树脂在pH=1.5时铀铼分离效果最佳，分离系数可达到41.68；树脂的饱和吸附容量达到129.3 mg·g^-1；从热力学和动力学角度分析，吸附过程符合Langmuir吸附等温模型和准二级动力学模型，且吸附是自发的吸热过程。动态吸附解吸试验中，控制溶液流速0.5 ml·min^-1，动态饱和吸附容量达到76.17 g·L^-1，饱穿比为2.35，用1 mol·L^-1 氨水进行解吸铼效果较好，8个树脂床体积可将其解吸完全，由此可见富集倍数接近70倍，具有良好的工业应用前景。

关键词: 铼, 分离富集, LSC-Re树脂, 动力学, 吸附, 解吸

CLC Number:

O 614.8

Yu ZHANG, Rong HUA, Xiaokang KOU, Fuping LIU, Jie KONG, Feng ZHANG, Feifan HE, Yu FENG. Preparation of amino modified styrene-divinylbenzene resin and its adsorption of rhenium[J]. CIESC Journal, 2020, 71(5): 2109-2117.

张雨, 花榕, 寇晓康, 刘付平, 孔杰, 张峰, 何非凡, 冯宇. 氨基改性苯乙烯树脂的合成及其对铼的吸附[J]. 化工学报, 2020, 71(5): 2109-2117.

Figures/Tables 15

Fig.1 Polymerization

Fig.2 Chloromethylation reaction

Fig.3 Functionalization reaction

Fig.4 FT-IR spectra of LSC-Re resin before and after rhenium adsorption

Fig.5 SEM images of LSC-Re resin before and after rhenium adsorption

Fig.6 EDS spectra of LSC-Re resin before(a) and after(b) rhenium adsorption

Fig. 7 Relationship between solution pH and adsorption capacityC0(Re)=100 mg·L-1, V=20 ml; m(resin)=0.02 g; t=5 h; T=298 K

Table 1 Distribution coefficient and separation coefficient of Re(Ⅶ) and U(Ⅵ) at different pH of LSC-Re resin

pH	D_Re×10²	D_U×10²	β_Re/U
1.5±0.1	20.21	0.48	41.68
2.0±0.1	33.56	1.22	27.62
2.5±0.1	20.02	1.79	11.17
3.0±0.1	15.95	1.35	1.82
3.5±0.1	21.71	2.23	9.74
4.0±0.1	16.9	0.91	18.61
5.0±0.1	16.6	2.83	5.86
6.0±0.1	19.11	2.41	7.93

Fig. 8 Relationship between DU、DRe、βRe/U and pHC0(Re)=100 mg·L-1, C0(U)=100 mg·L-1, V=20 ml; m(resin)=0.02 g; t=5 h; T=298 K

Fig. 9 Relationship between adsorption time and adsorption capacityC0(Re)=100 mg·L-1, pH=2.0, V=20 ml; m(resin)=0.02 g; T=298 K

Fig.10 Quasi-first-order, quasi-second-order dynamic curves

Fig. 11 Relationship between solution concentration and adsorption capacityC0(Re)= 10~500 mg·L-1, pH=2.0, V=20 ml; m(resin)=0.02 g; t=6 h,T=298 K

Fig.12 Langmuir, Freundlich adsorption isotherm curve

Fig.13 Relationship between temperature and adsorption capacity (a) and thermodynamic fitting curve (b)C0(Re)=100 mg·L-1, pH=2.0, V=20 ml; m(resin)=0.02 g; t=6 h

Fig.14 Dynamic adsorption-desorption curve

References 31

1	Amer A. The hydrometallurgical extraction of rhenium from copper in dustrial wastes[J]. JOM, 2008, 60(8): 52.
2	杨尚磊, 陈艳, 薛小怀, 等. 铼的性质及应用研究现状[J]. 上海金属, 2005, 27(1): 45.
	Yang S L, Chen Y, Xue X H, et al. The property and application research situation of rhenium[J]. Shanghai Metals, 2005, 27(1): 45.
3	Benes V, Boitsov A V, Fazluilin M, et al. Manual of Acid In Situ Uranium Mining Technology[M]. Beijing: Atomic Energy Press, 2003: 289.
4	董海刚, 刘杨, 范兴祥, 等. 铼的回收技术研究进展[J]. 有色金属(冶炼部分), 2013, (6): 30-33.
	Dong H G, Liu Y, Fan X X, et al. Research progress on recovery technology of rhenium[J]. Non-Ferrous Metals (Smelting Part), 2013, (6): 30-33.
5	彭真, 罗明标, 蒋小辉, 等. 协同萃取法回收地浸采铀工艺树脂中铼[J]. 稀有金属, 2011, 35(6): 922.
	Peng Z, Luo M B, Jiang X H, et al. Synergistic extraction of rhenium from in-situ leach uranium mining technology resin[J]. Chinese Journal of Rare Metals, 2011, 35(6): 922.
6	潘慧珍, 陈念貽. 胺型萃取剂N-208萃取铼和钼[J]. 原子能科学技术, 1964, (6): 731-733.
	Pan H Z, Chen N T. Extraction of rhenium and molybdenum with amine extractant N-208[J]. Atomic Energy Science and Technology, 1964, (6): 731-733.
7	宋金如, 龚治湘, 刘淑娟, 等. P350萃淋树脂吸附铼的性能研究及应用[J]. 华东地质学院学报, 2003, 26(3): 274.
	Song J R, Gong Z X, Liu S J, et al. Study and application of adsorption properties of rhenium by P350 extraction resin[J]. Journal of East China Geological Institute, 2003, 26(3): 274.
8	张俊, 姚林, 吕改芳, 等. D-314树脂动态分离钼铼的研究[J]. 稀有金属, 2010, 34(1): 85.
	Zhang J, Yao L, Lyu G F, et al. Dynamic separation of molybdenum and rhenium by D-314 resin[J]. Chinese Journal of Rare Metals, 2010, 34(1): 85.
9	井小静, 赵恒勤, 刘红召, 等. 钼精矿焙烧烟尘中回收铼的研究进展[J]. 有色金属(冶炼部分), 2018, (11): 42-46+55.
	Jing X J, Zhao H Q, Liu H Z, et al. Research progress on recovery of rhenium from roasted dust of moly date concentrate[J]. Non-Ferrous Metals (Smelting Part), 2018, (11): 42-46+55.
10	王华, 刘艳飞, 彭东明, 等. 膜分离技术的研究进展及应用展望[J]. 应用化工, 2013, 42(3): 532-534.
	Wang H, Liu Y F, Peng D M, et al. The development of membrane separation technology and its application prospect[J]. Applied Chemical Industry, 2013, 42(3): 532-534.
11	Xiong Y, Shan W J, Lou Z N, et al. Synergistic extraction of rhenium(Ⅶ) and molybdenum(Ⅵ) with mixtures of bis-(3,5-dimethylhexyl-4-methylhexyl) amine and tributylphosphate[J]. Journal of Phase Equilibria and Diffusion, 2011, 32(3): 193-197.
12	陈波, 包申旭, 张一敏. N235浸渍树脂的制备及对钒的吸附研究[J]. 稀有金属, 2018, 42(8): 891-896.
	Chen B, Bao S X, Zhang Y M. Preparation of N235 impregnated resin and its adsorption for vanadium[J]. Chinese Journal of Rare Metals, 2018, 42(8): 891-896.
13	Tolestof E A, Pan N L, Li P Z. Physical and Chemical Geotechnologies of Development of Gold and Uranium Deposits in Kyzylkum Region[M]. Beijing: Atomic Energy Press, 2003: 124.
14	刘红召, 曹耀华, 高照国. 辉钼矿焙烧烟气淋洗液中铼的富集[J]. 有色金属(冶炼部分), 2009, (6): 39-42.
	Liu H Z, Cao Y H, Gao Z G, et al. Enriching rhenium dissolving in washing water by ion exchange process[J]. Non-Ferrous Metals (Smelting Part), 2009, (6): 39-42.
15	彭真, 罗明标, 花榕, 等. 从矿石中回收铼的研究进展[J]. 湿法冶金. 2012, 31(2): 76-80.
	Peng Z, Luo M B, Hua R, et al. Research progress on recovery of rhenium from ores[J]. Hydrometallurgy of China, 2012, 31(2): 76-80.
16	刘洋, 邓丽, 刘莉, 等. D296树脂对高温合金电解液中Re的吸附研究[J]. 稀有金属, 2017, 41(6): 678-683.
	Liu Y, Deng L, Liu L, et al. Adsorption of Re from electrolyte of superalloy by using D296 resin[J]. Chinese Journal of Rare Metals, 2017, 41(6): 678-683.
17	宿颜涛, 任宇, 王凤菊, 等. 磁性N235萃淋树脂的制备及其对铼的吸附性能研究[J]. 铀矿冶, 2019, 38(1): 29-33.
	Su Y T, Ren Y, Wang F J, et al. Preparation of magnetic N235 extraction resin and its adsorption properties for rhenium[J]. Uranium Mining and Metallurgy, 2019, 38(1): 29-33.
18	刘红召, 王力军, 张博, 等. 一种弱碱性树脂对淋洗液中铼的静态吸附性能[J]. 稀有金属, 2017, 41(9): 1028-1034.
	Liu H Z, Wang L J, Zhang B, et al. Static adsorption properties of a kind of weak anion ion resin for rhenium in spraying water[J]. Chinese Journal of Rare Metals, 2017, 41(9): 1028-1034.
19	叶茂松, 俎建华, 王浦银, 等. 弱碱性阴离子交换树脂的合成及其对铼离子的吸附解吸行为研究[J]. 离子交换与吸附, 2015, 31(2): 107-114.
	Ye M S, Zu J H, Wang P Y, et al. Synthesis of weakly basic anion exchange resin and its adsorption and desorption behavior of rhenium ion[J]. Ion Exchange and Adsorption, 2015, 31(2): 107-114.
20	王晓龙, 俎建华, 韦悦周. AR-01 树脂对铼的吸附和解吸行为[J]. 核化学与放射化学, 2014, 36(4): 204-209.
	Wang X L, Zu J H, Wei Y Z, et al. Adsorption and elution behavior of rhenium using a porous silica-based anion exchanger[J]. Journal of Nuclear and Radiochemistry, 2014, 36(4): 204-209.
21	Chen L F, Yin X B, Yu Q, et al. Rapid and selective capture of perrhenate anion from groundwater by a mesoporous silica-supported anion exchanger[J]. Microporous and Mesoporous Materials, 2018, 274: 155-162.
22	Jia M, Cui H, Jin W, et al. Adsorption and separation of rhenium(Ⅶ) using N-ethylimidazolium functionalized strong basic anion exchange resin[J]. Chem. Technol. Biotechnol., 2013, 88: 437-443.
23	Miniakhmetov I A, Semenov S A, Musatova V Y, et al. Solvent extraction of rhenium with N-(2-hydroxy-5-nonylbenzyl)-β-hydroxyethylmethylamine[J]. Inorg. Chem., 2013, 58: 1380-1382.
24	张伟强, 马建国, 刘淑娟, 等. 改性石墨烯海绵材料对铀的吸附研究[J]. 东华理工大学学报(自然科学版), 2014, 37(2): 230-235.
	Zhang W Q, Ma J G, Liu S J, et al. Uranium adsorption on functionalized graphene sponge[J]. Journal of East China University of Technology (Natural Science), 2014, 37(2): 230-235.
25	Atia A A, Donia A M, Al-Amrani W A. Adsorption/desorption behavior of acid orange 10 on magnetic silica modified with amine groups[J]. Chemical Engineering Journal, 2009, 150(1): 55-62.
26	Senturk H B, Ozdes D, Gundogdu A, et al. Removal of phenol from aqueous solutions by adsorption onto organomodified tirebolu bentonite: equilibrium, kinetic and thermodynamic study [J]. Journal of Hazardous Materials, 2009, 172(1): 353-362.
27	Zhang J, Xiao H, Yang Y. Preparation of hemicellulose-containing latex and its application as absorbent toward dyes[J]. Journal of Materials Science, 2015, 50(4): 1673-1678.
28	李姜无忌, 朱巧影, 陈立芳, 等. 氧缺陷位MoO₃_-x的制备及其吸附性能研究[J]. 化工学报, 2019, 70(10): 3956-3966.
	Li J W J, Zhu Q Y, Chen L F, et al. Preparation of oxygen defect vacancies MoO₃_-x and its adsorption properties[J]. CIESC Journal, 2019, 70(10): 3956-3966.
29	周鹏, 袁花, 彭平英, 等. 球形聚合单宁-纤维素树脂的制备及吸附性能[J]. 化工学报, 2018, 69(7): 3076-3082.
	Zhou P, Yuan H, Peng P Y, et al. Preparation and adsorption properties of spherical poly(tannin)-cellulose resin[J]. CIESC Journal, 2018, 69(7): 3076-3082.
30	袁景香, 王超展, 卫引茂. 基于废弃固定化酶再利用的高容量强阳离子交换树脂及其对溶菌酶的吸附性能[J]. 分析化学, 2016, 44(12): 1892-1899.
	Yuan J X, Wang C Z, Wei Y M. High-capacity strong cation exchange resin based on reutilization of an inactivated immobilized enzyme and its adsorption properties for lysozyme[J]. Chinese Journal of Analytical Chemistry, 2016, 44(12): 1892-1899.
31	陈芳妮, 孙晓君, 魏金枝, 等. 磁性三乙烯四胺氧化石墨烯对Cu²⁺的吸附行为[J]. 化工学报, 2016, 68(5): 1949-1956.
	Chen F N, Sun X J, Wei J Z, et al. Adsorption behavior of magnetic triethylene tetramine-graphene oxide nanocomposite for Cu²⁺ [J]. CIESC Journal, 2016, 68(5): 1949-1956.

[1]	Cheng CHENG, Zhongdi DUAN, Haoran SUN, Haitao HU, Hongxiang XUE. Lattice Boltzmann simulation of surface microstructure effect on crystallization fouling [J]. CIESC Journal, 2023, 74(S1): 74-86.
[2]	Yan GAO, Peng WU, Chao SHANG, Zejun HU, Xiaodong CHEN. Preparation of magnetic agarose microspheres based on a two-fluid nozzle and their protein adsorption properties [J]. CIESC Journal, 2023, 74(8): 3457-3471.
[3]	Linzheng WANG, Yubing LU, Ruizhi ZHANG, Yonghao LUO. Analysis on thermal oxidation characteristics of VOCs based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3242-3255.
[4]	Bingchun SHENG, Jianguo YU, Sen LIN. Study on lithium resource separation from underground brine with high concentration of sodium by aluminum-based lithium adsorbent [J]. CIESC Journal, 2023, 74(8): 3375-3385.
[5]	Ruihang ZHANG, Pan CAO, Feng YANG, Kun LI, Peng XIAO, Chun DENG, Bei LIU, Changyu SUN, Guangjin CHEN. Analysis of key parameters affecting product purity of natural gas ethane recovery process via ZIF-8 nanofluid [J]. CIESC Journal, 2023, 74(8): 3386-3393.
[6]	Mengmeng ZHANG, Dong YAN, Yongfeng SHEN, Wencui LI. Effect of electrolyte types on the storage behaviors of anions and cations for dual-ion batteries [J]. CIESC Journal, 2023, 74(7): 3116-3126.
[7]	Ji CHEN, Ze HONG, Zhao LEI, Qiang LING, Zhigang ZHAO, Chenhui PENG, Ping CUI. Study on coke dissolution loss reaction and its mechanism based on molecular dynamics simulations [J]. CIESC Journal, 2023, 74(7): 2935-2946.
[8]	Jie WANG, Xiaolin QIU, Ye ZHAO, Xinyang LIU, Zhongqiang HAN, Yong XU, Wenhan JIANG. Preparation and properties of polyelectrolyte electrostatic deposition modified PHBV antioxidant films [J]. CIESC Journal, 2023, 74(7): 3068-3078.
[9]	Guangyu WANG, Kai ZHANG, Kaihua ZHANG, Dongke ZHANG. Heat and mass transfer and energy consumption for microwave drying of coal slime [J]. CIESC Journal, 2023, 74(6): 2382-2390.
[10]	Jipeng ZHOU, Wenjun HE, Tao LI. Reaction engineering calculation of deactivation kinetics for ethylene catalytic oxidation over irregular-shaped catalysts [J]. CIESC Journal, 2023, 74(6): 2416-2426.
[11]	Caihong LIN, Li WANG, Yu WU, Peng LIU, Jiangfeng YANG, Jinping LI. Effect of alkali cations in zeolites on adsorption and separation of CO₂/N₂O [J]. CIESC Journal, 2023, 74(5): 2013-2021.
[12]	Chenxin LI, Yanqiu PAN, Liu HE, Yabin NIU, Lu YU. Carbon membrane model based on carbon microcrystal structure and its gas separation simulation [J]. CIESC Journal, 2023, 74(5): 2057-2066.
[13]	Quanbi ZHANG, Yijin YANG, Xujing GUO. Catalytic degradation of dissolved organic matter in rifampicin pharmaceutical wastewater by Fenton oxidation process [J]. CIESC Journal, 2023, 74(5): 2217-2227.
[14]	Shaoyun CHEN, Dong XU, Long CHEN, Yu ZHANG, Yuanfang ZHANG, Qingliang YOU, Chenglong HU, Jian CHEN. Preparation and adsorption properties of monolayer polyaniline microsphere arrays [J]. CIESC Journal, 2023, 74(5): 2228-2238.
[15]	Hao WANG, Siyang TANG, Shan ZHONG, Bin LIANG. An investigation of the enhancing effect of solid particle surface on the CO₂ desorption behavior in chemical sorption process with MEA solution [J]. CIESC Journal, 2023, 74(4): 1539-1548.