DD295097A5 - METHOD FOR PRODUCING METALION -ELECTIVE INTERMESH CATION EXCHANGERS - Google Patents

Abstract

The invention relates to a process for the preparation of novel intermesh cation exchangers, which are distinguished by a metal ion selectivity with respect to Cu 2, Ni 2 and Co 2 ions. According to the invention, a divinylbenzene-crosslinked copolymer of * or its anhydride and acrylic acid or acrylonitrile is produced in the pores of a macroporous sulfonated resinate based on styrene and divinylbenzene. These cation exchangers can be used for selective enrichment of metal ions, in particular of copper, but also of nickel and cobalt, for recovering metal ions from waste waters, for chromatographic separations and in the charged state as catalysts. manufacture; Intermeshkationenaustauscher; Metallionenselektivitaet; Copper; Nickel; Cobalt; macroporous resinate; copolymer; * Acrylic acid; acrylonitrile}

Description

Acrylonitrile as the second monomer and divinylbenzene as a crosslinker is synthesized. The inert medium used to produce the degree of porosity is dimethylformamide or dimethyl sulfoxide. Matrices for intermesh polymerization are macroporous, sdfbnlerte resinates based on styrene and divinylbenzene. The produced intermesh-type catalyst exchangers clearly prefer the Cu ² "ions, but also the Ni ²⁺ and Co ²⁺ ions in a somewhat attenuated form compared to the ions of the alkaline earths and those of the other 3 d metals.

applications

The matrices used were styrene / divinylbenzene-based macroreticular resinates prepared using white spirit (boiling range 418-473K) as the inert medium. Suspendieron the prepared resinates in dichloroethane and subsequent sulfonation at 373 K with chlorosulfonic arise macroporous sulfonated matrices, in the pore framework an intermesh copolymerization was carried out. The monomers used were 7-oxa-bicyclo (2.2.1) hept-5-ene-2,3-exo, cis dicarboxylic acid (formula I) or its anhydride and acrylic acid or acrylonitrile. To crosslink the polymer chains, technical divinylbenzene was used from 54.1% p- and m-DVB, 32.9% ethylstyrene and 12.2% diethylbenzene. The degree of crosslinking is to be understood as meaning the% by mass of DVB, based on the mixture of polymerizable substances. The inert medium used was dimethylformamide or dimethyl sulfoxide or mixtures thereof with water. The amount of the inert agent, based on the amount of the monomer mixture and the inert agent, is defined at a degree of porosity. The determination of the selectivity coefficient K was carried out in the batch method according to the relationship

_k a (Yb ') s · (Va') r ^{B =}

Here, YA and Ye each denote the equivalent proportion, which is defined as Yi zimi / zjnij (z absolute valence and m amount of ions). The indices R and S characterize the resin phase and the aqueous solution.

example 1 In a sulfonated matrix with the degree of porosity of 40% and a degree of crosslinking of 10%, a mixture of

7-Oxa-bicyclo (2.2.1) hept-5-ene-2,3-exo, cis-dicarboxylic acid and acrylic acid in a molar ratio of 1: 2.6 swollen.

The degree of crosslinking determined by the amount of divinylbenzene used was 10%, that of the inert medium Dimethyl sulfoxide 30%. The total mass capacity of the intermesh exchanger is 3.4mmol / g. About 1 g of the air-dry intermesh exchanger present in the hydrogen ion form was batched

in each 100ml 0.04M salt solutions at varying hydrogen ion concentrations entered and the

Exchange equilibrium determined after 24 hours. The results obtained are shown in Table 1. Table 1: Coefficients of activity K in 0.04 M saline solutions at different hydrochloric acid concentrations

cation Concentration of HCl in mmol 2.0 8.0 M ²⁺ per 100 ml solution 51.9 25.0 0.5 42.3 19.8 Cu 82.3 39.9 19.2 Ni 70.1 23.3 17.9 Co 66.2 23.0 17.9 Zn 38.7 22.0 16.8 mg 36.2 Mn 36.0

Order of cations: Cu > Ni> Co *>Zn>Mg> Mn Example 2

As the matrix for intermesh polymerization, the same as in Example 1 is used. The working operations also correspond to those in Example 1. The Intermeshcopolymerisat is prepared from 7-oxa-bicyclo (2.2.1) hept-5-ene-2,3-exo, cis-dicarboxylic acid and acrylic acid in a molar ratio of 1: 2.4. The degree of crosslinking was 5%, the degree of porosity 50%, with a mixture of dimethylformamide and water in the ratio 3: 2 was used as the inert. The total mass capacity was 3.4 mmol / g. The determination of the selectivity coefficients K was carried out in the same way as in Example 1. The results obtained are shown in Table 2.

Table 2: Selectivity coefficients K in 0.04M saline solutions at different hydrochloric acid concentrations

cation Concentration of HCl in mmol 2.0 8.0 M ²⁺ per 100 ml solution 47.8 22.8 0.5 39.1 19.8 Cu 75.9 38.8 19.8 Ni 61.3 20.9 17.0 Co 60.3 21.1 16.7 Zn 35.7 20.0 16.5 Mn 31.2 mg 30.2

Order of cations: Cu *> Ni> Co *> Zn> Mn> Mg

Claims (1)

Process for the preparation of intermesh cation exchangers having pronounced metal ion selectivity, characterized in that 7-oxa-bicyclo (2.2.1) hept-5-ene-2,3-exo-cis-dicarboxylic acid or its anhydride is used as a monomer for the intermesh polymer becomes. A copolymerization in a molar ratio of 1: 1.8 to 1: 3 is carried out with acrylic acid or acrylonitrile. The crosslinking agent is divinylbenzene. The degree of crosslinking is 5-10%. The solvent used for the monomers is dimethylformamide or dimethyl sulfoxide or mixtures thereof with water. The required degree of porosity is at least 20% and a maximum of 50%. The copolymerization is carried out in sulfonated macroretikularen Resinaten based on styrene and divinylbenzene. Field of application of the invention The invention relates to a process for the preparation of intermesh cation exchangers, which have a pronounced metal ion selectivity towards the cations Cu ²⁺ , Ni ²⁺ and Co ²⁺ , the copper ion being clearly preferred. The intermesh polymer is prepared by free-radical copolymerization of 7-oxa-bicyclo (2.2.1) hept-5-ene-2,3-exo, cis dicarboxylic acid (formula I) or its anhydride with acrylic acid or acrylonitrile with simultaneous crosslinking with divinylbenzene in a sulfonated, macroreticular resinate based on styrene and divinylbenzene. Formula I COOH
COOH The intermesh exchangers thus produced can be used for enriching the divalent cations of copper, nickel and cobalt from mixtures in an aqueous medium, for recovering metal ions from waste water, for chromatographic separations and as possible catalysts in the loaded state. Characteristic of the known state of the art 7-oxa-bicyclo (2.2.1) hept-5-ene-2,3-exo, cis-dicarboxylic acid or its anhydride have hitherto not been used as a monomer for the preparation of ion exchangers. With respect to the metal ion selectivity of ion exchangers, Green, BR and Hancock, RD (Hydrometallurgy, 1981, β, 354) examined matrix effects on ion exchangers with pyridine and imidazole groups. High Cu ²⁺ ion selectivity on the polymer of sodium vinyl phosphate and acrylic acid is shown by Efendiev, AA et al. (Soc. Akad. Nauk., ASSR, 1980, [36], 37) and Yokoyama, T., Nikuchi, A. et al. (Tohoku Kogyo Gijutsu Shikensko Hokoku, 1983, [16j, 32]) on ion exchangers with a styrene / divinylbenzene backbone modified with pyridylalkylamines. Because of their high copper ion selectivity, a Japanese patent JP 6,009,815 (85-09815), Kl. C21C5 / 28 of 18.1.1985, protect a guanidine carbonate-modified acrylonitrile / divinylbenzene ion exchanger and US Pat. No. 4,666,683 KI.423- 24C01 G 3/00 the ion exchanger Dowex XFS 4195 functionalized with picolylamines. Sulfomethylated styrene / divinylbenzene ion exchangers show high Co ²⁺ selectivity (SU Pat. 1,011,544 Kl. C02 F1 / 42,1983) aminated to polyacrylonitrile in the presence of Cu ²⁺ and NI ²⁺ ions (Kasakevich, Yu., et al., Jonnyi Obmei Chromatogr., 1984, 11). A larger number of known ion exchangers have been tested for their metal ion selectivity by Yoshida, H., Ka '<aoka, T. and Fujikawa, S. (Chem. Eng. ScI., 1986, 41 (10), 2525) using the ion exchangers Dowex A1 and UR-10 have proved to be particularly advantageous over Cu ²⁺ and Co ²⁺ ions, and nickel recovery from saline solutions containing 3d transition metal ions is possible with ion exchangers having carboxyl groups as the fixed ions (Hubicki, Z., Hydrometallurgy, 1986 , 16, 361, Nikoforov, AF et al., Kompleksn, Ipoly, Miner, Syrya, 1988, 48). Object of the invention The aim of the invention is the preparation of easily accessible new intermesh cation exchangers, which have a pronounced selectivity towards some cations and allow their enrichment from aqueous solutions. Explanation of the essence of the invention The object of the invention is a process for the preparation of intermesh cation exchangers, which allows a selective separation of Cu ²⁺ , Co ²⁺ and Ni ² 'ions from aqueous solutions in which salt mixtures are present. According to the invention, intermesh cation exchangers, intermeshed polymers of a copolymer of 7-oxabicyclo (2.2.1) hept-5-ene-2,3-exo, cis-dicarboxylic acid (formula I) or their anhydride as a monomer, acrylic acid or