CS270845B1 - Method of metallic iones cu(ii),pb(ii),hg(ii),cd(ii),ni(ii),zn(ii),sr(ii),fe(iii),la(iii), uo2 2+,th(iv) removal from aqueous solutions - Google Patents
Method of metallic iones cu(ii),pb(ii),hg(ii),cd(ii),ni(ii),zn(ii),sr(ii),fe(iii),la(iii), uo2 2+,th(iv) removal from aqueous solutions Download PDFInfo
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- CS270845B1 CS270845B1 CS885771A CS577188A CS270845B1 CS 270845 B1 CS270845 B1 CS 270845B1 CS 885771 A CS885771 A CS 885771A CS 577188 A CS577188 A CS 577188A CS 270845 B1 CS270845 B1 CS 270845B1
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 241000575946 Ione Species 0.000 title 1
- 239000004094 surface-active agent Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000002244 precipitate Substances 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 Sr(II) Chemical compound 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000008929 regeneration Effects 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims abstract description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000007513 acids Chemical class 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 4
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 2
- 150000001455 metallic ions Chemical class 0.000 abstract 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract 1
- 230000003252 repetitive effect Effects 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000000605 extraction Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 102100032843 Beta-2-syntrophin Human genes 0.000 description 1
- 108050004003 Beta-2-syntrophin Proteins 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
(57) Podstatou spósobu odstranovania kovových iónov ako sú Cu(II), Pb(II), Hg(II), Cd(II), Ni(II) , Zn(II), Sr(II), Fe(III), La(III), UO2, Th(IV) z vodných roztokov s následnou regeneráciou použitého tenzidu je, že sa tenzidmi typu kyselin 2-/alkyl/-nitri lotrioctových s alkylom C^ až C20 Působí na vodné roztoky kovov tak, aby poměr tenzidu a kovu bol 1:1 až 2 v rozsahu pH 1 až 9, pričom vzniká separovatelná zrazenina komplexu kovu s tenzidom buď priamo, alebo sa potřebné pH pře tvorbu zrazeniny dosiahne prídavkom minerálnych kyselin ako sú kyselina dusičná, kyselina sírová, kyselina chlorovodíková s následným přidáním uvedených minerálnych kyselin v koncentrácii až 5 mol.dm} к izolovanej zrazenine komplexu sa izoluje kovový ión vo formě rozpustnej anorganickej soli za súčasného vyzrážania póvodného tenzidu. Uvedeným spósobom sa odstráni z vodných roztokou kovov 80 až 99,9 4 hmot, kovu a následnou regeneráciou tenzidu je možné získať pře opakované použitie 90 až 99 4 hmot, póvodného tenzidu.(57) The principle of removing metal ions such as Cu (II), Pb (II), Hg (II), Cd (II), Ni (II), Zn (II), Sr (II), Fe (III), La (III), UO2, Th (IV) from aqueous solutions followed by regeneration of the surfactant used is that 2- (alkyl) -nitri-lotriacetic acid surfactants with a C 1 to C 20 alkyl act on aqueous metal solutions so that the surfactant ratio and the metal was 1: 1 to 2 in the pH range of 1 to 9, whereby a separable precipitate of the metal-surfactant complex is formed either directly or the necessary pH for precipitate formation is achieved by addition of mineral acids such as nitric acid, sulfuric acid, hydrochloric acid The metal ion is isolated in the form of a soluble inorganic salt while precipitating the original surfactant. In this manner, metal from 80 to 99.9% by weight of the metal is removed from the aqueous metal solution and subsequent recovery of the surfactant to obtain 90 to 99% by weight of the original surfactant.
Vynález sa týká spósobu odstraňovania kovových iónov ako sú Cu(II), Pb(II), Hg(II), Cd(II), Ni(II), Zn(II), Sr(II), Fe(III), La(III), UO?2*, Th(IV) z vodných roztokov.The invention relates to a method for removing metal ions such as Cu (II), Pb (II), Hg (II), Cd (II), Ni (II), Zn (II), Sr (II), Fe (III), La (III) UO? 2 *, Th (IV) from aqueous solutions.
V súčasnosti sa к odstraňovaníu kovových iónov z vodných roztokov používajú viaceré spůsoby: metody extrakčné - Morrison G.A., Freiser H.: Extrakčné metody v analytické chemii, SNTL, Praha (1962); Calligaro L., Mantovani A., Belluco U., Acampora M. : Polyhedron 2, 1189 (1983); Malát M.: Fresenius Z. Anal. Chem. 297, 417 (1979); Pakalns P.: Water Res. 15, 7 (1981); Chakravortty V., Dash K.G., Mohanty S.R.: Radlochim. Acta 40, 89 (1986); Grimm R., Kolařík Z.: J. Inorg. Nucl. Chem. 36, 189 (1974); Schepper A.: Hydrometa1lurgy 4, 285 (1979). V klasickej extrakcii přítomnost tenzidov ovplyvňuje vlastnosti medzifázového povrchu, čím sa může negativné ovplyvnit rýchlosť extrakcie a extrakčné účinnost': Huttinger K.J., Schegk J.R.: Chem. Ing. Těch. 53, 574 (1981); Osseo-Asare K.: Proč. Int. Solv. Extr. Conf. ISEC 83, Denver 278 (1983). Při použití tenzidu ako súčasti vodnej fázy v extrakcii pozoruje sa interferencia tenzidu s obomi fázami za vzniku emulzií, čo celý proces negativné ovplyvňuje - Pakalns P.: Water Res. 15, 7 (1981). iónový flotačný proces zahrňuje prídavok ionogénneho tenzidu к roztokom iónov opačného náboja. Prebublávaním systému vzduchom alebo dusíkom sa tenzid adsorbuje spolu so separovanou zložkou na povrchu bublin a takto sa z roztoku oddel’uje - Berg E.W., Downey D.M.: Anal. Chim. Acta 120, 237 (1980); 121, 239 (1980); 123, 1 (1981); Liem-Fang-Wu, Rui-Chim Kuo, Schang0a Huang: J. Chines. Chim. Soc. 27, 165 (1980). К izolácii rady kovov boli použité chelatačné sorbenty: Kálalová E., Radová Z., Ulbert K., Kálal 3., Švec F.: Europ. Polym. 3.Several methods are currently used to remove metal ions from aqueous solutions: extraction methods - Morrison G.A., Freiser H .: Extraction Methods in Analytical Chemistry, SNTL, Prague (1962); Calligaro L., Mantovani A., Belluco U., Acampora M., Polyhedron 2, 1189 (1983); Malát M .: Fresenius Z. Anal. Chem. 297, 417 (1979); Pakalns P .: Water Res. 15, 7 (1981); Chakravortty V., Dash K. G., Mohanty S. R., Radlochim. Acta, 40, 89 (1986); Grimm R., Kolarik Z .: J. Inorg. Nucl. Chem. 36, 189 (1974); Schepper A .: Hydrometallurgy 4, 285 (1979). In classical extraction, the presence of surfactants affects the properties of the interfacial surface, which may negatively affect the extraction rate and extraction efficiency: Huttinger K.J., Schegk J.R .: Chem. Ing. Those. 53, 574 (1981); Osseo-Asare K .: Why. Int. Solv. Extr. Conf. ISEC 83, Denver 278 (1983). When using a surfactant as part of the aqueous phase in extraction, the surfactant interference with both phases is observed to form emulsions, which negatively affects the whole process - Pakalns P .: Water Res. 15, 7 (1981). the ion flotation process involves the addition of an ionogenic surfactant to the counterion ions solutions. By bubbling the system through air or nitrogen, the surfactant is adsorbed along with the separated component on the surface of the bubbles and is thus separated from the solution - Berg E.W., Downey D.M .: Anal. Chim. Acta 120,237 (1980); 121, 239 (1980); 123, 1 (1981); Liem-Fang-Wu, Rui-Chim-Kuo, Schang-Huang: J. Chines. Chim. Soc. 27, 165 (1980). Chelating sorbents were used to isolate many metals: Kálalová E., Radová Z., Ulbert K., Kálal 3., Švec F .: Europ. Polym. Third
13, 299 (1977); Radová Z., Kálalová E., Kálal 3., Kukuškin 3u. N., Simanova S.A., Konovalov L.V., Pak V.N.: Agnew, Makropol. Chem. 81, 55 (1979); Kálalová E.; Chem. Prum. 31, (1981). Ekonomickému využitiu týchto metod v mnohých prípadoch bráni nevratnost’ sorpčného procesu, použitie elučných kyselin o vysokej koncentrácii alebo vyhrievanie kolon pře zvýšenie efektu disorpcie kovov - Kanert G.A., Chow A.: Anal. Chem. Acta 78, 375 (1975). Pre získavanie kovov využívá sa aj technika ionomeničov - Brajter K., Slonawska K.: Talanta 27, 745 (1980); Korkisch 3.: Analytical techniques in eviroamental chemistry, Pergamon Press 449 (1981). Při viacstupňovej sepárácii je iónovýmenný proces kombinovaný s inými prekoncentračnými technikami - ako je odparovanie alebo extrakcia.13, 299 (1977); Radová Z., Kálalová E., Kálal 3rd, Kukuškin 3u. N., Simanova, S.A., Konovalov, L.V., and then V.N .: Agnew, Makropol. Chem. 81, 55 (1979); Kalalalova E .; Chem. Avg. 31, (1981). In many cases, the irreversibility of the sorption process, the use of high-concentration eluting acids or column heating to enhance the metal disorption effect prevent the economical use of these methods - Kanert G.A., Chow A .: Anal. Chem. Acta 78: 375 (1975). Ion exchange techniques are also used to obtain metals - Brajter K., Slonawska K .: Talanta 27, 745 (1980); Korkisch 3: Analytical techniques in eviroamental chemistry, Pergamon Press 449 (1981). In multi-stage separation, the ion exchange process is combined with other preconcentration techniques - such as evaporation or extraction.
Vyššie uvedené nedostatky sú odstránené spůsobom odstraňovaní a kovových iónov ako sú Cu(II), Pb(II), Hg(II), Cd(II), Ni(II), Zn(II), Sr(II), Fe(III), La(III), UO?2*, Th(IV) z vodných roztokov s následnou regeneráciou použitého tenzidu, ktorého podstatou je, že na vodný roztok kovov sa působí tenzidmi typu kyselin 2-/alkyl/-nitrilotrioctových s alkylom C^ až C2Q v pomere tenzid : kov 1 : 1 až 2 při pH 1 až 9 za vzniku separovateínej zrazeniny, komplexu kovu s tenzidom, ku ktorej sa přidá minerálna kyselina ako je kyselina sírová, dusičná, chlorovodíková v koncentrácii 1 až 5 mol.dm~\ pričom kovový ión sa izoluje vo formě rozpustnej anorganickej soli a tenzid sa oddělí vo formě zrazeniny.The above deficiencies are eliminated by the removal of metal ions such as Cu (II), Pb (II), Hg (II), Cd (II), Ni (II), Zn (II), Sr (II), Fe (III). ), La (III), US? 2 *, Th (IV) from aqueous solutions followed by regeneration of the surfactant used, which is based on the fact that the aqueous metal solution is treated with surfactants of the 2- (alkyl) -nitrilotriacetic acid type with C1 -C2 alkyl in the surfactant: metal ratio 1: 1-2 at pH 1-9 to form a separable precipitate, a metal-surfactant complex, to which a mineral acid such as sulfuric, nitric, hydrochloric acid is added at a concentration of 1 to 5 mol.dm -1, wherein the metal ion is isolated as a soluble the inorganic salt and the surfactant are collected as a precipitate.
Prídavkom minerálnej kyseliny ako je kyselina sírová, dusičná alebo chlorovodíková sa může upravit pH vodného roztoku kovov.The pH of the aqueous metal solution can be adjusted by the addition of a mineral acid such as sulfuric, nitric or hydrochloric acid.
Postup podl’a vynálezu je demonstrovaný na príkladoch.The process according to the invention is demonstrated by examples.
Příklad 1Example 1
К vodě obsahujúcej 3.1О’5 mol.dm^ Cu(II) sa přidá také množstvo sodnej soli kyseliny 2-/hexadecy1/-nitrilotrioctovej, aby poměr molárnych hmotností tenzidu a kovu bol 1:1 až 1:2. Při pH menšom ako 7 vytvára sa v takto pripravenom roztoku priamo zraženina komplexu kovu s tenzidom, ktorá sedimentuje v priebehu 1 až 10 minút. Po oddělení zrazeniny zníži sa obsah Cu(II) v roztoku maximálně o 99 ’-ί hmot.. Z izolovanej zrazeniny možno prídavkom kyseliny sírovej C/H2SO4/ = 3 mol.dm regenerovat’ 98 % hmot, původného tenzidu, ktorý sa oddělí ako zrazenina od roztoku súčasne získanej soli kovu a může sa opakované využit к ďalšiemu procesu zrážania kovových iónov.The amount of sodium 2- (hexadecyl) -nitrilotriacetic acid sodium salt is added to water containing 3.1 ° C to 5 mol.dm 2 Cu (II) such that the molar mass ratio of the surfactant to the metal is 1: 1 to 1: 2. At a pH of less than 7, a precipitate of the metal-surfactant complex is formed in the solution thus prepared, which sedimentes within 1 to 10 minutes. After separation of the precipitate, the Cu (II) content in the solution is reduced by a maximum of 99% by weight. 98% by weight of the original surfactant can be recovered from the precipitate by addition of sulfuric acid C (H2SO4) = 3 mol.dm. a precipitate from a solution of the co-obtained metal salt and can be reused for further metal ion precipitation process.
Příklad 2Example 2
К vodě obsahujúcej 5.10*^ mol.dm Th(IV) sa přidá také množstvo sodnej soli kyseliny 2-/decyl/-nitrilotrioctovej, aby poměr molárnych hmotností tenzidu a kovu bol 1:1 až 1:2. V oblasti pH váčšom ako 3 sa vytvára v takto pripravenom roztoku zrazenina komplexu kovu s tenzidom, ktorá sedimentuje v priebehu 1 až 10 minut. Po oddělení zrazeniny filtráciou poklesne obsah Th(IV) v roztoku maximálně o 90 % hmot.. Z izolovanej zrazeniny možno přídavkom kyseliny sírovej c/H^O^/ = 3 mol.dm“} regenerovat 98 % hmot. pĎvodného tenzidu, ktorý sa oddělí ako zrazenina od roztoku súčasne získanej soli kovu a móže sa opakované využit’ к člalšiemu procesu zrážania kovových iónov.The amount of 2- (decyl) -nitrilotriacetic acid sodium salt is added to water containing 5.10 .mu.m.dm of Th (IV) such that the molar mass ratio of surfactant to metal is 1: 1 to 1: 2. In the pH range greater than 3, a precipitate of the metal-surfactant complex is formed in the solution thus prepared, which sedimentes within 1 to 10 minutes. After separation of the precipitate by filtration, the content of Th (IV) in the solution decreases by a maximum of 90% by weight. 98% by weight can be recovered from the isolated precipitate by the addition of sulfuric acid c / H 2 O = 3 mol.dm -1. of the original surfactant, which is separated as a precipitate from the solution of the co-obtained metal salt and can be reused for a further metal ion precipitation process.
Příklad 3Example 3
К vodě obsahujúcej 5,10“^ mol.dm“} La(III) sa přidá ekvivalentně množstvo sodnej soli kyseliny 2-/hexadecyl/-nitrilotrioctovej. V oblasti pH 4,5 vytvára sa zrazenina kovu s tenzidom, ktorá sedimentuje v priebehu 1 až 10 minut. Po oddělení zrazeniny filtráciou poklesne obsah La(III) v roztoku o 98 % hmot., Z izolovanej zrazeniny možno prídavkom kyseliny dusičnej с/HNO-j/ = 2 mol.dm“} regenerovat 99 % hmot. pĎvodného tenzidu, ktorý sa oddělí ako zrazenina od roztoku súčasne získanej soli kovu a móže sa opakované využit к 3alŠiemu procesu zrážania kovových iónov.An equivalent amount of 2- (hexadecyl) -nitrilotriacetic acid sodium salt is added equivalently to water containing 5.10 " In the pH range of 4.5, a metal precipitate with a surfactant is formed, which settles within 1 to 10 minutes. After separation of the precipitate by filtration, the content of La (III) in the solution decreases by 98% by weight. From the isolated precipitate, 99% by weight of nitric acid can be recovered by adding nitric acid with a concentration of 2 mol.dm -1. of the original surfactant which is separated as a precipitate from the solution of the metal salt present and can be reused for a further metal ion precipitation process.
Příklad 4 ’Example 4 ’
К vodě obsahujúcej 2,5.10^ mol.dm“} Cd(II) sa přidá také množstvo sodnej soli kyseliny 2-/hexadecyl/-nitrilotrioctovej, aby poměr molárnych hmotností tenzidu a kovu bol 1:1. V oblasti pH 9 vytvára sa zrazenina kovu s tenzidom, ktorá sedimentuje v priebehu 1 až 10 minút. Po oddělení zrazeniny filtráciou zníži sa obsah Cd(II) v roztoku o 99 % hmot.. Z izolovanej zrazeniny možno prídavkom kyseliny sírovej c/H^O^/ = 2 mol.dm} regenerovat 98 % hmot, póvodného tenzidu, ktorý sa oddělí ako zrazenina od roztoku súčasne získanej soli kovu a móže sa opakované využit к óalšiemu procesu zrážania kovových iónov.The amount of 2- (hexadecyl) -nitrilotriacetic acid sodium salt is added to water containing 2.5 x 10 6 mol.dm -1 of Cd (II) such that the molar mass ratio of surfactant to metal is 1: 1. In the pH range of 9, a metal precipitate with a surfactant is formed which settles within 1 to 10 minutes. After separation of the precipitate by filtration, the content of Cd (II) in the solution is reduced by 99% by weight. 98% by weight of the original surfactant can be recovered from the isolated precipitate by the addition of sulfuric acid c / H 2 O = 2 mol.dm}. as a precipitate from a solution of the co-obtained metal salt, and can be reused for another metal ion precipitation process.
Separáciu kovových iónov s použitím chelátotvorných tenzidov typu kyselin 2-/alkyl/-nitrilotrioctových pri jednoduchej izolovatel’nosti chelátov kovu, vysokej výťažnosti procesu v přepojení s možnosťou vysokého stupňa regenerácie póvodných zložiek možno využit ako jednoduchú a ekonomicky výhodnú metodu v oblasti dekontaminácie odpadových vód a kontaminovaných povrchov vo vztahu к ochraně životného prostredia i ako metodu získavania kovov z priemyselných odpadov.Separation of metal ions using chelating surfactants of the 2- (alkyl) -nitrilotriacetic acid type with a simple isolation of the metal chelates, high interconnection process yields with the possibility of a high degree of regeneration of the parent components can be used as a simple and economically advantageous method in waste water decontamination and contaminated surfaces in relation to environmental protection and as a method of recovering metals from industrial waste.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS885771A CS270845B1 (en) | 1988-08-25 | 1988-08-25 | Method of metallic iones cu(ii),pb(ii),hg(ii),cd(ii),ni(ii),zn(ii),sr(ii),fe(iii),la(iii), uo2 2+,th(iv) removal from aqueous solutions |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS885771A CS270845B1 (en) | 1988-08-25 | 1988-08-25 | Method of metallic iones cu(ii),pb(ii),hg(ii),cd(ii),ni(ii),zn(ii),sr(ii),fe(iii),la(iii), uo2 2+,th(iv) removal from aqueous solutions |
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| Publication Number | Publication Date |
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| CS577188A1 CS577188A1 (en) | 1989-12-13 |
| CS270845B1 true CS270845B1 (en) | 1990-08-14 |
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| CS885771A CS270845B1 (en) | 1988-08-25 | 1988-08-25 | Method of metallic iones cu(ii),pb(ii),hg(ii),cd(ii),ni(ii),zn(ii),sr(ii),fe(iii),la(iii), uo2 2+,th(iv) removal from aqueous solutions |
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1988
- 1988-08-25 CS CS885771A patent/CS270845B1/en unknown
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