CA1193443A - Method for back extraction of indium from organic solvent phase - Google Patents
Method for back extraction of indium from organic solvent phaseInfo
- Publication number
- CA1193443A CA1193443A CA000412521A CA412521A CA1193443A CA 1193443 A CA1193443 A CA 1193443A CA 000412521 A CA000412521 A CA 000412521A CA 412521 A CA412521 A CA 412521A CA 1193443 A CA1193443 A CA 1193443A
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- Prior art keywords
- indium
- chloride
- acid
- con
- ion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A method for back-extracting indium from an indium-con-taining organic solvent phase based on an alkyl phosphonic acid monoalkyl ester is characterized in that an aqueous solution containing hydrochloric acid and a chloride of a metal less noble than indium is employed as the extractant.
The chloride is that of an alkali metal or alkaline earth metal.
A method for back-extracting indium from an indium-con-taining organic solvent phase based on an alkyl phosphonic acid monoalkyl ester is characterized in that an aqueous solution containing hydrochloric acid and a chloride of a metal less noble than indium is employed as the extractant.
The chloride is that of an alkali metal or alkaline earth metal.
Description
3 L/~ 43 METEOD FO:R :BACK EXTRACTION OF IN:DIIJM
FROM C)RGANIS: SoL~1ENT P~IAS~:
R~Rr~R~uND OF trH$ l~v t~;N l ION
Th:a ~ invention xelate~; to a Ineth~d of ~ecs:~vering indium by bac~ extraction ~r ~;~rippi~g from an illdium-con~i n; ng organic ~ol~ren~ p~ase ~a:~ on an alkyl phosphorl~c acid mono-al~l e~;ter.
In res::e~ ear~ ~ ~olvent ex~ract:io~ ha~ come in~o u3e in smelting prc:cess,, and vari~d method~ for recove:ring indium by the t,lsc:hni~e have hitherto been introduced.
In one method ~3apanese Paten~ ~pplication Publicati4n No. 148735/1980), an in~lium-ion-containing ~ueous solul~ n i~ brought into ccntact wi~h an organic ~olvent cont;~in~ng a~ an extractant a mix~ure o:~ a txi al}cyl phosphite and a mono- or dialkyl pho~phoxic acid to ~3xtract indium selec-tiLvely~ and the In-containing oryanic ~ol~rent pha~e thu~
o~tailled 18 contacted with an aqueou~ olution acidifi~d with hydrol::hloric acid ~o effec~ back extraction of indium the:re-frs:~mO Th~re are other methsa~ ~"30~rna~ of Japan ~lining I!ld.
A~30c.," 93, lû70 (1977 43 0 pp. 323~3251 which compri~e t:he ~lkeps e)~ e~ctrac~ g indium ~rom an In-con~ ~ n; ng aqueoue 8olu~ t with an organic~ ~o:Lv~nt cont~ining ~ril~utyl pho~-E3ha~3 (TBP~ as ~he ex~ractan~, and ~hen back extractiIlg i.ndiuim from ~he resulking organic ~olvent pha~e, u~ing w~ter as ~he ~ractaIIk~ or ~he ~3tep~ of ex~rac~ing indium fro~
* `
~34~3 an In~con~;~;n;r~g aqueous solu~ion by the u~3e of a t~rtiary fatty acid a~ an ion~exchange liquid, and carrying vut baek extraction of the el~nellt from the solvent with hydroch~ oric acid aæ ~.he ex~rac~an~. Still ano~er propose~l m~hod ~apa-ne~3e Pat.. ~pp~, Publis: Dlsclo~ure Mo. 148736~1980) consists in extracting indium from an In-con~;-;n;ng solution acidifiea wi~h ~ulfuric acid t wlth the aid o~ an organic: ~lv.on~
t;~in~ng di(2-met~lhexyl~pho~l?horic acîd ester (D2E~PA) a~
the extractant, and back-ext.ral::ting indium from the organic olv~nt ph~se, this tim~ by th~3 ac~ion of hydrochloric or ~ulfuxic acid. Yet another sug~eæ~ed me~hod i~ the same as the one d~cxibed ilmnedia~ely abc~ve with ~h~ ex~ception that D2E~IPA i~ replaced hy an alkyl phosphor~ic acid monoalkyl ~ster., Tncluding thoE;e cited a~ove for example, me~hod~
or indium recovery have been l-.nown in the art which gen~rally compri3e se31ecti~31y extrac:ting indium ~roDn an I~ on~; n~ n~
aqueou~ ~olu~ion, with an organic solvent containing one c)iE
varied extractant~, and back-ex~racting indium from the organic solvent phase by ~he ac~ion of hydrochloric or sulfuric acid or o water. Of those me~hod~ ~o far introduced, the one u3ing alkyï phosphonic acid ~o~o~l kyl e~ex~ ha~ b~en known to :be p~r ticularly ef f ective .
SU~ OF T~ NV~ Jl I ON
ghe pr~ent irl~rention iS charac~eriæed by ~he u~ o an aqueo~ solll~ion ~ which con~ain~ h~drs:~chlc: rir ac:id and a 3~
chloride of a metal 1 e.ns nol~le than indium, as the extractarlt for the bac:k e~straction in the la~3t~menl:ioned method that compris~s extraoking indium by the use of an oxganic ;olvent cont~ i n; ng alkyl phosp~onic acid monoalkyl ~ster a3 the extractarlt and then back~extracting indium fro~n the organic sol~en~ phase produced., As ~tated abo~re, it is know~ that hydroc:hloric acid i8 u~g~d as the axtrac:tant when back-ex~xacting indium fxom an organic sol~7ent pha~e corlt~in;ng the ele~ent. The use of an aqueou~ solu tion con~; n 1 ng not only hydrochloric acid but also a metal chloride of the type defin~3d above in accordance with the invention of:Eer~ advantages of reduced h~drochloric acid consumptiorl fox the back extraction, high indi~m concentration in the back extrac~ r reusabili~y of the metal chloride by r~cycling, and ease of purification o~ the back ex~r~ct.
Other eature~ and advan~ages of the ~nvention will hecnme apparen~ from ~he ~ollowin~ description ~aken in con~
junction with the accompanying drawingJ
BRIEF DESCRIPTION OF T~E ~WIN~
The single figure is a graph showing changes of indium SIn) conc~n~rati~n in ~he back ex~xac~s at varied h~dro~hlor-ic acid concentrations, wh~n an aqueous solution of hydro-chlorlc ac~a ron~ning sodium chloride was used or when an aqueou~ solu~ion of o~ly hydrochloric acid was employed as the ex tractant in ~he bac~ ex~rac~ion of indium :Erom an In-containing organic ~olvent pha~e,, DEql~TT~lF;n DESCIRIPII'ION OP' THE lNv~;N~ oN
In the p.racti~ of ~he in~ ion, ~he ind~ COn~A i n; ng oxganic: svlvent phase :frs:~m which ~h~3 ~301-slt;e indium i~ tc) b~3 back-~trac~ed is ob~ain~d by hx~r~ging an In-con~ i n i n~
aquaou~ solution into conta~t with an orgarlic solsTent which contains an alkyl phosphonic acid monoalkyl ester ~xtractant capable of ~electively ex~racting lndium from thP aqu~ou~
solution~, An alkyl phosphonic ~cid monoalkyl ester has the foll~w-ing s~ructural fo~mula~
Il ~ 1 ~ P ~ O~I
O
R~
where ~1 and ~2 r~p~e~ent alkyl groups having fxom 8 to 10 c~rbon at~ms a~d which may be th~ ~me or different.
Exampl~s of 8-carbon alkyl group~ are 2-ethyl-1-hexyl~
4-methyl~l~heptylt l~octyl, 3-eth~l-2 methyl-3~pentyl, and ~he l~ke~
Example~ o~ 9-carbon groupæ ax~ 3,5,5~trim~thy~-3~hexyl~
3~athyl- ~methyl-3-he~ylt l-nonyl, 2-meth~1-2-octyl, and the Exampl~s ~f lO~carhon groups are isodecyl, l-decyl, 4-~3 ~3 propyl-4~heptyl, 5~me~hy~ oE~rOpy~ Xyl ~ 3 ~ 7-di.lllÇ3t~y l~octylg 3-ethyl~3- 05tyl~ zlnd the l~ke.
lypic2l1 example~ lnclude 2-e~hyl l-h~yl phO8phOn:LC acid msno-2-~h~ hexy~ ester, 3 ~, 5 r 5-~rimethyl~3-hexyl phosphon-iG acid morlo-3 9 5, 5 ~rime~hyl 3-h~yl ester, i~ode~yl phos-ph~nic acid mons~ oaecyl es~er, 2 e~hyl l-hexyl phD~phonic acid mono r3, ~, 5-trimethyl-3-he~cy~ e~ter, 2-e~ h~xyl phosphoni~ aci d mono~odecyl ~ter, and the like~, U~uaîly, the extra~tant i~ u~ed af~er dilu~ n wi~h a organis:: 801~rent ~uc:h as kero~ene ~ alcohol, or the l:Lke.
In accordan~e wi~h ~he invention~ ~an ac:idiiEied aqueous solution of i ndi~ , prepared ~ leaching an indium con~ i n; n~
raw materi~l with a mineral ac:id ~uch as ~:ulfuric acid, i~
contacted in the usual manner with an orga~ic sol~ent corltain-~ng one of th~ abovemention~d ex~rac:taxlt~, and the In-contain-ing organic sol~rent thus obtained i~ contacted with an a~[ueous solu~ion c:on~ both hydrochloric acid and a chloride o a me~al less noble than indiuun, ~hu~ achievlng 3:ack e~tract~on of ~ndium fro~l the organi~ lvent pha~e.
Ex~pl~ o chlorid~ c~ metals 1~ nc:ble th~ indium which m y be employed in ~e Ibae~k ext3~ac:tion of lndi~ from th~3 organic ~31ve~ pha~e axe chlorld~s of ~1 k~ 7 ~ me~ J
~uch ~8 ~odi~ chlcar~de~ and po a~ium chlo~ideO and chlo-riae~ of alkaline earth metals, ~uch as magnesium chloride a~d ¢als:i~n chloride., ` :;;
In the method of the invent;ioll the chlo.ride o:f a metal less noble than indlum i~ u~ed to :Eacilitate the xecovery of indium ~in the form of InC13) rom ~he back extract in a sub~equent ~tep of displac:emen~ a~ precipita~io~ with ZiIlC or all3min~l.
As r~gard~ th~ ~olv~t~ or extractants for u~e in th~
back extxac~ion accoxding ~o this inventiont the concentra-tion o~ hydrochlori c acid in the aque~us solutivn is desixed ~o range ~Erom abou~ 0,.5 ~o about 5 ~ h~3 metal chloride give~ better result a; it~; concer~tration increas~, and its concen~ration may be rai~ed ~o a level clo~ely approaching ~he satuxation æolubility. There i~ no ~pecial l~itat:ion to the contact ratio of ~he organic ~olven~ pha~e (O) to ~h~
aqu~ous ex~ractant phase (~), i. e., O/A, but a ratio in the range of 1/5 to 10/1 give~ good resul~. ~he contac~ tempera ture iL.~ ;uch that, wher~as the applica~ion o~ hea~ i~ e~fec:~
ti~e ~ roo~n temperaturQ i~ adequate for practical purposeg .
~he con~ac:t time i~ desixably between n. s and 10 minutes~
Th~ back ex~raction of indium ~rom the organic solv~nt pha e in c~nformity with ~he in~rention permits the extracted indium to be recovered in 1;he form of InC13 rom the back ex~ract~ ~t~3r th~ rec~very o:~ indi~n, ~he metal chloridQ
~n the ~tract is recycle~ for r~u~e as an additi~e in the proc0~ ~ ba¢k extraetion.
T~st~ we~ ondu~t~d ~:o s~udy the ~ffec~ of the m~3tal ~ 6 ~
chloride pre~:~3nt in the exltractant or the back extractior u~on the indium cs:~nc~3ntra~ion in the back e~tract. The result~; are graphi~ally r~presen~ed ill the ac:companying draw~
ing.
The ~est procedurs3 was a~; ~ollows.
Usiny a ~c~lu~ion of 2-e~hyl-l~hexyl 1?hosp}~onic acid mono-Z- ethyl-l~hexyl e~ter at a concentxation of ~0~ l~y volume in ker~ene, indium wa~3 extracted from an aqueous solution of sulfuric acid con~in;rlg the ~lement to obtain an organic solven~ phase c:on~aining l9.g g o:E indium per lltqr. Thi~ organic svlvent phase ~0) was brought into contact with on~ of aqu~ou~ solu~ions (~ of hydrochloric acid at varied concentratio~s, ~ach cont~;ning 100 ~/~ of ~odium chloride or none a~ all, each in a ratio o~ 0~ = 100 m~20 mQ, and back extraction was carried out, with shaklng~
at ~0C ~or 10 mlnut~s. The vari~ions of the indlum con-c~ntra~ion in the back extract~ obtain~d w~re determined.
In th~ graph the mea~u~ed co~c~ntrat.ion of hydrochloric acld in ~he back extrac~ was taken a~ abscissaO
~ s can be seen from the gxaph, the aqueou~ solution o hydrochloric acld con~;ni~g sodium chloride (MaCl) as a back extractant mar~edly enhanc~s the back extraction e~ficlency ~ co~pared wi~h the aqueous ~olution o hydrochloric acid alon~0 Th~ pxe~e~t invention, as de~cxibQd above, m~kss possibl~
3~3 back extraction of in~ium at a high corlcen tration ~ w an organic solvenk phase. Addîtion~l advantagi3s are th~3 possibili~y of the metal c:h7 oride added to th~3 extractant being rec~cled or reuse, and consecl-lent economy on hydxo c:hloric acid and reduct:ion of cost.
A~ids ~rom these dvan~age~, it i~ wo.rt~ of spacial men~ion ~hat ~he presen:::e of sodium chloride or the like in the back extract le:3sens ~he hydrc)chlc~ric acid concerltratiorl, which is converlient for the sulfidiza~ion, a -~reatment required to remove tin, arsenlc, and other contaminants which would increlse in proportions in the hack ext~act with it5 repeated use.
The inventioIl is illus~rated by the ~ llowing examples.
Example 1 With 100 mQ of an organic solven~, prepared by diluting 40 m~ o~ 2~ethyl-1-hexyl pho~phonic acid mono-2~ethyl 1-hexyl estex" ~ndlum was selecti~Tely extracted from an indium-Co~ n; ng a~ueous sollltion. The organic solvent pha~e thu;
obtained, cont~;n;ng 14.,~ g S:3e indium per lit2r was sub~cted to back extract~on in the following way~, Extractant~ used for ~he ~ack extraction:
~a) ~n aqueous solu~ion con~; ni ng 7~! g o:f h~drochloric acid and 12~ g of po~assium chloride (KCl) per liter.
(b) An aq~eous 501Ul:iOll con~; n ~ ng 7 ~ g of hydroc}lloric acid and 95 g of calcium chloride (CaC12~ per liter.
(c) AT1 aqueou~ ~olukion cont;lin~n~J 72 g o:E hydrochloric acid and ~2 g o magne~i.um chïoride (MgC12) per liter~, Th organ~c solven~ ph~s~ (C)~ and each aqueous extractan phase ~A) of khe ~olu~ions ~a~, (b), and ~c~ ~ in an O/A ratio of 100 mQJ20 mQ~ were ~cept in corltact~ with shaking, at rot~m ~mperature for 10 minute~.. Tabl.e 1 givç~s the results, For the sake of compari~on arl a~ueous solution contP~in;ng hydrochloric acia oilly wa~ all~wed ~o con~act a~ an ~xtrac:t-ant with the organic solven~ phase~. The re~ are al~o ~h~wn in ~he same ~able~.
T a b 1 e Extractant ~or In co~c. in ~i~3tri~
back extraction back ~xtract bution ~0 ~nQ) tg~Q~ ~~ *
This inventlon:
Extractant (a) 44 . 3 0.13 4 2 . 5 0 . 15 ~a) 47.1 0<,11 Comparative example~
~olll~ contg. onLy HCl 72 g/~ 34 4 0. 23 * Di~tribu~ioll co~fficient -In concO irl th~3 or~anic solvenlt pha~e In conc. in the ba k extract A~ wi:Ll be unders~ood fr~m the ~able, the conc2ntration~of ~indiu~ back-e~z~rac~ed ~ the use o~ ~he aqueous ~;olutions ~L~ag3~3 of hydroehloric ac~d cont;~ ~ n~ ng I~l, CaCl~ J C)X' Mgt::l 2 as extractants wer~3 higher thall wh~n orlly the aqu ou5 HCl solu-tion was employ~d~
Example 2 E:ach of the extractant~ mentioned ~elow w~s used in ~electlYely extracting indium frc~n an In~con~ n~ ng aqueou~;
solutioIl,. Each organic solvent phase t~lls obt~; ne~ with ar~
indium s::ontent o~ 0 g/~ wals c~ tacted wi~h an aqueous solutic~n cont~; n~ ng 72 ~ t>f h~droc:hloric arid and lOG g of ~odium chlorid~ ~NaCl) per li~er, in an O/A ratio o~ 1~0 mQ/20 m~, wit~h ~ha}cing, at roo~n t~nperature fox 10 minutes.
In thi~ way, indium was back-extracted ~rom eac:h organic 801ven~ pha~e.
C~mpo~iti 0~5 o organic ~ol~ent phase~:
~i) For~y mi:Llili~ex~ of 2-ethyl-1-hexyl pho~phonic acid mono-2-eth~ hexyl ~ster and 10 m~ vf tributyl phosphate diluted with 50 mQ o kero~ene (to a total volume o~ 100 mQ~.
(ii) For~y m~ ter~ of 2-ethyl-1-h~xyl phosphonic acid mono-2 ethyl~l-hexyl e~er diluted with 50 m~ of kero~ene and 10 mQ of ~ridecyl alcohol (to a total volume of 100 mQ).
The r~ult~ of the back ex~raction runs were a~ summariz-ed in ~able 2 By way o c~mpari~on, the results with aque-OU8 solution~ cont~ n ~ ~g only 72 g of h~drochl~ric ac~d p~r liker ~re al~o ~hown,, A~5 i8 obviou~ fro~n the table, ~e u~;e of a NaCl ~ontai~-irlg aqueous ~olultion oiE hy~rochloric acid in the baclc sxtrac~
tion of indi~ from an org~ic 80~ ven1; pha ~ leads ~o a high indi um c:oncerltration ~n ~h~ ~ack exltract., T a b 1 e 2 CompoJ3itiorl o~E Extrac~an~ u~ed In conc. Di~ri-org 1~ 801vo pha~e or back extraction irl back bution (total lûO mQ~ otal 20 m~3 ~3x O (g/Q) coef:f ~, *
C~mpo~ition (i) ~el 72g/~, NaCl lûOg/Q 42., 5 0.14 ~Cl 72 g,~'Q 31~. 9 0. 2~
Compo~ io~51i) EICl 72gfQ, NaCl lOûg/Q 49.4 0.09 ~Cl 72 ~Q 38.~ 0.
~ample 3 In the ~ame manner a~ de~cribed in Example 1, an organic ~olvent phase con~in~ng 17 g of indium per liter wa~ back-extracted under the condition of O/A ~ 1/1.
Two diff~r~t back extractants, i~e.~ a ~olution con~ ning ~0 g of hydrochloric acid and 1~5 g of ~odium chloride per liter and a ~olution co~t~in~n~ only hydrochloric acid, were used but both were adjuæted t~ the ~ame Cl concentratio~ of 148 g~.
~ndex ~he~e condl~io~ he ~wo ~xtrac~ants exhibited ~u~-~ta~tial~y th~ ~ame back ex~ractab~lity, ~n~ ti~ the pos~i~ility o ~aCl largely replacing ~ydrochloric acid.
~h~ re~ult~ are ~hown in Table 3~
3~3 T a b 1 2 3 Cl con- Result~ of Back extract c~ntrxl~, back ~trn~, ~ICl 40 g~ ~ NaCl 125 g/Q 148 g~Q 0.05 ~g~Q orga~ic pha~e) 17 . 7 ~g~Q aqueous phase) Only ~Cl 1- 0, 06 Ig/R organic phafie~
17 . 7 (y/Q aqueous phase)
FROM C)RGANIS: SoL~1ENT P~IAS~:
R~Rr~R~uND OF trH$ l~v t~;N l ION
Th:a ~ invention xelate~; to a Ineth~d of ~ecs:~vering indium by bac~ extraction ~r ~;~rippi~g from an illdium-con~i n; ng organic ~ol~ren~ p~ase ~a:~ on an alkyl phosphorl~c acid mono-al~l e~;ter.
In res::e~ ear~ ~ ~olvent ex~ract:io~ ha~ come in~o u3e in smelting prc:cess,, and vari~d method~ for recove:ring indium by the t,lsc:hni~e have hitherto been introduced.
In one method ~3apanese Paten~ ~pplication Publicati4n No. 148735/1980), an in~lium-ion-containing ~ueous solul~ n i~ brought into ccntact wi~h an organic ~olvent cont;~in~ng a~ an extractant a mix~ure o:~ a txi al}cyl phosphite and a mono- or dialkyl pho~phoxic acid to ~3xtract indium selec-tiLvely~ and the In-containing oryanic ~ol~rent pha~e thu~
o~tailled 18 contacted with an aqueou~ olution acidifi~d with hydrol::hloric acid ~o effec~ back extraction of indium the:re-frs:~mO Th~re are other methsa~ ~"30~rna~ of Japan ~lining I!ld.
A~30c.," 93, lû70 (1977 43 0 pp. 323~3251 which compri~e t:he ~lkeps e)~ e~ctrac~ g indium ~rom an In-con~ ~ n; ng aqueoue 8olu~ t with an organic~ ~o:Lv~nt cont~ining ~ril~utyl pho~-E3ha~3 (TBP~ as ~he ex~ractan~, and ~hen back extractiIlg i.ndiuim from ~he resulking organic ~olvent pha~e, u~ing w~ter as ~he ~ractaIIk~ or ~he ~3tep~ of ex~rac~ing indium fro~
* `
~34~3 an In~con~;~;n;r~g aqueous solu~ion by the u~3e of a t~rtiary fatty acid a~ an ion~exchange liquid, and carrying vut baek extraction of the el~nellt from the solvent with hydroch~ oric acid aæ ~.he ex~rac~an~. Still ano~er propose~l m~hod ~apa-ne~3e Pat.. ~pp~, Publis: Dlsclo~ure Mo. 148736~1980) consists in extracting indium from an In-con~;-;n;ng solution acidifiea wi~h ~ulfuric acid t wlth the aid o~ an organic: ~lv.on~
t;~in~ng di(2-met~lhexyl~pho~l?horic acîd ester (D2E~PA) a~
the extractant, and back-ext.ral::ting indium from the organic olv~nt ph~se, this tim~ by th~3 ac~ion of hydrochloric or ~ulfuxic acid. Yet another sug~eæ~ed me~hod i~ the same as the one d~cxibed ilmnedia~ely abc~ve with ~h~ ex~ception that D2E~IPA i~ replaced hy an alkyl phosphor~ic acid monoalkyl ~ster., Tncluding thoE;e cited a~ove for example, me~hod~
or indium recovery have been l-.nown in the art which gen~rally compri3e se31ecti~31y extrac:ting indium ~roDn an I~ on~; n~ n~
aqueou~ ~olu~ion, with an organic solvent containing one c)iE
varied extractant~, and back-ex~racting indium from the organic solvent phase by ~he ac~ion of hydrochloric or sulfuric acid or o water. Of those me~hod~ ~o far introduced, the one u3ing alkyï phosphonic acid ~o~o~l kyl e~ex~ ha~ b~en known to :be p~r ticularly ef f ective .
SU~ OF T~ NV~ Jl I ON
ghe pr~ent irl~rention iS charac~eriæed by ~he u~ o an aqueo~ solll~ion ~ which con~ain~ h~drs:~chlc: rir ac:id and a 3~
chloride of a metal 1 e.ns nol~le than indium, as the extractarlt for the bac:k e~straction in the la~3t~menl:ioned method that compris~s extraoking indium by the use of an oxganic ;olvent cont~ i n; ng alkyl phosp~onic acid monoalkyl ~ster a3 the extractarlt and then back~extracting indium fro~n the organic sol~en~ phase produced., As ~tated abo~re, it is know~ that hydroc:hloric acid i8 u~g~d as the axtrac:tant when back-ex~xacting indium fxom an organic sol~7ent pha~e corlt~in;ng the ele~ent. The use of an aqueou~ solu tion con~; n 1 ng not only hydrochloric acid but also a metal chloride of the type defin~3d above in accordance with the invention of:Eer~ advantages of reduced h~drochloric acid consumptiorl fox the back extraction, high indi~m concentration in the back extrac~ r reusabili~y of the metal chloride by r~cycling, and ease of purification o~ the back ex~r~ct.
Other eature~ and advan~ages of the ~nvention will hecnme apparen~ from ~he ~ollowin~ description ~aken in con~
junction with the accompanying drawingJ
BRIEF DESCRIPTION OF T~E ~WIN~
The single figure is a graph showing changes of indium SIn) conc~n~rati~n in ~he back ex~xac~s at varied h~dro~hlor-ic acid concentrations, wh~n an aqueous solution of hydro-chlorlc ac~a ron~ning sodium chloride was used or when an aqueou~ solu~ion of o~ly hydrochloric acid was employed as the ex tractant in ~he bac~ ex~rac~ion of indium :Erom an In-containing organic ~olvent pha~e,, DEql~TT~lF;n DESCIRIPII'ION OP' THE lNv~;N~ oN
In the p.racti~ of ~he in~ ion, ~he ind~ COn~A i n; ng oxganic: svlvent phase :frs:~m which ~h~3 ~301-slt;e indium i~ tc) b~3 back-~trac~ed is ob~ain~d by hx~r~ging an In-con~ i n i n~
aquaou~ solution into conta~t with an orgarlic solsTent which contains an alkyl phosphonic acid monoalkyl ester ~xtractant capable of ~electively ex~racting lndium from thP aqu~ou~
solution~, An alkyl phosphonic ~cid monoalkyl ester has the foll~w-ing s~ructural fo~mula~
Il ~ 1 ~ P ~ O~I
O
R~
where ~1 and ~2 r~p~e~ent alkyl groups having fxom 8 to 10 c~rbon at~ms a~d which may be th~ ~me or different.
Exampl~s of 8-carbon alkyl group~ are 2-ethyl-1-hexyl~
4-methyl~l~heptylt l~octyl, 3-eth~l-2 methyl-3~pentyl, and ~he l~ke~
Example~ o~ 9-carbon groupæ ax~ 3,5,5~trim~thy~-3~hexyl~
3~athyl- ~methyl-3-he~ylt l-nonyl, 2-meth~1-2-octyl, and the Exampl~s ~f lO~carhon groups are isodecyl, l-decyl, 4-~3 ~3 propyl-4~heptyl, 5~me~hy~ oE~rOpy~ Xyl ~ 3 ~ 7-di.lllÇ3t~y l~octylg 3-ethyl~3- 05tyl~ zlnd the l~ke.
lypic2l1 example~ lnclude 2-e~hyl l-h~yl phO8phOn:LC acid msno-2-~h~ hexy~ ester, 3 ~, 5 r 5-~rimethyl~3-hexyl phosphon-iG acid morlo-3 9 5, 5 ~rime~hyl 3-h~yl ester, i~ode~yl phos-ph~nic acid mons~ oaecyl es~er, 2 e~hyl l-hexyl phD~phonic acid mono r3, ~, 5-trimethyl-3-he~cy~ e~ter, 2-e~ h~xyl phosphoni~ aci d mono~odecyl ~ter, and the like~, U~uaîly, the extra~tant i~ u~ed af~er dilu~ n wi~h a organis:: 801~rent ~uc:h as kero~ene ~ alcohol, or the l:Lke.
In accordan~e wi~h ~he invention~ ~an ac:idiiEied aqueous solution of i ndi~ , prepared ~ leaching an indium con~ i n; n~
raw materi~l with a mineral ac:id ~uch as ~:ulfuric acid, i~
contacted in the usual manner with an orga~ic sol~ent corltain-~ng one of th~ abovemention~d ex~rac:taxlt~, and the In-contain-ing organic sol~rent thus obtained i~ contacted with an a~[ueous solu~ion c:on~ both hydrochloric acid and a chloride o a me~al less noble than indiuun, ~hu~ achievlng 3:ack e~tract~on of ~ndium fro~l the organi~ lvent pha~e.
Ex~pl~ o chlorid~ c~ metals 1~ nc:ble th~ indium which m y be employed in ~e Ibae~k ext3~ac:tion of lndi~ from th~3 organic ~31ve~ pha~e axe chlorld~s of ~1 k~ 7 ~ me~ J
~uch ~8 ~odi~ chlcar~de~ and po a~ium chlo~ideO and chlo-riae~ of alkaline earth metals, ~uch as magnesium chloride a~d ¢als:i~n chloride., ` :;;
In the method of the invent;ioll the chlo.ride o:f a metal less noble than indlum i~ u~ed to :Eacilitate the xecovery of indium ~in the form of InC13) rom ~he back extract in a sub~equent ~tep of displac:emen~ a~ precipita~io~ with ZiIlC or all3min~l.
As r~gard~ th~ ~olv~t~ or extractants for u~e in th~
back extxac~ion accoxding ~o this inventiont the concentra-tion o~ hydrochlori c acid in the aque~us solutivn is desixed ~o range ~Erom abou~ 0,.5 ~o about 5 ~ h~3 metal chloride give~ better result a; it~; concer~tration increas~, and its concen~ration may be rai~ed ~o a level clo~ely approaching ~he satuxation æolubility. There i~ no ~pecial l~itat:ion to the contact ratio of ~he organic ~olven~ pha~e (O) to ~h~
aqu~ous ex~ractant phase (~), i. e., O/A, but a ratio in the range of 1/5 to 10/1 give~ good resul~. ~he contac~ tempera ture iL.~ ;uch that, wher~as the applica~ion o~ hea~ i~ e~fec:~
ti~e ~ roo~n temperaturQ i~ adequate for practical purposeg .
~he con~ac:t time i~ desixably between n. s and 10 minutes~
Th~ back ex~raction of indium ~rom the organic solv~nt pha e in c~nformity with ~he in~rention permits the extracted indium to be recovered in 1;he form of InC13 rom the back ex~ract~ ~t~3r th~ rec~very o:~ indi~n, ~he metal chloridQ
~n the ~tract is recycle~ for r~u~e as an additi~e in the proc0~ ~ ba¢k extraetion.
T~st~ we~ ondu~t~d ~:o s~udy the ~ffec~ of the m~3tal ~ 6 ~
chloride pre~:~3nt in the exltractant or the back extractior u~on the indium cs:~nc~3ntra~ion in the back e~tract. The result~; are graphi~ally r~presen~ed ill the ac:companying draw~
ing.
The ~est procedurs3 was a~; ~ollows.
Usiny a ~c~lu~ion of 2-e~hyl-l~hexyl 1?hosp}~onic acid mono-Z- ethyl-l~hexyl e~ter at a concentxation of ~0~ l~y volume in ker~ene, indium wa~3 extracted from an aqueous solution of sulfuric acid con~in;rlg the ~lement to obtain an organic solven~ phase c:on~aining l9.g g o:E indium per lltqr. Thi~ organic svlvent phase ~0) was brought into contact with on~ of aqu~ou~ solu~ions (~ of hydrochloric acid at varied concentratio~s, ~ach cont~;ning 100 ~/~ of ~odium chloride or none a~ all, each in a ratio o~ 0~ = 100 m~20 mQ, and back extraction was carried out, with shaklng~
at ~0C ~or 10 mlnut~s. The vari~ions of the indlum con-c~ntra~ion in the back extract~ obtain~d w~re determined.
In th~ graph the mea~u~ed co~c~ntrat.ion of hydrochloric acld in ~he back extrac~ was taken a~ abscissaO
~ s can be seen from the gxaph, the aqueou~ solution o hydrochloric acld con~;ni~g sodium chloride (MaCl) as a back extractant mar~edly enhanc~s the back extraction e~ficlency ~ co~pared wi~h the aqueous ~olution o hydrochloric acid alon~0 Th~ pxe~e~t invention, as de~cxibQd above, m~kss possibl~
3~3 back extraction of in~ium at a high corlcen tration ~ w an organic solvenk phase. Addîtion~l advantagi3s are th~3 possibili~y of the metal c:h7 oride added to th~3 extractant being rec~cled or reuse, and consecl-lent economy on hydxo c:hloric acid and reduct:ion of cost.
A~ids ~rom these dvan~age~, it i~ wo.rt~ of spacial men~ion ~hat ~he presen:::e of sodium chloride or the like in the back extract le:3sens ~he hydrc)chlc~ric acid concerltratiorl, which is converlient for the sulfidiza~ion, a -~reatment required to remove tin, arsenlc, and other contaminants which would increlse in proportions in the hack ext~act with it5 repeated use.
The inventioIl is illus~rated by the ~ llowing examples.
Example 1 With 100 mQ of an organic solven~, prepared by diluting 40 m~ o~ 2~ethyl-1-hexyl pho~phonic acid mono-2~ethyl 1-hexyl estex" ~ndlum was selecti~Tely extracted from an indium-Co~ n; ng a~ueous sollltion. The organic solvent pha~e thu;
obtained, cont~;n;ng 14.,~ g S:3e indium per lit2r was sub~cted to back extract~on in the following way~, Extractant~ used for ~he ~ack extraction:
~a) ~n aqueous solu~ion con~; ni ng 7~! g o:f h~drochloric acid and 12~ g of po~assium chloride (KCl) per liter.
(b) An aq~eous 501Ul:iOll con~; n ~ ng 7 ~ g of hydroc}lloric acid and 95 g of calcium chloride (CaC12~ per liter.
(c) AT1 aqueou~ ~olukion cont;lin~n~J 72 g o:E hydrochloric acid and ~2 g o magne~i.um chïoride (MgC12) per liter~, Th organ~c solven~ ph~s~ (C)~ and each aqueous extractan phase ~A) of khe ~olu~ions ~a~, (b), and ~c~ ~ in an O/A ratio of 100 mQJ20 mQ~ were ~cept in corltact~ with shaking, at rot~m ~mperature for 10 minute~.. Tabl.e 1 givç~s the results, For the sake of compari~on arl a~ueous solution contP~in;ng hydrochloric acia oilly wa~ all~wed ~o con~act a~ an ~xtrac:t-ant with the organic solven~ phase~. The re~ are al~o ~h~wn in ~he same ~able~.
T a b 1 e Extractant ~or In co~c. in ~i~3tri~
back extraction back ~xtract bution ~0 ~nQ) tg~Q~ ~~ *
This inventlon:
Extractant (a) 44 . 3 0.13 4 2 . 5 0 . 15 ~a) 47.1 0<,11 Comparative example~
~olll~ contg. onLy HCl 72 g/~ 34 4 0. 23 * Di~tribu~ioll co~fficient -In concO irl th~3 or~anic solvenlt pha~e In conc. in the ba k extract A~ wi:Ll be unders~ood fr~m the ~able, the conc2ntration~of ~indiu~ back-e~z~rac~ed ~ the use o~ ~he aqueous ~;olutions ~L~ag3~3 of hydroehloric ac~d cont;~ ~ n~ ng I~l, CaCl~ J C)X' Mgt::l 2 as extractants wer~3 higher thall wh~n orlly the aqu ou5 HCl solu-tion was employ~d~
Example 2 E:ach of the extractant~ mentioned ~elow w~s used in ~electlYely extracting indium frc~n an In~con~ n~ ng aqueou~;
solutioIl,. Each organic solvent phase t~lls obt~; ne~ with ar~
indium s::ontent o~ 0 g/~ wals c~ tacted wi~h an aqueous solutic~n cont~; n~ ng 72 ~ t>f h~droc:hloric arid and lOG g of ~odium chlorid~ ~NaCl) per li~er, in an O/A ratio o~ 1~0 mQ/20 m~, wit~h ~ha}cing, at roo~n t~nperature fox 10 minutes.
In thi~ way, indium was back-extracted ~rom eac:h organic 801ven~ pha~e.
C~mpo~iti 0~5 o organic ~ol~ent phase~:
~i) For~y mi:Llili~ex~ of 2-ethyl-1-hexyl pho~phonic acid mono-2-eth~ hexyl ~ster and 10 m~ vf tributyl phosphate diluted with 50 mQ o kero~ene (to a total volume o~ 100 mQ~.
(ii) For~y m~ ter~ of 2-ethyl-1-h~xyl phosphonic acid mono-2 ethyl~l-hexyl e~er diluted with 50 m~ of kero~ene and 10 mQ of ~ridecyl alcohol (to a total volume of 100 mQ).
The r~ult~ of the back ex~raction runs were a~ summariz-ed in ~able 2 By way o c~mpari~on, the results with aque-OU8 solution~ cont~ n ~ ~g only 72 g of h~drochl~ric ac~d p~r liker ~re al~o ~hown,, A~5 i8 obviou~ fro~n the table, ~e u~;e of a NaCl ~ontai~-irlg aqueous ~olultion oiE hy~rochloric acid in the baclc sxtrac~
tion of indi~ from an org~ic 80~ ven1; pha ~ leads ~o a high indi um c:oncerltration ~n ~h~ ~ack exltract., T a b 1 e 2 CompoJ3itiorl o~E Extrac~an~ u~ed In conc. Di~ri-org 1~ 801vo pha~e or back extraction irl back bution (total lûO mQ~ otal 20 m~3 ~3x O (g/Q) coef:f ~, *
C~mpo~ition (i) ~el 72g/~, NaCl lûOg/Q 42., 5 0.14 ~Cl 72 g,~'Q 31~. 9 0. 2~
Compo~ io~51i) EICl 72gfQ, NaCl lOûg/Q 49.4 0.09 ~Cl 72 ~Q 38.~ 0.
~ample 3 In the ~ame manner a~ de~cribed in Example 1, an organic ~olvent phase con~in~ng 17 g of indium per liter wa~ back-extracted under the condition of O/A ~ 1/1.
Two diff~r~t back extractants, i~e.~ a ~olution con~ ning ~0 g of hydrochloric acid and 1~5 g of ~odium chloride per liter and a ~olution co~t~in~n~ only hydrochloric acid, were used but both were adjuæted t~ the ~ame Cl concentratio~ of 148 g~.
~ndex ~he~e condl~io~ he ~wo ~xtrac~ants exhibited ~u~-~ta~tial~y th~ ~ame back ex~ractab~lity, ~n~ ti~ the pos~i~ility o ~aCl largely replacing ~ydrochloric acid.
~h~ re~ult~ are ~hown in Table 3~
3~3 T a b 1 2 3 Cl con- Result~ of Back extract c~ntrxl~, back ~trn~, ~ICl 40 g~ ~ NaCl 125 g/Q 148 g~Q 0.05 ~g~Q orga~ic pha~e) 17 . 7 ~g~Q aqueous phase) Only ~Cl 1- 0, 06 Ig/R organic phafie~
17 . 7 (y/Q aqueous phase)
Claims (3)
1. A method for the back extraction of indium from an indium-containing organic solvent phase based on an alkyl phosphonic acid monoalkyl ester, characterized in that an aqueous solution containing hydrochloric acid and a chloride of a metal less noble than indium is employed as the extractant.
2. A method according to claim 1, wherein said chloride of a metal is a chloride of an alkali metal.
3. A method according to claim 1, wherein said chloride of a metal is a chloride of an alkaline earth metal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP156529/1981 | 1981-10-01 | ||
| JP56156529A JPS606896B2 (en) | 1981-10-01 | 1981-10-01 | Method for back extraction of indium in organic solvent phase |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1193443A true CA1193443A (en) | 1985-09-17 |
Family
ID=15629778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000412521A Expired CA1193443A (en) | 1981-10-01 | 1982-09-30 | Method for back extraction of indium from organic solvent phase |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS606896B2 (en) |
| BE (1) | BE894530A (en) |
| CA (1) | CA1193443A (en) |
| DE (1) | DE3235693C2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60145913A (en) * | 1984-01-05 | 1985-08-01 | Sumitomo Chem Co Ltd | Elution of indium absorbed to chelate resin |
| JPS62141125A (en) * | 1985-12-09 | 1987-06-24 | Nitto Boseki Co Ltd | Method for infusibilization and carbonization treatment of pitch fiber and apparatus therefor |
| FR2623522B1 (en) * | 1987-11-24 | 1990-04-20 | Metaleurop Sa | HYDROMETALLURGICAL TREATMENT PROCESS FOR INDIUM CHLORIDE SOLUTION |
| FI125933B (en) * | 2014-06-05 | 2016-04-15 | Outotec Finland Oy | Gold extraction with solvents |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55148737A (en) * | 1979-05-11 | 1980-11-19 | Nippon Mining Co Ltd | Selective separation of indium |
-
1981
- 1981-10-01 JP JP56156529A patent/JPS606896B2/en not_active Expired
-
1982
- 1982-09-27 DE DE3235693A patent/DE3235693C2/en not_active Expired
- 1982-09-29 BE BE0/209114A patent/BE894530A/en not_active IP Right Cessation
- 1982-09-30 CA CA000412521A patent/CA1193443A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5860619A (en) | 1983-04-11 |
| DE3235693C2 (en) | 1985-05-02 |
| DE3235693A1 (en) | 1983-04-21 |
| JPS606896B2 (en) | 1985-02-21 |
| BE894530A (en) | 1983-01-17 |
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