CN108060305B - A method of the recovery indium germanium from the chlorinated distillation raffinate of the germanium containing indium - Google Patents
A method of the recovery indium germanium from the chlorinated distillation raffinate of the germanium containing indium Download PDFInfo
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- CN108060305B CN108060305B CN201711330085.XA CN201711330085A CN108060305B CN 108060305 B CN108060305 B CN 108060305B CN 201711330085 A CN201711330085 A CN 201711330085A CN 108060305 B CN108060305 B CN 108060305B
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- Prior art keywords
- germanium
- indium
- organic phase
- chlorinated distillation
- recovery
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Links
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 94
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 82
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- SAZXSKLZZOUTCH-UHFFFAOYSA-N germanium indium Chemical compound [Ge].[In] SAZXSKLZZOUTCH-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000004821 distillation Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000011084 recovery Methods 0.000 title claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 69
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 33
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011975 tartaric acid Substances 0.000 claims abstract description 21
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 19
- 239000003350 kerosene Substances 0.000 claims abstract description 15
- 239000012074 organic phase Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 239000012071 phase Substances 0.000 claims description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 4
- DECJQEOSXYARRQ-UHFFFAOYSA-L [OH-].[OH-].[Ge+2] Chemical compound [OH-].[OH-].[Ge+2] DECJQEOSXYARRQ-UHFFFAOYSA-L 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 229910021617 Indium monochloride Inorganic materials 0.000 abstract description 3
- 150000005838 radical anions Chemical class 0.000 abstract description 3
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 15
- 239000003513 alkali Substances 0.000 description 9
- 239000000284 extract Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910006113 GeCl4 Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 229910005831 GeO3 Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- -1 tartrate anion Chemical class 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- GGVZNJXCXSCLIG-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;germanium Chemical compound [Ge].OC(=O)C(O)C(O)C(O)=O GGVZNJXCXSCLIG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K Indium trichloride Inorganic materials Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- XHYDMKPNRXAZOY-UHFFFAOYSA-N germanium;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Ge].OC(=O)CC(O)(C(O)=O)CC(O)=O XHYDMKPNRXAZOY-UHFFFAOYSA-N 0.000 description 1
- MDFDUWDOZDWRSU-UHFFFAOYSA-N germanium;oxalic acid Chemical compound [Ge].OC(=O)C(O)=O MDFDUWDOZDWRSU-UHFFFAOYSA-N 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- C22B41/00—Obtaining germanium
-
- 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
- C22B58/00—Obtaining gallium or indium
-
- 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
Abstract
The present invention relates to technical field of wet metallurgy, the method for recovery indium germanium in especially a kind of chlorinated distillation raffinate from the germanium containing indium, by distillation Liquid Residue by containing InCl so that obtaining in the presence of tartaric acid4 ‑Or InCl6 3‑Winestone germanium acid radical anion (Ge (A)3 2‑, A is tartaric acid) and mixed liquor, and indium is stripped using the indium germanium extraction simultaneously of N235- kerosene system extractant, then using diluted acid, sodium hydroxide solution is stripped germanium, so that indium germanium separation costs reduce, extractant regeneration ability is strong, separating difficulty is reduced, simple process is easy to operate.
Description
Technical field
The present invention relates to technical field of wet metallurgy, recovery indium germanium in especially a kind of chlorinated distillation raffinate from the germanium containing indium
Method.
Background technique
The produced hard zinc of pyrometallurgy of zinc, after vacuum drying oven distilled zinc, it is residue obtained in, indium Ge content reaches 1% or more, and
Its processing mode is mainly included the following three types: (1) by residue after oxidizing roasting, can directly carry out chlorinated distillation chlorination
Germanium, indium enter vinasse；(2) indium germanium smelting charge of lead and zinc being leached through repeatedly neutral, indium germanium is enriched in neutral phase analysis,
Chlorinated distillation GeCl can also directly be carried out4, indium enters vinasse；(3) by after Acid leaching, tannin sinking germanium, so that indium is also therewith
Precipitating so that in the germanium concentrate that heavy germanium obtains, also containing 0.5% or more indium, using chlorinated distillation GeCl4Afterwards, indium also enters
Vinasse.
Currently, most of smelters, will contain indium germanium material after Acid leaching, and prepare germanium concentrate using tannin sinking germanium,
And chlorinated distillation GeCl4, indium is caused inevitably to enter in vinasse.In chlorinated distillation GeCl4When, it is in 8% or more salt
In acid solution, for addition calcium chloride as carrying out under the activator of chloride ion, vinasse hydrochloric 6% or more, that is, be exactly chlorine
Ion concentration is about 250g/L or more.But under peracid high chloride ion content, indium is mainly with InCl4 -Or InCl6 3-In the presence of residual
The germanium deposited is with GeCl6 2-Or GeO3 2-In the presence of so that using P2O4InCl cannot be extracted etc. Phosphorus cation extractant4 -, can not yet
Use pH for 4-5 in the environment of be hydrolyzed precipitating indium hydroxide, realize in vinasse, the separation of indium and germanium.Simultaneously as
In raffinate, 5g/L or more is not achieved in indium content, causes to carry out indium using metal replacement method and germanium is separated, higher cost,
And separating effect is also undesirable.
In consideration of it, this researcher passes through the trial and effort of many years, in vinasse, indium and germanium carry out separation and recovery and mention
For a kind of new approaches, so that the cost recovery of indium and germanium is low in vinasse, the separating effect of indium and germanium is ideal.
Summary of the invention
In order to solve the above technical problems existing in the prior art, the present invention provides a kind of chlorinated distillation from the germanium containing indium
The method of recovery indium germanium in raffinate.
It is achieved particular by following technical scheme:
A method of chlorinated distillation raffinate is pressed germanium theoretical content by the recovery indium germanium from the chlorinated distillation raffinate of the germanium containing indium
3-5 times is added tartaric acid, then is extracted simultaneously using N235- kerosene system extractant progress indium and germanium, and it is organic to obtain load indium germanium
Phase and poor indium germanium water phase；It loads indium germanium organic phase and indium is stripped using diluted acid, obtain water phase containing indium and germanic organic phase；Water phase containing indium
Return is stripped load indium germanium organic phase, Enrichment Indium, after purification and impurity removal, replaces sponge indium using aluminium sheet；It is germanic organic
Germanium is mutually stripped using sodium hydroxide solution, obtains germanic strip liquor and poor indium germanium organic phase；Germanic strip liquor return has to germanic
Machine is mutually stripped, and after enriched germanium, hydrolytic precipitation obtains hydroxide germanium precipitating；Poor indium germanium organic phase is returned to greening vinasse extraction
It takes.
The N235Kerosene system, N235Volume fraction is 30-40%.
The chlorinated distillation raffinate, contain indium >=200mg/L, germanic >=100mg/L, chloride ion >=250g/L, hydrochloric acid >=
6%.
The N235- kerosene system, when extraction, organic phase/water phase is comparably 0.2-1；Extracting series is 5-6 grades,
Room temperature extraction.
The diluted acid is the acid solution that mass concentration is 1-5%.
The acid solution is sulfuric acid solution, hydrochloric acid solution, oxalic acid solution, tartaric acid solution, one in citric acid solution
Kind.
The chlorinated distillation raffinate is to will be enriched in indium germanium raw material after chlorinated distillation germanium tetrachloride, acquisition.
The chlorinated distillation will be enriched in carrying out after indium germanium raw material is mixed with mixed liquor, and wherein mixed liquor is quality point
The calcium chloride solution that the hydrochloric acid that number is >=12% is 10-20% with mass fraction is mixed according to isometric ratio.
The diluted acid back extraction indium is to carry out at normal temperature, and back extraction series is 3-4 grades, and organic phase/water phase is comparably 1-
2。
The sodium hydroxide solution back extraction germanium is to carry out at normal temperature, and back extraction series is 3-4 grades, organic phase/water phase
It is comparably 1-2.
Compared with prior art, it has following technical effect that
1. the extraction of indium germanium uses N in the solution of peracid high chloride ion235Kerosene system anion extractant extracts simultaneously
Indium germanium is taken, P is overcome204、P507、C-272Equal cation extractants must dilute or neutralize chlorinated distillation raffinate to low acid, low chlorine
Ion makes InCl4 -And InCl6 3-It is converted into InCl3Or other In3+, the high cost process of ability extraction of indium.Overcome neutralizing hydrolysis
Method consumes a large amount of neutralizer, obtains indium germanium hydrolytic precipitation mixture, then diluted acid dissolution, then carry out the tradition of separation and Extraction indium germanium
Fall behind technique.
2. loading indium germanium organic phase is stripped indium with diluted acid first, especially plus the organic acids such as tartaric acid are stripped indium, even if having
A small amount of germanium is eluted into strip liquor, also can be by N235Extraction, makes indium germanium good separating effect.Then anti-with sodium hydroxide solution again
Extract germanium, not only germanium back extraction ratio is high, but also chloride ion and other impurities are also stripped in organic phase, make N235Alkalescent is regenerated.
And N235Acidizing process then by extracting when peracid high chloride ion condition be naturally done.The advantage cannot first alkali back extraction, rear acid is anti-
Extraction, because indium is also entered in lye by suitable back extraction and cannot separate with germanium mixing when alkali is stripped.
③N235Acid and chloride ion are all reduced in extraction of indium germanium raffinate, are handled convenient for subsequent technique, thus environmental protection is controlled
It manages at low cost.
To sum up, the invention will distill Liquid Residue by containing InCl so that obtaining in the presence of tartaric acid4 -Or InCl6 3-Wine
Stone germanium acid radical anion (Ge (A)3 2-, A is tartaric acid) and mixed liquor, and indium germanium extracts simultaneously using N235- kerosene system extractant
It taking, then indium is stripped using diluted acid, sodium hydroxide solution is stripped germanium, so that indium germanium separation costs reduce, extractant regeneration ability is strong,
Separating difficulty is reduced, simple process is easy to operate.
Specific embodiment
It is limited below with reference to specific embodiment technical solution of the present invention is further, but claimed
Range is not only limited to made description.
In certain embodiments, from the chlorinated distillation raffinate of the germanium containing indium recovery indium germanium method, by chlorinated distillation raffinate
Tartaric acid is added by 3-5 times of germanium theoretical content, then is extracted simultaneously using N235- kerosene system extractant progress indium and germanium, obtains
Load indium germanium organic phase and poor indium germanium water phase；It loads indium germanium organic phase and indium is stripped using diluted acid, obtain water phase containing indium has with germanic
Machine phase；Water phase containing indium, which returns, is stripped load indium germanium organic phase, Enrichment Indium, after purification and impurity removal, replaces sea using aluminium sheet
Continuous indium；Germanic organic phase is stripped germanium using sodium hydroxide solution, obtains germanic strip liquor and poor indium germanium organic phase；Germanic strip liquor
It returns and germanic organic phase is stripped, after enriched germanium, hydrolytic precipitation obtains hydroxide germanium precipitating；Poor indium germanium organic phase is returned to green
Change vinasse extraction.
In certain embodiments, the N235Kerosene system, N235Volume fraction is 30-40%.
In certain embodiments, the chlorinated distillation raffinate contains indium >=200mg/L, germanic >=100mg/L, chloride ion
>=250g/L, hydrochloric acid >=6%.
In certain embodiments, the N235- kerosene system, when extraction, organic phase/water phase is comparably 0.2-1；Extraction
Taking series is 5-6 grades, room temperature extraction.
In certain embodiments, the diluted acid is the acid solution that mass concentration is 1-5%.
In certain embodiments, the acid solution is sulfuric acid solution, hydrochloric acid solution, oxalic acid solution, tartaric acid solution, lemon
One of lemon acid solution.
In certain embodiments, the chlorinated distillation raffinate is to will be enriched in indium germanium raw material by chlorinated distillation germanium tetrachloride
Afterwards, acquisition.
In certain embodiments, the chlorinated distillation will be enriched in carrying out after indium germanium raw material is mixed with mixed liquor,
The calcium chloride solution that middle mixed liquor is the hydrochloric acid that mass fraction is >=12% and mass fraction is 10-20% is according to isometric than mixed
It closes.
In certain embodiments, diluted acid back extraction indium is to carry out at normal temperature, and back extraction series is 3-4 grades, organic phase/
Water phase is comparably 1-2.
In certain embodiments, sodium hydroxide solution back extraction germanium is to carry out at normal temperature, and back extraction series is 3-4
Grade, organic phase/water phase are comparably 1-2.
In certain embodiments, specifically according to following operation:
(1) tartaric acid is added according to 3-5 times of the theoretical content of germanium in chlorinated distillation raffinate, make germanium with tartrate anion bear from
Son exists, and increases the extraction competitiveness of germanium in poor germanium liquid, obtains and contains InCl4 -Or InCl6 3-Winestone germanium acid radical anion (Ge
(A)3 2-, A is tartaric acid) and mixed liquor.
(2) N is used235Kerosene system extractant is comparing=0.5-1,5-6 grades of extraction is carried out under normal temperature condition, is made
It obtains indium germanium and organic phase is entered with anion simultaneously, it is separated from the water.Wherein N235Percentage by volume is 30-40%.
(3) load indium germanium organic phase compares (having/water)=1-2 in back extraction with the diluted acid of 1-5%, carries out 3-4 grades under room temperature
It is stripped indium.The strip liquor can be one of sulfuric acid, hydrochloric acid, oxalic acid, tartaric acid, citric acid, preferably tartaric acid organic acid.
Indium is with In3+Entered in water phase by back extraction, and germanium continues to stay in organic phase, when using organic acid strip liquor, can make to be stripped on a small quantity
The germanium of liquid elution is preferably extracted by N235 in the form of tartaric acid germanium or the anions such as oxalic acid germanium or citric acid germanium again, is stripped indium
The germanic micro of liquid
(4) load germanium organic phase is comparing (having/water)=1-2 with the sodium hydroxide solution of 30-40%, carries out 3- under room temperature
4 grades of back extraction, germanium is with Na2GeO3Form is stripped into water phase.N235Display alkalescent is saponified to be reproduced.
(5) indium germanium strip liquor can be recycled for multiple times, and so that the indium in sour strip liquor is enriched to 10g/L or more, then more
Strip liquor is changed, germanium is enriched to 6g/L or more and replaces strip liquor again in alkali strip liquor.
(6) rich indium strip liquor produces sponge indium with conventional method.Briquetting founding indium ingot.Rich germanium strip liquor is heavy using hydrolysis
Shallow lake legal system takes germanium concentrate.
Embodiment 1
Certain enterprise after chlorinated distillation, specifically will be enriched in carrying out after indium germanium raw material is mixed with mixed liquor rich in indium germanium raw material
, wherein mixed liquor is the hydrochloric acid that mass fraction is >=12% and the calcium chloride solution that mass fraction is 10-20% according to grade bodies
Product ratio mixes, and by after its distillation processing, obtains distillation Liquid Residue.Vinasse 720mg/L containing indium, germanium 83mg/L, salt
Sour 6N, chloride ion 285g/L.
Into vinasse, tartaric acid is added by tartaric acid/germanium=5, after dissolution, 30% N235 is accounted for percentage by volume
Extractant is formed with kerosene, carries out 4 grades of extractions, compares (having/water)=1, temperature room temperature obtains load indium germanium organic phase and extraction
Raffinate.
Extraction raffinate 105mg/L containing indium, germanium 6.5mg/L, the extraction yield 85.4% of indium, the extraction yield 92.2% of germanium.
Load indium germanium organic phase first uses 2% dilute sulfuric acid to be stripped, and compares (having/water)=1.5, and room temperature is stripped 3 grades of series,
Obtain level-one strip liquor；
875.2mg/L containing indium, indium acid back extraction ratio 92.8%, germanium 15.2mg/L back extraction ratio 18.5%；
Poor indium organic phase is obtained, with 30% sodium hydroxide solution, room temperature compares (having/water)=2.5, is stripped 4 grades, obtains
Obtain level-one alkali strip liquor；
Germanic 325mg/L, germanium alkali back extraction ratio 91.4%, 25mg/L containing indium, indium back extraction ratio 6.3%.
Embodiment 2
Certain enterprise after chlorinated distillation, specifically will be enriched in carrying out after indium germanium raw material is mixed with mixed liquor rich in indium germanium raw material
, wherein mixed liquor is the hydrochloric acid that mass fraction is >=12% and the calcium chloride solution that mass fraction is 10-20% according to grade bodies
Product ratio mixes, and by after its distillation processing, obtains chlorinated distillation raffinate.Chlorinated distillation raffinate 530mg/L containing indium, germanium
98mg/L, hydrochloric acid 6.5N, chloride ion 280g/L.
Into chlorinated distillation raffinate, tartaric acid is added by tartaric acid/germanium=5, and dissolve.It is 40% with volume basis accounting
N235With the extractant of kerosene composition, 5 grades of extractions are carried out, (having/water)=1, temperature room temperature are compared.
Extraction raffinate 21.5mg/L containing indium, germanium 1.2mg/L, the extraction yield 95.9% of indium, the extraction yield 98.8% of germanium.
Load indium germanium organic phase, first use 5% oxalic acid solution, compare (having/water)=2, room temperature, 4 grades be stripped, level-one
Strip liquor 635mg/L containing indium, germanium 5.2mg/L；
Poor indium organic phase is obtained, with 35% sodium hydroxide solution, carries out 4 grades of room temperature back extraction, level-one alkali strip liquor is germanic
310mg/L, indium 12mg/L, the total back extraction ratio of indium germanic acid alkali are 99.5% or so.
Embodiment 3
Indium germanium extraction is carried out by the N235 extractant and extraction conditions of example 2 with the chlorinated distillation raffinate of example 1, is used
3% tartaric acid solution carries out indium back extraction, level-one strip liquor 892.5mg/L containing indium, germanic 0.5mg/L, then with 40% hydrogen-oxygen
Change sodium solution and carries out germanium back extraction, level-one strip liquor germanic 365mg/L, indium 8.5mg/L.Lean organic phase returns to extraction.The acid of indium is anti-
Extraction liquid does not extract indium, and return continues indium back extraction enrichment, and the alkali strip liquor of germanium does not extract germanium, and it is rich that return continues germanium back extraction
Collection.Continue 5 recyclings, the median extraction rate 93.8% of indium, back extraction ratio 97.5%, level-one strip liquor 4.2g/ containing indium
L.The median extraction rate 98.4% of germanium, back extraction ratio 99.2%, germanic 1.52g/L in level-one strip liquor.
Embodiment 4
N235 is carried out by the condition of example 3 and extracts indium germanium from chlorinated distillation raffinate, carries out 15 cycling extractions, and indium is put down
Equal extraction yield 90.5%, controls tartaric acid strip liquor PH=1.5-2, obtains average back extraction ratio 94.6%, and primary acids strip liquor contains
Indium 11.8g/L, germanic 0.15mg/L, the median extraction rate 96.3% of germanium, averagely back extraction ratio 98.8%, level-one alkali strip liquor are germanic
5.2g/L, indium level-one strip liquor replace to obtain sponge indium, germanium level-one strip liquor sulfuric acid tune PH=10 with aluminium sheet, and hydrolysis obtains germanic
10.5% germanium concentrate.
Claims (9)
1. a kind of method of recovery indium germanium in chlorinated distillation raffinate from the germanium containing indium, which is characterized in that press chlorinated distillation raffinate
Tartaric acid is added in 3-5 times of germanium theoretical content, then is extracted simultaneously using N235- kerosene system extractant progress indium and germanium, is born
Carry indium germanium organic phase and poor indium germanium water phase；Load indium germanium organic phase using diluted acid be stripped indium, obtain water phase containing indium with it is germanic organic
Phase；Water phase containing indium, which returns, is stripped load indium germanium organic phase, Enrichment Indium, after purification and impurity removal, replaces sponge using aluminium sheet
Indium；Germanic organic phase is stripped germanium using sodium hydroxide solution, obtains germanic strip liquor and poor indium germanium organic phase；Germanic strip liquor returns
It returns and germanic organic phase is stripped, after enriched germanium, hydrolytic precipitation obtains hydroxide germanium precipitating；Poor indium germanium organic phase is returned to chlorination
Vinasse extraction；
The chlorinated distillation raffinate contains indium >=200mg/L, germanic >=100mg/L, chloride ion >=250g/L, hydrochloric acid >=6%.
2. as described in claim 1 from the chlorinated distillation raffinate of the germanium containing indium recovery indium germanium method, which is characterized in that it is described
N235- kerosene system, N235 volume fraction be 30-40%.
3. as described in claim 1 from the chlorinated distillation raffinate of the germanium containing indium recovery indium germanium method, which is characterized in that it is described
N235- kerosene system, when extraction, organic phase/water phase is comparably 0.2-1；Extracting series is 5-6 grades, room temperature extraction.
4. as described in claim 1 from the chlorinated distillation raffinate of the germanium containing indium recovery indium germanium method, which is characterized in that it is described
Diluted acid be acid solution that mass concentration is 1-5%.
5. as claimed in claim 4 from the chlorinated distillation raffinate of the germanium containing indium recovery indium germanium method, which is characterized in that it is described
Acid solution be one of sulfuric acid solution, hydrochloric acid solution, oxalic acid solution, tartaric acid solution, citric acid solution.
6. as described in claim 1 from the chlorinated distillation raffinate of the germanium containing indium recovery indium germanium method, which is characterized in that it is described
Chlorinated distillation raffinate be that will be enriched in indium germanium raw material after chlorinated distillation germanium tetrachloride, acquisition.
7. as claimed in claim 6 from the chlorinated distillation raffinate of the germanium containing indium recovery indium germanium method, which is characterized in that it is described
Chlorinated distillation will be enriched in carrying out after indium germanium raw material is mixed with mixed liquor, wherein mixed liquor be mass fraction be >=12%
Hydrochloric acid is mixed with the calcium chloride solution that mass fraction is 10-20% according to isometric ratio.
8. as described in claim 1 from the chlorinated distillation raffinate of the germanium containing indium recovery indium germanium method, which is characterized in that it is described
Diluted acid back extraction indium be to carry out at normal temperature, back extraction series be 3-4 grades, organic phase/water phase is comparably 1-2.
9. as described in claim 1 from the chlorinated distillation raffinate of the germanium containing indium recovery indium germanium method, which is characterized in that it is described
Sodium hydroxide solution back extraction germanium be to carry out at normal temperature, back extraction series be 3-4 grades, organic phase/water phase is comparably 1-2.
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| CN109929997B (en) * | 2019-03-14 | 2021-05-18 | 贵州宏达环保科技有限公司 | Method for producing germanium concentrate by using N235 extracting agent |
| CN114921665B (en) * | 2022-06-01 | 2023-08-22 | 朝阳金美镓业有限公司 | Method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by extraction method |
| CN115404363A (en) * | 2022-08-29 | 2022-11-29 | 云南驰宏国际锗业有限公司 | Method for recovering germanium from germanium mud by utilizing germanium concentrate distillation waste hydrochloric acid |
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| US4666686A (en) * | 1985-03-07 | 1987-05-19 | Preussag Aktiengesellschaft Metall | Process for the fluid-fluid extraction of gallium, germanium or indium from liquid solutions |
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| US4666686A (en) * | 1985-03-07 | 1987-05-19 | Preussag Aktiengesellschaft Metall | Process for the fluid-fluid extraction of gallium, germanium or indium from liquid solutions |
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