CN118234878A - Method for separating rhodium - Google Patents
Method for separating rhodium Download PDFInfo
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- CN118234878A CN118234878A CN202280075689.7A CN202280075689A CN118234878A CN 118234878 A CN118234878 A CN 118234878A CN 202280075689 A CN202280075689 A CN 202280075689A CN 118234878 A CN118234878 A CN 118234878A
- Authority
- CN
- China
- Prior art keywords
- rhodium
- hydrochloric acid
- iridium
- complex
- ruthenium
- Prior art date
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- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 59
- 239000010948 rhodium Substances 0.000 title claims abstract description 59
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000000460 chlorine Substances 0.000 claims abstract description 51
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 51
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 48
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920000768 polyamine Polymers 0.000 claims abstract description 43
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 42
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 9
- XXVRGGCHZUCJCX-UHFFFAOYSA-N [Cl].[Rh] Chemical compound [Cl].[Rh] XXVRGGCHZUCJCX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 58
- 238000001556 precipitation Methods 0.000 claims description 22
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 8
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- RBNNPWUKDNRSMD-UHFFFAOYSA-N [Cl].[Ir] Chemical compound [Cl].[Ir] RBNNPWUKDNRSMD-UHFFFAOYSA-N 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 description 22
- 239000002253 acid Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- -1 hexachlororhodium (III) Chemical compound 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- 230000000875 corresponding effect Effects 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- QTNLQPHXMVHGBA-UHFFFAOYSA-H hexachlororhodium Chemical compound Cl[Rh](Cl)(Cl)(Cl)(Cl)Cl QTNLQPHXMVHGBA-UHFFFAOYSA-H 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- ZYSSNSIOLIJYRF-UHFFFAOYSA-H Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl Chemical compound Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl ZYSSNSIOLIJYRF-UHFFFAOYSA-H 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- ZFBIHEFLSPUZGE-UHFFFAOYSA-H ruthenium(3+);hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ru+3] ZFBIHEFLSPUZGE-UHFFFAOYSA-H 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- YDVQBPXDKJKDME-UHFFFAOYSA-J tetrachloroiridium;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Ir](Cl)(Cl)Cl YDVQBPXDKJKDME-UHFFFAOYSA-J 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- C22B3/28—Amines
- C22B3/282—Aliphatic amines
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by 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
- C22B11/00—Obtaining noble metals
- C22B11/06—Chloridising
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for separating rhodium from aqueous hydrochloric acid solutions containing at least one chlorine complex of rhodium and at least one chlorine complex of iridium and/or at least one chlorine complex of ruthenium, characterized in that aliphatic polyamines are used as sparingly soluble rhodium chlorine complex salts, the rhodium being precipitated from aqueous hydrochloric acid solutions having an oxidation-reduction potential of from greater than or equal to 950mV to 1050mV, while the joint separation previously carried out with the iridium and/or the ruthenium being explicitly dispensed with.
Description
The present invention relates to an efficient process for separating rhodium in the form of a poorly soluble rhodium chloride complex salt from an aqueous solution containing a (hydrochloric) noble metal chloride complex.
The term "noble metal chloride complex" as used herein refers to a chloride complex of the noble metals rhodium, iridium, ruthenium, gold, platinum or palladium.
Precipitation of poorly soluble noble metal chloride complex salts from aqueous hydrochloric acid solutions containing noble metal chloride complexes is prior art in wet chemical noble metal recovery or wet chemical noble metal refining. In addition to hydrochloric acid, such aqueous hydrochloric acid solutions may also contain other acids, in particular mineral acids, such as nitric acid. The pH of such aqueous hydrochloric acid solutions is typically in the range < 2.
The term "sparingly-soluble noble metal chloride complex salt" as used herein refers to its low solubility in hydrochloric acid or in aqueous hydrochloric acid medium at a pH in the range < 2. The solubility of the noble metal present in the sparingly-soluble noble metal chloride complex salt is quantified and expressed, which means that the solubility of the noble metal under consideration is <100mg per liter.
The concentration of the noble metal dissolved in the aqueous hydrochloric acid solution can be determined by ICP-OES (inductively coupled plasma emission spectrometry).
Examples of the noble metal chloride complex contained in the aqueous hydrochloric acid solution (i.e., the noble metal chloride complex dissolved therein) include, in particular, a chloronoble metal acid, in the case of rhodium, hexachlororhodium (III) acid H 3RhCl6; in the case of iridium, depending on the redox potential of the solution, it is hexachloroiridium (III) acid H 3IrCl6 and/or hexachloroiridium (IV) acid H 2IrCl6; in the case of ruthenium, it is ruthenium (IV) hexachloride acid H 2RuCl6; in the case of gold, gold (III) tetrachloride acid HAuCl 4; in the case of platinum, hexachloroplatinic (IV) acid H 2PtCl6; and in the case of palladium, tetrachloropalladium (II) acid H 2PdCl4 and/or hexachloropalladium (IV) acid H 2PdCl6, depending on the redox potential of the solution.
The term "redox potential" as used in the present specification and claims means the redox potential of an aqueous solution measured at 20 ℃ relative to an Ag/AgCl electrode.
In the case of the wet-chemical noble metal recovery or the wet-chemical noble metal refining, the joint separation of rhodium, iridium and ruthenium is customary in the art, which is carried out at relatively low redox potentials (for example in the range from 400mV to 550 mV) by coprecipitation by means of aliphatic polyamines in the form of sparingly-soluble chlorine complex salts. The sparingly-soluble chlorine complex salts are in particular the corresponding polyamines hexachlororhodium (III), hexachloroiridium (III), hexachlororuthenate (III) or hexachlororuthenate (IV); it is not necessary to note to the person skilled in the art that the nitrogen atoms of the corresponding aliphatic polyamine component are protonated in such chlorine complex salts. Any gold that may be present may, for example, have been isolated by preliminary reduction, i.e. prior to rhodium/iridium/ruthenium co-precipitation, while optionally platinum and palladium may be isolated by precipitation, for example by ammonium chloride or potassium chloride in the form of sparingly soluble chloride complex salts, either before or after rhodium/iridium/ruthenium co-precipitation. The poorly soluble chlorine complex salts of rhodium, iridium and ruthenium co-precipitated by aliphatic polyamines can then be first evaporated in aqua regia for further processing. In this case, the organic components degrade by oxidation and eventually form aqueous hydrochloric acid solutions containing dissolved rhodium, iridium and ruthenium chloride complexes, in particular in the form of their aforementioned chloronoble metal acids. A typical way of further refining is to separate rhodium having a relatively high redox potential by precipitation with aliphatic polyamines as poorly soluble chlorine complex salts, followed by further refining of the rhodium to obtain metallic rhodium or a purified rhodium compound such as, for example, hexachlororhodium (III) acid H 3RHCl6. Iridium and ruthenium can then be separated from the aqueous hydrochloric acid phase containing the dissolved iridium and ruthenium chloride complexes by precipitation with aliphatic polyamines as poorly soluble chloride complex salts at relatively low redox potentials and then supplied to further iridium or ruthenium refining.
US 5 478 376 discloses a process for separating rhodium and/or iridium from a starting solution containing at least one ruthenium chloride complex, hydrochloric acid and rhodium and/or iridium chloride complex, wherein the process comprises converting the ruthenium chloride complex into nitrosyl complexes in the divalent state and precipitating the rhodium and/or iridium by manipulating their oxidation states.
The object of the present invention is to enable particularly efficient separation of rhodium from aqueous hydrochloric acid solutions containing rhodium and iridium and/or ruthenium chloride complexes (rhodium and iridium chloride complex, or rhodium and ruthenium chloride complex, or rhodium and iridium and ruthenium chloride complex).
The present invention achieves this object in a surprisingly simple manner by a process for separating rhodium from an aqueous hydrochloric acid solution comprising at least one chlorine complex of rhodium and at least one chlorine complex of iridium and/or at least one chlorine complex of ruthenium (i.e. at least one chlorine complex of rhodium and at least one chlorine complex of iridium, or at least one chlorine complex of rhodium and at least one chlorine complex of ruthenium, or at least one chlorine complex of rhodium, at least one chlorine complex of iridium and at least one chlorine complex of ruthenium), which is characterized in that rhodium is precipitated from an aqueous hydrochloric acid solution having an oxidation-reduction potential of from greater than or equal to 950mV to 1050mV (oxidation-reduction potential in the range of greater than or equal to 950mV to 1050 mV) using aliphatic polyamines as sparingly soluble rhodium chlorine complex salts, while the combined separation from the aqueous hydrochloric acid solution with iridium and/or ruthenium is explicitly avoided.
To avoid misunderstanding, the process according to the invention is not aware of any nitrosyl complexes, let alone of the noble metals rhodium, iridium and ruthenium. The method according to the invention does not comprise any type of nitrosyl complex. During the process according to the invention, no nitrosyl complex has ever been found in the aqueous hydrochloric acid solution which contains at least one chlorine complex of rhodium and at least one chlorine complex of iridium and/or at least one chlorine complex of ruthenium. All further substances used during the process according to the invention are free of nitrosyl complexes or of substances capable of forming nitrosyl complexes with the aqueous hydrochloric acid solution. In other words, in the process according to the invention, not only is no nitrosyl complex formed or used at any time, but also is not required to be formed.
The method according to the invention comprises in particular the following steps (1) to (4):
(1) Providing an aqueous hydrochloric acid solution comprising:
at least one chlorine complex of rhodium and at least one chlorine complex of iridium, or
At least one chlorine complex of rhodium and at least one chlorine complex of ruthenium, or
At least one chlorine complex of rhodium, at least one chlorine complex of iridium and at least one chlorine complex of ruthenium;
(2) Ensuring that the oxidation-reduction potential of the aqueous hydrochloric acid solution is within the range of 950mV to 1050 mV;
(3) Adding an aliphatic polyamine in an amount at least sufficient or even in excess for complete precipitation of at least one rhodium chlorine complex as a poorly soluble rhodium chlorine complex salt; and
(4) The precipitated sparingly-soluble rhodium chloride complex salt is separated from the aqueous hydrochloric acid solution.
The method according to the invention preferably comprises further steps (5) to (7) after step (4):
(5) Setting the oxidation-reduction potential of the aqueous hydrochloric acid solution in the range of 400mV to 550mV by adding a reducing agent;
(6) If still desired, adding at least a sufficient or even an excess amount of an aliphatic polyamine for complete precipitation of at least one iridium chloride complex as a poorly soluble iridium chloride complex salt and/or at least one ruthenium chloride complex as a poorly soluble ruthenium chloride complex salt; and
(7) The precipitated poorly soluble iridium chloride complex salt and/or the precipitated poorly soluble ruthenium chloride complex salt is separated from the aqueous hydrochloric acid solution.
In step (1) of the process according to the invention, an aqueous hydrochloric acid solution is provided, which comprises at least one chlorine complex of rhodium and at least one chlorine complex of iridium, or at least one chlorine complex of rhodium and at least one chlorine complex of ruthenium, or at least one chlorine complex of rhodium, at least one chlorine complex of iridium and at least one chlorine complex of ruthenium. The proportion of the at least one dissolved rhodium chloride complex in the aqueous hydrochloric acid solution may be in the range corresponding to, for example, 0.5g/l rhodium to 15g/l rhodium, and is preferably hexachlororhodium acid. The proportion of the chlorine complex of the at least one dissolved iridium in the aqueous hydrochloric acid solution may for example be in the range corresponding to 0.5g/l iridium to 15g/l iridium, and is preferably hexachloroiridic acid. The proportion of the at least one dissolved ruthenium chloride complex in the aqueous hydrochloric acid solution may be in the range corresponding to, for example, 0.5g/l ruthenium to 15g/l ruthenium, and is preferably hexachlororuthenic acid. For possible additional components of the aqueous hydrochloric acid solution and the pH, reference is made to what has already been mentioned above.
It is important to the present invention that the process according to the invention explicitly eliminates the joint separation of rhodium with iridium, or with ruthenium, or with iridium and ruthenium.
For this purpose, in step (2) of the process according to the invention, it is initially ensured that the redox potential of the aqueous hydrochloric acid solution is in the range from.gtoreq.950 mV to 1050mV, for example in the range from.gtoreq.950 mV to 1000 mV. If this is not the case, such redox potential is set by adding an oxidizing agent. The setting of the redox potential may be achieved by mixing the aqueous hydrochloric acid solution with one or more oxidizing agents under potential control customary in the art. The oxidizing agent may be added to the aqueous hydrochloric acid solution as such or as an aqueous solution. Examples of particularly suitable oxidizing agents include chlorine, bromates, chlorates and perchlorates. When using oxidizing agents in aqueous solution, the person skilled in the art will advantageously strive to use those oxidizing agents which do not have an unnecessarily low concentration.
During step (2), it may be advantageous to ensure good mixing, for example by stirring. Step (2) may advantageously be carried out at a temperature in the range of, for example, 55 ℃ to 90 ℃.
If the relatively high redox potential of the aqueous hydrochloric acid solution is dominant, or has been set by the addition of an oxidizing agent, according to step (2), the aliphatic polyamine is added to the aqueous hydrochloric acid solution in step (3) in an amount sufficient or even excessive to cause complete precipitation of the at least one rhodium chloride complex as a poorly soluble rhodium chloride complex salt. The amount of aliphatic polyamine that is at least sufficient to cause complete precipitation of the at least one rhodium chloride complex as a poorly soluble rhodium chloride complex salt is an amount that does not cause any further precipitation even upon further addition; in this regard, the term "complete precipitation" is understood by those skilled in the art to be precipitation of materials that exceed the solubility product. The aliphatic polyamine may be added as such or in an aqueous solution, preferably as an aqueous solution neutralized with an acid, in particular with hydrochloric acid. The aliphatic polyamine may be one aliphatic polyamine or a combination of two or more aliphatic polyamines, the use of a single aliphatic polyamine being preferred. The proportion of aliphatic polyamines in such aqueous solutions neutralized with acids can be, for example, in the range from 15 to 25% by weight. Examples of aliphatic polyamines suitable as such precipitants include Diethylenetriamine (DETA), triethylenetriamine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine, tris (2-aminoethyl) amine (TAEA), dipropylenetriamine, 1- (2-aminoethyl) piperazine, one aliphatic polyamine or a combination of two or more aliphatic polyamines may be selected from such precipitants. DETA is particularly suitable and is therefore preferably used.
In other words, aliphatic polyamines are used as sparingly-soluble rhodium-chlorine complex salts, the rhodium being precipitated directly and at least largely selectively at oxidation-reduction potentials of from > 950mV to 1050mV, for example in the range from > 950mV to 1000mV, and the rhodium thus being separated from iridium and/or ruthenium first.
The material precipitated during step (3) is a sparingly soluble salt of a chlorine complex of an aliphatic polyamine (e.g., DETA) and rhodium (such as hexahydrohexachlororhodium acid), i.e., diethylenetriamine hexachlororhodium salt of formula H 3(DETA)RhCl6 or (H 3NC2H4NH2C2H4NH3)(RhCl6), for example.
During step (3), it may be advantageous to ensure good mixing, for example by stirring. Step (3) may advantageously be carried out at a temperature in the range of, for example, 55 ℃ to 90 ℃.
At the end of step (3) or between steps (3) and (4), it may be advantageous to rest the formed mixture, for example by leaving it for one to three hours. Thus, sedimentation of the precipitated material and formation of the supernatant in the form of an aqueous hydrochloric acid solution can be effectively supported.
After its precipitation, the sparingly soluble rhodium chloride complex salt may be separated from the supernatant aqueous hydrochloric acid solution in step (4) of the process according to the invention by typical solid-liquid separation. Examples of suitable solid-liquid separation methods include methods known to those skilled in the art, such as decantation, extrusion, filtration, suction filtration, centrifugation, or combinations thereof.
It has been found that rhodium separation on the order of 80% to 99% can be achieved based on the rhodium content of the aqueous hydrochloric acid solution provided in step (1). This is achieved at least to a large extent selectively and in the following sense: based on the iridium or ruthenium content of the original aqueous hydrochloric acid solution provided in step (1), co-precipitation of iridium or ruthenium does not occur or occurs on the order of, for example, only >0 to 15%.
The separated poorly soluble rhodium chloride complex salt may be fed to a typical rhodium refining process.
The separated aqueous hydrochloric acid solution also contains iridium and/or ruthenium in the form of its dissolved non-precipitated chlorine complexes.
Steps (1) to (4) of the process according to the invention are successive steps. As already stated, the method according to the invention preferably comprises further steps (5) to (7), wherein steps (5) and (6) can be carried out in step sequence (5) - (6) or (6) - (5), but step sequence (5) - (6) is preferred.
In step (5), the relatively low redox potential of the aqueous hydrochloric acid solution is set in the range of 400mV to 550mV, preferably 440mV to 470mV, by adding a reducing agent. The redox potential setting may advantageously be carried out by mixing the aqueous hydrochloric acid solution with a reducing agent under potential control. The reducing agent may be added to the aqueous hydrochloric acid solution as such or as an aqueous solution. The reducing agent may be one reducing agent or a combination of two or more reducing agents. Examples of suitable reducing agents include tin (II) salts such as tin (II) chloride and tin (II) sulfate, but in particular iron (II) salts such as iron (II) chloride, iron (II) sulfate and iron (II) nitrate. When using reducing agents in aqueous solution, the person skilled in the art will advantageously strive to use those reducing agents which do not have an unnecessarily low concentration.
During step (5), it may be advantageous to ensure good mixing, for example by stirring. Step (5) may advantageously be carried out at a temperature in the range of, for example, 50 ℃ to 70 ℃.
If still necessary, further aliphatic polyamines, i.e. at least a sufficient or even an excess amount of aliphatic polyamines, may be added to the aqueous hydrochloric acid solution in this connection optionally in optional step (6) before or preferably after the low redox potential has been set in step (5) for complete precipitation of the at least one iridium chloride complex as poorly soluble iridium chloride complex salt and/or the at least one ruthenium chloride complex as poorly soluble ruthenium chloride complex salt. The amount of aliphatic polyamine that is at least sufficient to cause complete precipitation of at least one iridium or ruthenium chloride complex as a poorly soluble chloride complex salt is an amount that does not cause any more precipitation even when further added; in this regard, the term "complete precipitation" is understood by those skilled in the art to be precipitation of materials that exceed the solubility product. The need to add the aliphatic polyamine and thus to achieve step (6) depends on whether the aliphatic polyamine necessary for complete precipitation is absent, more precisely, whether and to what extent the added aliphatic polyamine from step (2) is contained in the aqueous hydrochloric acid solution. If this is not the case or is not the case in sufficient or even excessive amounts, step (6) is performed. In this case, the aliphatic polyamine may be added as such or in the form of an aqueous solution, but is preferably added in the form of an acid, in particular in the form of an aqueous solution neutralized with hydrochloric acid. The proportion of aliphatic polyamines in such aqueous solutions neutralized with acids can be, for example, in the range from 15 to 25% by weight. Examples of aliphatic polyamines suitable as such precipitants include the aliphatic polyamines already mentioned above.
If step (6) can be omitted, if not necessary, i.e. if a sufficient amount of the aliphatic polyamine added during step (2) is contained in the aqueous hydrochloric acid solution during step (5), precipitation of iridium and/or ruthenium can be said to occur "automatically".
In this regard, the material precipitated during or after completion of step (5) or step (6) is a poorly soluble salt consisting of a chlorine complex of an aliphatic polyamine and iridium and/or a chlorine complex of ruthenium.
During step (6), it may be advantageous to ensure good mixing, for example by stirring. Step (6) may advantageously be carried out at a temperature in the range of, for example, 55 ℃ to 90 ℃. At the end of step (6) or between steps (6) and (7), it may be advantageous to rest the formed mixture, for example by leaving it for one to six hours. Thus, sedimentation of the precipitated material and formation of the supernatant in the form of an aqueous hydrochloric acid solution can be effectively supported.
After its precipitation, the precipitated sparingly-soluble iridium chloride complex salt and/or the precipitated sparingly-soluble ruthenium chloride complex salt may be separated from the aqueous hydrochloric acid solution in step (7) by typical solid-liquid separation. Examples of suitable solid-liquid separation methods include methods known to those skilled in the art, such as decantation, extrusion, filtration, suction filtration, centrifugation, or combinations thereof.
The isolated sparingly soluble iridium and/or ruthenium chloride complex salts may be fed into a typical iridium or ruthenium refining process.
The advantages of the method according to the invention compared to the method according to the prior art mentioned at the beginning are less chemical consumption and increased efficiency. Unlike the prior art, the rhodium and iridium and/or ruthenium separated off can be processed in parallel with little time delay.
Exemplary embodiments 1 to 3, general procedure:
200ml of an aqueous noble metal hydrochloride solution set to a redox potential of 950mV by adding a sodium chlorate solution (acid content 3 mol/l; dissolved noble metal: platinum, palladium, rhodium, iridium, ruthenium) were added dropwise to the beaker with stirring at 75℃with a stoichiometric excess of DETA calculated as 1.5 times the rhodium content. For this purpose, an aqueous DETA solution neutralized with hydrochloric acid with a DETA content of 19% by weight was used. The mixture was then stirred for an additional 5 minutes and the beaker covered with the dish was allowed to cool. The precipitate consisting essentially of DETA hexachlororhodium salt was suction filtered off and washed with some distilled water. The filtrate volume was determined on the one hand and the corresponding noble metal content of the filtrate on the other hand and they were correlated by ICP-OES to a volume of 200ml and the noble metal content of the original noble metal solution.
The following table shows the precious metal content of the original precious metal solution and the corresponding yield of precipitated precious metal.
Claims (9)
1. A process for separating rhodium from aqueous hydrochloric acid solutions containing at least one chlorine complex of rhodium and at least one chlorine complex of iridium and/or at least one chlorine complex of ruthenium, characterized in that aliphatic polyamines are used as sparingly soluble rhodium chlorine complex salts, the rhodium being precipitated from aqueous hydrochloric acid solutions having an oxidation-reduction potential of from greater than or equal to 950mV to 1050mV, while the joint separation previously carried out with the iridium and/or the ruthenium being explicitly dispensed with.
2. The method according to claim 1, comprising steps (1) to (4):
(1) Providing an aqueous hydrochloric acid solution containing at least one chlorine complex of rhodium and at least one chlorine complex of iridium, or
At least one chlorine complex of rhodium and at least one chlorine complex of ruthenium, or
At least one chlorine complex of rhodium, at least one chlorine complex of iridium and at least one chlorine complex of ruthenium;
(2) Ensuring that the oxidation-reduction potential of the aqueous hydrochloric acid solution is in the range of 950mV to 1050mV or more;
(3) Adding an aliphatic polyamine in an amount of at least sufficient or even excessive for complete precipitation of the at least one rhodium chlorine complex as a poorly soluble rhodium chlorine complex salt; and
(4) Separating the precipitated poorly soluble rhodium chloride complex salt from the aqueous hydrochloric acid solution.
3. The method according to claim 2, comprising steps (5) to (7) after step (4):
(5) Setting the oxidation-reduction potential of the aqueous hydrochloric acid solution in the range of 400mV to 550mV by adding a reducing agent;
(6) If still desired, adding at least a sufficient or even an excess amount of an aliphatic polyamine for complete precipitation of the at least one iridium chloride complex as a poorly soluble iridium chloride complex salt and/or the at least one ruthenium chloride complex as a poorly soluble ruthenium chloride complex salt; and
(7) The precipitated sparingly-soluble iridium chloride complex salt and/or the precipitated sparingly-soluble ruthenium chloride complex salt is separated from the aqueous hydrochloric acid solution.
4. A process according to claim 2 or 3, wherein the proportion of the at least one dissolved chlorine complex of rhodium in the aqueous hydrochloric acid solution is in the range corresponding to 0.5g/l rhodium to 15g/l rhodium.
5. The process according to any one of claims 2 to 4, wherein the proportion of the at least one dissolved iridium chlorine complex in the aqueous hydrochloric acid solution is in the range corresponding to 0.5g/l iridium to 15g/l iridium.
6. The process according to any one of claims 2 to 5, wherein the proportion of the at least one dissolved ruthenium chloride complex in the aqueous hydrochloric acid solution is in the range corresponding to 0.5g/l ruthenium to 15g/l ruthenium.
7. The method according to any one of claims 2 to 6, wherein the redox potential in step (2) is set by adding an oxidizing agent.
8. The process of any one of claims 2 to 7, wherein the aliphatic polyamine is added in step (3) as an aqueous solution neutralized with hydrochloric acid.
9. The method of any one of claims 2 to 8, wherein the aliphatic polyamine is one aliphatic polyamine selected from the group consisting of two aliphatic polyamines, or a combination of two or more aliphatic polyamines: diethylenetriamine (DETA), triethylenetriamine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (TAEA), dipropylenetriamine, 1- (2-aminoethyl) piperazine.
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| EP21211870 | 2021-12-02 | ||
| EP21211870.7 | 2021-12-02 | ||
| PCT/EP2022/079164 WO2023099076A1 (en) | 2021-12-02 | 2022-10-20 | Method for separating rhodium |
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| KR (1) | KR20240093908A (en) |
| CN (1) | CN118234878A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ZA763680B (en) * | 1976-06-21 | 1978-02-22 | Nat Inst Metallurg | The separation and purification of ruthenium |
| GB2293372B (en) | 1994-09-21 | 1998-05-27 | Matthey Rustenburg Refiners | Improvements in refining |
| CN106282562B (en) * | 2016-08-29 | 2018-04-10 | 金川集团股份有限公司 | A kind of technique of separate rhodium iridium |
| RU2693285C1 (en) * | 2018-11-06 | 2019-07-02 | Игорь Владимирович Федосеев | METHOD OF SEPARATING METALS FROM PLATINUM, PALLADIUM, RHODIUM Pt-Pd-Rh |
| RU2742994C1 (en) * | 2020-06-09 | 2021-02-12 | Игорь Владимирович Федосеев | Method for selective extraction of rhodium rh, ruthenium ru and iridium ir from hydrochloric acid solutions of chlorine complexes of platinum pt (iv), palladium pd (ii), gold au (iii), silver ag (i), rhodium rh (iii), ruthenium ru (iv) and iridium ir (iv) |
| CN113430376A (en) * | 2021-07-06 | 2021-09-24 | 湖南省南铂新材料有限公司 | Method for efficiently separating noble metals in solution and preparing high-purity noble metals |
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