CN102959103B - Recovery method for high purity platinum - Google Patents
Recovery method for high purity platinum Download PDFInfo
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- CN102959103B CN102959103B CN201180030294.7A CN201180030294A CN102959103B CN 102959103 B CN102959103 B CN 102959103B CN 201180030294 A CN201180030294 A CN 201180030294A CN 102959103 B CN102959103 B CN 102959103B
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- ruthenium
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 294
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 146
- 238000011084 recovery Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 88
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 83
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 16
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 abstract description 30
- 229910017052 cobalt Inorganic materials 0.000 abstract description 16
- 239000010941 cobalt Substances 0.000 abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052804 chromium Inorganic materials 0.000 abstract description 13
- 239000011651 chromium Substances 0.000 abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 239000010949 copper Substances 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000005477 sputtering target Methods 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 150000003057 platinum Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 5
- 150000003303 ruthenium Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 platinum metals Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 230000000803 paradoxical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000003245 working effect Effects 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
-
- 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
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/025—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper, or baths
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A high purity platinum recovery method for obtaining a platinum sponge by dissolving a platinum alloy containing ruthenium in aqua regia, wherein the platinum concentration is adjusted above 15g/L, and the ruthenium concentration is adjusted below 6g/L, removing the residue and then reacting the acid wherein platinum is dissolved and an ammonium chloride solution, separating out cholorplatanic acid ammonium, and reducing the chloroplatanic acid ammonium. The method is characterised in that the acid wherein the platinum is dissolved and the ammonium chloride solution are reacted at a temperature of at least 40 DEG C. Provided is a method which enables the recovery of a high yield of high purity platinum which can be reused in platinum and platinum alloy-containing targets and from which ruthenium, cobalt, chromium, copper, iron, nickel, and silicon, etcetera, mixed into scraps such as mill ends, sawdust, or surface grinding scraps generated in the manufacturing process or similar for a target or in used platinum alloy sputtering targets, particularly magnetic targets, have been efficiently removed.
Description
Technical field
The present invention relates to from containing platinum and ruthenium as reclaim the recovery method of the high purity platinum of highly purified platinum the waste material of the platinum alloy of composition, particularly magneticsubstance target etc. with high yield.
Background technology
In recent years, along with the remarkable development of semiconductor integrated circuit, in circuit layout or in order to form various electric electronic elements, be formed with various films, wherein, as magneticthin film or semiconductor material purposes for recording medium, also use platiniferous alloy sputtering targets to form specific film.Such platinum alloy target in most cases also contains ruthenium as alloying element.
The target of the alloy manufacture that these films contain platinum etc. by use carries out sputter and forms under the inert atmospheres such as argon gas.
In the stage of making this target, produce a large amount of scrap stock such as cutting swarf.These all become waste material.In addition, the target after use also becomes waste material.
In being made as the operation of target, after melting and casting due to the mechanical workouts such as the plastic workings such as the forging of ingot, rolling or cutting and with the bonding process of backing plate, the pollution that produces the part contacting with target.Particularly remarkable from the pollution of heavy metal etc. of material that forms the cutting tool of mechanical workout or the machining tool of periphery.
Platinum is material at high price, recycling after therefore need to being reclaimed, still, the problem that the material of the above-mentioned pollution of existence generation can not directly be used.
Above-mentioned impurity is the reason that makes the degradation of recording medium, hard disk or semiconductor device components, and likely in sputter, cause splash, paradoxical discharge, generation powder etc., thereby the character of film is declined.
Conventionally proceed as follows: platiniferous waste material dissolved with acid such as chloroazotic acid and remove after residue, thereby making the acid that is dissolved with platinum react the form recovery precipitation with ammonium chloroplatinate with ammonium chloride solution, then by this ammonium chloroplatinate roasting, reclaiming thus platinum.
Contain platinum as the magneticthin film of the main component of Constitution Elements or a part for Constitution Elements, mostly also contain ruthenium as a part for Constitution Elements.Ruthenium is platinum family element, so the two character is similar, and existence is difficult to the platinum problem separated with ruthenium.
Even if sneak in platinum this Special Circumstances that ruthenium can not throw into question to material behavior yet, only otherwise platinum is separated with ruthenium, ruthenium is exactly impurity.Platinum itself is material very at high price, therefore need to reclaim with high yield.
About reclaiming the technology of platinum, several schemes have been proposed in patent documentation, below they are introduced, still, thereby can't say for by the efficient recovery method of ruthenium recovery separated with platinum high purity platinum.
Following technology is disclosed in following patent documentation 1: thus platinum is extracted in the process of platinum with ammonium chloride salt form precipitation, regulate the pH that contains gold, the muriatic aqueous solution in platinum metals, thereby then carry out two step neutralizations filtration separating tellurium.
Following technology is disclosed in following patent documentation 2: thereby ammonium chloroplatinate or platinum are carried out to heat in oxygen flow, remove impurity ruthenium.
Following technology is disclosed in following patent documentation 3: in the process by oxidation distillation separated ruthenium from the solution that contains platinum family, after regulator solution pH, use sodium bromate to change ruthenium into ruthenium tetroxide, then carry out oxidation distillation, thereby by ruthenium Separation and Recovery.
The manufacture method at following platinum powder end is disclosed in following patent documentation 4: in forming the process of ammonium chloroplatinate, thereby in ammonium chloride solution, use dispersion stabilizer to obtain fine ammonium chloroplatinate, and it is calcined at low temperatures and manufacture platinum powder end.
The recovery method of following high purity platinum is disclosed in following patent documentation 5: after with acid, platiniferous waste material being dissolved, it is reacted with ammonium chloride solution, and reclaim precipitation with ammonium chloroplatinate form, will after precipitation roasting, obtain spongy platinum.
Following technology is disclosed in following patent documentation 6: after with acid, platiniferous waste material being dissolved, it is reacted with ammonium chloride solution, and reclaim precipitation with ammonium chloroplatinate form, then make residual platinum in spent ion exchange resin, gac recovering liquid.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 10-102156 communique
Patent documentation 2: TOHKEMY 2006-183099 communique
Patent documentation 3: TOHKEMY 2006-161096 communique
Patent documentation 4: TOHKEMY 2008-106349 communique
Patent documentation 5: TOHKEMY 2003-27154 communique
Patent documentation 6: TOHKEMY 2003-129145 communique
Summary of the invention
In view of above content, the invention provides and can effectively remove platinum alloy for sputter, especially for form the cobalt of sneaking in the waste materials such as the target waste material (target after use) of platiniferous of magneticthin film or the scrap stock that produce, cutting swarf, flat stone mill swarf, chromium, copper, iron, nickel, silicon etc. in the manufacturing process of target, and the ruthenium that particularly sputter can be contained in the waste material with platinum alloy is separated, thus, the high purity platinum that can be used as platinum and platiniferous target recycling is reclaimed with low-cost and high yield.
The invention provides:
1) a kind of recovery method of high purity platinum, comprise with chloroazotic acid the platinum alloy containing ruthenium is dissolved, remove residue, then make the acid that is dissolved with platinum react with ammonium chloride solution and ammonium chloroplatinate is salted out, thereby this Platinic chloride ammonium salt reduction is obtained to spongy platinum, it is characterized in that, the acid that is dissolved with platinum described in making is reacted at more than 40 ℃ temperature with ammonium chloride solution.
2) as above-mentioned 1) as described in the recovery method of high purity platinum, it is characterized in that, by the platinum concentration adjustment of the liquid that utilizes aqua regia dissolution to contain the platinum alloy of ruthenium and obtain for more than 15g/L.
3) as above-mentioned 1) or 2) as described in the recovery method of high purity platinum, it is characterized in that, by the ruthenium concentration adjustment of the liquid that utilizes aqua regia dissolution to contain the platinum alloy of ruthenium and obtain for below 6g/L.
The present invention also provides:
4) as above-mentioned 1) to 3) in the recovery method of high purity platinum as described in any one, it is characterized in that, the content as the ruthenium of impurity in the spongy platinum that the roasting of Platinic chloride ammonium salt is obtained is below 2%.
5) as above-mentioned 4) as described in the recovery method of high purity platinum, it is characterized in that, the content of ruthenium is below 1%.
6) as above-mentioned 1) to 5) in the recovery method of high purity platinum as described in any one, its feature in, containing the platinum alloy of ruthenium, be the waste material of magneticsubstance target, and the platinum rate of recovery in this waste material is more than 99%.
Invention effect
The present invention has following excellent results: can remove the cobalt of sneaking in the waste material such as the waste material (target after use) of platiniferous target or the scrap stock that produce, cutting swarf, flat stone mill swarf for sputter, chromium, copper, iron, nickel, silicon etc. in the manufacturing process of target by fairly simple operation, and particularly can be effectively that the platinum family element ruthenium containing in magneticsubstance target is separated with platinum.
Embodiment
In the present invention, first with acid, the waste material that contains platinum and ruthenium and contain impurity element cobalt, chromium, copper, iron, nickel, silicon etc. is dissolved.Use chloroazotic acid as the acid of dissolving use.Also can use other acid to dissolve, still, for example, dissolve not exclusively when the dissolving with hydrochloric acid, thereby and produce the possibility that hydrogen exists hydrogen explosion.
While using chloroazotic acid, can dissolve fully, and produce oxynitride and hydrogen while dissolving simultaneously, thereby therefore have advantages of that dilution hydrogen does not exist explosion hazard.Use in the situation of chloroazotic acid, initial stage platinum not too easily dissolves, but little by little platinum becomes dissolving well.
Platiniferous waste material is removed the tantalum pentoxide (Ta as residue after dissolving with acid
2o
5), boron oxide compound (B
2o
3) etc. impurity.
Remove after this residue, in containing the solution of platinum, add the caustic alkali such as sodium hydroxide (NaOH) pH regulator to 3 ~ 6 are neutralized, cobalt, copper etc. are precipitated with hydroxide form, and removed by filter.
In solution, contain in the situation of palladium, in precipitation, remove after the oxyhydroxide of cobalt, copper etc., thereby utilize solvent extraction that palladium is extracted.After extraction of palladium, with ammoniacal liquor, the palladium after this extraction is stripped, and will reduce containing palladium liquid with reductive agent such as hydrazine etc., thereby can reclaim highly purified palladium sponge.
Then, thus the acid that makes to be dissolved with platinum react with ammonium chloride solution and make ammonium chloroplatinate ((NH
4)
2ptCl
6) crystalline deposit.Now, expectation is added the chloroazotic acid that is dissolved with platinum in ammonium chloride solution to.
Conventionally in being dissolved with the chloroazotic acid of platinum, adding ammonium chloride solution is general knowledge, but while adopting such method, finds following phenomenon: ammonium chloroplatinate can dissolve again, become and be difficult to separate out, thereby in liquid residual platinum, the yield of platinum declines.
Therefore,, in order to improve the yield of platinum, it is important that the chloroazotic acid that is dissolved with platinum is added in ammonium chloride solution.
Then, by the ammonium chloroplatinate ((NH obtaining like this
4)
2ptCl
6) crystallization roasting at 600 ~ 1000 ℃, obtain high purity spongy platinum.Thus, the yield of platinum reaches 97%, thereby can with good yield, reclaim high purity platinum by fairly simple method.Above operation is disclosed method in the patent documentation 6 researched and developed of predecessor's day pit wood material (Business Name change) of applicant, is the efficient recovery method of high purity platinum.
But problem is, in above-mentioned waste material, does not study the separation of ruthenium.This be because: past is not added ruthenium widely as the formation of magnetic film or the Constitution Elements of target, and the separation of therefore not recognizing ruthenium is an individual problem greatly.But it is becoming urgent affairs now.
Therefore on the other hand, as mentioned above, ruthenium belongs to platinum family element, separated and remarkable with platinum.The present application provides can be simply and the technology of separated ruthenium effectively.
The recovery method of the high purity platinum of the present application, comprise with chloroazotic acid the platinum alloy containing ruthenium is dissolved, remove residue, then make the acid that is dissolved with platinum react with ammonium chloride solution and ammonium chloroplatinate is salted out, thereby this platinichloride reduction is obtained to spongy platinum, wherein, the acid that is dissolved with platinum described in making is reacted at more than 40 ℃ temperature with ammonium chloride solution.
The upper limit of temperature is not particularly limited, and can say that expectation is set as not making below 100 ℃ of liquid evaporation.
Until described in obtain the operation of sponge, belong to prior art.But ruthenium is difficult to separation, not yet realize the separation of having a mind to.But, by raise a little approximately 10 ~ approximately 20 ℃ than normal temperature, can improve the rate of recovery of platinum, and can reduce the containing ratio of ruthenium in platinum salt.This very unexpected result.
That is, the described technology that the reduction of Platinic chloride ammonium salt is obtained to spongy platinum, is fairly simple and effective manufacturing process, and the technology of expanding out by it, makes the possibility that is separated into of ruthenium.
This technology looks fairly simple, but as mentioned above, is difficult to expect, and can obtains significant effect.
In addition, in the recovery method of the high purity platinum of the present application, expect the platinum concentration adjustment of the liquid that utilizes aqua regia dissolution to contain the platinum alloy of ruthenium and obtain for more than 15g/L.This be because: platinum concentration is during lower than 15g/L, and the solubleness of platinum salt rises, so the platinum rate of recovery in waste material decline (lower than 99%).
More than platinum containing ratio in waste material is generally 30 % by weight, when it is used to aqua regia dissolution under common condition, the platinum concentration in lysate is the concentration that substantially exceeds 15g/L, if need not dilute by a large amount of water, concentration just can not be lower than 15g/L.But thereby relatively low etc. at the containing ratio of the high platinum of containing ratio of ruthenium, concentration, just in the situation lower than 15g/L, is carried out aqua regia dissolution after the waste material high with platinum containing ratio mixes originally.
In addition, in the recovery method of the high purity platinum of the present application, expect the ruthenium concentration adjustment of the solution that utilizes aqua regia dissolution to contain the platinum alloy of ruthenium and obtain for below 6g/L.
This is because although above-mentioned temperature of reaction is also influential, when this ruthenium concentration surpasses 6g/L, ruthenium easily enters into precipitate.For the reduction of this ruthenium concentration, as long as dilute with water.But, on the other hand, because meeting makes the platinum density loss of liquid, so need mutually to regulate.
The recovery method of high purity platinum of the present invention, by as above scheme, can make roasting ammonium chloroplatinate and in the spongy platinum that obtains the content as the ruthenium of impurity be below 2%, be further below 1%.In addition, contain containing the platinum rate of recovery in the waste material of the magneticsubstance target of the platinum alloy of ruthenium and can reach more than 99%.The present application provides the recovery method of such high purity platinum.
Embodiment
Below, based on embodiment, describe.In addition, these examples are used for making easy to understand of the present invention, and the invention is not restricted to these examples.That is the technological thought that, the present application is recorded in claims and specification sheets limits.
(embodiment 1)
In the present embodiment 1, the waste material of the magneticsubstance target that contains platinum, cobalt, chromium, ruthenium is dissolved in chloroazotic acid, removes residue, dilute with water then, obtains the aqua regia dissolution liquid of platinum concentration 30g/L, ruthenium concentration 5g/L.
Thereby this aqua regia dissolution liquid is reacted at 45 ℃ with ammonium chloride and obtain Platinic chloride ammonium salt ((NH
4)
2ptCl
6) crystallization.Then, its roasting at 800 ℃ is obtained to spongy platinum, measure the platinum rate of recovery in aqua regia dissolution liquid and as the containing ratio of the ruthenium of impurity.Result is as shown in table 1.
Table 1
| ? | The platinum rate of recovery (%) | Ruthenium containing ratio (% by weight) in platinum salt |
| Embodiment 1 | 99.5 | 0.5 |
| Embodiment 2 | 99.3 | 0.3 |
| Embodiment 3 | 99.2 | 1.7 |
| Comparative example 1 | 96.0 | 0.6 |
| Comparative example 2 | 99.5 | 2.3 |
| Comparative example 3 | 99.2 | 3.5 |
As shown in the Table 1., the platinum rate of recovery reaches 99.5%, and the ruthenium containing ratio in platinum salt is down to 0.5 % by weight.This ruthenium content is for using regenerate platinum fully to reduce for the situation of target.In addition, about the temperature of reaction of aqua regia dissolution liquid and ammonium chloride, as long as be more than 40 ℃, just can realize same platinum purity and the minimizing of ruthenium.In addition, maturing temperature is not particularly limited, and can suitably regulate, and conventionally can at random select to obtain the temperature of spongy platinum.Same below.
(embodiment 2)
In the present embodiment 2, the waste material of the magneticsubstance target that contains platinum, cobalt, chromium, ruthenium is dissolved in chloroazotic acid, removes residue, dilute with water then, obtains the aqua regia dissolution liquid of platinum concentration 18g/L, ruthenium concentration 3g/L.
Thereby make this aqua regia dissolution liquid react ammonium chloroplatinate is salted out at 90 ℃ with ammonium chloride, precipitate roasting at 800 ℃ is obtained to spongy platinum, measure the platinum rate of recovery in aqua regia dissolution liquid and as the containing ratio of the ruthenium of impurity.
Result is as shown in table 1.
As shown in the Table 1., the platinum rate of recovery reaches 99.3%, and the ruthenium containing ratio in platinum salt is down to 0.3 % by weight.This ruthenium content is for using regenerate platinum fully to reduce for the situation of target.In addition, about the temperature of reaction of aqua regia dissolution liquid and ammonium chloride, as long as be more than 40 ℃, just can realize same platinum purity and the minimizing of ruthenium.
(embodiment 3)
In the present embodiment 3, the waste material of the magneticsubstance target that contains platinum, cobalt, chromium, ruthenium is dissolved in chloroazotic acid, removes residue, dilute with water then, obtains the aqua regia dissolution liquid of platinum concentration 16g/L, ruthenium concentration 5g/L.
Thereby make this aqua regia dissolution liquid react ammonium chloroplatinate is salted out at 50 ℃ with ammonium chloride, precipitate roasting at 800 ℃ is obtained to spongy platinum, measure the platinum rate of recovery in aqua regia dissolution liquid and as the containing ratio of the ruthenium of impurity.
Result is as shown in table 1.
As shown in the Table 1., the platinum rate of recovery reaches 99.2%, and the ruthenium containing ratio in platinum salt is down to 1.7 % by weight.This ruthenium content is for using regenerate platinum fully to reduce for the situation of target.In addition, about the temperature of reaction of aqua regia dissolution liquid and ammonium chloride, as long as be more than 40 ℃, just can realize same platinum purity and the minimizing of ruthenium.
(comparative example 1)
The waste material of the magneticsubstance target that contains platinum, cobalt, chromium, ruthenium is dissolved in chloroazotic acid, removes residue, dilute with water then, obtains the aqua regia dissolution liquid of platinum concentration 12g/L, ruthenium concentration 2g/L.Now, the concentration of platinum is low, lower than the 15g/L of the present application.
Thereby make this aqua regia dissolution liquid react ammonium chloroplatinate is salted out at 70 ℃ with ammonium chloride, precipitate roasting at 800 ℃ is obtained to spongy platinum, measure the platinum rate of recovery in aqua regia dissolution liquid and as the containing ratio of the ruthenium of impurity.
Result is as shown in table 1.As shown in the Table 1., the ruthenium containing ratio in platinum salt is down to 0.6 % by weight, ruthenium meet goal condition containing there is something special, still, the platinum rate of recovery is low to moderate 96.0%.The recovery rate variance of the low explanation platinum of platinum concentration, not preferred.
(comparative example 2)
The waste material of the magneticsubstance target that contains platinum, cobalt, chromium, ruthenium is dissolved in chloroazotic acid, removes residue, dilute with water then, obtains the aqua regia dissolution liquid of platinum concentration 48g/L, ruthenium concentration 8g/L.Now, the concentration of ruthenium surpasses the upper limit 6g/L of the present application.
Thereby make this aqua regia dissolution liquid react ammonium chloroplatinate is salted out at 70 ℃ with ammonium chloride, precipitate roasting at 800 ℃ is obtained to spongy platinum, measure the platinum rate of recovery in aqua regia dissolution liquid and the containing ratio of making the ruthenium of this impurity.
Result is as shown in table 1.As shown in the Table 1., the platinum rate of recovery is up to 99.5%, and still, the ruthenium containing ratio in platinum salt is increased to 2.3 % by weight.Can find out, the ruthenium concentration height in chloroazotic acid is not preferred.
(comparative example 3)
The waste material of the magneticsubstance target that contains platinum, cobalt, chromium, ruthenium is dissolved in chloroazotic acid, removes residue, dilute with water then, obtains the aqua regia dissolution liquid of platinum concentration 30g/L, ruthenium concentration 5g/L.Thereby make this aqua regia dissolution liquid react ammonium chloroplatinate is salted out at 30 ℃ with ammonium chloride, precipitate roasting at 800 ℃ is obtained to spongy platinum, measure the platinum rate of recovery in aqua regia dissolution liquid and as the containing ratio of the ruthenium of impurity.Now, the temperature of reaction of aqua regia dissolution liquid and ammonium chloride does not meet the more than 40 ℃ of condition as the present application.
Result is as shown in table 1.As shown in the Table 1., the platinum rate of recovery is up to 99.2%, and still, the ruthenium containing ratio in platinum salt is increased to 3.5 % by weight.Can find out, when the temperature of reaction of aqua regia dissolution and ammonium chloride is low, the content of ruthenium increases, therefore not preferred.
Platinum, cobalt, chromium, the ruthenium in above-described magneticsubstance waste material not only, even such as copper, iron, nickel, cobalt etc. of a large amount of other impurity of the scrap stock that produce in the manufacturing process of containing next comfortable platiniferous target, cutting swarf, flat stone mill swarf, the present invention also can remove them substantially, can obtain high purity platinum, and the yield of platinum reaches 99%.
In addition, can obtain following effect: can reduce and be difficult to the ruthenium separated with platinum.
The waste material of the magneticsubstance target that above-mentioned use contains platinum, cobalt, chromium, ruthenium is illustrated, and still, the present invention also can similarly be applied to the waste material that contains other impurity.
Industrial applicability
The present invention has following excellent results: can remove the cobalt of sneaking in the waste material of platinum and the scrap stock that produce, cutting swarf, flat stone mill swarf for sputter, chromium, copper, iron, nickel, silicon etc. in the manufacturing process of platiniferous target by fairly simple operation, the high yield of can usining reclaims can be as the high purity platinum of platinum and the target that contains them recycling.There is in addition following effect: particularly it is generally acknowledged and be difficult to the ruthenium separated with platinum, also can in fairly simple method, reduce.Therefore, the present invention can provide the method that reclaims high purity platinum with low-cost and high yield.
Claims (4)
1. the recovery method of a high purity platinum, comprise with chloroazotic acid the platinum alloy containing ruthenium is dissolved, by the platinum concentration adjustment of liquid, be more than 15g/L, ruthenium concentration adjustment is below 6g/L, remove residue, then make the acid that is dissolved with platinum react with ammonium chloride solution and ammonium chloroplatinate is salted out, thereby this Platinic chloride ammonium salt reduction is obtained to spongy platinum, it is characterized in that, the acid that is dissolved with platinum described in making is reacted at more than 40 ℃ temperature with ammonium chloride solution.
2. the recovery method of high purity platinum as claimed in claim 1, is characterized in that, the content as the ruthenium of impurity in the spongy platinum that the roasting of Platinic chloride ammonium salt is obtained is below 2%.
3. the recovery method of high purity platinum as claimed in claim 2, is characterized in that, the content of ruthenium is below 1%.
4. the recovery method of high purity platinum as claimed any one in claims 1 to 3, is characterized in that, be the waste material of magneticsubstance target, and the platinum rate of recovery in this waste material is more than 99% containing the platinum alloy of ruthenium.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010198024 | 2010-09-03 | ||
| JP2010-198024 | 2010-09-03 | ||
| PCT/JP2011/064096 WO2012029379A1 (en) | 2010-09-03 | 2011-06-21 | Recovery method for high purity platinum |
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| CN102959103A CN102959103A (en) | 2013-03-06 |
| CN102959103B true CN102959103B (en) | 2014-03-05 |
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| US (1) | US20130139648A1 (en) |
| JP (1) | JP5399510B2 (en) |
| CN (1) | CN102959103B (en) |
| MY (1) | MY160898A (en) |
| SG (1) | SG186401A1 (en) |
| WO (1) | WO2012029379A1 (en) |
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| DE102013203743A1 (en) * | 2013-03-05 | 2014-09-11 | Heraeus Precious Metals Gmbh & Co. Kg | Process for the preparation of high purity platinum powder and platinum powder obtainable by this process and use |
| CN103627902B (en) * | 2013-04-25 | 2015-12-23 | 上海派特贵金属环保科技有限公司 | A kind of method reclaiming rhodium from inactive noble metal catalyst |
| FR3026110B1 (en) * | 2014-09-24 | 2016-11-18 | Commissariat Energie Atomique | PROCESS FOR RECOVERING THE PLATINUM PRESENT IN A MEMBRANE-ELECTRODE ASSEMBLY |
| TWI623623B (en) * | 2017-04-17 | 2018-05-11 | 國立中山大學 | Treating method for recycling noble metal |
| DE102019217188A1 (en) * | 2019-11-07 | 2021-05-12 | Robert Bosch Gmbh | Process for the extraction of platinum and / or ruthenium |
| CN110964912A (en) * | 2019-12-20 | 2020-04-07 | 有研亿金新材料有限公司 | Method for recovering and purifying platinum from platinum-tungsten alloy |
| CN111676371A (en) * | 2020-04-27 | 2020-09-18 | 励福(江门)环保科技股份有限公司 | Method for separating and purifying platinum from tungsten crucible |
| CN111690819A (en) * | 2020-06-24 | 2020-09-22 | 广东金正龙科技有限公司 | Platinum purification method and reaction kettle |
| CN111926195B (en) * | 2020-06-24 | 2022-03-08 | 重庆材料研究院有限公司 | Method for preparing high-purity platinum powder from platinum alloy waste |
| CN112126789A (en) * | 2020-09-17 | 2020-12-25 | 朱俊 | Chloroplatinic acid solution concentration process and equipment |
| CN115125398A (en) * | 2022-08-09 | 2022-09-30 | 顾秀华 | Preparation process of semi-metallic compound of metal platinum |
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| JP4865156B2 (en) * | 2001-07-18 | 2012-02-01 | Ｊｘ日鉱日石金属株式会社 | Method for recovering high-purity platinum and palladium |
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| JP5408412B2 (en) * | 2009-03-20 | 2014-02-05 | 三菱マテリアル株式会社 | Platinum recovery process |
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- 2011-06-21 SG SG2012093555A patent/SG186401A1/en unknown
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- 2011-06-21 US US13/813,354 patent/US20130139648A1/en not_active Abandoned
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- 2011-06-21 JP JP2011539574A patent/JP5399510B2/en not_active Expired - Fee Related
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| US20130139648A1 (en) | 2013-06-06 |
| JPWO2012029379A1 (en) | 2013-10-28 |
| SG186401A1 (en) | 2013-01-30 |
| WO2012029379A1 (en) | 2012-03-08 |
| CN102959103A (en) | 2013-03-06 |
| JP5399510B2 (en) | 2014-01-29 |
| MY160898A (en) | 2017-03-31 |
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