CN113862483A - Green and efficient separation and purification method for high-purity platinum - Google Patents
Green and efficient separation and purification method for high-purity platinum Download PDFInfo
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- CN113862483A CN113862483A CN202111192031.8A CN202111192031A CN113862483A CN 113862483 A CN113862483 A CN 113862483A CN 202111192031 A CN202111192031 A CN 202111192031A CN 113862483 A CN113862483 A CN 113862483A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 325
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 145
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000000746 purification Methods 0.000 title claims abstract description 29
- 238000000926 separation method Methods 0.000 title claims abstract description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 38
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 33
- 238000001556 precipitation Methods 0.000 claims abstract description 22
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 18
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 18
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 3
- 239000000706 filtrate Substances 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 23
- 150000003057 platinum Chemical class 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 15
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 14
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000005070 sampling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- SJSWRKNSCWKNIR-UHFFFAOYSA-N azane;dihydrochloride Chemical compound N.Cl.Cl SJSWRKNSCWKNIR-UHFFFAOYSA-N 0.000 claims 1
- -1 ammonium amide Chemical class 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000011086 high cleaning Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 56
- 239000011521 glass Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QSKKXNSTGHZSQB-UHFFFAOYSA-N azane;platinum(2+) Chemical class N.[Pt+2] QSKKXNSTGHZSQB-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 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
- C22B7/007—Wet processes by acid leaching
-
- 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
- C22B11/06—Chloridising
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of precious metal secondary resource recycling, in particular to a green and efficient separation and purification method for high-purity platinum. The invention adopts NaClO to oxidize and decompose yellow (NH) in an alkaline medium4)2PtCl6Platinum salt-FeCl3Coprecipitation impurity removal, NaOH hydrolysis and ammonium amide precipitation are carried out to realize green and efficient separation and purification of the platinum. The green and efficient separation and purification method of the high-purity platinum comprises the following steps in sequence: A. ball milling; B. chlorination and dissolution; C. ammonium chloride precipitation; D. slurrying; E. oxidative dissolution-hydrolysis; F. ammonium chloride precipitation; G. reducing hydrazine hydrate; H. and (5) drying. The recovery rate of the platinum is high and is more than 99 percent; the production flow is short, the production efficiency is high, and the economic benefit is good; high cleaning efficiency, green and environment-friendly.
Description
Technical Field
The invention relates to the field of precious metal secondary resource recycling, in particular to a green and efficient separation and purification method for high-purity platinum.
Background
The noble metal comprises 8 elements including gold, silver and platinum group metals, wherein the platinum group gold comprises 6 elements including platinum, palladium, rhodium, iridium, ruthenium and osmium. The chemical properties of the platinum group metals are similar, the existing state of the hydrochloric acid medium platinum group metal aqueous solution is very complicated, the chlorine complexes and hydrates of the platinum group metals are very large in amount, and the thermodynamic instability is caused, so that the separation of the platinum group metals in the solution is very difficult. The mutual separation of platinum group metals is carried out by utilizing different oxidation states and reaction kinetics of the platinum group elements, and the separation is usually carried out by adopting methods such as oxidation distillation, ion exchange, solution extraction, chemical precipitation and the like.
The separation and purification of platinum has 2 main processes widely applied in the industry: ammonium chloride precipitation, aqua regia dissolution, ammonium chloride repeated precipitation method and carrier-oxidation hydrolysis method. Wherein, the method of ammonium chloride precipitation, aqua regia dissolution and ammonium chloride repeated precipitation has the defects of uncontrollable water dissolution step, generation of a large amount of NOx and the like, and the method of carrier-oxidation hydrolysis has poor removal effect on impurity palladium and the like. A new process and a new method for efficiently and environmentally separating and purifying platinum are needed to be developed, so that the aims of improving the production efficiency, saving energy, reducing emission and protecting the environment are achieved.
Chinese patent 201711037866.X discloses a preparation method of ultra-pure platinum powder, which comprises the following steps: (1) precipitating platinum by ammonium chloride; (2) controlling potential reduction: precipitating ammonium chloroplatinate with deionized water to prepare a suspension, adding a reducing agent, and controlling the potential of the solution to reduce to obtain an ammonium platinochloride solution; (3) removing impurities by ion exchange: passing the ammonium platinochloride solution through a cation exchange column to further remove cation impurities to obtain a pure platinochloride solution; (4) deep reduction of chloroplatinic acid: adding hydrazine hydrate into the chloroplatinic acid solution for deep reduction, so that the platinum is reduced into a powder form; (6) acid boiling to remove impurities: and boiling and washing the obtained platinum powder with a mixed solution of nitric acid and hydrofluoric acid, fully washing with deionized water, and drying to obtain the high-purity platinum powder. The whole process of the invention adopts the conventional hydrometallurgy process technology, does not relate to the high-temperature calcination process, and has the advantages of low energy consumption, low cost, short process, high product purity and the like.
Chinese patent 201310471954.6 discloses a new process for refining platinum, which comprises the following steps: platinum group metal-containing concentrate (slag, secondary resources and the like), chlorination dissolution, acid adjustment of dissolved solution, ammonium oxalate precipitation of organic reducing agent, and filtration and separation of precious metals. The process has wide material adaptability and simple operation, can efficiently and quickly dissolve and precipitate the ammonium chloroplatinate containing platinum group metal materials containing the ammonium chloroplatinate, has the dissolution efficiency of 95 to 99 percent in the whole refining process, the precipitation rate of 99 percent and the refining direct yield of 90 to 95 percent, effectively solves the problem that nitrogen oxides are difficult to discharge up to the standard compared with the traditional ammonium chloride repeated precipitation method, and can simultaneously solve the problems of high labor intensity and low production efficiency in the nitrate removing process of aqua regia dissolving solution. Meanwhile, the reducing agent ammonium oxalate is an organic reagent, pollution-free gas generated in the reaction process is directly discharged, and a solution system is not changed, so that the influence on the platinum precipitation of ammonium chloride in the next step is avoided, and the yield and the quality of platinum group metal products can be greatly improved.
Chinese patent 201610738573.3 discloses a platinum refining process, which comprises the following process steps: (1) dissolving various platinum-containing feed liquids and crude platinum ammonium salts by aqua regia, driving acid and nitrate, and filtering; (2) pumping the filtrate into a reaction kettle, introducing chlorine gas for hydrolysis while heating, and stopping introducing chlorine gas when the potential is raised to over 1000 mV; (3) stirring, adding liquid alkali to adjust pH, and directly cooling and filtering when pH =8-9 is stable for more than 5min to obtain orange filtrate; (4) returning the filtrate to acid, repeating the step 2 and the step 3 for three times, finally returning the obtained three hydrolyzed solutions to acid to control the acidity of the feed liquid, adding a saturated ammonium chloride solution after boiling to precipitate platinum, cooling and filtering after boiling again; (5) calcining the obtained ammonium chloroplatinate at 680 ℃ to obtain the spongy platinum. The beneficial effects of the invention are as follows: 1. the production cycle is shortened by more than 40 percent; 2. nitrate removal is reduced to one time, which is beneficial to the improvement of the production capacity and the environment improvement; 3. the direct yield of the platinum is improved by 1.94 percent.
Disclosure of Invention
The invention provides a green and efficient separation and purification method of high-purity platinum, which adopts NaClO in an alkaline medium to oxidize and decompose yellow (NH)4)2PtCl6The green and efficient separation and purification of the platinum are realized by platinum salt-NaOH hydrolysis-ammonium amide precipitation.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the green and efficient separation and purification method of the high-purity platinum comprises the following steps in sequence:
A. ball mill
Ball-milling platinum ash in a ball mill to 40 meshes, and sampling and analyzing to obtain a noble metal platinum content of more than 10%;
B. dissolving by chlorination
The weight Kg of platinum ash is as follows: volume L of 12M hydrochloric acid: volume L =1 of 45% sodium chlorate solution: 4-6: 0.5 to 5; adding 12M hydrochloric acid into a reactor, starting stirring, slowly adding the platinum ash subjected to ball milling in the step A, heating to 70-90 ℃, then slowly adding a 45% sodium chlorate solution, preserving heat for 4 hours, cooling and filtering; the filtrate is sent to the next platinum refining section, and the platinum is collected and recycled from the filter residue;
C. precipitation of ammonium chloride
Transferring the platinum filtrate obtained in the step B into a reactor, adding a 45% sodium chlorate solution, and mixing the weight Kg of platinum in the platinum filtrate: volume L =1 of 45% sodium chlorate solution: 0.1-0.2, heating to 60-95 ℃, preserving heat for 1-4 hours, then stirring and adding solid ammonium chloride, wherein the weight Kg of platinum in the platinum filtrate is as follows: weight Kg of ammonium chloride = 1: 1.2-3; reacting for 1-3 hours, cooling and filtering; yellow (NH)4)2PtCl6Filtering the filter cake to a next platinum purification working section, and uniformly collecting and recovering platinum from the filtrate; yellow (NH)4)2PtCl6The Pt content in the filter cake is 40-44%;
D. slurrying
The yellow (NH) obtained in step C4)2PtCl6Putting the filter cake and water into a reactor, and adding a small amount of solid ferric trichloride under the stirring state; the material is slurried and has the mixture ratio of (NH)4)2PtCl6Weight Kg of platinum in the filter cake: volume L of deionized water: weight g =1 of ferric chloride: 15-25: 10-30 parts of;
E. oxidative dissolution-hydrolysis
C, slowly adding a sodium hypochlorite solution and a sodium hydroxide solution into the reactor pulped in the step D under the stirring state; the sodium hypochlorite solution has very strong oxidizing property and can make yellow (NH)4)2PtCl6Dissolving the platinum salt to generate H2PtCl6Decomposition of sodium hypochlorite solution (NH)4)2PtCl6Reacting according to the formula (1):
(NH4)2PtCl6+3NaClO®H2PtCl6+N2+3H2O+3NaCl （1）
generation of H2PtCl6Hydrolyzed by sodium hydroxide to generate sodium hydroxyplatinate [ Na ]2Pt(OH)6]The chemical reaction of the solution is shown in the formula (2):
H2PtCl6+8NaOH®Na2Pt(OH)6+6NaCl+2H2O （2）
under the stirring state, respectively and slowly adding a 30% sodium hydroxide solution and a 5% sodium hypochlorite solution into the reactor slurried in the step D, wherein the material ratio is (NH)4)2PtCl6Weight Kg of platinum in salt: volume L of 30% sodium hydroxide solution: volume L =1 of 5% sodium hypochlorite solution: 5-10: 1-10, heating to 50-80 ℃, reacting for 5-8 hours, cooling and filtering; the filtrate is sent to the next platinum purification section, and the platinum is collected and recovered from the filter residue;
F. precipitation of ammonium chloride
Hydrochloric acid can react Na2Pt(OH)6Reaction to form H2PtCl6The chemical reaction is shown in formula (3):
Na2Pt(OH)6+8HCl®H2PtCl6+6H2O+2NaCl （3）
ammonium chloride precipitate H2PtCl6To form (NH)4)2PtCl6Platinum is yellow (NH)4)2PtCl6The platinum salt and other impurities exist in the solution, so that the separation of the platinum and the other impurities is realized;
and E, putting the platinum filtrate obtained in the step E into a reactor, adjusting the pH of the solution to 0.5-1 by hydrochloric acid, heating to 60-80 ℃, adding hydrogen peroxide, and mixing the weight Kg of platinum in the platinum filtrate: volume L =1 of 35% hydrogen peroxide: 0.1-0.5, reacting for 2-5 hours, adding solid ammonium chloride, and mixing the weight Kg of platinum in the platinum filtrate: weight Kg of ammonium chloride = 1: 1.2-2; the reaction time is 0.5 to 1 hour, and the mixture is cooled and filtered; yellow filter cake (NH)4)2PtCl6Continuously refining platinum by using platinum salt, and uniformly collecting and recycling platinum from filtrate;
repeating the step D-F2-3 times to obtain high-purity yellow (NH)4)2PtCl6A platinum salt;
G. reduction of hydrazine hydrate
Adding deionized water into a platinum reduction reactor, stirring, adding multiple times of purification to obtain qualified high-purity yellow (NH)4)2PtCl6Slurrying, the material slurrying proportion is (NH)4)2PtCl6Weight Kg of platinum in platinum salt: volume L =1 of deionized water: 40-50. The slurried yellow (NH) is then treated as in step E4)2PtCl6Dissolution-hydrolysis of platinum salts to Na2Pt(OH)6Reducing the solution with hydrazine hydrate to obtain high-purity spongy platinum and hydrazine hydrate N2H4.H2Reduction of Na by O2Pt(OH)6The chemical reaction of the solution is shown in formula (4):
Na2Pt(OH)6+N2H4.H2O®Pt+N2+5H2O+2NaOH （4）
mixing Na2Pt(OH)6Putting the solution into a reduction reactor, heating to 70-95 ℃, and slowly adding 80% hydrazine hydrate in the proportion of Na2Pt(OH)6Weight Kg of platinum in the solution: volume L =1 of 80% hydrazine hydrate: 0.8-2, preserving heat for 2-4 hours, cleaning the reducing solution, cooling, washing and filtering;
H. drying by baking
And D, drying the sponge platinum washed in the step G for 2 hours at 150 ℃, heating to 750 ℃, preserving heat for 1 hour, cooling, weighing and sampling, wherein the recovery rate of the platinum is more than 99%.
The invention has the beneficial effects that:
1. the recovery rate of the platinum is high and is more than 99%.
2. The invention has short production flow, high production efficiency and good economic benefit.
3. The invention is efficient, clean, green and environment-friendly.
4. The purpose of chlorination and dissolution in the step B of the invention is to effectively dissolve platinum in the platinum ash and dissolve a small amount of other non-metallic impurities, thereby realizing the dissolution and rough separation of the platinum.
5. FeCl added in the step D pulping process of the invention3Can be coprecipitated with other small amount of Pd and Rh noble metal impurities and other base metal impurities to realizeSeparation of platinum from other impurities.
Description of the drawings:
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
The green and efficient separation and purification method of the high-purity platinum comprises the following steps in sequence:
A. ball mill
Ball-milling platinum ash in a ball mill to 40 meshes, sampling and analyzing, wherein the content of platinum is 35.32%;
B. dissolving by chlorination
Putting 20 liters of 12M hydrochloric acid into a 50 liter glass kettle, stirring, heating to 70 ℃, putting 5 kg of platinum ash subjected to ball milling in the step A into the glass kettle, slowly dropwise adding 2.5 liters of 45% sodium chlorate solution, preserving heat for 4 hours, cooling and filtering; the filtrate is sent to the next platinum refining section, and the platinum is collected and recycled from the filter residue;
C. precipitation of ammonium chloride
B, putting the platinum filtrate obtained in the step B into a PP (polypropylene) barrel of 100 liters, slowly dropwise adding 0.18 liter of 45% sodium chlorate solution, heating to 60 ℃, keeping the temperature for 1 hour, stirring, adding 2.12 kg of solid ammonium chloride, reacting for 1 hour, cooling and filtering; yellow (NH)4)2PtCl6The filter cake reaches the next platinum purification section, and the filtrate is collected uniformly to recover platinum;
D. slurrying
The yellow (NH) obtained in step C4)2PtCl6Putting the filter cake into a reactor of a 150L glass kettle, and adding 26.49L deionized water and 17.66 g solid ferric trichloride while stirring;
E. oxidative dissolution-hydrolysis
C, slowly adding 8.8 liters of 30% NaOH solution and 1.76 liters of 5% NaClO solution into the slurried material obtained in the step D under stirring, heating to 50 ℃, reacting for 5 hours, cooling and filtering; the filtrate is sent to the next platinum purification section, and the platinum is collected and recovered from the filter residue;
F. precipitation of ammonium chloride
Adding Na obtained in the step E2Pt(OH)6The solution was placed in a 150 liter glass kettle, the pH of the solution was adjusted to 0.5 with 12M hydrochloric acid, heated to 60 ℃ and added to 0.18Adding 35% hydrogen peroxide, keeping the temperature for 2 hours, adding 2.11 kg of solid ammonium chloride, reacting for 0.5 hour, cooling and filtering; yellow filter cake (NH)4)2PtCl6Continuously refining platinum by using platinum salt, and uniformly collecting and recycling platinum from filtrate;
repeating the step D-F2-3 times to obtain high-purity yellow (NH)4)2PtCl6A platinum salt;
G. reduction of hydrazine hydrate
70.22 liters of deionized water was added to a 200 liter platinum reduction reactor and, with agitation, multiple purifications were added to yield a qualified high purity yellow (NH)4)2PtCl6And slurrying. Following the procedure of step E, yellow (NH)4)2PtCl6Dissolving platinum salt to generate Na2Pt(OH)6Heating the solution to 70 ℃, slowly adding 1.4 liters of 80% hydrazine hydrate, preserving the temperature for 2 hours, cooling, washing and filtering when the reducing solution is clear;
H. drying by baking
And F, putting the sponge platinum washed in the step F into an electric furnace, drying for 2 hours at 150 ℃, heating to 750 ℃, preserving heat for 1 hour, cooling, weighing, sampling and analyzing to obtain 1750.46 g of high-purity platinum with the purity of 99.99%, wherein the recovery rate of the platinum is 99.11%.
Example 2
The green and efficient separation and purification method of the high-purity platinum comprises the following steps in sequence:
A. ball mill
Ball-milling platinum ash in a ball mill to 40 meshes, sampling and analyzing, wherein the content of platinum is 35.74%;
B. dissolving by chlorination
Putting 25 liters of 12M hydrochloric acid into a 50 liter glass kettle, stirring, heating to 80 ℃, putting 5 kg of platinum ash subjected to ball milling in the step A into the glass kettle, slowly dropwise adding 15 liters of 45% sodium chlorate solution, preserving heat for 4 hours, cooling and filtering; the filtrate is sent to the next platinum refining section, and the platinum is collected and recycled from the filter residue;
C. precipitation of ammonium chloride
B, putting the platinum filtrate obtained in the step B into a PP (polypropylene) barrel of 100 liters, slowly and dropwise adding 0.27 liter of 45% sodium chlorate solution, heating to 80 ℃, preserving the temperature for 2.5 hours, stirring and adding 2.86 kg of solid ammonium chloride, and reactingCooling for 2 hours, and filtering; yellow (NH)4)2PtCl6The filter cake reaches the next platinum purification section, and the filtrate is collected uniformly to recover platinum;
D. slurrying
The yellow (NH) obtained in step C4)2PtCl6Putting the filter cake into a reactor of a 150L glass kettle, and adding 35.74L deionized water and 35.74 g solid ferric trichloride while stirring;
E. oxidative dissolution-hydrolysis
D, slowly adding 13.36 liters of 30 percent NaOH solution and 9.8 liters of 5 percent NaClO solution into the slurried material obtained in the step D under stirring, heating to 65 ℃, reacting for 6.5 hours, cooling and filtering; the filtrate is sent to the next platinum purification section, and the platinum is collected and recovered from the filter residue;
F. precipitation of ammonium chloride
Adding Na obtained in the step E2Pt(OH)6Putting the solution into a 150L glass kettle, adjusting the pH value of the solution to 0.75 by using 12M hydrochloric acid, heating to 70 ℃, adding 0.53L of 35% hydrogen peroxide, preserving the temperature for 3.5 hours, adding 2.84 kg of solid ammonium chloride, reacting for 0.8 hour, cooling and filtering; yellow filter cake (NH)4)2PtCl6Continuously refining platinum by using platinum salt, and uniformly collecting and recycling platinum from filtrate;
repeating the step D-F2-3 times to obtain high-purity yellow (NH)4)2PtCl6A platinum salt;
G. reduction of hydrazine hydrate
79.96L of deionized water was added to a 200L platinum reduction reactor and, with stirring, multiple purifications were added to yield a qualified high purity yellow (NH)4)2PtCl6And slurrying. Following the procedure of step E, yellow (NH)4)2PtCl6Dissolving platinum salt to generate Na2Pt(OH)6Heating the solution to 80 ℃, slowly adding 2.49 liters of 80% hydrazine hydrate, preserving the heat for 3 hours, cooling, washing and filtering when the reducing solution is clear;
H. drying by baking
And F, putting the sponge platinum washed in the step F into an electric furnace, drying for 2 hours at 150 ℃, heating to 750 ℃, preserving heat for 1 hour, cooling, weighing, sampling and analyzing to obtain 1771.99 g of high-purity platinum with the purity of 99.99%, wherein the recovery rate of the platinum is 99.15%.
Example 3
The green and efficient separation and purification method of the high-purity platinum comprises the following steps in sequence:
A. ball mill
Ball-milling platinum ash in a ball mill to 40 meshes, sampling and analyzing to obtain 36.16% of platinum content;
B. dissolving by chlorination
Putting 30 liters of 12M hydrochloric acid into a 50 liter glass kettle, stirring, heating to 90 ℃, putting 5 kg of platinum ash subjected to ball milling in the step A into the glass kettle, slowly dropwise adding 25 liters of 45% sodium chlorate solution, preserving heat for 4 hours, cooling and filtering; the filtrate is sent to the next platinum refining section, and the platinum is collected and recycled from the filter residue;
C. precipitation of ammonium chloride
B, putting the platinum filtrate obtained in the step B into a PP (polypropylene) barrel of 100 liters, slowly dropwise adding 0.36 liter of 45% sodium chlorate solution, heating to 95 ℃, preserving the temperature for 4 hours, stirring, adding 5.42 kg of solid ammonium chloride, reacting for 3 hours, cooling and filtering; yellow (NH)4)2PtCl6The filter cake reaches the next platinum purification section, and the filtrate is collected uniformly to recover platinum;
D. slurrying
The yellow (NH) obtained in step C4)2PtCl6Putting the filter cake into a reactor of a 150L glass kettle, and adding 45.2L deionized water and 54.24 g solid ferric trichloride while stirring;
E. oxidative dissolution-hydrolysis
C, slowly adding 18.03 liters of 30 percent NaOH solution and 18.03 liters of 5 percent NaClO solution into the slurried material obtained in the step D under stirring, heating to 80 ℃, reacting for 8 hours, cooling and filtering; the filtrate is sent to the next platinum purification section, and the platinum is collected and recovered from the filter residue;
F. precipitation of ammonium chloride
Adding Na obtained in the step E2Pt(OH)6Putting the solution into a 150L glass kettle, adjusting the pH value of the solution to 1.0 by using 12M hydrochloric acid, heating to 80 ℃, adding 0.9L of 35% hydrogen peroxide, preserving the temperature for 5 hours, adding 3.6 kg of solid ammonium chloride, reacting for 1 hour, cooling and filtering; yellow filter cake (NH)4)2PtCl6The platinum salt continues to be refined into platinum,uniformly collecting the filtrate and recovering platinum;
repeating the step D-F2-3 times to obtain high-purity yellow (NH)4)2PtCl6A platinum salt;
G. reduction of hydrazine hydrate
89.94L of deionized water was added to a 200L platinum reduction reactor and, with stirring, multiple purifications were added to yield a qualified high purity yellow (NH)4)2PtCl6And slurrying. Following the procedure of step E, yellow (NH)4)2PtCl6Dissolving platinum salt to generate Na2Pt(OH)6Heating the solution to 95 ℃, slowly adding 3.6 liters of 80% hydrazine hydrate, preserving the heat for 4 hours, cooling, washing and filtering when the reducing solution is clear;
H. drying by baking
And F, putting the sponge platinum washed in the step F into an electric furnace, drying for 2 hours at 150 ℃, heating to 750 ℃, preserving heat for 1 hour, cooling, weighing, sampling and analyzing to obtain 1794.26 g of high-purity platinum with the purity of 99.99%, wherein the recovery rate of the platinum is 99.23%.
Claims (1)
1. The green high-efficiency separation and purification method of the high-purity platinum is characterized by comprising the following steps: the method comprises the following steps:
A. ball mill
Ball-milling platinum ash in a ball mill to 40 meshes, and sampling and analyzing to obtain a noble metal platinum content of more than 10%;
B. dissolving by chlorination
The weight Kg of platinum ash is as follows: volume L of 12M hydrochloric acid: volume L =1 of 45% sodium chlorate solution: 4-6: 0.5 to 5; adding 12M hydrochloric acid into a reactor, starting stirring, slowly adding the platinum ash subjected to ball milling in the step A, heating to 70-90 ℃, then slowly adding a 45% sodium chlorate solution, preserving heat for 4 hours, cooling and filtering; the filtrate is sent to the next platinum refining section, and the platinum is collected and recycled from the filter residue;
C. precipitation of ammonium chloride
Transferring the platinum filtrate obtained in the step B into a reactor, adding a 45% sodium chlorate solution, and mixing the weight Kg of platinum in the platinum filtrate: volume L =1 of 45% sodium chlorate solution: 0.1 to 0.2, heating to 60 to 95 ℃, preserving heat for 1 to 4 hours, and then stirring and adding solid ammonium chlorideThe weight Kg of platinum in the platinum filtrate is as follows: weight Kg of ammonium chloride = 1: 1.2-3; reacting for 1-3 hours, cooling and filtering; yellow (NH)4)2PtCl6The filter cake reaches the next platinum purification section, and the filtrate is collected uniformly to recover platinum; yellow (NH)4)2PtCl6The Pt content in the filter cake is 40-44%;
D. slurrying
The yellow (NH) obtained in step C4)2PtCl6Putting the filter cake and water into a reactor, and adding a small amount of solid ferric trichloride under the stirring state; the material is slurried and has the mixture ratio of (NH)4)2PtCl6Weight Kg of platinum in the filter cake: volume L of deionized water: weight g =1 of ferric chloride: 15-25: 10-30 parts of;
E. oxidative dissolution-hydrolysis
C, slowly adding a sodium hypochlorite solution and a sodium hydroxide solution into the reactor pulped in the step D under the stirring state; the sodium hypochlorite solution has very strong oxidizing property and can make yellow (NH)4)2PtCl6Dissolving the platinum salt to generate H2PtCl6Decomposition of sodium hypochlorite solution (NH)4)2PtCl6Reacting according to the formula (1):
(NH4)2PtCl6+3NaClO®H2PtCl6+N2+3H2O+3NaCl （1）
generation of H2PtCl6Hydrolyzed by sodium hydroxide to generate sodium hydroxyplatinate [ Na ]2Pt(OH)6]The chemical reaction of the solution is shown in the formula (2):
H2PtCl6+8NaOH®Na2Pt(OH)6+6NaCl+2H2O （2）
under the stirring state, respectively and slowly adding a 30% sodium hydroxide solution and a 5% sodium hypochlorite solution into the reactor slurried in the step D, wherein the material ratio is (NH)4)2PtCl6Weight Kg of platinum in salt: volume L of 30% sodium hydroxide solution: volume L =1 of 5% sodium hypochlorite solution: 5-10: 1-10, heating to 50-80 ℃, reacting for 5-8 hours, cooling and filtering; the filtrate goes to the next platinum purification section,uniformly collecting filter residues and recovering platinum;
F. precipitation of ammonium chloride
Hydrochloric acid can react Na2Pt(OH)6Reaction to form H2PtCl6The chemical reaction is shown in formula (3):
Na2Pt(OH)6+8HCl®H2PtCl6+6H2O+2NaCl （3）
ammonium chloride precipitate H2PtCl6To form (NH)4)2PtCl6Platinum is yellow (NH)4)2PtCl6The platinum salt and other impurities exist in the solution, so that the separation of the platinum and the other impurities is realized;
and E, putting the platinum filtrate obtained in the step E into a reactor, adjusting the pH of the solution to 0.5-1 by hydrochloric acid, heating to 60-80 ℃, adding hydrogen peroxide, and mixing the weight Kg of platinum in the platinum filtrate: volume L =1 of 35% hydrogen peroxide: 0.1-0.5, reacting for 2-5 hours, adding solid ammonium chloride, and mixing the weight Kg of platinum in the platinum filtrate: weight Kg of ammonium chloride = 1: 1.2-2; the reaction time is 0.5 to 1 hour, and the mixture is cooled and filtered; yellow filter cake (NH)4)2PtCl6Continuously refining platinum by using platinum salt, and uniformly collecting and recycling platinum from filtrate;
repeating the step D-F2-3 times to obtain high-purity yellow (NH)4)2PtCl6A platinum salt;
G. reduction of hydrazine hydrate
Adding deionized water into a platinum reduction reactor, stirring, adding multiple times of purification to obtain qualified high-purity yellow (NH)4)2PtCl6Slurrying, the material slurrying proportion is (NH)4)2PtCl6Weight Kg of platinum in platinum salt: volume L =1 of deionized water: 40-50;
the slurried yellow (NH) is then treated as in step E4)2PtCl6Dissolution-hydrolysis of platinum salts to Na2Pt(OH)6Reducing the solution with hydrazine hydrate to obtain high-purity spongy platinum and hydrazine hydrate N2H4.H2Reduction of Na by O2Pt(OH)6The chemical reaction of the solution is shown in formula (4):
Na2Pt(OH)6+N2H4.H2O®Pt+N2+5H2O+2NaOH （4）
mixing Na2Pt(OH)6Putting the solution into a reduction reactor, heating to 70-95 ℃, and slowly adding 80% hydrazine hydrate in the proportion of Na2Pt(OH)6Weight Kg of platinum in the solution: volume L =1 of 80% hydrazine hydrate: 0.8-2, preserving heat for 2-4 hours, cleaning the reducing solution, cooling, washing and filtering;
H. drying by baking
And D, drying the sponge platinum washed in the step G for 2 hours at 150 ℃, heating to 750 ℃, preserving heat for 1 hour, cooling, weighing and sampling, wherein the recovery rate of the platinum is more than 99%.
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