CN112537808B - Method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste - Google Patents
Method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste Download PDFInfo
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000010948 rhodium Substances 0.000 title claims abstract description 126
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 54
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002244 precipitate Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 34
- 238000001556 precipitation Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 29
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000004090 dissolution Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000003283 rhodium Chemical class 0.000 claims description 8
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical group [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 81
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- QTNLQPHXMVHGBA-UHFFFAOYSA-H hexachlororhodium Chemical compound Cl[Rh](Cl)(Cl)(Cl)(Cl)Cl QTNLQPHXMVHGBA-UHFFFAOYSA-H 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- NDBYXKQCPYUOMI-UHFFFAOYSA-N platinum(4+) Chemical compound [Pt+4] NDBYXKQCPYUOMI-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste, which comprises the following steps: adjusting the acid concentration in the rhodium-containing waste leaching solution to 4-5 mol/L, and then heating and refluxing to obtain rhodium acid solution; adding a precipitant into the rhodium acid solution, heating to 100-110 ℃ and refluxing for 12-24 hours to obtain a mixture containing brown-black precipitate, and cooling, filtering, dissolving, filtering, washing and dissolving to obtain rhodium-containing solution; exchanging rhodium-containing solution by hydrogen cation resin, adding the rhodium-containing solution with trace impurities removed into potassium hydroxide solution for precipitation reaction, washing and drying to obtain high-purity rhodium hydroxide solid; adding the high-purity rhodium hydroxide solid into a nitric acid solution for dissolution reaction, and filtering to obtain a rhodium nitrate solution. The method has the advantages of strong process applicability, simple operation, low cost, high purity of the synthesized rhodium nitrate product and good stability.
Description
Technical Field
The invention relates to the field of chemical synthesis of noble metals, in particular to a method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste.
Background
Rhodium is an important noble metal of the platinum group and has an irreplaceable role in many critical areas. 90% of rhodium in the world is mainly used as an automobile exhaust catalyst, is also commonly used as a hydrogenation catalyst, a thermocouple, a platinum-rhodium alloy and the like, is also commonly plated on searchlight and reflectors, is used as a polishing agent for precious stones and an electric contact part, and can be used as a plating film for other metals. In recent years, the market demand of rhodium catalysts is huge, the demand of rhodium nitrate solution which is a precursor substance for rhodium catalyst synthesis is directly driven, and the direct synthesis of rhodium nitrate from rhodium-containing waste materials is inevitably carried out in the face of the huge market demand.
The traditional rhodium nitrate synthesis process comprises the following steps: rhodium powder is subjected to the procedures of oxidation, leaching, filtering, hydrolysis, washing, filtering, acid dissolution and the like in sequence to obtain the lao nitrate. The rhodium nitrate synthesized by the process has the advantages of about 70 percent of yield, longer working procedure and low product purity, and particularly, the chloridion in the product is difficult to remove, so that the catalyst is poisoned, and the service life of the catalyst is seriously influenced.
At present, the direct synthesis of rhodium nitrate from rhodium-containing waste is mainly limited by a rhodium recovery method, and the recovery and purification methods of rhodium in the waste mainly comprise a precipitation separation method, an electrolysis method, a solvent extraction method, a resin separation method, an adsorption method, a metal replacement method and the like. The traditional precipitation method purification refers to sodium nitrite complexation method, ammonification method, ammonium sulfite method and the like. Sodium nitrite complexation method utilizes sodium nitrite and rhodium to generate stable soluble sodium nitrite complex Na 3 Rh(NO 2 ) 6 While the base metal hydrolyzes to form a hydroxide precipitate which separates from rhodium, other platinum group metal solutions in solution are also complexed to similar soluble sodium nitrite complexes which cannot be completely separated from rhodium by this method. The ammoniation method is to react hexachlororhodium acid ammonia with ammonia water to generate [ Rh (NH) 3 ) 5 Cl]Cl 2 Precipitation, but the operation process is complicated and the recovery rate is low. The method for recovering rhodium from waste rhodium catalyst in oxo reaction by CN1414125A includes incinerating and ashing waste catalyst residual liquid, melting the residue by acid sulfate to generate soluble rhodium salt, separating rhodium by electrolysis technology to obtain metal rhodium, and the single pass recovery rate of rhodium powder is more than 96%, and the purity is 99.95%. However, the rhodium coating obtained by the electrolytic method is inconvenient for rhodium powder conversion, which is a great limitation affecting the application thereof.
Rhodium nitrate synthesized by rhodium-containing waste is greatly influenced by impurities, generally rhodium recovery liquid contains a large amount of impurities such as sodium, potassium, aluminum, iron, nickel, copper, calcium and the like, and also contains other platinum group metals, and the platinum group metals are difficult to separate and purify due to similar chemical properties.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the method for synthesizing the rhodium nitrate solution by utilizing the rhodium-containing waste material, which has the advantages of simple process, controllable process, high purity of rhodium hydroxide intermediate products, capability of avoiding poisoning of rhodium nitrate, improving the stability of rhodium nitrate and prolonging the service life of rhodium nitrate.
The invention adopts the following technical scheme:
a method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste, characterized in that the method comprises the following steps:
(1) Adjusting the acid concentration in the rhodium-containing waste leaching solution to 4-5 mol/L, and then heating and refluxing until the rhodium concentration in the rhodium-containing waste leaching solution is 50-70 g/L, so as to obtain rhodium acid solution;
(2) Adding a precipitant into rhodium acid solution, heating to 100-110 ℃ and refluxing for 12-24 hours to obtain a mixture containing brown-black precipitate, cooling and filtering the mixture containing the brown-black precipitate, dissolving the mixture in ethanol at 40-50 ℃ for 5-6 hours, filtering and washing to obtain rhodium salt precipitate, and dissolving the rhodium salt precipitate to obtain rhodium-containing solution;
(3) Exchanging rhodium-containing solution by hydrogen type cation resin to obtain rhodium-containing solution with trace impurities removed;
(4) Adding rhodium-containing solution with trace impurities removed into potassium hydroxide solution for precipitation reaction, and then washing and drying to obtain high-purity rhodium hydroxide solid; the technological conditions of the precipitation reaction are as follows: the pH of the reaction is 8-9, the reaction temperature is 50-60 ℃ and the reaction time is 2-3 h;
(5) Adding high-purity rhodium hydroxide solid into a nitric acid solution for dissolution reaction, and filtering to obtain a rhodium nitrate solution; the process conditions of the dissolution reaction are as follows: the dissolution temperature is 40-50 ℃ and the dissolution time is 2-3 h.
The method for synthesizing the rhodium nitrate solution by utilizing the rhodium-containing waste is characterized in that in the step (1), the acid concentration in the leaching solution of the rhodium-containing waste is adjusted to be 4mol/L-5mol/L, and then the leaching solution is heated and refluxed for 18h-24h.
The method for synthesizing the rhodium nitrate solution by utilizing the rhodium-containing waste material is characterized in that the precipitant in the step (2) is benzyl triethyl ammonium bromide, and the mass ratio of the precipitant to the rhodium acid solution is (5-7): 1.
The method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste is characterized in that the mixture containing brown-black precipitate is cooled, filtered, dissolved and filtered in the step (2), and then is washed by adopting a mixed solution formed by ethanol and methanol.
The method for synthesizing the rhodium nitrate solution by utilizing the rhodium-containing waste is characterized in that the mass percentage concentration of the potassium hydroxide solution in the step (4) is 16-20%, pure water and ethanol are adopted for washing after precipitation reaction, and then the rhodium hydroxide solid with high purity is obtained.
The method for synthesizing the rhodium nitrate solution by utilizing the rhodium-containing waste is characterized in that the mass percentage concentration of the rhodium nitrate solution in the step (5) is 50% -60%, and the high-purity rhodium hydroxide solid is added into the nitric acid solution for dissolution reaction and then filtered by a Buchner funnel.
The beneficial technical effects of the invention are as follows: rhodium, other noble metals and base metals are separated, purified and synthesized from rhodium-containing waste leachate to obtain rhodium nitrate solution. The invention adopts benzyl triethyl ammonium bromide as a precipitator, platinum (IV) and rhodium (III) acid solutions and excessive tetramethyl ammonium chloride can be used for reacting to generate platinum salt and rhodium salt precipitate, palladium (II) and other base metals do not generate precipitate and remain in the solution, the platinum salt precipitate dissolves ethanol, so that rhodium is separated from other impurities, residual trace impurities are removed by utilizing ion exchange resin, and rhodium hydroxide with high purity is obtained through conversion, and rhodium hydroxide is synthesized by dissolving rhodium hydroxide in nitric acid. The method utilizes a mode of combining a precipitation method and an ion exchange method to separate and purify rhodium, the purity of the obtained rhodium hydroxide is high, the purity of the synthesized rhodium nitrate product is high, the stability is good, the poisoning of rhodium nitrate is avoided, the stability of rhodium nitrate is improved, and the service life of rhodium nitrate is prolonged. The invention has the advantages of strong process applicability, simple operation, controllable process, low cost, zero emission and no environmental pollution.
Detailed Description
The invention discloses a method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste, which comprises the following steps:
(1) And (3) liquid preparation: adjusting the acid concentration in the rhodium-containing waste leaching liquid to 4-5 mol/L, and then heating and refluxing for 18-24 h. On the one hand due to RhCl 6 3- Can generate hydration, hydroxylation, acid dissociation or chlorination of hydrated ions along with the change of acidity, chloride ion concentration, temperature, standing time and the like of the solution to generate a series of chlorine, hydration complex or chlorine, water and hydroxyl complex [ RhCl ] 6 ] 3- 、[RhCl 5 (H 2 O)] 2- 、[RhCl 4 (H 2 O)]-、[RhCl 3 (H 2 O) 3 ]、[RhCl 2 (H 2 O) 4 ] + 、[RhCl 2 (H 2 O) 5 ] + 、[Rh(H 2 O) 6 ] 3+ . The formation of these chlorine water complexes makes rhodium difficult to separate. Therefore, in order to improve the rhodium separation and extraction efficiency, it is necessary to convert these complexes into complexes [ RhCl ] having good separation performance as much as possible 6 ] 3- . On the other hand, refluxing may convert tetravalent palladium in solution to divalent palladium to facilitate separation of rhodium from palladium. The rhodium concentration in the leaching solution of the rhodium-containing waste is 50g/L to 70g/L, so as to obtain rhodium acid solution; the impurity content therein was detected by ICP.
(2) And (3) precipitation and purification: adding a precipitant into the rhodium acid solution, heating to 100-110 ℃ and boiling and refluxing for 12-24 hours until rhodium and platinum in the solution generate a large amount of brown black precipitates to obtain a mixture containing the brown black precipitates, cooling and filtering the mixture containing the brown black precipitates, dissolving the mixture in ethanol at 40-50 ℃ for 5-6 hours, filtering and washing to obtain brown rhodium salt precipitates, and dissolving the rhodium salt precipitates in boiled water with enough amount to obtain the rhodium-containing solution. When rhodium is precipitated, the adding amount of the precipitant is greatly excessive, so that the concentration of the precipitant reaches saturation, the precipitant is benzyl triethyl ammonium bromide, the mass ratio of the precipitant to rhodium acid solution is (5-7): 1, and the adding amount of the precipitant is controlled to be 500-700g/L. And cooling, filtering, dissolving and filtering the mixture containing the brown-black precipitate, and washing the mixture with a mixed solution formed by ethanol and methanol to remove impurities and redundant precipitants in the precipitate.
(3) Ion exchange purification: exchanging rhodium-containing solution by hydrogen cation resin to remove residual trace impurities in the solution, thereby obtaining rhodium-containing solution with trace impurities removed;
(4) Rhodium hydroxide preparation: adding rhodium-containing solution with trace impurities removed into potassium hydroxide solution to perform precipitation reaction so as to enable rhodium to be completely precipitated, and then washing and drying to obtain high-purity rhodium hydroxide solid; the technological conditions of the precipitation reaction are as follows: the pH of the reaction is 8-9, the reaction temperature is 50-60 ℃ and the reaction time is 2-3 h; the mass percentage concentration of the potassium hydroxide solution is 16% -20%, pure water and ethanol are adopted for washing after precipitation reaction, and then drying is carried out, so that the high-purity rhodium hydroxide solid is obtained. The high-purity rhodium hydroxide solid can be used as a raw material for preparing rhodium powder conforming to GB/T1421-2004 standard.
(5) Synthesis of rhodium nitrate: adding the high-purity rhodium hydroxide solid into a nitric acid solution for dissolution reaction, and filtering by using a Buchner funnel to remove insoluble impurities to obtain a rhodium nitrate solution. The process conditions of the dissolution reaction are as follows: stirring and reacting for 2-3 h at 40-50 ℃. The mass percentage concentration of the nitric acid solution is 50% -60%. The pH value of the rhodium solution purified and dissolved by the precipitation method is 2-4, the acidity of the solution is low, and the hydrogen type cationic resin is easier to adsorb impurity ions on the resin, so that trace impurity ions are easier to remove.
The invention is further illustrated by the following examples, which are intended to illustrate the invention further and are not to be construed as limiting the invention.
Example 1
And (3) adjusting the acid concentration in the rhodium-containing waste leaching liquid to 4mol/L, and then heating and refluxing for 24 hours to obtain the rhodium acid solution. The rhodium concentration in the rhodium acid solution was measured to be 55.51g/L, the impurity content Pt was 0.37g/L, pd was 0.85g/L, al was 0.53g/L, fe was 0.29g/L, ca was 0.33g/L, mg was 0.26g/L, cu was 0.41g/L, ni was 0.33g/L, and Si was 0.18g/L.
500mL of rhodium acid solution is measured and placed in a flask, 250g of benzyl triethyl ammonium bromide is added, the temperature is raised to 100 ℃ to enable the solution to be boiled and refluxed for 12 hours, until platinum and rhodium in the solution form brown-black precipitation, and a mixture containing the brown-black precipitation is obtained. The mixture containing the brown-black precipitate is cooled to room temperature and then filtered, the mixture containing the brown-black precipitate is added into 100mL of ethanol, the temperature is raised to 50 ℃ for dissolution for 6 hours, the mixture is cooled to room temperature and then filtered, washed with ethanol and methanol, and the mixture is filtered to dryness by suction, and then the obtained rhodium precipitate is dissolved in boiled water with enough quantity to obtain rhodium-containing solution.
And exchanging the rhodium-containing solution by hydrogen type cation resin to obtain the rhodium-containing solution with trace impurities removed. Adding a rhodium-containing solution with trace impurities removed into a potassium hydroxide solution with the mass percent concentration of 20% to carry out a precipitation reaction to obtain light yellow rhodium hydroxide, wherein the process conditions of the precipitation reaction are as follows: the pH of the reaction is 8, and the reaction is stirred for 2 hours at 50 ℃; and (3) after precipitation, fully washing the precipitate with water and ethanol, and drying. Transferring the light yellow rhodium hydroxide into 100mL of 60% nitric acid solution by mass percentage concentration, heating to 40 ℃ and stirring for reaction for 2 hours to enable rhodium hydroxide precipitate to be completely dissolved, filtering by using a Buchner funnel to remove insoluble impurities to obtain 166.71 g of rhodium nitrate solution, detecting the rhodium content to be 16.33% by ICP, and purifying the rhodium to be 98.11%.
Example 2
And (3) adjusting the acid concentration in the rhodium-containing waste leaching liquid to 4.5mol/L, and then heating and refluxing for 24 hours to obtain the rhodium acid solution. The rhodium concentration in the rhodium acid solution was measured to be 60.61g/L, the impurity content Pt was 0.38g/L, pd was 0.82g/L, al was 0.51g/L, fe was 0.23g/L, ca was 0.31g/L, mg was 0.27g/L, cu was 0.38g/L, ni was 0.31g/L, and Si was 0.15g/L.
500mL of rhodium acid solution is measured and placed in a flask, 300g of benzyl triethyl ammonium bromide is added, the temperature is raised to 105 ℃ to enable the solution to be boiled and refluxed for 18 hours, until platinum and rhodium in the solution form brown-black precipitation, and a mixture containing the brown-black precipitation is obtained. The mixture containing the brown-black precipitate is cooled to room temperature and then filtered, the mixture containing the brown-black precipitate is added into 100mL of ethanol, the temperature is raised to 50 ℃ for dissolution for 6 hours, the mixture is cooled to room temperature and then filtered, washed with ethanol and methanol, and the mixture is filtered to dryness by suction, and then the obtained rhodium precipitate is dissolved in boiled water with enough quantity to obtain rhodium-containing solution.
And exchanging the rhodium-containing solution by hydrogen type cation resin to obtain the rhodium-containing solution with trace impurities removed. Adding a rhodium-containing solution with trace impurities removed into a potassium hydroxide solution with the mass percent concentration of 20% to carry out a precipitation reaction to obtain light yellow rhodium hydroxide, wherein the process conditions of the precipitation reaction are as follows: the pH of the reaction is 8.5, and the reaction is stirred for 2.5 hours at 55 ℃; and (3) after precipitation, fully washing the precipitate with water and ethanol, and drying. Transferring the light yellow rhodium hydroxide into 100mL of 60% nitric acid solution by mass percentage concentration, heating to 45 ℃ and stirring for reaction for 2.5h to enable rhodium hydroxide precipitate to be completely dissolved, filtering by using a Buchner funnel to remove insoluble impurities to obtain 169.82 g of rhodium nitrate solution, detecting that the rhodium content is 17.56% by ICP, and the rhodium purification rate is 98.38%.
Example 3
And (3) adjusting the acid concentration in the rhodium-containing waste leaching liquid to 4.5mol/L, and then heating and refluxing for 24 hours to obtain the rhodium acid solution. The rhodium concentration in the rhodium acid solution was measured to be 70.16g/L, the impurity content Pt was 0.33g/L, pd was 0.84g/L, al was 0.49g/L, fe was 0.26g/L, ca was 0.36g/L, mg was 0.23g/L, cu was 0.34g/L, ni was 0.35g/L, and Si was 0.12g/L.
500mL of rhodium acid solution is measured and placed in a flask, 350g of benzyl triethyl ammonium bromide is added, the temperature is raised to 110 ℃ to enable the solution to be boiled and refluxed for 24 hours, until platinum and rhodium in the solution form brown-black precipitation, and a mixture containing the brown-black precipitation is obtained. The mixture containing the brown-black precipitate is cooled to room temperature and then filtered, the mixture containing the brown-black precipitate is added into 100mL of ethanol, the temperature is raised to 50 ℃ for dissolution for 6 hours, the mixture is cooled to room temperature and then filtered, washed with ethanol and methanol, and the mixture is filtered to dryness by suction, and then the obtained rhodium precipitate is dissolved in boiled water with enough quantity to obtain rhodium-containing solution.
And exchanging the rhodium-containing solution by hydrogen type cation resin to obtain the rhodium-containing solution with trace impurities removed. Adding a rhodium-containing solution with trace impurities removed into a potassium hydroxide solution with the mass percent concentration of 20% to carry out a precipitation reaction to obtain light yellow rhodium hydroxide, wherein the process conditions of the precipitation reaction are as follows: the pH of the reaction is 9, and the reaction is stirred for 3 hours at 60 ℃; and (3) after precipitation, fully washing the precipitate with water and ethanol, and drying. Transferring the light yellow rhodium hydroxide into 100mL of 60% nitric acid solution by mass percentage concentration, heating to 50 ℃ and stirring for reaction for 3 hours to enable rhodium hydroxide precipitate to be completely dissolved, filtering by using a Buchner funnel to remove insoluble impurities to obtain 182.15 g of rhodium nitrate solution, detecting the rhodium content to be 19.03% by ICP, and purifying the rhodium to be 98.82%.
Claims (5)
1. A method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste, characterized in that the method comprises the following steps:
(1) Adjusting the acid concentration in the rhodium-containing waste leaching solution to 4-5 mol/L, and then heating and refluxing until the rhodium concentration in the rhodium-containing waste leaching solution is 50-70 g/L, so as to obtain rhodium acid solution;
(2) Adding a precipitant into rhodium acid solution, heating to 100-110 ℃ and refluxing for 12-24 hours to obtain a mixture containing brown-black precipitate, cooling and filtering the mixture containing the brown-black precipitate, dissolving the mixture in ethanol at 40-50 ℃ for 5-6 hours, filtering and washing to obtain rhodium salt precipitate, and dissolving the rhodium salt precipitate to obtain rhodium-containing solution; the precipitant is benzyl triethyl ammonium bromide, and the mass ratio of the precipitant to rhodium acid solution is (5-7) 1;
(3) Exchanging rhodium-containing solution by hydrogen type cation resin to obtain rhodium-containing solution with trace impurities removed;
(4) Adding rhodium-containing solution with trace impurities removed into potassium hydroxide solution for precipitation reaction, and then washing and drying to obtain high-purity rhodium hydroxide solid; the technological conditions of the precipitation reaction are as follows: the pH of the reaction is 8-9, the reaction temperature is 50-60 ℃ and the reaction time is 2-3 h;
(5) Adding high-purity rhodium hydroxide solid into a nitric acid solution for dissolution reaction, and filtering to obtain a rhodium nitrate solution; the process conditions of the dissolution reaction are as follows: the dissolution temperature is 40-50 ℃ and the dissolution time is 2-3 h.
2. The method for synthesizing rhodium nitrate solution using rhodium-containing waste material according to claim 1, wherein in step (1), the concentration of acid in the leaching solution of rhodium-containing waste material is adjusted to 4mol/L to 5mol/L, and then the leaching solution is heated and refluxed for 18h to 24h.
3. The method for synthesizing rhodium nitrate solution using rhodium-containing waste material according to claim 2, wherein the mixture containing the brown-black precipitate is cooled, filtered, dissolved, and filtered, and then washed with a mixture of ethanol and methanol.
4. The method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste material according to claim 1, wherein the mass percentage concentration of potassium hydroxide solution in the step (4) is 16% -20%, and the rhodium hydroxide solid with high purity is obtained by washing with pure water and ethanol and drying after precipitation reaction.
5. The method for synthesizing rhodium nitrate solution by utilizing rhodium-containing waste material according to claim 4, wherein the mass percentage concentration of the nitric acid solution in the step (5) is 50% -60%, and the high-purity rhodium hydroxide solid is added into the nitric acid solution for dissolution reaction and then filtered by using a buchner funnel.
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