CN116716484B - Method for recovering palladium and dimethylglyoxime from palladium-refining palladium-removing slag - Google Patents
Method for recovering palladium and dimethylglyoxime from palladium-refining palladium-removing slag Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 265
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 133
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 title claims abstract description 111
- 239000002893 slag Substances 0.000 title claims abstract description 68
- 238000007670 refining Methods 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 39
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000004537 pulping Methods 0.000 claims description 12
- 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 description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000003265 pulping liquor Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 54
- 238000011084 recovery Methods 0.000 abstract description 16
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000012670 alkaline solution Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- -1 palladium ions Chemical class 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000010668 complexation reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LJHFIVQEAFAURQ-ZPUQHVIOSA-N (NE)-N-[(2E)-2-hydroxyiminoethylidene]hydroxylamine Chemical compound O\N=C\C=N\O LJHFIVQEAFAURQ-ZPUQHVIOSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 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
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding 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
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 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
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Classifications
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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
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/14—Separation; Purification; Stabilisation; Use of additives
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (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 a method for recovering palladium and dimethylglyoxime from palladium-removing slag in platinum refining, belonging to the technical field of precious metal secondary resource recovery. The method comprises four steps of pretreatment, reduction, palladium refining and dimethylglyoxime regeneration. Palladium in the platinum refining slag mainly exists in the form of dimethylglyoxime palladium, palladium is reduced into metal palladium by a reducing agent in alkali liquor and separated from dimethylglyoxime, dimethylglyoxime is dissolved in the alkali liquor and enriched in the solution, and the metal palladium is enriched in the reducing slag; dissolving, refining and purifying the reducing slag by aqua regia to obtain metallic palladium; regulating the potential of alkaline solution containing dimethylglyoxime to separate dimethylglyoxime out in acid system to obtain pure dimethylglyoxime. The method has the advantages of simple process flow, easy large-scale implementation, high efficiency, low energy consumption, palladium purity of more than 99.99%, recovery rate of more than 99.0%, and dimethylglyoxime regeneration rate of more than 95%, and can effectively save production cost.
Description
Technical Field
The invention relates to a method for recovering palladium and dimethylglyoxime from palladium-removing slag in platinum refining, belonging to the technical field of precious metal secondary resource recovery.
Background
In the refining and purifying process of noble metals such as platinum, rhodium, iridium and ruthenium, the impurity element palladium in the noble metals is generally separated by using the dimethylglyoxime, so that trace palladium ions and the dimethylglyoxime generate a dimethylglyoxime palladium precipitate to be separated. The precipitate slag contains noble metal palladium and needs to be recycled. In general, the organic matter is removed by roasting after the precipitation of the palladium ions by the dimethylglyoxime to recover the palladium element, but no report on the recovery and utilization of the palladium ions and the dimethylglyoxime is found.
In the method for recovering palladium in silver electrolyte by using dimethylglyoxime, dimethylglyoxime is added into the electrolyte to precipitate palladium, and solid-liquid separation is carried out; aqua regia dissolves the glyoxime palladium; precipitating palladium with ammonium chloride; complexing palladium with ammonia water; and (3) reducing hydrazine hydrate. According to the method, the dimethylglyoxime palladium is directly dissolved and recycled, the purity of a palladium product is more than 99.99%, and dimethylglyoxime is not recycled.
An improved process method for extracting high-purity palladium from silver-and copper-containing industrial waste at one time mainly comprises the following steps: roasting industrial waste containing silver and copper, removing organic matters, grinding into powder, soaking the powder in sulfuric acid solution to remove copper, adding nitric acid into filtered copper-removed filter residues to obtain silver-and palladium-containing solution, adding sodium tetraphenylborate into the solution to precipitate silver ions, filtering again, adding dimethylglyoxime and ammonium chloride into palladium-containing filtrate under the condition of cold water bath to precipitate palladium, filtering to obtain palladium salt solid, boiling and dissolving the palladium salt solid with pure water to obtain high-purity ammonium chloropalladate, and washing, reducing and calcining to obtain high-purity sponge palladium. The invention improves the traditional palladium recovery and extraction process, can improve the purity of the sponge palladium extracted from the silver-containing waste, but does not effectively recycle the dimethylglyoxime.
The method for selectively leaching and recovering palladium in the waste palladium plating piece comprises the following specific steps: adding waste printed circuit board powder into an anhydrous polar aprotic solvent according to a solid-liquid mass volume ratio of 1:5-1:20 g/ml, then adding bromide salt, performing leaching experiments for 30-90 min, filtering after leaching to obtain leaching liquid and filter residues, adding a dimethylglyoxime precipitant solution into the leaching liquid, wherein the concentration of the precipitant solution is 0.01-0.5mol/L, the volume ratio of the precipitant solution to the leaching liquid is 1:1-1:5, and precipitating palladium ion liquid in the leaching liquid. The method is characterized in that waste palladium plating pieces are used as raw materials, a eutectic system is used as leaching solution for leaching reaction, after leaching is finished, filtration is carried out, a dimethylglyoxime precipitant is added into the leaching solution to precipitate palladium in the leaching solution, after precipitation is finished, filtration is carried out to obtain dimethylglyoxime palladium and filtrate, but the palladium is separated only in a dimethylglyoxime palladium precipitation mode, and further recovery and purification of the palladium and regeneration and recycling of the dimethylglyoxime are not carried out.
Gong Jie and the like are used for researching the extraction process of palladium in the waste three-way catalyst, and the adopted wet process flow is pretreatment, primary leaching, aqua regia leaching, nitrate expelling, glyoxime-chloroform extraction of palladium, naOH back extraction of palladium, ammonia water complexing palladium, and the palladium extraction rate can reach 97.2 percent.
In summary, the dimethylglyoxime is a better precipitant for separating palladium, and for the treatment of the dimethylglyoxime palladium, the prior method generally adopts a direct incineration method to decompose the dimethylglyoxime to obtain palladium oxide, and then uses aqua regia for refining and purifying the palladium. However, no report on recycling of both palladium ions and dimethylglyoxime has been found.
Disclosure of Invention
Aiming at the technical blank of recovering palladium and dimethylglyoxime from the palladium-removing slag of the platinum refining, the invention provides a method for recovering palladium and dimethylglyoxime from the palladium-removing slag of the platinum refining, which comprises four steps of pretreatment, reduction, palladium refining and dimethylglyoxime regeneration. Palladium in the platinum refining slag mainly exists in the form of dimethylglyoxime palladium, palladium is reduced into metal palladium by a reducing agent in alkali liquor and separated from dimethylglyoxime, dimethylglyoxime is dissolved in the alkali liquor and enriched in the solution, and the metal palladium is enriched in the reducing slag; dissolving, refining and purifying the reducing slag by aqua regia to obtain metallic palladium; regulating the potential of alkaline solution containing dimethylglyoxime to separate dimethylglyoxime out in acid system to obtain pure dimethylglyoxime. The method has the advantages of simple process flow, easy large-scale implementation, high efficiency, low energy consumption, palladium purity of more than 99.99%, recovery rate of more than 99.0%, and dimethylglyoxime regeneration rate of more than 95%, and can effectively save production cost.
A method for recovering palladium and dimethylglyoxime from palladium-refining palladium-removing slag comprises the following specific steps:
(1) Uniformly mixing platinum refining palladium-removed slag and alkali liquor, and pulping to obtain a pulping liquor; the palladium-removing slag of the platinum refining contains 10-30wt% of palladium and 20-40wt% of dimethylglyoxime;
(2) Heating the slurry to a temperature of 40-95 ℃, slowly adding a reducing agent for reduction treatment for 60-120 min, and carrying out solid-liquid separation to obtain a palladium slag-containing solid and a dimethylglyoxime-containing solution;
(3) Refining and purifying the palladium-containing slag solid to obtain metal palladium; specifically, the palladium-containing slag solid is dissolved by aqua regia to be refined and purified, so that the metal palladium with the purity of more than 99.99 percent is obtained, and the recovery rate of the palladium is more than 99 percent;
(4) Adding a dilute hydrochloric acid solution into the solution containing the dimethylglyoxime for potential regulation, maintaining the acidity of the solution to be pH 0.5-2.0, standing for 8-24 hours, separating out dimethylglyoxime solid, carrying out solid-liquid separation to obtain the dimethylglyoxime solid, and washing and drying the dimethylglyoxime solid.
The alkali liquor in the step (1) is sodium hydroxide or sodium carbonate solution, and the mass concentration of the alkali liquor is 1-20%.
And (3) the solid-liquid ratio g/mL of the palladium-removing slag and the alkali liquor in the platinum refining in the step (1) is 1:2-10.
The reducing agent in the step (2) is one or more of hydrazine hydrate, oxalic acid, ascorbic acid, sodium borohydride and potassium borohydride.
The addition amount of the reducing agent in the step (2) is 120-600% of the mass of the palladium-removing slag in the step (1) of platinum refining.
The beneficial effects of the invention are as follows:
(1) According to the invention, the palladium-removing slag of platinum refining is directly reduced in alkali liquor, so that the metallized reduction of palladium ions is realized, the separation of dimethylglyoxime and palladium is realized, roasting is not needed, the energy consumption is low, the volatilization loss of palladium in the roasting process and the air pollution generated in the organic matter decomposition process of dimethylglyoxime palladium are avoided, and the recovery rate of metal palladium is high;
(2) The invention regulates and controls the potential of the alkaline solution containing the dimethylglyoxime, so that the dimethylglyoxime is separated out under an acidic system to obtain pure dimethylglyoxime, and the regenerative cycle utilization of the dimethylglyoxime is realized;
(3) The invention has simple process flow, easy implementation, high efficiency, low energy consumption, palladium recovery rate of more than 99 percent and dimethylglyoxime recovery rate of more than 95 percent.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a SEM image of the sponge palladium of example 1;
FIG. 3 is a sponge palladium XRD pattern of example 1;
figure 4 is the XRD pattern of the dimethylglyoxime of example 1.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: the platinum refining palladium-removing slag of the example contains 23.5wt.% of palladium and 36.6wt.% of dimethylglyoxime;
a method for recovering palladium and dimethylglyoxime from palladium refining palladium-removing slag (see figure 1) comprises the following specific steps:
(1) Uniformly mixing platinum refining palladium-removed slag and 10% sodium hydroxide solution by mass concentration, and pulping for 30min to obtain a pulping solution; wherein the solid-to-liquid ratio g of the palladium slag removed by platinum refining and the alkali liquor is 1:2;
(2) Heating the slurry to 80 ℃, slowly adding a reducing agent (hydrazine hydrate solution with the mass concentration of 40%) to perform reduction treatment for 60min, and performing solid-liquid separation to obtain a palladium slag-containing solid and a dimethylglyoxime-containing solution; wherein the addition amount of the reducing agent (hydrazine hydrate solution) is 150% of the mass of the palladium-removing slag in the platinum refining in the step (1);
(3) Refining and purifying the palladium-containing slag solid sequentially through working procedures such as aqua regia dissolution, ammonia water complexation, hydrazine hydrate reduction and the like to obtain sponge palladium; the SEM image of palladium in this example is shown in fig. 2, and as can be seen from fig. 2, the palladium powder is in a sponge shape; as can be seen from the figure 3, the recovered palladium diffraction peak is identical to the standard palladium diffraction peak, and no other interference impurity peak exists;
the analysis results of the components of the sponge palladium are shown in Table 1, and the purity of the sponge palladium is more than 99.99 percent;
(4) Adding a dilute hydrochloric acid solution with the mass concentration of 10% into the solution containing the dimethylglyoxime for potential regulation, maintaining the acidity of the solution to be pH 0.5, standing for 12 hours, separating out dimethylglyoxime solid, carrying out solid-liquid separation to obtain dimethylglyoxime solid, and washing and drying the dimethylglyoxime solid;
in this example, the solid XRD of dimethylglyoxime is shown in fig. 4, and as can be seen from fig. 4, the diffraction peak of the recovered dimethylglyoxime coincides with the diffraction peak of the standard dimethylglyoxime, and no other interference peak exists;
the purity of the sponge palladium in this example was 99.995%, the recovery rate of palladium was 99.1%, and the yield of dimethylglyoxime was 95.7%.
Example 2: the platinum refining palladium-removing slag of the example contains 21.3wt.% of palladium and 32.3wt.% of dimethylglyoxime;
a method for recovering palladium and dimethylglyoxime from palladium-refining palladium-removing slag comprises the following specific steps:
(1) Uniformly mixing platinum refining palladium-removed slag and sodium hydroxide solution with the mass concentration of 15%, and pulping for 60min to obtain a pulping solution; wherein the solid-liquid ratio g of the palladium-removed slag and the alkali liquor in the platinum refining is 1:4;
(2) Heating the slurry to 85 ℃, slowly adding a reducing agent (oxalic acid solution with the mass concentration of 30%) to perform reduction treatment for 90min, and performing solid-liquid separation to obtain a palladium-containing slag solid and a dimethylglyoxime-containing solution; wherein the addition amount of the reducing agent (oxalic acid solution) is 300% of the mass of the palladium-removing slag in the platinum refining in the step (1);
(3) Refining and purifying the palladium-containing slag solid sequentially through working procedures such as aqua regia dissolution, ammonia water complexation, hydrazine hydrate reduction and the like to obtain sponge palladium; the analysis results of the components of the sponge palladium are shown in Table 1, and the purity of the sponge palladium is more than 99.99 percent;
(4) Adding a dilute hydrochloric acid solution with the mass concentration of 10% into the solution containing the dimethylglyoxime for potential regulation, maintaining the acidity of the solution to be pH 1.0, standing for 24 hours, separating out dimethylglyoxime solid, carrying out solid-liquid separation to obtain dimethylglyoxime solid, and washing and drying the dimethylglyoxime solid;
the purity of the sponge palladium in this example was 99.996%, the recovery rate of palladium was 99.03%, and the yield of dimethylglyoxime in this example was 96.1%.
Example 3: the platinum refining palladium-removing slag of the example contains 24.3wt.% of palladium and 31.2wt.% of dimethylglyoxime;
a method for recovering palladium and dimethylglyoxime from palladium-refining palladium-removing slag comprises the following specific steps:
(1) Uniformly mixing platinum refining palladium-removed slag and sodium hydroxide solution with the mass concentration of 20%, and pulping for 40min to obtain a pulping solution; wherein the solid-liquid ratio g of the palladium-removed slag and the alkali liquor in the platinum refining is 1:6;
(2) Heating the slurry to 90 ℃, slowly adding a reducing agent (ascorbic acid) to perform reduction treatment for 120min, and carrying out solid-liquid separation to obtain a palladium-containing slag solid and a dimethylglyoxime-containing solution; wherein the addition amount of the reducing agent (ascorbic acid) is 300% of the mass of the palladium-removing slag in the platinum refining in the step (1);
(3) Refining and purifying the palladium-containing slag solid sequentially through working procedures such as aqua regia dissolution, ammonia water complexation, hydrazine hydrate reduction and the like to obtain sponge palladium; the analysis results of the components of the sponge palladium are shown in Table 1, and the purity of the sponge palladium is more than 99.99 percent;
TABLE 1 analysis of sponge palladium composition
| Detecting items | Example 1 | Example 2 | Example 3 |
| Analysis element | Analytical results% | Analytical results% | Analytical results% |
| Pt | 0.0015 | 0.0020 | <0.0005 |
| Rh | <0.0005 | <0.0005 | <0.0005 |
| Ir | <0.0005 | <0.0005 | <0.0005 |
| Ru | <0.0005 | <0.0005 | <0.0005 |
| Au | <0.0005 | <0.0005 | <0.0005 |
| Ag | <0.0005 | <0.0005 | <0.0005 |
| Al | <0.0005 | <0.0005 | <0.0005 |
| Bi | <0.0005 | <0.0005 | <0.0005 |
| Cr | <0.0005 | <0.0005 | <0.0005 |
| Cu | <0.0005 | <0.0005 | <0.0005 |
| Fe | <0.0005 | <0.0005 | <0.0005 |
| Ni | <0.0005 | <0.0005 | <0.0005 |
| Pb | <0.0005 | <0.0005 | <0.0005 |
| Sn | <0.001 | <0.001 | <0.001 |
| Mg | <0.0005 | <0.0005 | <0.0005 |
| Mn | <0.0005 | <0.0005 | <0.0005 |
| Si | <0.001 | <0.001 | <0.001 |
| Zn | <0.0005 | <0.0005 | <0.0005 |
| Ca | <0.001 | <0.001 | <0.001 |
| Sb | <0.001 | <0.001 | <0.001 |
| Na | 0.0035 | 0.0020 | 0.0057 |
| Ti | <0.0005 | <0.0005 | <0.0005 |
(4) Adding a dilute hydrochloric acid solution with the mass concentration of 15% into the solution containing the dimethylglyoxime for potential regulation, maintaining the acidity of the solution to be pH 1.5, standing for 15 hours, separating out dimethylglyoxime solid, carrying out solid-liquid separation to obtain dimethylglyoxime solid, and washing and drying the dimethylglyoxime solid;
the purity of the sponge palladium in the embodiment is 99.994 percent, and the recovery rate of palladium is 99.02 percent; the yield of dimethylglyoxime was 95.9%.
Example 4: the platinum refining palladium-removing slag of the example contains 24.3wt.% wt wt.% of palladium and 31.2wt.% of dimethylglyoxime;
a method for recovering palladium and dimethylglyoxime from palladium-refining palladium-removing slag comprises the following specific steps:
(1) Uniformly mixing platinum refining palladium-removed slag and sodium carbonate solution with the mass concentration of 20%, and pulping for 50min to obtain a pulping solution; wherein the solid-liquid ratio g of the palladium-removed slag and the alkali liquor in the platinum refining is 1:8;
(2) Heating the slurry to 60 ℃, slowly adding a reducing agent (sodium borohydride solution with the mass concentration of 30%) to perform reduction treatment for 60min, and performing solid-liquid separation to obtain a palladium slag-containing solid and a dimethylglyoxime-containing solution; wherein the addition amount of the reducing agent (sodium borohydride solution) is 150% of the mass of the palladium-removing slag in the platinum refining in the step (1);
(3) Refining and purifying the palladium-containing slag solid sequentially through working procedures such as aqua regia dissolution, ammonia water complexation, hydrazine hydrate reduction and the like to obtain sponge palladium; the purity of the sponge palladium in the embodiment is 99.995%, and the recovery rate of palladium is 99.2%;
(4) Adding a dilute hydrochloric acid solution with the mass concentration of 15% into the solution containing the dimethylglyoxime for potential regulation, maintaining the acidity of the solution to be pH 0.5, standing for 18 hours, separating out dimethylglyoxime solid, carrying out solid-liquid separation to obtain dimethylglyoxime solid, and washing and drying the dimethylglyoxime solid;
the yield of the dimethylglyoxime in this example was 95.7%.
Example 5: the platinum refining palladium-removing slag of the example contains 23.5wt.% of palladium and 36.6wt.% of dimethylglyoxime;
a method for recovering palladium and dimethylglyoxime from palladium-refining palladium-removing slag comprises the following specific steps:
(1) Uniformly mixing platinum refining palladium-removed slag and sodium carbonate solution with the mass concentration of 10%, and pulping for 60min to obtain a pulping solution; wherein the solid-to-liquid ratio g of the palladium slag removed by platinum refining and the alkali liquor is 1:5;
(2) Heating the slurry to 50 ℃, slowly adding a reducing agent (potassium borohydride solution with the mass concentration of 30%) to perform reduction treatment for 90min, and performing solid-liquid separation to obtain a palladium slag-containing solid and a dimethylglyoxime-containing solution; wherein the addition amount of the reducing agent (potassium borohydride solution) is 200% of the mass of the palladium-removing slag in the platinum refining in the step (1);
(3) Refining and purifying the palladium-containing slag solid sequentially through working procedures such as aqua regia dissolution, ammonia water complexation, hydrazine hydrate reduction and the like to obtain sponge palladium; the purity of the sponge palladium in the embodiment is 99.992%, and the palladium recovery rate is 99.2%;
(4) Adding a dilute hydrochloric acid solution with the mass concentration of 15% into the solution containing the dimethylglyoxime for potential regulation, maintaining the acidity of the solution to be pH 0.5, standing for 16 hours, separating out dimethylglyoxime solid, carrying out solid-liquid separation to obtain dimethylglyoxime solid, and washing and drying the dimethylglyoxime solid;
the yield of dimethylglyoxime in this example was 96.0%.
While the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. A method for recovering palladium and dimethylglyoxime from palladium-refining palladium-removing slag is characterized by comprising the following specific steps:
(1) Uniformly mixing platinum refining palladium-removed slag and alkali liquor, and pulping to obtain a pulping liquor; the palladium-removing slag of the platinum refining contains 10-30wt% of palladium and 20-40wt% of dimethylglyoxime;
(2) Heating the slurry to a temperature of 40-95 ℃, slowly adding a reducing agent for reduction treatment for 60-120 min, and carrying out solid-liquid separation to obtain a palladium slag-containing solid and a dimethylglyoxime-containing solution;
(3) Refining and purifying the palladium-containing slag solid to obtain metal palladium;
(4) Adding a dilute hydrochloric acid solution into the solution containing the dimethylglyoxime for potential regulation, maintaining the acidity of the solution to be pH 0.5-2.0, standing for 8-24 hours, separating out dimethylglyoxime solid, carrying out solid-liquid separation to obtain the dimethylglyoxime solid, and washing and drying the dimethylglyoxime solid.
2. The method for recovering palladium and dimethylglyoxime from a platinum refining palladium removing slag according to claim 1, characterized in that: the alkali liquor in the step (1) is sodium hydroxide or sodium carbonate solution, and the mass concentration of the alkali liquor is 1-20%.
3. The method for recovering palladium and dimethylglyoxime from a platinum refining palladium-removing slag according to claim 1 or 2, characterized in that: and (3) the solid-liquid ratio g/mL of the palladium-removed slag and the alkali liquor in the step (1) is 1:2-10.
4. The method for recovering palladium and dimethylglyoxime from a platinum refining palladium removing slag according to claim 1, characterized in that: the reducing agent in the step (2) is one or more of hydrazine hydrate, oxalic acid, ascorbic acid, sodium borohydride and potassium borohydride.
5. The method for recovering palladium and dimethylglyoxime from a platinum refining palladium removing slag according to claim 1 or 4, characterized in that: the addition amount of the reducing agent in the step (2) is 120-600% of the mass of the palladium-removing slag in the step (1) of platinum refining.
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