CN112063851B - Method for recycling platinum ions in waste platinum plating solution - Google Patents
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- CN112063851B CN112063851B CN202010881834.3A CN202010881834A CN112063851B CN 112063851 B CN112063851 B CN 112063851B CN 202010881834 A CN202010881834 A CN 202010881834A CN 112063851 B CN112063851 B CN 112063851B
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 58
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 238000007747 plating Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 27
- -1 platinum ions Chemical class 0.000 title claims abstract description 22
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 85
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 68
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims abstract description 22
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910019032 PtCl2 Inorganic materials 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000006479 redox reaction Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 10
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 10
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 7
- 229940021013 electrolyte solution Drugs 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910018965 MCl2 Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 240000007817 Olea europaea Species 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000009713 electroplating Methods 0.000 description 22
- 238000003756 stirring Methods 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- GIGQFSYNIXPBCE-UHFFFAOYSA-N alumane;platinum Chemical compound [AlH3].[Pt] GIGQFSYNIXPBCE-UHFFFAOYSA-N 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000012720 thermal barrier coating 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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)
- Manufacturing & Machinery (AREA)
- 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 discloses platinum in waste platinum plating solutionA method for recycling ions belongs to the technical field of inorganic chemistry and electrochemistry. The method comprises the steps of firstly, using one or more elementary metals to react chloroplatinic acid (H)2PtCl6) Platinum ions in the waste plating solution are reduced to platinous chloride (PtCl) in aqueous solution2) Precipitating, then using PtCl2Preparation of H2PtCl6An electrolyte solution. The method realizes the recycling of platinum ions in the waste platinum plating solution through simple redox reaction, has simple process and is suitable for engineering application.
Description
Technical Field
The invention relates to the technical field of inorganic chemistry and electrochemistry, in particular to a method for recycling platinum ions in waste platinum plating solution.
Background
With the continuous development of aero-engines, the thrust-weight ratio is continuously improved, and the service temperature of engine blades is also gradually improved. At present, the moving blades of the aero-engine are basically cast by using single-crystal high-temperature alloy, but because the development of the single-crystal high-temperature alloy enters the bottleneck period, the temperature bearing capacity of the existing single-crystal high-temperature alloy cannot meet the increasing requirement of the use temperature of the aero-engine, and therefore, the research and development of the high-temperature resistant coating becomes a research hotspot of some scholars.
The platinum-aluminum (Pt-Al) coating is a modified aluminide coating, is mainly applied to a moving blade protective coating of an aeroengine, and can also be used as a bonding layer of a thermal barrier coating of a turbine blade of a gas turbine. The preparation process of the Pt-Al coating comprises the following steps: firstly plating a layer of platinum (Pt) on the surface of a workpiece, and then forming a Pt-Al coating on the surface of the workpiece by an aluminizing (Al) method.
In the electroplating stage, because hollow work piece inner chamber structure is comparatively complicated, there is some plating solution to get into the work piece inner chamber among the electroplating process, when taking out the work piece after the electroplating, usually there are some raffinate from the inside outflow of work piece, again because before work piece electroplating, sometimes can carry out fluorescence detection, some fluorescent agent can be remained to the inner chamber, consequently, the raffinate of taking out of back work piece inner chamber of electroplating is for possibly mixing with the fluorescent agent, adopt special container to collect these raffinate of taking out usually, thereby avoid pouring the raffinate of taking out that contains the fluorescent agent into former electroplating solution and cause the pollution, these raffinate of taking out can be handled as waste solution usually, only a small part is recycled.
Chloroplatinic acid (H)2PtCl6) Plating Pt as an electrolyte solution is a simple and easy-to-prepare electroplating solution. However, in the presence of H2PtCl6The plating solution usually contains, in addition to the main electrolyte solution, disodium hydrogen phosphate (Na), which is an easily ionizable neutralizing agent2HPO4) And sodium citrate (Na)3C6H5O7) And sodium acetate (C)2H3NaO2) And complexing agents and stabilizers. This results in the inclusion of H2PtCl6The composition of the plating solution becomes complicated.
The residual liquid of the workpiece contains H2PtCl6The component Pt is used as a noble metal, and the value of recycling Pt ions is high. From the perspective of engineering application and cost control, it is very important to recycle Pt ions in the waste electroplating solution. However, the residual liquid component carried by the workpiece is complex and contains inorganic and organic solvents, which causes certain difficulties in extraction of Pt ions.
The invention utilizes active elementary metal pairs H2PtCl6By combining platinous chloride (PtCl)2) To the content of H2PtCl6The recovery and reuse of Pt ions in the plating solution of (1) was explained.
Disclosure of Invention
The invention aims to provide a method for recycling platinum ions in waste platinum plating solution, which realizes the recycling of the platinum ions in the waste platinum plating solution through simple redox reaction, has simple process and is suitable for engineering application.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for recycling platinum ions in waste platinum plating solution is characterized by comprising the following steps: the method firstly uses simple substance metal to reduce platinum ions in the waste platinum plating solution into platinous chloride (PtCl) in aqueous solution2) Precipitating, then using PtCl2Preparation of H2PtCl6An electrolyte solution.
The waste platinizing liquid contains electrolytic chloroplatinic acid (H)2PtCl6) And Na2HPO4Chloroplatinic acid (H)2PtCl6) Concentration 15-45 wt.%, Na2HPO4The concentration is 5-20 wt.%.
The waste platinum plating solution also contains a complexing agent and/or a stabilizing agent, wherein the complexing agent is Na3C6H5O7Complexing agent concentration 0.5-2.4 wt.%; the stabilizer is C2H3NaO2Stabilizer concentration 0.3-2.0 wt.%.
The simple substance metal has stronger activity than Pt metal and can react with H in the waste platinum plating solution2PtCl6Oxidation-reduction reaction takes place to produce PtCl2. The chemical reactions that take place are of formulae (1) and (2):
M+H2PtCl6＝MCl2+PtCl4+H2↑ (1)；
M+PtCl4＝MCl2+PtCl2↓ (2)；
m in the formulas (1) and (2) is elementary metal, Pt ions with the valence of +4 are reduced into Pt ions with the valence of +2 in the formula (2), and the elementary metal is a reducing agent.
The elementary metal is one or more of Mg, Zn, Sn and Pb, and the purity of the Mg, Zn, Sn and Pb elementary metal is more than or equal to 99.9%.
Platinous chloride (PtCl) in said aqueous solution2) The precipitate is insoluble in water and organic solvent, and PtCl is generated when the simple substance metal reacts with the waste platinizing liquid2Precipitated as a precipitate phase.
The method for recycling the platinum ions in the waste platinum plating solution comprises the following steps:
(1) weighing a proper amount of simple substance metal (the accurate value of an electronic balance used for weighing is 0.0001g), and grinding and polishing each surface of the simple substance metal smoothly to ensure that the surface has no oxide or impurity;
(2) carrying out ultrasonic cleaning on the elemental metal by using an organic solvent to remove oil stains on the surface for use;
(3) putting a proper amount of waste platinum plating solution into a container, and putting the container into a water bath for heating;
(4) putting the elementary metal into the heated waste platinum plating solution, and taking out the residual elementary metal after the reaction is completed;
(5) filtering out precipitate from the reacted solution, filtering and washing the filtered precipitate with deionized water, and drying;
(6) heating the dried precipitate in a container, and introducing chlorine (Cl)2) Until the precipitate became a brownish red crystal, and the crystal was weighed;
(7) and dissolving the brownish red crystals in a proper amount of hydrochloric acid (HCl), and adding a proper amount of water to finally present orange yellow liquid, namely hexachloroplatinic acid.
In the step (3), the waste platinum plating solution is heated to 60-80 ℃, and when the temperature reaches a preset value, the single metal is put into the waste platinum plating solution to excite the single metal and H in the solution2PtCl6A chemical reaction is carried out.
In the step (5), the filtered chemical precipitate is PtCl2The green olive is obtained, and the drying temperature is 80-120 ℃; in step (6), is substituted with Cl2The brownish red crystal obtained after oxidation is PtCl4The precise value of an electronic balance used for weighing is 0.0001g, and the chemical reaction is shown as the formula (3):
PtCl2+Cl2↑＝PtCl4 (3)。
in the step (7), the concentration of HCl is 30-40ml/L, the water used for diluting the solvent is deionized water, and the chemical reaction is as shown in the formula (4):
PtCl4+HCl＝H2PtCl6 (4)。
the invention has the following advantages and beneficial effects:
(1) the invention relates to the use of one or more elementary metals for the treatment of chloroplatinic acid (H)2PtCl6) Platinum ions in the waste plating solution are reduced to platinous chloride (PtCl) in aqueous solution2) Precipitating with PtCl2Preparation of H2PtCl6The electrolyte solution is realized through simple oxidation-reduction reaction, and can still be used as the electrolyte in the electroplating solution after simple treatment; different from the traditional method, the method needs to extract organic matters in the electroplating solution and then recover metal ions in the inorganic matters.
(2) The invention relates to the use of one or more elementary metals for the treatment of chloroplatinic acid (H)2PtCl6) Platinum ions in the waste plating solution are reduced to platinous chloride (PtCl) in aqueous solution2) Precipitating with PtCl2Preparation of H2PtCl6The electrolyte solution is beneficial to engineering application and plays an important role in saving cost for scientific research units and enterprises.
Drawings
FIG. 1 shows elemental metal reduction H2PtCl6After generation of PtCl2And (4) precipitating.
Detailed Description
The invention provides a method for recycling platinum ions in waste platinum plating solution, wherein the main component of the waste platinum plating solution is H2PtCl6(15-45 wt.%) and Na2HPO4(5-20 wt.%) and Na3C6H5O7(0.5-2.4wt.％)、C2H3NaO2(0.3-2.0 wt.%) complexing agent and/or stabilizer, and the rest is water. I.e. complexing agents and/or stabilizers containing organic constituents in inorganic electrolyte solutions, where H2PtCl6And Na2HPO4As an electrolyte, Na3C6H5O7And/or C2H3NaO2Is a complexing agent and/or a stabilizer.
The elementary metal in the invention has stronger activity than Pt and can react with H in the waste platinum plating solution2PtCl6Oxidation-reduction reaction takes place to produce PtCl2。
PtCl in aqueous solution as described in the present invention2The precipitate is insoluble in water and organic solvent, and contains H2PtCl6、Na2HPO4、Na3C6H5O7And/or C2H3NaO2In the reaction, PtCl2Precipitated as a precipitate phase.
Example 1
(1) Preparing reduced metal: selecting simple substance Mg as reducing metal, weighing 7.6324g by balance, and grinding the metal surface to be bright by 400# abrasive paper to ensure that the metal surface is free of oxides and impurities.
(2) Reducing metal to remove oil: and (3) putting the polished elemental metal Mg into a container of a mixed solution of acetone and alcohol, and carrying out oil removal treatment by using an ultrasonic cleaning machine for use.
(3) 1000ml of waste electroplating solution is poured into a beaker, and the beaker is placed in a water bath heating pot to be heated, wherein the preset heating temperature is 65 ℃.
(4) And (3) putting the single metal into the electroplating solution which reaches the heating temperature, continuously stirring the electroplating solution by using a stirring rod, wherein precipitates can appear in the solution, continuously stirring the solution, stopping stirring when the precipitates are not continuously generated in the solution, and removing the residual metal.
(5) The reacted solution was filtered with filter paper and a funnel, and the filtered precipitate was repeatedly washed twice with deionized water and dried with a drying oven set at 100 deg.c (fig. 1).
(6) Putting the dried precipitate into a heatable vessel for heating, and introducing Cl2During the heating process, the color of the precipitate is observed, and Cl is blocked when the precipitate turns into brownish red crystals2And the heating was stopped and the red-brown crystals weighed about 2.4513 g.
(7) Will reactPutting the brownish red crystals into 10ml (with the concentration of 30ml/L) of HCl, continuously stirring until the crystals are completely dissolved, and adding 150ml of deionized water into the solution for dilution to prepare H2PtCl6And (3) solution. And dissolving the brownish red crystals in a proper amount of HCl, and adding a proper amount of water to finally present orange yellow liquid, namely hexachloroplatinic acid.
Example 2
(1) Preparing reduced metal: the simple substance Zn is selected as reducing metal, 5.2423g of weight is weighed by balance, and 400# abrasive paper is used for grinding the surface of the metal to be bright, so that the surface of the metal is free from oxides and impurities.
(2) Reducing metal to remove oil: and (3) putting the polished elemental metal Zn into a container of a mixed solution of acetone and alcohol, and carrying out oil removal treatment by using an ultrasonic cleaning machine for use.
(3) 1000ml of waste electroplating solution is poured into a beaker, and the beaker is placed in a water bath heating pot to be heated, wherein the heating temperature is 80 ℃.
(4) And (3) putting the single metal into the electroplating solution which reaches the heating temperature, continuously stirring the electroplating solution by using a stirring rod, wherein precipitates can appear in the solution, continuously stirring the solution, stopping stirring when the precipitates are not continuously generated in the solution, and removing the residual metal.
(5) And filtering the solution after reaction by using filter paper and a funnel, repeatedly washing the filtered precipitate twice by using deionized water, and drying by using a drying oven with the preset temperature of 80 ℃.
(6) Putting the dried precipitate into a heatable vessel for heating, and introducing Cl2During the heating process, the color of the precipitate is observed, and Cl is blocked when the precipitate turns into brownish red crystals2And the heating was stopped and the red-brown crystals weighed about 2.3765 g.
(7) Putting the reacted brownish red crystals into 9ml (with the concentration of 40ml/L) of HCl, continuously stirring until the crystals are completely dissolved, and adding 150ml of deionized water into the solution for dilution to prepare H2PtCl6And (3) solution. And dissolving the brownish red crystals in a proper amount of HCl, and adding a proper amount of water to finally present orange yellow liquid, namely hexachloroplatinic acid.
Example 3
(1) Preparing reduced metal: simple substance Sn is selected as reducing metal, 6.2133g of weight is weighed by balance, and 400# abrasive paper is used for grinding the surface of the metal to be bright, so that the surface of the metal is free from oxides and impurities.
(2) Reducing metal to remove oil: and putting the polished elemental metal Sn into a container of a mixed solution of acetone and alcohol, and carrying out oil removal treatment by using an ultrasonic cleaning machine for use.
(3) 1000ml of waste electroplating solution is poured into a beaker, and the beaker is placed in a water bath heating pot to be heated, wherein the preset heating temperature is 70 ℃.
(4) And (3) putting the single metal into the electroplating solution which reaches the heating temperature, continuously stirring the electroplating solution by using a stirring rod, wherein precipitates can appear in the solution, continuously stirring the solution, stopping stirring when the precipitates are not continuously generated in the solution, and removing the residual metal.
(5) And filtering the solution after reaction by using filter paper and a funnel, repeatedly washing the filtered precipitate twice by using deionized water, and drying by using a drying oven with the preset temperature of 120 ℃.
(6) Putting the dried precipitate into a heatable vessel for heating, and introducing Cl2During the heating process, the color of the precipitate is observed, and Cl is blocked when the precipitate turns into brownish red crystals2And the heating was stopped and the red-brown crystals weighed about 2.3323 g.
(7) Putting the reacted brownish red crystals into 9ml (with the concentration of 30ml/L) of HCl, continuously stirring until the crystals are completely dissolved, and adding 150ml of deionized water into the solution for dilution to prepare H2PtCl6And (3) solution. And dissolving the brownish red crystals in a proper amount of HCl, and adding a proper amount of water to finally present orange yellow liquid, namely hexachloroplatinic acid.
Example 4
(1) Preparing reduced metal: selecting simple substance Pb as reducing metal, weighing 7.9837g by balance, and grinding the metal surface to be bright by 400# abrasive paper to ensure that the metal surface is free from oxides and impurities.
(2) Reducing metal to remove oil: the polished elemental metal Pb is put into a container of a mixed solution of acetone and alcohol, and is subjected to degreasing treatment by an ultrasonic cleaner to be ready for use.
(3) 1000ml of waste electroplating solution is poured into a beaker, and the beaker is placed in a water bath heating pot to be heated, wherein the preset heating temperature is 60 ℃.
(4) And (3) putting the single metal into the electroplating solution which reaches the heating temperature, continuously stirring the electroplating solution by using a stirring rod, wherein precipitates can appear in the solution, continuously stirring the solution, stopping stirring when the precipitates are not continuously generated in the solution, and removing the residual metal.
(5) And filtering the solution after reaction by using filter paper and a funnel, repeatedly washing the filtered precipitate twice by using deionized water, and drying by using a drying oven with the preset temperature of 90 ℃.
(6) Putting the dried precipitate into a heatable vessel for heating, and introducing Cl2During the heating process, the color of the precipitate is observed, and Cl is blocked when the precipitate turns into brownish red crystals2And the heating was stopped and the red-brown crystals weighed about 2.2785 g.
(7) Putting the reacted brownish red crystals into 9ml (with the concentration of 40ml/L) of HCl, continuously stirring until the crystals are completely dissolved, and adding 150ml of deionized water into the solution for dilution to prepare H2PtCl6And (3) solution. And dissolving the brownish red crystals in a proper amount of HCl, and adding a proper amount of water to finally present orange yellow liquid, namely hexachloroplatinic acid.
Claims (8)
1. A method for recycling platinum ions in waste platinum plating solution is characterized by comprising the following steps: the method firstly uses simple substance metal to reduce platinum ions in the waste platinum plating solution into platinous chloride (PtCl) in aqueous solution2) PrecipitateThen using PtCl2Preparation of H2PtCl6An electrolyte solution; the waste platinizing liquid contains electrolytic chloroplatinic acid (H)2PtCl6) And Na2HPO4Chloroplatinic acid (H)2PtCl6) Concentration 15-45 wt.%, Na2HPO4Concentration 5-20 wt.%;
the waste platinum plating solution also contains a complexing agent and/or a stabilizing agent, wherein the complexing agent is Na3C6H5O7Complexing agent concentration 0.5-2.4 wt.%; the stabilizer is C2H3NaO2Stabilizer concentration 0.3-2.0 wt.%.
2. The method for recycling platinum ions in the waste platinum plating solution according to claim 1, characterized in that: the simple substance metal has stronger activity than Pt metal and can react with H in the waste platinum plating solution2PtCl6Oxidation-reduction reaction takes place to produce PtCl2(ii) a The chemical reactions that take place are of formulae (1) and (2):
M+H2PtCl6=MCl2+PtCl4+H2↑ （1）；
M+PtCl4=MCl2+PtCl2↓ （2）；
m in the formulas (1) and (2) is elementary metal, Pt ions with the valence of +4 are reduced into Pt ions with the valence of +2 in the formula (2), and the elementary metal is a reducing agent.
3. The method for recycling platinum ions in the waste platinum plating solution according to claim 2, characterized in that: the elementary metal is one or more of Mg, Zn, Sn and Pb, and the purity of the Mg, Zn, Sn and Pb elementary metal is more than or equal to 99.9%.
4. The method for recycling platinum ions in the waste platinum plating solution according to claim 1, characterized in that: platinous chloride (PtCl) in said aqueous solution2) The precipitate is insoluble in water and organic solvent, when the simple substance metal reacts with the waste platinizing liquid,PtCl2precipitated as a precipitate phase.
5. The method for recycling platinum ions from a waste platinum plating solution according to any one of claims 1 to 4, wherein: the method specifically comprises the following steps:
(1) weighing a proper amount of simple substance metal, and grinding and polishing each surface of the simple substance metal smoothly to ensure that the surface is free of oxides and impurities;
(2) carrying out ultrasonic cleaning on the elemental metal by using an organic solvent to remove oil stains on the surface for use;
(3) putting a proper amount of waste platinum plating solution into a container, and putting the container into a water bath for heating;
(4) putting the elementary metal into the heated waste platinum plating solution, and taking out the residual elementary metal after the reaction is completed;
(5) filtering out precipitate from the reacted solution, filtering and washing the filtered precipitate with deionized water, and drying;
(6) heating the dried precipitate in a container, and introducing chlorine (Cl)2) Until the precipitate became a brownish red crystal, and the crystal was weighed;
(7) and dissolving the brownish red crystals in a proper amount of hydrochloric acid (HCl), and adding a proper amount of water to finally present orange yellow liquid, namely hexachloroplatinic acid.
6. The method for recycling platinum ions in the waste platinum plating solution according to claim 5, wherein: in the step (3), the waste platinum plating solution is heated to 60-80 ℃, and when the temperature reaches a preset value, the single metal is put into the waste platinum plating solution to excite the single metal and H in the solution2PtCl6A chemical reaction is carried out.
7. The method for recycling platinum ions in the waste platinum plating solution according to claim 5, wherein: in the step (5), the filtered chemical precipitate is PtCl2Is olive green, and has oven drying temperature of 80-120 deg.C(ii) a In step (6), is substituted with Cl2The brownish red crystal obtained after oxidation is PtCl4The precise value of an electronic balance used for weighing is 0.0001g, and the chemical reaction is shown as the formula (3):
PtCl2 +Cl2↑＝PtCl4 （3）。
8. the method for recycling platinum ions in the waste platinum plating solution according to claim 5, wherein: in the step (7), the concentration of HCl is 30-40ml/L, water used for diluting a solvent is deionized water, and the chemical reaction is as shown in a formula (4):
PtCl4+HCl= H2PtCl6 （4）。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55164042A (en) * | 1979-06-08 | 1980-12-20 | Agency Of Ind Science & Technol | Method of separating and recovering platinum from platinum plating waste liquid |
| JP2004143527A (en) * | 2002-10-24 | 2004-05-20 | Nippon Mining & Metals Co Ltd | Method for removing platinum and palladium in solution |
| CN102978407A (en) * | 2012-12-17 | 2013-03-20 | 四会市鸿明贵金属有限公司 | Method for recovering platinum from silver electrolyte |
| CN104745836A (en) * | 2015-04-21 | 2015-07-01 | 昆山鸿福泰环保科技有限公司 | Platinum recovery refining process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55164042A (en) * | 1979-06-08 | 1980-12-20 | Agency Of Ind Science & Technol | Method of separating and recovering platinum from platinum plating waste liquid |
| JP2004143527A (en) * | 2002-10-24 | 2004-05-20 | Nippon Mining & Metals Co Ltd | Method for removing platinum and palladium in solution |
| CN102978407A (en) * | 2012-12-17 | 2013-03-20 | 四会市鸿明贵金属有限公司 | Method for recovering platinum from silver electrolyte |
| CN104745836A (en) * | 2015-04-21 | 2015-07-01 | 昆山鸿福泰环保科技有限公司 | Platinum recovery refining process |
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