CN113481373B - Method for separating and recovering palladium from activating solution - Google Patents
Method for separating and recovering palladium from activating solution Download PDFInfo
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- CN113481373B CN113481373B CN202110776305.1A CN202110776305A CN113481373B CN 113481373 B CN113481373 B CN 113481373B CN 202110776305 A CN202110776305 A CN 202110776305A CN 113481373 B CN113481373 B CN 113481373B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000003213 activating effect Effects 0.000 title abstract description 15
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 37
- 230000004913 activation Effects 0.000 claims abstract description 24
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 83
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 74
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- 238000001179 sorption measurement Methods 0.000 claims description 24
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 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 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- -1 palladium ions Chemical class 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910008066 SnC12 Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
-
- 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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- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (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 a method for separating and recovering palladium from an activation solution, which comprises the following steps: pretreating and activating polyamide resin; pretreating with a colloidal palladium activating solution; adsorbing palladium by using a colloidal palladium activating solution; removing palladium from polyamide resin; purifying the palladium-containing solution; reducing the high-purity sponge palladium; the technical scheme of the invention finds a process route which is economic, feasible, easy to operate, green and environment-friendly and has high palladium separation and recovery efficiency to recycle the palladium in the colloidal palladium activating solution.
Description
Technical Field
The invention relates to the technical field of precious metal recovery, in particular to a method for separating and recovering palladium from an activation solution
Background
One of the most critical processes in the manufacture of printed circuit boards is the hole metallization process. In order to achieve the connection of electronic components in printed circuits, the PCB must be perforated and the surface metallized, requiring activation with colloidal palladium. In the chemical copper plating process of the colloidal palladium activating solution, the colloidal palladium activating solution in the tank is contacted with air for a long time, so that the colloidal palladium activating solution is precipitated or loses efficacy, the colloid palladium activating solution is inevitably scrapped, and waste colloid palladium is generated when the colloid palladium is developed and produced.
The colloidal palladium is a colloidal solution in which atomic palladium is used as a colloidal core. The colloidal palladium is prepared from PdCl2Reacting with a reducing agent to obtain the product. The reducing agent is sodium hypophosphite, hydrazine hydrate, stannous compound and the like, wherein SnC12Most commonly used. At present, the most common is Pd/Sn type colloidal palladium which is an activator with excellent catalytic performance for the metallization of non-metallic materials. Because the palladium resource is precious, the method has the advantages of low cost and low costThe method has great significance for recovering the metal palladium in the waste colloid palladium activation solution.
The traditional recovery method has long time consumption, high cost and low separation effect, and a large amount of aqua regia is used, so that the complicated nitrate removing step exists, and the environment is polluted to a certain extent.
Accordingly, the prior art is deficient and needs improvement.
Disclosure of Invention
The invention mainly aims to provide a method for separating and recovering palladium from an activation solution, and aims to find a process route which is economical, feasible, easy to operate, green and environment-friendly and has high palladium separation and recovery efficiency for recycling palladium in a colloid palladium activation solution.
In order to achieve the purpose, the invention provides a method for separating and recovering palladium from an activation solution, which comprises the following steps:
s1: soaking a certain amount of polyamide resin in ethanol for a period of time, washing with water until no ethanol exists, eluting with NaOH aqueous solution, deionized water and hydrochloric acid in sequence, washing with water until the solution is neutral, and drying for later use;
s2: soaking the polyamide resin treated in the step S1 in a mixed solution of thiourea and hydrochloric acid, washing the polyamide resin to be neutral, and filling a certain amount of activated polyamide resin into an adsorption tower;
s3: taking a certain amount of colloidal palladium activation solution, adding water for dilution, putting the solution into a microwave instrument for microwave gel breaking, stopping microwave gel breaking when the solution is clear and transparent and the bottom of the solution is black precipitate, filtering the solution, mixing obtained filter residue with slurry, adding a mixed solution of hydrochloric acid and hydrogen peroxide, and performing oxidation treatment to obtain H2PdCl4The solution is prepared, wherein the molar ratio of the hydrochloric acid to the hydrogen peroxide is 4-6: 1;
s4: adsorbing the colloidal palladium activation solution treated in the step S3 by an adsorption tower in a step S2;
s5: adding an eluent into polyamide resin with saturated adsorption for desorption to obtain a solution rich in palladium;
s6: the palladium-rich solution obtained in S5 was adjusted with ammonium chloride to obtain PdCl in solution4 2-Conversion to water-soluble Pd (NH)3)4Cl2Then hydrochloric acid is used for adjusting the pH of the solution to lead Pd (NH)3)4Cl2Conversion to Pd (NH)3)2Cl2Yellow flocculent precipitate;
s7: and (4) adding a reducing agent into the yellow flocculent precipitate obtained in the step (S6) in an ammonium chloride medium for reduction, filtering, and washing palladium with clear water until the palladium is neutral to obtain the high-purity sponge palladium.
Preferably, in step S1, the polyamide resin has a particle size of 0.3 to 0.6mm, an ethanol concentration of 90 to 95%, a soaking time of 12 to 24 hours, a NaOH aqueous solution concentration of 2 to 10%, a hydrochloric acid concentration of 0.5 to 2mol/L, and is dried in a drying oven at 60 ℃.
Preferably, in step S2, the thiourea concentration is 2-6%, and the hydrochloric acid concentration is 0.2-0.6 mol/L.
Preferably, in the step S3, the amount of water for dilution is 3-5 times of the colloidal palladium activation solution, and the microwave power of a microwave instrument is 10-50; the concentration of the hydrochloric acid is 5-20%, and the concentration of the hydrogen peroxide is 5-20%; the oxidation treatment specifically includes: and heating the filter residue added with the mixed solution to 90 ℃ and keeping the temperature for 1 h.
Preferably, the step S4 specifically includes passing the colloidal palladium activation solution through an adsorption tower at a flow rate of 5-25 Bv/h for adsorption, measuring the palladium concentration in the effluent and calculating the adsorption rate, and discharging the effluent into a recovery tank.
Preferably, the eluent in step S5 is a mixture of thiourea with a concentration of 2-6% and hydrochloric acid with a concentration of 0.2-0.6%, the addition amount of the eluent is 2-3 times of the volume of the polyamide resin, desorption is performed by an adsorption tower at a flow rate of 10-30 Bv/h to obtain a solution rich in palladium, and the palladium concentration of the solution is measured and the desorption rate is calculated.
Preferably, in the step S6, the mass fraction of the ammonium chloride is 60-90 g/L, and the pH of the hydrochloric acid adjusting solution is 1-1.5.
Preferably, the reducing agent in the step S7 is hydrazine hydrate, and the content ratio of the reducing agent to palladium ions is 200-400: 1 ml/Kg.
Preferably, the method also comprises the step of regenerating the polyamide resin, and specifically comprises the following steps: and (3) washing the polyamide resin after the elution agent is desorbed with 2-10% of NaOH aqueous solution, washing with water, washing with a mixed solution of 2-6% of thiourea and 0.2-0.6 mol/L of hydrochloric acid, and washing with water to be neutral to regenerate the polyamide resin.
Compared with the prior art, the invention has the beneficial effects that:
1. the hydrochloric acid-hydrogen peroxide mixed solution replaces aqua regia to oxidize the colloidal palladium, thereby avoiding the phenomenon that NO which is a toxic gas with strong irritation is often released in the process of using the aqua regia for oxidation2The environment is seriously polluted;
2. the microwave gel breaking method is adopted to replace the traditional heating gel breaking method, so that the time is saved, and the energy consumption is reduced;
3. the resin column is applied to the adsorption of palladium, so that the complicated operation of repeated precipitation and filtration in the traditional method is avoided, and the use of medicaments is reduced;
4. compared with the traditional process, the polyamide resin has the advantages of environmental protection, strong operability and the like through the selective adsorption performance and the resin regeneration performance of the polyamide resin;
5. the method is suitable for recovering the waste colloidal palladium activating solution with low palladium content, has high recovery rate of palladium in the waste colloidal palladium activating solution, and obtains the high-purity sponge palladium.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic flow chart of the present invention;
the implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The method for separating and recovering palladium from the activating solution proposed in this example, with reference to fig. 1, includes the following steps:
s1: soaking a certain amount of polyamide resin in ethanol for a period of time, washing with water until no ethanol exists, eluting with NaOH aqueous solution, deionized water and hydrochloric acid in sequence, washing with water until the solution is neutral, and drying for later use;
wherein the particle size of the polyamide resin is 0.3-0.6 mm, the ethanol concentration is 90-95%, the soaking time is 12-24 h, the NaOH aqueous solution concentration is 2-10%, the hydrochloric acid concentration is 0.5-2 mol/L, and the polyamide resin is dried in a drying oven at 60 ℃.
S2: soaking the polyamide resin treated in the step S1 in a mixed solution of thiourea and hydrochloric acid, washing the polyamide resin to be neutral, and filling a certain amount of activated polyamide resin into an adsorption tower; wherein the concentration of the thiourea is 2-6%, and the concentration of the hydrochloric acid is 0.2-0.6 mol/L.
S3: taking a certain amount of colloidal palladium activation solution, adding water for dilution, putting the solution into a microwave instrument for microwave gel breaking, stopping microwave gel breaking when the solution is clear and transparent and the bottom of the solution is black precipitate, filtering the solution, mixing obtained filter residue with slurry, adding a mixed solution of hydrochloric acid and hydrogen peroxide, and performing oxidation treatment to obtain H2PdCl4The solution is prepared, wherein the molar ratio of the hydrochloric acid to the hydrogen peroxide is 4-6: 1;
wherein the water consumption for dilution is 3-5 times of that of the colloidal palladium activation solution, and the microwave power of a microwave instrument is 10-50; the concentration of the hydrochloric acid is 5-20%, and the concentration of the hydrogen peroxide is 5-20%; the oxidation treatment specifically includes: and heating the filter residue added with the mixed solution to 90 ℃ and keeping the temperature for 1 h.
S4: adsorbing the colloidal palladium activation solution treated in the step S3 by an adsorption tower in a step S2; specifically, the method comprises the steps of adsorbing a colloidal palladium activating solution through an adsorption tower at a flow speed of 5-25 Bv/h, measuring the concentration of palladium in an effluent liquid, calculating the adsorption rate, and discharging the effluent liquid into a recovery tank.
S5: adding an eluent into polyamide resin with saturated adsorption for desorption to obtain a solution rich in palladium; wherein the eluent is a mixed solution of thiourea with the concentration of 2-6% and hydrochloric acid with the concentration of 0.2-0.6%, the addition amount of the eluent is 2-3 times of the volume of the polyamide resin, desorption is carried out through an adsorption tower at the flow rate of 10-30 Bv/h, a solution rich in palladium is obtained, the palladium concentration of the solution is measured, and the desorption rate is calculated.
S6: adjusting with ammonium chloride to obtain S5To the palladium-rich solution, to cause PdCl in the solution4 2-Conversion to water-soluble Pd (NH)3)4Cl2Then hydrochloric acid is used for adjusting the pH of the solution to lead Pd (NH)3)4Cl2Conversion to Pd (NH)3)2Cl2Yellow flocculent precipitate; wherein the mass fraction of the ammonium chloride is 60-90 g/L, and the pH value of the hydrochloric acid adjusting solution is 1-1.5.
S7: and (3) adding a reducing agent into the yellow flocculent precipitate obtained in the step (S6) in an ammonium chloride medium for reduction, filtering, washing palladium with clear water until the palladium is neutral to obtain high-purity sponge palladium, wherein the recovery rate of the obtained sponge palladium is 95-99%. Wherein the reducing agent is hydrazine hydrate, and the content ratio of the reducing agent to palladium ions is 200-400: 1 ml/Kg.
Further, the method also comprises the step of regenerating the polyamide resin, and specifically comprises the following steps: and (3) washing the polyamide resin after the elution agent is desorbed with 2-10% of NaOH aqueous solution, washing with water, washing with a mixed solution of 2-6% of thiourea and 0.2-0.6 mol/L of hydrochloric acid, and washing with water to be neutral to regenerate the polyamide resin.
The invention is further illustrated by the following specific examples:
s1: taking 10L of waste colloidal palladium activating solution, adding 3-5 times of water for dilution, putting the solution into a microwave instrument, performing microwave power of 10-50, stopping microwave gel breaking when the solution is clear and transparent and black precipitate is formed at the bottom, filtering, mixing obtained filter residue, adding 10% hydrochloric acid and 5% hydrogen peroxide according to a volume ratio of 4-6: 1, mixing obtained hydrochloric acid-hydrogen peroxide mixed solution, heating to 90 ℃, keeping the temperature for 1H to obtain H2PdCl4And (4) solution, and determining the concentration of palladium.
S2: h obtained after pretreatment of S12PdCl4The solution was passed through an adsorption column packed with a bed of 2Kg of activated polyamide resin material at a flow rate of 6Bv/h, the concentration of palladium in the effluent was measured and the adsorption rate was calculated, and the effluent was discharged into a recovery tank.
S3: and (3) selecting a mixed solution of 4% thiourea and 0.4mol/L hydrochloric acid as an eluent, and enabling the mixed solution with the volume 2-3 times of that of the resin to pass through an adsorption tower at the flow rate of 12Bv/h to obtain a solution rich in palladium and calculating the desorption rate.
S4: and washing the resin after palladium elution with a 5% NaOH aqueous solution, washing with water, washing with a 4% thiourea-0.4 mol/L hydrochloric acid mixed solution, and washing with water to be neutral to regenerate the polyamide resin.
S5: adjusting the palladium-rich solution by using ammonium chloride, adjusting the pH value of the solution to 1-1.5 by using hydrochloric acid, and separating out a large amount of yellow flocculent precipitates;
s6: reducing the obtained yellow flocculent precipitate in an ammonium chloride medium by using a reducing agent hydrazine hydrate, wherein the ratio of the amount of the reducing agent to the content of palladium ions is 200-400: 1ml/Kg, filtering, washing palladium by using clear water until the palladium is neutral, and the recovery rate of the obtained sponge palladium is 98.5%.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (9)
1. A method for separating and recovering palladium from an activation solution is characterized by comprising the following steps:
s1: soaking a certain amount of polyamide resin in ethanol for a period of time, washing with water until no ethanol exists, eluting with NaOH aqueous solution, deionized water and hydrochloric acid in sequence, washing with water until the solution is neutral, and drying for later use;
s2: soaking the polyamide resin treated in the step S1 in a mixed solution of thiourea and hydrochloric acid, washing the polyamide resin to be neutral, and filling a certain amount of activated polyamide resin into an adsorption tower;
s3: taking a certain amount of colloidal palladium activation solution, adding water for dilution, putting the solution into a microwave instrument for microwave gel breaking, stopping microwave gel breaking when the solution is clear and transparent and the bottom of the solution is black precipitate, filtering the solution, mixing obtained filter residue with slurry, adding a mixed solution of hydrochloric acid and hydrogen peroxide, and performing oxidation treatment to obtain H2PdCl4The solution is prepared, wherein the molar ratio of the hydrochloric acid to the hydrogen peroxide is 4-6: 1;
s4: adsorbing the colloidal palladium activation solution treated in the step S3 by an adsorption tower in a step S2;
s5: adding an eluent into polyamide resin with saturated adsorption for desorption to obtain a solution rich in palladium;
s6: the palladium-rich solution obtained in S5 was adjusted with ammonium chloride to obtain PdCl in solution4 2-Conversion to water-soluble Pd (NH)3)4Cl2Then hydrochloric acid is used for adjusting the pH of the solution to lead Pd (NH)3)4Cl2Conversion to Pd (NH)3)2Cl2Yellow flocculent precipitate;
s7: and (4) adding a reducing agent into the yellow flocculent precipitate obtained in the step (S6) in an ammonium chloride medium for reduction, filtering, and washing palladium with clear water until the palladium is neutral to obtain the high-purity sponge palladium.
2. The method for separating and recovering palladium from an activation solution according to claim 1, wherein in step S1, the polyamide resin has a particle size of 0.3 to 0.6mm, an ethanol concentration of 90 to 95%, a soaking time of 12 to 24 hours, a NaOH aqueous solution concentration of 2 to 10%, a hydrochloric acid concentration of 0.5 to 2mol/L, and is dried in a drying oven at 60 ℃.
3. The method for separating and recovering palladium from an activation solution according to claim 1, wherein in step S2, the thiourea concentration is 2 to 6% and the hydrochloric acid concentration is 0.2 to 0.6 mol/L.
4. The method for separating and recovering palladium from an activation solution according to claim 1, wherein in step S3, the amount of water used for dilution is 3 to 5 times of that of the colloidal palladium activation solution, and the microwave power of a microwave instrument is 10 to 50; the concentration of the hydrochloric acid is 5-20%, and the concentration of the hydrogen peroxide is 5-20%; the oxidation treatment specifically includes: and heating the filter residue added with the mixed solution to 90 ℃ and keeping the temperature for 1 h.
5. The method for separating and recovering palladium from an activated solution according to claim 1, wherein the step S4 comprises adsorbing the activated solution of colloidal palladium by an adsorption tower at a flow rate of 5-25 Bv/h, measuring the palladium concentration in the effluent and calculating the adsorption rate, and discharging the effluent into a recovery tank.
6. The method for separating and recovering palladium from an activated solution according to claim 1, wherein the eluent used in step S5 is a mixture of thiourea with a concentration of 2-6% and hydrochloric acid with a concentration of 0.2-0.6%, the amount of the eluent is 2-3 times the volume of the polyamide resin, the desorption is performed by an adsorption tower at a flow rate of 10-30 Bv/h to obtain a palladium-rich solution, and the palladium concentration of the solution is measured to calculate the desorption rate.
7. The method for separating and recovering palladium from an activation solution according to claim 1, wherein in step S6, the mass fraction of ammonium chloride is 60 to 90g/L, and the pH of the solution is adjusted to 1 to 1.5 with hydrochloric acid.
8. The method for separating and recovering palladium from an activation solution according to claim 1, wherein the reducing agent in step S7 is hydrazine hydrate, and the content ratio of the reducing agent to palladium ions is 200-400: 1 ml/Kg.
9. The method for separating and recovering palladium from an activation solution according to any one of claims 1 to 8, further comprising regenerating a polyamide resin, specifically comprising: and (3) washing the polyamide resin after the elution agent is desorbed with 2-10% of NaOH aqueous solution, washing with water, washing with a mixed solution of 2-6% of thiourea and 0.2-0.6 mol/L of hydrochloric acid, and washing with water to be neutral to regenerate the polyamide resin.
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