CN112080765B - Method for recovering palladium chloride in waste colloidal palladium activation solution - Google Patents
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 250
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 124
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 41
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 title claims abstract description 39
- 230000004913 activation Effects 0.000 title claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 84
- 239000012528 membrane Substances 0.000 claims abstract description 79
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 238000000409 membrane extraction Methods 0.000 claims abstract description 18
- 150000001450 anions Chemical class 0.000 claims abstract description 16
- 238000000151 deposition Methods 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims description 41
- 239000000839 emulsion Substances 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 5
- 229940057995 liquid paraffin Drugs 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012744 reinforcing agent Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 4
- 239000003623 enhancer Substances 0.000 claims 2
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 239000008384 inner phase Substances 0.000 claims 1
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- 238000013517 stratification Methods 0.000 claims 1
- 239000006228 supernatant Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 12
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 14
- 150000001768 cations Chemical class 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 230000009471 action Effects 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- 229960001484 edetic acid Drugs 0.000 description 5
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 chemical engineering Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- RTTCFFTVCUNXLX-UHFFFAOYSA-N n,n-di(octan-2-yl)acetamide Chemical compound CCCCCCC(C)N(C(C)=O)C(C)CCCCCC RTTCFFTVCUNXLX-UHFFFAOYSA-N 0.000 description 1
- 239000008385 outer phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
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- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
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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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/32—Carboxylic acids
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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
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25B1/26—Chlorine; Compounds thereof
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Abstract
本发明公开一种回收废胶体钯活化液中氯化钯的方法。包括：S1：将废胶体钯活化液预处理；S2：对经过预处理后的废胶体钯活化液进行液膜萃取，得到富含钯的水溶液；S3：将富含钯的水溶液作为阴极液，进行阳离子膜电解，在阴极上沉积单质钯；S4：将沉积单质钯的阴极作为阳极，然后加入含氯离子的电解液，进行阴离子膜电解造液，将电解后的阳极液浓缩，结晶，得到氯化钯。本发明通过将液膜萃取工序与离子膜电解及造液工序相结合，简化了工艺，降低了成本；且回收过程中使用少量王水，省去了繁琐的赶硝过程，减少对环境的污染，提高了社会经济效益和环境效益；本发明的方法适用于低含量的钯的回收，提高了对废胶体钯活化液中氯化钯的回收率。
The invention discloses a method for recovering palladium chloride in waste colloidal palladium activation solution. The method includes: S1: pretreating the waste colloidal palladium activation solution; S2: performing liquid membrane extraction on the pretreated waste colloidal palladium activation solution to obtain a palladium-rich aqueous solution; S3: using the palladium-rich aqueous solution as a catholyte, Carry out cationic membrane electrolysis, deposit elemental palladium on the cathode; S4: use the cathode for depositing elemental palladium as an anode, then add an electrolyte solution containing chloride ions, carry out anion membrane electrolysis, and concentrate the electrolyzed anolyte, crystallize, and obtain Palladium chloride. By combining the liquid membrane extraction process with the ionic membrane electrolysis and liquid making process, the invention simplifies the process and reduces the cost; and a small amount of aqua regia is used in the recovery process, which saves the tedious process of catching nitrate and reduces the pollution to the environment. , the social and environmental benefits are improved; the method of the invention is suitable for the recovery of low-content palladium, and improves the recovery rate of palladium chloride in the waste colloidal palladium activation solution.
Description
Technical Field
The invention relates to the technical field of precious metal recovery, in particular to a method for recovering palladium chloride in waste colloidal palladium activation solution.
Background
Palladium chloride (PdCl)2) Is a reddish brown crystalline powder, is deliquescent, is easily soluble in dilute hydrochloric acid, is stable in air, and is soluble in ethanol, propanol and hydrobromic acid. Palladium chloride is a palladium compound which is commonly used as a precursor at present, is widely applied to the fields of petroleum, chemical engineering, water treatment, automobile exhaust purification and the like, and has important application in the aspects of preparing catalysts, molecular sieves, gas sensitive elements, analytical reagents and the like. The colloidal palladium activating solution prepared from palladium chloride and stannous chloride is widely applied to the hole metallization process for manufacturing Printed Circuit Boards (PCBs).
The colloidal palladium is firstly developed successfully by Shipley scholars through the reaction of palladium chloride and stannous chloride, and the most common palladium is Pd/Sn type colloidal palladium at present, which is taken as an activating agent with excellent catalytic performance and has great significance for the metallization of non-metallic materials. 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, and metal oxidants brought by other components and parts due to incomplete cleaning are accumulated for a long time, so that the colloidal palladium activating solution is easy to be precipitated or lose efficacy, and the colloidal palladium activating solution is inevitably scrapped, so that a large amount of waste colloidal palladium activating solution exists, and the recovery of palladium chloride in the waste colloidal palladium activating solution is of great significance due to precious palladium resources.
The traditional recovery method is long in time consumption, high in cost and low in separation efficiency, is usually suitable for recovering high-content palladium, and a large amount of aqua regia is used in the common recovery method of palladium chloride, so that a complicated nitrate removing step exists, and certain pollution is caused to the environment.
Disclosure of Invention
The invention aims to provide a method for recovering palladium chloride in a waste colloidal palladium activating solution, which solves the problems of complicated recovery process, low recovery efficiency and high recovery cost of palladium in the traditional waste colloidal palladium activating solution; the recovery method has wide application range and small environmental pollution.
The invention is realized by the following technical scheme:
a method for recovering palladium chloride in waste colloidal palladium activation solution comprises the following steps:
s1: pretreating the waste colloidal palladium activating solution;
s2: performing liquid membrane extraction on the pretreated waste colloid palladium activation solution to obtain a palladium-rich aqueous solution;
s3: taking the water solution rich in palladium as catholyte, and performing cation membrane electrolysis to deposit simple substance palladium on a cathode;
s4: and taking the cathode deposited with the elemental palladium as an anode, adding an electrolyte containing chloride ions, carrying out anion membrane electrolysis to produce a solution, and concentrating and crystallizing the electrolyzed anode solution to obtain the palladium chloride.
Further, the pretreatment in step S1 is a thiocyanate decoppering and oxidation gel breaking treatment.
Further, the liquid membrane extraction of the pretreated waste colloidal palladium activation solution in step S2 includes the following steps:
(1) forming a membrane phase by using a mobile carrier, a surfactant, a reinforcing agent and a membrane solvent, mixing the membrane phase with an internal phase reagent, and stirring to obtain an emulsion liquid membrane;
(2) mixing the pretreated waste colloid palladium activation solution with the emulsion liquid membrane, and then fully oscillating to form a W/O/W type multiple emulsion liquid membrane system;
(3) standing and layering the W/O/W type multiple emulsion membrane system (enriching Pd2+The emulsion is layered with the residual liquid under the action of gravity due to density difference), and then the residual liquid on the upper layer is removed to obtain the emulsion;
(4) and heating the emulsion for demulsification, cooling, standing for layering, removing the upper layer liquid (the upper layer is an organic oil phase), and taking the lower layer aqueous solution to obtain the aqueous solution rich in palladium. The mechanism of obtaining the palladium-rich aqueous solution by performing liquid membrane extraction on the pretreated waste colloidal palladium activation solution is shown in fig. 1: firstly, a mobile carrier generates a complex reaction at the interface of a membrane phase and an external water phase; under the action of mass transfer force, the generated complex is directionally diffused in a membrane phase and carries out back extraction reaction with an internal phase reagent at the junction of the membrane phase and the inward direction, and the mobile carrier is decomplexed to generate a new complex which is accumulated in the internal phase; and returning the decomplexed mobile carrier to the membrane phase, and repeating the mass transfer and migration process. H+For transport of fluid carriers to and from two interfaces within the membrane
Provide power and enable Pd2+The inverse concentration gradient migrates from the outer phase into the inner aqueous phase.
Further, in the step (1), the flow carrier is N503 extractant (N, N-di (1-methylheptyl) acetamide), the surfactant is Span80, the reinforcing agent is liquid paraffin, the membrane solvent is sulfonated kerosene, and the internal phase reagent is 0.2mol/L of Ethylene Diamine Tetraacetic Acid (EDTA) aqueous solution; the mobile carrier accounts for 5-10% of the volume of the membrane phase, the surfactant accounts for 2-6% of the volume of the membrane phase, the reinforcing agent accounts for 1-5% of the volume of the membrane phase, and the balance is a membrane solvent; the volume ratio of the membrane phase to the internal phase is 1: 1.
Further, the volume ratio of the waste colloidal palladium activating solution to the emulsion membrane in the step (2) is 1: 5.
Further, step (4): and (3) placing the emulsion in a water bath kettle, heating and demulsifying for 0.5-1 hour, cooling to room temperature, standing for layering after cooling, and removing an upper layer liquid (organic oil phase) to obtain a water solution rich in palladium.
Further, the step of electrolyzing the cationic membrane in the step S3 to deposit elemental palladium on the cathode includes the following steps:
(1) dividing the electrolytic cell into a cathode chamber and an anode chamber by using a cation membrane, taking inert electrodes as a cathode and an anode, and adding the water solution rich in palladium into the cathode chamber;
(2) and adding anolyte into the anode chamber, then electrifying and electrolyzing, and depositing elemental palladium on the cathode at normal temperature.
Further, the inert electrode in the step (1) is a titanium mesh; in the step (2), the anolyte is a sodium hydroxide solution with the concentration of 0.02-0.05 mol/L; the electrolysis time is 1-2 hours. The aqueous solution rich in palladium is used as catholyte, cation membrane electrolysis is carried out, and the reaction process of depositing elemental palladium on the cathode is shown in figure 2: under the action of an external direct current electric field, H+Reducing the hydrogen gas at a cathode, allowing sodium ions to penetrate through a cation membrane to enter a cathode chamber, reducing palladium ions at the cathode chamber to generate a palladium simple substance, and generating oxygen gas by an anode reaction, wherein the reaction formula is as follows:
and (3) anode reaction: 4OH--4e＝O2↑+2H2O
And (3) cathode reaction: pd2++4e＝Pd↓
2H++2e＝H2↑
Further, the anion membrane electrolytic solution in step S4 includes the steps of:
(1) an anion membrane is used for dividing the electrolytic cell into a cathode chamber and an anode chamber, a cathode for depositing simple substance palladium is used as an anode, an inert electrode is used as a cathode, electrolyte containing chloride ions is added into the cathode chamber and the anode chamber,electrolyzing at room temperature to obtain electrolyzed anolyte (the anolyte is PdCl)4 2-)；
(2) And concentrating and crystallizing the electrolyzed anode solution to obtain the palladium chloride.
Further, the electrolyte in the step (1) is hydrochloric acid with the concentration of 0.25-1.0 mol/L; the electrolysis time is 1-2.5 hours. Taking the cathode for depositing the elemental palladium as an anode and hydrochloric acid as electrolyte, and carrying out a cathode film electrolysis solution-making reaction process as shown in fig. 3: under the action of an external direct current electric field, Cl-The Pd generated by anode electrolysis enters the anode chamber through the anion membrane2+With Cl-Combined to produce PdCl4 2-And the cathode generates hydrogen evolution reaction, and the reaction formula is as follows:
and (3) anode reaction: 2Cl--2e＝Cl2↑
Pd-2e＝Pd2+
Pd2++4Cl-＝PdCl4 2-
And (3) cathode reaction: 2H++2e＝H2↑
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for recovering palladium chloride in the waste colloidal palladium activating solution, the liquid membrane extraction process is combined with the ionic membrane electrolysis and liquid making process, so that compared with the traditional process, the process is simplified and the cost is reduced; on the other hand, a small amount of aqua regia is used in the recovery process of the method, so that the complicated nitrate removing process is omitted, and the pollution to the environment is reduced, thereby improving the social and economic benefits and the environmental benefits;
(2) the method for recovering palladium chloride from the waste colloidal palladium activating solution is suitable for recovering the waste colloidal palladium activating solution with low palladium content, and the recovery rate of palladium chloride in the waste colloidal palladium activating solution is high.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a diagram of the migration mechanism of the liquid membrane extraction of palladium according to the present invention;
FIG. 2 is a schematic diagram of the reaction of the cathode to deposit elemental palladium in the cation membrane electrolysis of the present invention;
FIG. 3 is a reaction scheme of the anion membrane electrolyte according to the present invention;
FIG. 4 is an XRD pattern of palladium chloride prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for recovering palladium chloride in waste colloidal palladium activation solution comprises the following steps:
s1: pretreating a waste colloidal palladium activating solution: taking 250mL of waste colloid palladium activation solution, adding 1.42g of sodium thiocyanate and 0.33g of sodium sulfite, and aging at 35 ℃ for 12 hours to remove copper; adding 20mL of aqua regia into the colloidal palladium activation solution after copper removal, heating at 100 ℃ for 3 minutes for oxidation gel breaking treatment, and cooling the solution to room temperature;
s2: performing liquid membrane extraction on the waste colloidal palladium activation solution pretreated by the S1 to obtain a palladium-rich aqueous solution; the liquid membrane extraction comprises the following steps:
(1) mixing 9% N503 extractant (9% refers to that the N503 extractant accounts for 9% of the volume of the membrane phase, the balance is sulfonated kerosene), 4% Span80, 2% liquid paraffin and sulfonated kerosene in a beaker to form a membrane phase, then mixing 20mL of the membrane phase and 20mL of 0.2mol/L ethylenediaminetetraacetic acid aqueous solution (internal phase reagent) in a 100mL beaker, and fully stirring to obtain a white emulsion liquid membrane;
(2) mixing 200mL of waste colloidal palladium activation solution pretreated by S1 with 40mL of white emulsion film, and fully oscillating to form a W/O/W type multiple emulsion film system;
(3) standing and layering the obtained W/O/W type multiple emulsion membrane system to enrich Pd2+The emulsion and the residual liquid are layered due to density difference under the action of gravity, and the residual liquid on the upper layer is removed after standing to obtain the emulsion;
(4) placing the obtained emulsion in a water bath kettle, heating for demulsification for 40 minutes, naturally cooling to room temperature, standing for layering, removing the upper layer liquid (the upper layer is an organic oil phase), and taking the lower layer aqueous solution to obtain a palladium-rich aqueous solution; separating out the water solution rich in palladium and calculating the extraction rate;
s3: the obtained water solution rich in palladium is used as catholyte to carry out cation membrane electrolysis, and elemental palladium is deposited on a cathode, and the method comprises the following steps:
(1) dividing the electrolytic cell into a cathode chamber and an anode chamber by using a cation membrane, taking a titanium net as a cathode and an anode, and adding the water solution rich in palladium into the cathode chamber;
(2) then 100mL of 0.05mol/L sodium hydroxide solution is added into the anode chamber to be used as anolyte, direct current is electrified for electrolysis for 2 hours at room temperature, and elemental palladium is deposited on the cathode titanium mesh;
s4: taking a titanium mesh deposited with elemental palladium as an anode and 1mol/L hydrochloric acid as electrolyte to carry out anion membrane electrolyte preparation, and the method comprises the following steps:
(1) an anion membrane is used for dividing the electrolytic cell into a cathode chamber and an anode chamber, a titanium mesh for depositing simple substance palladium is used as an anode, an inert electrode is used as a cathode, then 100mL of hydrochloric acid (electrolyte) with the concentration of 1mol/L is respectively added into the cathode chamber and the anode chamber, and direct current is electrified at room temperature for electrolysis for 2.5 hours to obtain an electrolyzed anolyte (the anolyte is PdCl)4 2-)；
(2) And concentrating and crystallizing the electrolyzed anode solution to obtain the palladium chloride.
After measurement and calculation, the extraction rate of the liquid membrane extraction palladium in the example 1 is 96.6%, and the recovery rate of the palladium chloride recovered by the ion membrane electrolysis is 98.79%.
Example 2
A method for recovering palladium chloride in waste colloidal palladium activation solution comprises the following steps:
s1: pretreating a waste colloidal palladium activating solution: taking 250mL of waste colloid palladium activation solution, adding 1.42g of sodium thiocyanate and 0.33g of sodium sulfite, and aging at 35 ℃ for 12 hours to remove copper; adding 20mL of aqua regia into the colloidal palladium activation solution after copper removal, heating at 100 ℃ for 3 minutes for oxidation gel breaking treatment, and cooling the solution to room temperature;
s2: performing liquid membrane extraction on the waste colloidal palladium activation solution pretreated by the S1 to obtain a palladium-rich aqueous solution; the liquid membrane extraction comprises the following steps:
(1) mixing a 5% N503 extraction agent (5% means that the N503 extraction agent accounts for 5% of the volume of the membrane phase, and the balance is sulfonated kerosene), 6% Span80, 5% liquid paraffin and sulfonated kerosene in a beaker to form a membrane phase, then mixing 20mL of the membrane phase and 20mL of 0.2mol/L ethylenediaminetetraacetic acid aqueous solution (internal phase reagent) in a 100mL beaker, and fully stirring to obtain a white emulsion liquid membrane;
(2) mixing 200mL of waste colloidal palladium activation solution pretreated by S1 with 40mL of white emulsion film, and fully oscillating to form a W/O/W type multiple emulsion film system;
(3) standing and layering the obtained W/O/W type multiple emulsion membrane system to enrich Pd2+The emulsion and the residual liquid are layered due to density difference under the action of gravity, and the residual liquid on the upper layer is removed after standing to obtain the emulsion;
(4) placing the obtained emulsion in a water bath kettle, heating for demulsification for 30 minutes, naturally cooling to room temperature, standing for layering, removing the upper layer liquid (the upper layer is an organic oil phase), and taking the lower layer aqueous solution to obtain a palladium-rich aqueous solution; separating out the water solution rich in palladium and calculating the extraction rate;
s3: the obtained water solution rich in palladium is used as catholyte to carry out cation membrane electrolysis, and elemental palladium is deposited on a cathode, and the method comprises the following steps:
(1) dividing the electrolytic cell into a cathode chamber and an anode chamber by using a cation membrane, taking a titanium net as a cathode and an anode, and adding the water solution rich in palladium into the cathode chamber;
(2) then 100mL of 0.02mol/L sodium hydroxide solution is added into the anode chamber as anolyte, direct current is electrified at room temperature for electrolysis for 1 hour, and elemental palladium is deposited on the titanium mesh;
s4: taking a titanium mesh deposited with elemental palladium as an anode and 0.5mol/L hydrochloric acid as electrolyte to carry out anion membrane electrolyte preparation, and the method comprises the following steps:
(1) an anion membrane is used for dividing the electrolytic bath into a cathode chamber and an anode chamber, a titanium mesh for depositing simple substance palladium is used as an anode, an inert electrode is used as a cathode, then 100mL of 0.5mol/L hydrochloric acid (electrolyte) is respectively added into the cathode chamber and the anode chamber, and direct current is electrified at room temperature for electrolysis for 1.5 hours to obtain an electrolyzed anolyte (the anolyte is PdCl)4 2-)；
(2) And concentrating and crystallizing the electrolyzed anode solution to obtain the palladium chloride.
After measurement and calculation, the extraction rate of the liquid membrane extraction palladium in the embodiment 2 is 96.3%, and the recovery rate of the palladium chloride recovered by the ion membrane electrolysis is 98.56%.
Example 3
A method for recovering palladium chloride in waste colloidal palladium activation solution comprises the following steps:
s1: pretreating a waste colloidal palladium activating solution: taking 250mL of waste colloid palladium activation solution, adding 1.42g of sodium thiocyanate and 0.33g of sodium sulfite, and aging at 35 ℃ for 12 hours to remove copper; adding 20mL of aqua regia into the colloidal palladium activation solution after copper removal, heating at 100 ℃ for 3 minutes for oxidation gel breaking treatment, and cooling the solution to room temperature;
s2: performing liquid membrane extraction on the waste colloidal palladium activation solution pretreated by the S1 to obtain a palladium-rich aqueous solution; the liquid membrane extraction comprises the following steps:
(1) mixing 7% of N503 extractant (7% means that the N503 extractant accounts for 7% of the volume of the membrane phase, and the balance is sulfonated kerosene), 2% of Span80, 1% of liquid paraffin and sulfonated kerosene in a beaker to form a membrane phase, then mixing 20mL of the membrane phase and 20mL of 0.2mol/L ethylenediaminetetraacetic acid aqueous solution (internal phase reagent) in a 100mL beaker, and fully stirring to obtain a white emulsion liquid membrane;
(2) mixing 200mL of waste colloidal palladium activation solution pretreated by S1 with 40mL of white emulsion film, and fully oscillating to form a W/O/W type multiple emulsion film system;
(3) standing and layering the obtained W/O/W type multiple emulsion membrane system to enrich Pd2+The emulsion and the residual liquid are layered due to density difference under the action of gravity, and the residual liquid on the upper layer is removed after standing to obtain the emulsion;
(4) placing the obtained emulsion in a water bath kettle, heating for demulsification for 60 minutes, naturally cooling to room temperature, standing for layering, removing the upper layer liquid (the upper layer is an organic oil phase), and taking the lower layer aqueous solution to obtain a palladium-rich aqueous solution; separating out the water solution rich in palladium and calculating the extraction rate;
s3: the obtained water solution rich in palladium is used as catholyte to carry out cation membrane electrolysis, and elemental palladium is deposited on a cathode, and the method comprises the following steps:
(1) dividing the electrolytic cell into a cathode chamber and an anode chamber by using a cation membrane, taking a titanium net as a cathode and an anode, and adding the water solution rich in palladium into the cathode chamber;
(2) then 100mL of 0.03mol/L sodium hydroxide solution is added into the anode chamber to be used as anolyte, direct current is electrified for electrolysis for 1.5 hours at room temperature, and elemental palladium is deposited on a cathode titanium mesh;
s4: taking a titanium mesh deposited with elemental palladium as an anode and 0.25mol/L hydrochloric acid as electrolyte to carry out anion membrane electrolyte preparation, and the method comprises the following steps:
(1) an anion membrane is used for dividing the electrolytic cell into a cathode chamber and an anode chamber, a titanium net for depositing simple substance palladium is used as an anode, an inert electrode is used as a cathode, then 100mL of 0.25mol/L hydrochloric acid (electrolyte) is respectively added into the cathode chamber and the anode chamber, and direct current is electrified at room temperature for electrolysis for 1 hour to obtain electrolyzed anolyte (anolyte)The polar liquid is PdCl4 2-)；
(2) And concentrating and crystallizing the electrolyzed anode solution to obtain the palladium chloride.
After measurement and calculation, the extraction rate of the liquid membrane extraction palladium in the embodiment 3 is 96.2%, and the recovery rate of the palladium chloride recovered by the ion membrane electrolysis is 98.37%.
Example 4
The palladium chloride obtained in the example 1 is characterized by X-ray diffraction, and the result is shown in fig. 4, and the obtained palladium chloride crystal shown in fig. 4 has a sharp diffraction peak and high crystallinity, and has good matching property compared with a standard palladium chloride card, thereby proving that the palladium chloride crystal with better crystallinity can be prepared by using the method of the invention.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (4)
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