CN113106252B - Method for removing palladium from silver electrolyte by utilizing multifunctional silica gel adsorbent - Google Patents
Method for removing palladium from silver electrolyte by utilizing multifunctional silica gel adsorbent Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000000741 silica gel Substances 0.000 title claims abstract description 98
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 98
- 239000003463 adsorbent Substances 0.000 title claims abstract description 93
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 81
- 239000004332 silver Substances 0.000 title claims abstract description 81
- 239000003792 electrolyte Substances 0.000 title claims abstract description 60
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 238000004458 analytical method Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000008929 regeneration Effects 0.000 claims description 15
- 238000011069 regeneration method Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 239000011669 selenium Substances 0.000 claims description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000012492 regenerant Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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- 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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- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of separation of noble metals in solution, in particular to a method for removing palladium from silver electrolyte by utilizing a multifunctional silica gel adsorbent. The method comprises the following steps: 1) Obtaining a multifunctional silica gel adsorbent; 2) Adsorption: adding a multifunctional silica gel adsorbent into silver electrolyte for stirring and adsorbing treatment; wherein, the silver electrolyte comprises the following components in percentage by weight: 25-250 g/L of silver, 0.005-1 g/L of palladium, 0-40 g/L of copper and 1-15 g/L of nitric acid; the addition amount of the multifunctional silica gel adsorbent is 0.5-100 g/L; 3) Analyzing; 4) And (5) regenerating. The method for removing palladium from the silver electrolyte by utilizing the multifunctional silica gel adsorbent can realize high-efficiency selective adsorption of palladium, wherein the adsorption rate of palladium in the silver electrolyte with the silver content of 25-250 g/L and the palladium content of 0.005-1 g/L is more than 99%, and the adsorption rate of silver is 0%.
Description
Technical Field
The invention relates to the technical field of separation of noble metals in solution, in particular to a method for removing palladium from silver electrolyte by utilizing a multifunctional silica gel adsorbent.
Background
The refining of silver mainly adopts an electrolytic refining method, and the electrolyte is silver nitrate solution. As electrorefining proceeds, the metal in the anode plate is continuously dissolved, resulting in Pd 2+ 、Cu 2+ 、Bi 3+ The plasma builds up in the silver electrolyte. After a few electrolysis cycles, metals in the electrolyte are continuously enriched and increased, are easily reduced into metals, and are precipitated and separated out on a cathode, so that the quality of silver products is influenced, wherein palladium becomes a main impurity influencing the quality of the silver products due to the fact that palladium and silver reduction potentials are similar, and therefore, the purification and the removal of palladium from the silver electrolyte are very necessary.
Many studies and developments have been made so far for a process for removing palladium from silver electrolyte. Such as substitution method, concentrated baking method, precipitation method, extraction and separation palladium method, active carbon adsorption method, ion exchange resin adsorption and separation palladium method, etc. The method can separate noble metal palladium from silver electrolyte to a certain extent, but the separation process is not thorough, and the separated silver-containing solution cannot be directly returned to the silver electrolysis process, so that the subsequent treatment process is complicated.
The invention discloses a method for separating palladium from silver electrolyte, which is disclosed in the Chinese patent application document with the application number of 201110260270.2, and adopts amidocyanogen to adsorb the silver electrolyte which is primarily purified and removed with heavy metal impurities, so that palladium in the solution is loaded on the resin, then an acidic thiourea solution is adopted for carrying out primary analysis to obtain a palladium-containing analysis solution, then a high-concentration hydrochloric acid solution is adopted for carrying out secondary analysis to obtain the silver-containing analysis solution, and the resin after the secondary analysis is subjected to regeneration treatment by adopting a hydroxylamine hydrochloride solution again and then returns to the resin to adsorb the palladium-silver-containing electrolyte. The separation of palladium and silver can be effectively realized, the liquid after adsorption can be directly returned to silver electrolysis, but the analysis liquid adopts acidic thiourea and high-concentration hydrochloric acid, the analysis can be completed only by secondary analysis, the adsorption rate of silver is more than 5%, and the content of Ag in the precious metal Pd in the analysis liquid is more than Pd, so that the recovery of the precious metal Pd increases the Ag separation process.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a method for removing palladium from a silver electrolyte using a multifunctional silica gel adsorbent, which can achieve efficient selective adsorption of palladium.
In order to achieve the above object, the method for removing palladium from silver electrolyte by using multifunctional silica gel adsorbent according to the present invention is characterized by comprising the steps of:
1) Multifunctional silica gel adsorbent
The multifunctional silica gel adsorbent is a compound of a chemical formula I:
[(O 3/2 )Si(CH 2 ) x NH(CH 2 CH 2 NH) y H] a [Si(O 4/2 )] b (formula I);
wherein x is an integer from 2 to 12; y is an integer from 0 to 100; a, b are integers, and a: b is in the range of 0.000001 to 100;
2) Adsorption of
Adding a multifunctional silica gel adsorbent into silver electrolyte for stirring and adsorbing treatment; wherein, the silver electrolyte comprises the following components in percentage by weight: 25-250 g/L of silver, 0.005-1 g/L of palladium, 0-40 g/L of copper and 1-15 g/L of nitric acid; the addition amount of the multifunctional silica gel adsorbent is 0.5-100 g/L;
3) Analysis:
filtering the silver electrolyte after the adsorption is completed to obtain a silver electrolyte after palladium is removed and a multifunctional silica gel adsorbent adsorbed with palladium, and adding the multifunctional silica gel adsorbent adsorbed with palladium into an acidic resolving agent for resolving reaction;
4) Regeneration:
and after the analysis reaction is completed, filtering to obtain the analyzed multifunctional silica gel adsorbent, adding the multifunctional silica gel adsorbent into an alkaline regenerant for regeneration reaction, and finally obtaining the recyclable multifunctional silica gel adsorbent.
Preferably, the particle size of the multifunctional silica gel adsorbent in the step 2) is 37 to 500um.
Preferably, the acid resolving agent in the step 3) is one of 2 to 12mol/L hydrochloric acid solution, 2 to 6mol/L nitric acid solution and 1 to 3mol/L sulfuric acid solution.
Preferably, the alkaline regenerant in the step 4) is one of sodium hydroxide of 0.00001-0.01 mol/L, potassium hydroxide of 0.00001-0.01 mol/L, sodium bicarbonate of 0.01-2 mol/L, sodium carbonate of 0.01-2 mol/L and ammonia of 0.01-2 mol/L.
The synthesis steps of the multifunctional silica gel adsorbent are as follows: in a first step, the (CH 3 O) 3 Si(CH 2 ) x Cl and polyethylene polyamine NH 2 (CH 2 CH 2 NH) y H, heating and refluxing for 30 minutes to 48 hours at the temperature of 20 to 160 ℃ to obtain a polyamine silane coupling agent; and secondly, heating and refluxing the polyamine silane coupling agent in a solvent system and silica gel at 20-160 ℃ for 30 minutes-48 hours to obtain the multifunctional silica gel adsorbent shown in the chemical formula I.
Preferably, in the step 2), the silver electrolyte includes the following components and contents thereof: 50-100 g/L of silver, 0.02-0.1 g/L of palladium, 10-40 g/L of copper, 10-15 g/L of nitric acid, 0-15 mg/L of bismuth, 0-30 mg/L of selenium and 0-20mg/L of tellurium.
Preferably, in the step 2), the adding amount of the multifunctional silica gel adsorbent is 20-50g/L.
Preferably, in the step 2), the temperature of the adsorption treatment is 20 to 80 ℃ and the time is 15 minutes to 8 hours.
Preferably, in the step 3), the temperature of the analysis reaction is 20 to 80 ℃, the time is 15 minutes to 6 hours, and the addition amount of the multifunctional silica gel adsorbent after adsorption in the analysis reaction is 50 to 500g/L.
Preferably, in the step 4), the temperature of the regeneration reaction is 20 to 80 ℃, the time is 15 minutes to 6 hours, and the addition amount of the multifunctional silica gel adsorbent after analysis in the regeneration reaction is 50 to 500g/L.
The invention utilizes the principle that the multifunctional silica gel adsorbent removes palladium from silver electrolyte, and utilizes the principle that the amine group of the multifunctional silica gel adsorbent absorbs different metals under different pH values, realizes selective adsorption of palladium by regulating and controlling the addition amount of the multifunctional silica gel adsorbent, controlling the nitric acid content in the solution and further regulating and controlling the pH value, and controls the concentration of acid and alkali of an acid resolving agent and an alkaline regenerating agent to elute and regenerate palladium.
Compared with the prior method for removing palladium from silver electrolyte, the invention has the advantages that:
1, the invention adopts the multifunctional silica gel adsorbent to realize the efficient selective adsorption of palladium, the adsorption rate of palladium in silver electrolyte with the silver content of 25 g-250 g/L and the palladium content of 0.005-1 g/L reaches more than 99 percent, and the adsorption rate of silver is 0 percent.
2, the multifunctional silica gel adsorbent has high regeneration utilization rate, the one-time analysis rate reaches more than 98 percent, the 10-time regeneration utilization rate is more than 90 percent, and the analysis rate is more than 97 percent.
And 3, after palladium is removed from the silver electrolyte by utilizing the multifunctional silica gel adsorbent, the silver electrolyte can be returned to the electrolytic tank for recycling without damaging the properties of the silver electrolyte.
4, after the multifunctional silica gel adsorbent after the desorption is analyzed, palladium can be efficiently recovered.
The method for removing palladium from the silver electrolyte by utilizing the multifunctional silica gel adsorbent has the characteristics of simplicity in operation, low cost, high efficiency and environmental friendliness.
Detailed Description
For a better understanding of the present invention, the following detailed description will be given in connection with specific examples.
Example 1 a method for removing palladium from silver electrolyte using a multifunctional silica gel adsorbent comprising the steps of:
1) Preparation of multifunctional silica gel adsorbent
Tetraethylenepentamine (13.68 kg,72 mol) and (CH) were charged into a 100L reactor 3 O) 3 Si(CH 2 ) 3 Cl (48 mol) was stirred and heated at 120℃for 6 hours, then cooled to 60℃and ethanol (10L) was added thereto and refluxed for 2 hours until the liquid became transparent, cooled and transferred to a 200L reactor, and xylene (80.0L) and silica gel (32.0 kg,37 to 500 μm,) The temperature of the oil bath is set at 150 ℃, and after the temperature of the oil bath reaches a set value, ethanol is collected, and the whole process lasts for 3 hours. Removing liquid, adding water (100L) into the solid, stirring for 30min, filtering, adding more water (100L) into the solid, stirring the mixture for 30min, filtering, and drying to obtain multifunctional silica gel adsorbent; the chemical formula of the multifunctional silica gel adsorbent is as follows: [ (O) 3/2 )Si(CH 2 ) x NH(CH 2 CH 2 NH) y H] a [Si(O 4/2 )] b (formula I); wherein x=3; y=4.
2) Adsorption of
Weighing 20g of multifunctional silica gel adsorbent with the particle size of 100um, adding the multifunctional silica gel adsorbent into 1000ml of silver electrolyte, wherein the silver electrolyte contains 60.79g/L of silver, 0.063g/L of palladium, 34.23g/L of copper, 12.6g/L of nitric acid, 5.6mg/L of bismuth, 12.1mg/L of selenium and 9.6mg/L of tellurium; after magnetically stirring at room temperature for 4 hours, the mixture was filtered and subjected to ICP-MS measurement, and the results are shown in Table 1.
TABLE 1 adsorption of silver electrolyte by multifunctional silica gel adsorbents
As can be seen from Table 1, the use of the multifunctional silica gel adsorbent in this example can realize efficient selective adsorption of palladium, and the adsorption rate of palladium in the silver electrolyte having a silver content of 60.79g/L, a palladium content of 0.063g/L and a copper content of 34.23g/L reaches 99.52%, the adsorption rate of silver is 0%, the adsorption rate of copper is 0%, the adsorption rate of bismuth is 0%, the adsorption rate of selenium is 0% and the adsorption rate of tellurium is 0%.
3) Resolution
Filtering silver electrolyte after adsorption to obtain multifunctional silica gel adsorbent, adding the multifunctional silica gel adsorbent into 100ml of 3mol/L nitric acid solution, stirring at room temperature for 2h, filtering, measuring by ICP-MS, wherein the concentration of palladium is 0.614g/L, and the resolution is 0.622 g/L100 x 10 -3 L/[(0.063-0.0003)g/L*1L]＝98.73％。
4) Regeneration of
After the analysis reaction is completed, filtering to obtain the analyzed multifunctional silica gel adsorbent, adding the multifunctional silica gel adsorbent into 50ml of 2mol/L ammonia water solution, stirring for 2 hours at 40 ℃, filtering, washing the solid with deionized water until the pH value measured by the water is close to neutral, and vacuum drying the solid at 60 ℃ to obtain the recyclable multifunctional silica gel adsorbent.
The adsorption effect and the resolution of the multifunctional silica gel adsorbent on the silver electrolyte after repeated use are shown in table 2:
TABLE 2 adsorption effect and resolution ratio of multifunctional silica gel adsorbent to silver electrolyte after repeated use
As can be seen from Table 2, the multifunctional silica gel adsorbent of this example has a high regeneration rate, a one-time analysis rate of 98% or more, a 10-time adsorption rate of >90% and an analysis rate of >97%.
Example 2 a method for removing palladium from silver electrolyte using a multifunctional silica gel adsorbent comprising the steps of:
1) Preparation of multifunctional silica gel adsorbent
Into a 100L reactor were charged diethylenetriamine (7.49 kg,72 mol) and (CH) 3 O) 3 Si(CH 2 ) 3 Cl (48 mol) was stirred and heated at 160℃for 8 hours, then cooled to 60℃and ethanol (10L) was added thereto and refluxed for 2 hours until the liquid became transparent, cooled and transferred to a 200L reactor, and xylene (80.0L) and silica gel (32.0 kg,37 to 500 μm,) The temperature of the oil bath is set at 150 ℃, and after the temperature of the oil bath reaches a set value, ethanol is collected, and the whole process lasts for 3 hours. Removing liquid, adding water (100L) into the solid, stirring for 30min, filtering, adding more water (100L) into the solid, stirring for 30min, filtering, and drying to obtain multifunctional silica gel adsorbent with chemical formula of [ (O) 3/2 )Si(CH 2 ) x NH(CH 2 CH 2 NH) y H] a [Si(O 4/2 )] b (formula I); where x=3 and y=2.
2) Adsorption of
100g of multifunctional silica gel adsorbent with the particle size of 50um is weighed and added into 1000ml of silver electrolyte, wherein the silver electrolyte contains 50.02g/L of silver, 0.023g/L of palladium, 10.65g/L of copper, 10g/L of nitric acid, 12.6mg/L of bismuth, 5.3mg/L of selenium and 4.9mg/L of tellurium; after magnetically stirring at 50℃for 1h, the mixture was filtered and subjected to ICP-MS measurement, and the results are shown in Table 3.
TABLE 3 adsorption of silver electrolyte by multifunctional silica gel adsorbents
3) Resolution
After the adsorption is completed, the silver electrolyte is filtered to obtain the multifunctional silica gel adsorbent after the adsorption, and the multifunctional silica gel adsorbent is added into 100ml of 2mol/L hydrochloric acid solution, and after stirring for 1h at 50 ℃, the multifunctional silica gel adsorbent is filtered, and is subjected to ICP-MS (inductively coupled plasma-mass spectrometry) sample measurement, wherein the palladium concentration is 0.023g/L, and the resolution ratio is 100%.
4) Regeneration of
After the analysis reaction is completed, filtering to obtain the analyzed multifunctional silica gel adsorbent, adding the multifunctional silica gel adsorbent into 100ml of 1mol/L sodium bicarbonate solution, stirring for 2 hours at 40 ℃, filtering, washing the solid with deionized water until the pH value measured by the water is close to neutral, and vacuum drying the solid at 60 ℃ to obtain the recyclable multifunctional silica gel adsorbent.
The adsorption effect and the resolution of the multifunctional silica gel adsorbent on the silver electrolyte after repeated use are shown in table 4:
TABLE 4 adsorption effect and resolution ratio of multifunctional silica gel adsorbent to silver electrolyte after repeated use
Example 3 a method for removing palladium from silver electrolyte using a multifunctional silica gel adsorbent comprising the steps of:
1) Preparation of multifunctional silica gel adsorbent
Polyethylene polyamine (27.36 kg,72 mol) and (CH) were added to a 100L reactor 3 O) 3 Si(CH 2 ) 3 Cl (48 mol) was stirred and heated at 160℃for 8 hours, then cooled to 60℃and ethanol (10L) was added thereto and refluxed for 2 hours until the liquid became transparent, cooled and transferred to a 200L reactor, and xylene (80.0L) and silica gel (32.0 kg,37 to 500 μm,) The temperature of the oil bath is set at 150 ℃, and after the temperature of the oil bath reaches a set value, ethanol is collected, and the whole process lasts for 3 hours. Removing liquid, adding water (100L) into the solid, stirring for 30min, filtering, adding more water (100L) into the solid, stirring for 30min, filtering, and drying to obtain multifunctional silica gel adsorbent with chemical formula of [ (O) 3/2 )Si(CH 2 ) x NH(CH 2 CH 2 NH) y H] a [Si(O 4/2 )] b Wherein x=3 and y=9.
2) Adsorption of
Weighing 10g of multifunctional silica gel adsorbent with the particle size of 300um, adding the multifunctional silica gel adsorbent into 1000ml of silver electrolyte, wherein the silver electrolyte contains the components of silver 100.06g/L, palladium 0.098g/L, copper 39.18g/L, nitric acid 15g/L, bismuth 14.9mg/L, selenium 29.7mg/L and tellurium 18.6mg/L; after 15 minutes of magnetic stirring at 80 ℃, filtration, ICP-MS measurement, results are shown in table 5.
Table 5 adsorption of silver electrolyte by multifunctional silica gel adsorbent
3) Resolution
After the adsorption is completed, the silver electrolyte is filtered to obtain the multifunctional silica gel adsorbent after the adsorption, and the multifunctional silica gel adsorbent is added into 100ml of 3mol/L sulfuric acid solution, and after stirring for 15 minutes at 80 ℃, the multifunctional silica gel adsorbent is filtered, and is subjected to ICP-MS (inductively coupled plasma-mass spectrometry) sample measurement, wherein the concentration of palladium is 0.968g/L, and the resolution ratio is 99.69%.
4) Regeneration of
After the analysis reaction is completed, filtering to obtain the analyzed multifunctional silica gel adsorbent, adding the multifunctional silica gel adsorbent into 200ml of 0.01mol/L potassium hydroxide solution, stirring for 15 minutes at 80 ℃, filtering, washing the solid with deionized water until the pH value measured by the water is close to neutral, and vacuum drying the solid at 60 ℃ to obtain the recyclable multifunctional silica gel adsorbent.
The adsorption effect and the resolution of the multifunctional silica gel adsorbent on the silver electrolyte after repeated use are shown in table 6:
table 6 adsorption effect and resolution ratio of multifunctional silica gel adsorbent to silver electrolyte after repeated use
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (2)
1. A method for removing palladium from silver electrolyte using a multifunctional silica gel adsorbent comprising the steps of:
1) Multifunctional silica gel adsorbent
The multifunctional silica gel adsorbent is a compound of a chemical formula I:
[(O 3/2 )Si(CH 2 ) x NH(CH 2 CH 2 NH) y H] a [Si(O 4/2 )] b (formula I);
wherein x is an integer from 2 to 12; y is an integer from 0 to 100; a, b are integers, and a: b is in the range of 0.000001 to 100;
2) Adsorption of
Adding a multifunctional silica gel adsorbent into silver electrolyte for stirring and adsorbing treatment; wherein, the silver electrolyte comprises the following components in percentage by weight: 25-250 g/L of silver, 0.005-1 g/L of palladium, 0-40 g/L of copper and 1-15 g/L of nitric acid; the addition amount of the multifunctional silica gel adsorbent is 0.5-100 g/L;
3) Analysis:
filtering the silver electrolyte after the adsorption is completed to obtain a silver electrolyte after palladium is removed and a multifunctional silica gel adsorbent adsorbing palladium, and adding the multifunctional silica gel adsorbent adsorbing palladium into an acidic resolving agent for resolving reaction;
4) Regeneration:
after the analysis reaction is completed, filtering to obtain an analyzed multifunctional silica gel adsorbent, adding the analyzed multifunctional silica gel adsorbent into an alkaline regenerant for regeneration reaction, and finally obtaining the recyclable multifunctional silica gel adsorbent;
the particle size of the multifunctional silica gel adsorbent in the step 2) is 37-500 um;
the acid resolving agent in the step 3) is one of 2-12 mol/L hydrochloric acid solution, 2-6 mol/L nitric acid solution and 1-3 mol/L sulfuric acid solution;
the alkaline regenerant in the step 4) is one of sodium hydroxide with the concentration of 0.00001-0.01 mol/L, potassium hydroxide with the concentration of 0.00001-0.01 mol/L, sodium bicarbonate with the concentration of 0.01-2 mol/L, sodium carbonate with the concentration of 0.01-2 mol/L and ammonia water with the concentration of 0.01-2 mol/L;
in the step 1), the synthesis steps of the multifunctional silica gel adsorbent are as follows: in a first step, the (CH 3 O) 3 Si(CH 2 ) x Cl and polyethylene polyamine NH 2 (CH 2 CH 2 NH) y H, heating and refluxing for 30 minutes to 48 hours at the temperature of 20 to 160 ℃ to obtain a polyamine silane coupling agent; secondly, heating and refluxing the polyamine silane coupling agent in a solvent system and silica gel at 20-160 ℃ for 30 minutes-48 hours to obtain the multifunctional silica gel adsorbent shown in the chemical formula I;
in the step 2), the adding amount of the multifunctional silica gel adsorbent is 20-50 g/L;
in the step 3), the temperature of the analysis reaction is 20-80 ℃, the time is 15 minutes-6 hours, and the addition amount of the multifunctional silica gel adsorbent after adsorption in the analysis reaction is 50-500 g/L;
in the step 4), the temperature of the regeneration reaction is 20-80 ℃, the time is 15 minutes-6 hours, and the addition amount of the multifunctional silica gel adsorbent analyzed in the regeneration reaction is 50-500 g/L;
in the step 2), the temperature of the adsorption treatment is 20-80 ℃ and the time is 15 minutes-8 hours.
2. The method for removing palladium from silver electrolyte using multifunctional silica gel adsorbent according to claim 1, wherein in the step 2), the silver electrolyte comprises the following components and contents: 50-100 g/L of silver, 0.02-0.1 g/L of palladium, 10-40 g/L of copper, 10-15 g/L of nitric acid, 0-15 mg/L of bismuth, 0-30 mg/L of selenium and 0-20mg/L of tellurium.
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| CN102329959A (en) * | 2011-09-05 | 2012-01-25 | 中南大学 | Separation method of palladium from silver electrolyte |
| CN103526233A (en) * | 2013-10-11 | 2014-01-22 | 金川集团股份有限公司 | Method for high-efficiency separation of palladium from silver electrolyte |
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| CN110368905A (en) * | 2019-06-15 | 2019-10-25 | 苏州硒诺唯新新材料科技有限公司 | A kind of sulfydryl amine type functional silica gel material and its application |
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| CN102329959A (en) * | 2011-09-05 | 2012-01-25 | 中南大学 | Separation method of palladium from silver electrolyte |
| CN103526233A (en) * | 2013-10-11 | 2014-01-22 | 金川集团股份有限公司 | Method for high-efficiency separation of palladium from silver electrolyte |
| CN105695750A (en) * | 2016-03-07 | 2016-06-22 | 紫金矿业集团股份有限公司 | Method for removing platinum and palladium out of silver electrolyte and concentrating platinum and palladium |
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