CN102019167A - Functionalized mesoporous molecular sieve and application of functionalized mesoporous molecular sieve in recovering noble metal - Google Patents
Functionalized mesoporous molecular sieve and application of functionalized mesoporous molecular sieve in recovering noble metal Download PDFInfo
- Publication number
- CN102019167A CN102019167A CN2010101098333A CN201010109833A CN102019167A CN 102019167 A CN102019167 A CN 102019167A CN 2010101098333 A CN2010101098333 A CN 2010101098333A CN 201010109833 A CN201010109833 A CN 201010109833A CN 102019167 A CN102019167 A CN 102019167A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- ion
- mesoporous molecular
- noble metal
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 118
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 palladium ions Chemical class 0.000 claims abstract description 41
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 125000003368 amide group Chemical group 0.000 claims abstract description 4
- 229910052737 gold Inorganic materials 0.000 claims description 32
- 239000010931 gold Substances 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 10
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000006396 nitration reaction Methods 0.000 claims description 2
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 27
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- 229910021645 metal ion Inorganic materials 0.000 description 28
- 239000010970 precious metal Substances 0.000 description 21
- 125000000524 functional group Chemical group 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 239000006166 lysate Substances 0.000 description 6
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a functionalized mesoporous molecular sieve and application of the functionalized mesoporous molecular sieve in recovering noble metal. The functionalized mesoporous molecular sieve is a silicon mesoporous molecular sieve grafted with amido or sulfydryl. The application of the functionalized mesoporous molecular sieve in recovering the noble metal comprises the following steps: processing a waste electronic circuit board to obtain metal dissolving solution; regulating the pH of the metal dissolving solution to about 1, and selectively absorbing palladium ions and/or platinum ions in the metal dissolving solution by using the functionalized mesoporous molecular sieve; regulating the pH of the metal dissolving solution to about 2.5, and selectively absorbing aurum ions in the metal dissolving solution by using the functionalized mesoporous molecular sieve; and respectively washing the molecular sieve carried with palladium ions and/or molecular sieve carried with platinum ions and the molecular sieve carried with aurum ions, thereby enabling the noble metal to enter the solution through desorption and simultaneously reactivating the molecular sieve. The method for recovering the noble metal has the advantages of simple process and high noble metal absorption rate, and is environment-friendly.
Description
One, technical field:
The present invention is specifically related to the mesopore molecular sieve of a kind of grafting functional group amino or sulfydryl and reclaims as the application of noble metals such as gold, palladium, platinum at noble metal from the waste electronic wiring board.
Three, background technology:
Data show according to the relevent statistics, contain quite high metal in discarded electronic circuit board, and generally 20～40%, particularly bullion content is quite high, is tens times even hundred times of natural mineral reserve.Wherein comprise 3～8% gold, 0.1～1% platinum and palladium also have metals such as copper that content do not wait, tin, aluminium, nickel, lead certainly.From the content of noble metals such as gold, platinum and palladium, from discarded electronic circuit board, reclaim noble metal and have very big economic benefit, the key of its recovery is how noble metal to be separated from other metals and enrichment.
Common molecular sieve (as SBA-15, MCM-41) is to have a novel nano functional material that is arranged with ordered meso-porous structure, and its duct size homogeneous, the aperture is adjustable in the 2-50nm scope, and higher specific surface area is arranged, and its BET specific area generally can reach 1000m
2About/g.These characteristics make mesopore molecular sieve in fields such as big Molecular Adsorption, catalytic reaction, medicament transport good application prospects be arranged.But these molecular sieves do not have suction-operated to precious metal ion in the aqueous solution.
Therefore, a kind of molecular sieve that in the aqueous solution, precious metal ion is had a selective absorption effect of design with realize noble metal separate with common metal with enrichment highly significant.
Three, summary of the invention:
The primary technical problem that the present invention will solve is to provide a kind of functional mesoporous molecular sieve of energy high selectivity absorption noble metal.
At above-mentioned technical problem, research thinking of the present invention is: make full use of the big advantages of mesopore molecular sieve specific area such as SBA-15, MCM-41, by some absorption precious metal ion functional groups in grafting on the meso-hole structure (as-NH
2Or-SH), thus the function of selective absorption noble metal had.
The following technical scheme of the concrete employing of the present invention:
A kind of functional mesoporous molecular sieve, make by the following method: with silicon is that mesopore molecular sieve places the dry toluene that contains 0.1～0.5mol/L aminopropane or propanethiol to reflux 12～24 hours in 100～120 ℃, filtration and dry with evaporation toluene under 150～180 ℃ of temperature obtains amido or mercapto-functionalized mesopore molecular sieve then.
Described silicon is preferred SBA-15 of mesopore molecular sieve or MCM-41 mesopore molecular sieve, more preferably MCM-41 mesopore molecular sieve.
The prepared functional mesoporous molecular sieve of the present invention, energy high selectivity ADSORPTION OF GOLD ion, platinum ion and palladium ion under acid condition, and the adsorption capacity of functional amido mesopore molecular sieve is more better compared to mercapto-functionalized mesopore molecular sieve.
Second technical problem that the present invention will solve is described functional mesoporous molecular sieve is applied to reclaim noble metals such as gold, platinum and palladium from the waste electronic wiring board.
At above-mentioned technical problem, research thinking of the present invention is: the functional group that utilizes grafting to have to adsorb precious metal ion (as-NH
2Or-SH) mesopore molecular sieve optionally adsorbs precious metal ion, do not adsorb the characteristics of other metal ions under certain condition, effectively with precious metal ion and common metal ion isolation in acid solution; By the pH value of regulator solution, make the precious metal ion desorption that is adsorbed on the molecular sieve simultaneously, realize the enrichment of precious metal ion and reactivating of molecular sieve.
The technical scheme that reclaims noble metals such as gold, platinum and palladium from the waste electronic wiring board of the present invention is specific as follows:
Described recovery method comprises the steps:
(a) the waste electronic wiring board pulverized, separated and obtain non-metal powder and metal dust, metal dust is dissolved with strong acid, contain one or both and gold ion in platinum ion and the palladium ion in the gained dissolving metal liquid;
(b) regulate about the pH value to 1 of dissolving metal liquid, functional mesoporous molecular sieve is put into dissolving metal liquid, at room temperature stirred 8～12 hours, filter the molecular sieve and the filtrate A that are loaded with platinum ion and/or palladium ion accordingly; The functional mesoporous molecular sieve that the application makes is about 1 at pH, all can adsorb by high selectivity for platinum ion and palladium ion, gold ion and other metal ions then continue to stay among the filtrate A, so, be loaded with the molecular sieve of platinum ion or palladium ion or platinum ion and palladium ion accordingly according to the difference of precious metal ion composition in the metallic solution.
(c) clean the molecular sieve that is loaded with platinum ion and/or palladium ion with 3～6M hydrochloric acid (preferred 5M hydrochloric acid), filter and obtain platinum chloride and/or palladium chloride solution and the functional mesoporous molecular sieve that reactivates;
(d) regulate about the pH value to 2.5 of filtrate A, functional mesoporous molecular sieve is put into filtrate A, at room temperature stirred 8～12 hours, filtration obtains carrying golden molecular sieve, clean a year golden molecular sieve with 3～6M hydrochloric acid (preferred 5M hydrochloric acid), filter the functional mesoporous molecular sieve that obtains chlorogold solution and reactivate.The functional mesoporous molecular sieve that the present invention makes, when the pH value is 2.5 left and right sides, can selective absorption gold ion, other metal ions then continue to stay in the filtrate, thereby realize separating of precious metal ion and other general ions.
In above-mentioned recovery method, after the fragmentation of waste electronic wiring board, can adopt ultrafine crusher to pulverize, separate with High-pressure Static Selector then and obtain based on the non-metal powder of glass fibre, resin and be the metal dust of leading with copper, tin, lead, gold, platinum, palladium (, may only contain platinum in the electronic circuit board that has or only contain palladium) etc. about platinum and palladium.
In the scheme of above-mentioned recovery noble metal, the described strong acid of step (a) preferably uses the nitration mixture or the chloroazotic acid of 2: 1 red fuming nitric acid (RFNA) of volume ratio and concentrated hydrochloric acid in order to the dissolution of metals powder.Regulate the pH value in step (b) and the step (d) and can use alkali lye commonly used such as sodium hydroxide solution.Be loaded with the molecular sieve of platinum ion and/or palladium ion and carry golden molecular sieve and handle by 3～6M hydrochloric acid solution, preferably handle, can make to be adsorbed on noble metal desorption on the molecular sieve, enter in the solution by the 5M hydrochloric acid solution, molecular sieve reactivates simultaneously, and is reusable.Mixed solution as for the palladium chloride solution that obtains, platinum chloride solution or palladium bichloride and platinum chloride then can make corresponding noble metal platinum and palladium by existing technologies such as electrolysis; When obtain be the mixed solution of palladium bichloride and platinum chloride the time, by in electrolytic process control current potential difference can obtain palladium and platinum respectively.And chlorogold solution can adopt the hydrometallurgical technology electrolysis to obtain purity is 99.99% gold.
In addition, because the functional mesoporous molecular sieve that the present invention makes has its adsorption capacity for precious metal ion under different condition, those skilled in the art can determine both usage ratio according to the adsorption capacity of precious metal ion content in the pulp slurry and functional mesoporous molecular sieve in actual mechanical process.
Compared with prior art, the present invention adopts the functional mesoporous molecular sieve of energy selective absorption noble metal to reclaim noble metal, and technology is simple, and the acidity of only adjusting solution simply can reach the purpose of precious metal ion separation, parsing and enrichment; The adsorption efficiency height of functional mesoporous molecular sieve, the efficient of its ADSORPTION OF GOLD ion reaches more than 98%, and the efficient of absorption palladium ion and platinum ion is also more than 90%; Removal process of the present invention does not relate to extremely toxic substance, has environment-friendly advantage.
Four, description of drawings
Fig. 1 utilizes SH-MCM-41 to reclaim the process chart of noble metal from the waste electronic wiring board in the embodiment of the invention three.
Five, the specific embodiment
With specific embodiment technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Embodiment one:
1, the grafting of functional group
2.5g MCM-41 powder is placed in contains 0.1mol/L aminopropane (C
3H
7NH
2) in 250 milliliters the dry toluene, under 120 ℃ of temperature, refluxed 18 hours grafting functional group-NH on molecular sieve
2, filter then and mention the MCM-41 powder, and this powder drying under 110 ℃ of temperature was obtained NH to evaporate complete toluene in 12 hours
2-MCM-41 selective absorption noble metal functional molecular sieve.Adopt the grafting functional group-SH that uses the same method, obtain SH-MCM-41 selective absorption noble metal functional molecular sieve.The NH that makes
2The physical and chemical performance of-MCM-41, SH-MCM-41 sees Table 1.
2, the selective absorption of noble metal and desorption
With 50g NH
2-MCM-41 selective absorption noble metal functional molecular sieve is put into 2.5 liters and is contained 276g chlorauride (AuCl
3) and 59g palladium bichloride (PdCl
3) solution in, the pH value of solution is adjusted to 1.0, at room temperature stir after 2 hours and filter out the molecular sieve that is loaded with precious metal ion, measure the content of GOLD FROM PLATING SOLUTION, palladium ion.Clean the molecular sieve that is loaded with precious metal ion with 5M HCl solution then, only contained PdCl
3The solution and the molecular sieve of resolving.Again the functional molecular sieve is put into the solution that contains after the last time filters, the pH value of solution is adjusted to 2.5, equally at room temperature stir and filter the molecular sieve that is loaded with gold ion after 2 hours, measure the content of GOLD FROM PLATING SOLUTION, palladium ion.And clean the molecular sieve be loaded with gold ion with 5M HCl solution, obtain AuCl
3Solution and molecular sieve, molecular sieve can utilize again.
Equally, to adopt SH-MCM-41 be the selective absorption of carrying out noble metal of selective absorption noble metal functional molecular sieve and separate.
NH
2The absorption property of-MCM-41, SH-MCM-41 sees Table 1.
Table 1: physics, chemistry and the absorption property of mesopore molecular sieve before and after the grafting functional group
Table 1 is the situation of physics, chemistry and the absorption precious metal ion performance of three kinds of different molecular sieves.From N
2The cryogenic absorption result of the test can be seen ,-NH
2Or-in the grafting, also successful grafting on the mesoporous inwall of molecular sieve makes the internal diameter of mesopore molecular sieve diminish to the SH group on the molecular sieve surface, as in the grafting-NH
2Behind the group, internal diameter reduces to 2.92nm from 3.09nm, and like this, the specific area of molecular sieve reduces to some extent before and after the grafting functional group, and the BET specific surface is from 1140m
2/ g reduces to 774m
2/ g, but do not have the molecular sieve of grafting functional group not possess the effect of absorption precious metal ion, and grafting the molecular sieve of functional group in acid solution, have the ability of the strong efficient absorption noble metal of selectivity.Can see NH from the adsorption test result
2-MCM-41 molecular sieve almost can adsorbent solution in all precious metal ions, 100% gold ion and 99.2% palladium ion are adsorbed in the solution; And simply the pH of solution is adjusted to 2.5 from 1.0, just can realize separating of gold and palladium ion preferably.With NH
2-MCM-41 molecular sieve is compared, and the adsorption capacity of SH-MCM-41 molecular sieve is a bit weaker.Adopt the SH-MCM-41 molecular sieve, 99.3% gold ion can be adsorbed and separate effectively with 91.9% palladium ion in the solution.
Embodiment two: utilize SBA-15 molecular sieve grafting functional group and the application in SEPARATION OF GOLD and platinum
1, the grafting of functional group
2.5g SBA-15 powder is placed in contains 0.1mol/L aminopropane (C
3H
7NH
2) in 250 milliliters the dry toluene, under 120 ℃ of temperature, refluxed 18 hours grafting functional group-NH on molecular sieve
2, filter then and mention the SBA-15 powder, and this powder drying under 110 ℃ of temperature was obtained NH to evaporate complete toluene in 12 hours
2-SBA-15 selective absorption noble metal functional molecular sieve.
2, the gold, platinum selective absorption with separate
With 25g NH
2-SBA-15 selective absorption noble metal functional molecular sieve is put into 2 liters and is contained 76g chlorauride (AuCl
3) and 24g platinum chloride (PtCl
3) solution in, the pH value of solution is adjusted to 1.0, at room temperature stir to filter out after 2 hours and be loaded with gold and the functional molecular of platinum ion sieve, the content of mensuration GOLD FROM PLATING SOLUTION, platinum ion.Clean the molecular sieve that is loaded with precious metal ion with 5M HCl solution then, only contained PtCl
3The solution and the molecular sieve of resolving.Again the functional molecular sieve is put into the solution that contains after the last time filters, the pH value of solution is adjusted to 2.5, equally at room temperature stir and filter the molecular sieve that is loaded with gold ion after 2 hours, measure the content of GOLD FROM PLATING SOLUTION, platinum ion, and clean the molecular sieve be loaded with gold ion with 5M HCl solution, obtain AuCl
3Solution and molecular sieve, absorption result sees Table 2.The result shows, by the pH value of regulator solution, NH
2-SBA-15 reaches the purpose of separation and enrichment gold and platinum.The molecular sieve that 5M HCl solution washes down can utilize again.
Table 2: physical property and the adsorbing separation of SBA-15 before and after the grafting functional group
Embodiment three:
Selective absorption noble metal functional molecular sieve reclaims noble metal from the waste electronic wiring board.Discarded mobile phone electronic wiring board is pulverized, and ultramicro grinding is separated with high-pressure electrostatic, and the metal dust that obtains is through 1: 2 concentrated hydrochloric acid of volume ratio: red fuming nitric acid (RFNA) obtains after dissolving contains metal ion solution.Contain golden 0.015mol in the solution; Platinum 0.009mol; Copper 0.47mol; Tin 0.21mol; Plumbous 0.077mol; Iron 0.27mol; Nickel 0.17mol.With sodium hydroxide solution the pH value of lysate is adjusted to about 1.0,5g SH-MCM-41 molecular sieve is put into dissolving metal liquid, at room temperature stirred 12 hours, allow molecular sieve fully adsorb precious metal ion.Obtain being loaded with the molecular sieve of precious metal ion behind the filtering solution and contain the lysate that does not adsorb metal.
Adopt 5M HCl to clean the supported noble metal molecular sieve, obtain the chlorauride (1.3% gold ion) of 0.009 platinum chloride (i.e. 100% platinum ion) and 0.0002mol.Containing has not had platinum ion in the lysate that does not adsorb metal, illustrate that platinum ion is separated by the absorption of functional molecular sieve, and most of gold ion and other metals are stayed in the lysate still.
The lysate pH value that obtains after filtering is adjusted to about 2.5,, at room temperature stirred 12 hours, allow the abundant adsorbing metal ions of molecular sieve being reentered in the dissolving metal liquid through above-mentioned molecular sieve after the 5MHCl cleaning.Obtain being loaded with the chlorauride (AuCl of 0.0148mol after filtering
3) and the molecular sieve of other metals (Cu and Ni) of trace and contain the lysate that does not adsorb metal, realized separating of gold ion and other metal ions like this.Then, adopt 5M HCl to clean again and carry golden functional molecular sieve, obtain chlorogold solution, the functional molecular sieve that obtains after the filtration can also be reused for the absorption noble metal.What Fig. 1 showed is to utilize SH-MCM-41 to reclaim the experimental data of noble metal technical process and embodiment three from the waste electronic wiring board.
Claims (5)
1. functional mesoporous molecular sieve, make by the following method: with silicon is that mesopore molecular sieve places the dry toluene that contains 0.1～0.5mol/L aminopropane or propanethiol to reflux 12～24 hours in 100～120 ℃, filtration and dry under 150～180 ℃ of temperature obtains amido or mercapto-functionalized mesopore molecular sieve then.
2. functional mesoporous molecular sieve as claimed in claim 1 is characterized in that described silicon is that mesopore molecular sieve is SBA-15 or MCM-41 mesopore molecular sieve.
3. functional mesoporous molecular sieve as claimed in claim 1 or 2 is in the application of reclaiming from the waste electronic wiring board in the noble metal, described noble metal is one or both and the gold in platinum and the palladium, and the described noble metal that reclaims from the waste electronic wiring board comprises the steps:
(a) the waste electronic wiring board pulverized, separated and obtain non-metal powder and metal dust, metal dust is dissolved with strong acid, contain one or both and gold ion in platinum ion and the palladium ion in the gained dissolving metal liquid;
(b) regulate about the pH value to 1 of dissolving metal liquid, functional mesoporous molecular sieve is put into dissolving metal liquid, at room temperature stirred 8～12 hours, filter the molecular sieve and the filtrate A that obtain being loaded with platinum ion and/or palladium ion;
(c) clean the molecular sieve be loaded with platinum ion and/or palladium ion with 3～6M hydrochloric acid, filter the functional mesoporous molecular sieve that obtains platinum chloride and/or palladium chloride solution and reactivate;
(d) regulate about the pH value to 2.5 of filtrate A, functional mesoporous molecular sieve is put into filtrate A, at room temperature stirred 8～12 hours, filter and obtain carrying golden molecular sieve, clean a year golden molecular sieve with 3～6M hydrochloric acid, filter the functional mesoporous molecular sieve that obtains chlorogold solution and reactivate.
4. functional mesoporous molecular sieve as claimed in claim 3 is characterized in that in the application of reclaiming in the noble metal the described strong acid of step (a) is the nitration mixture or the chloroazotic acid of 2: 1 red fuming nitric acid (RFNA) of volume ratio and concentrated hydrochloric acid from the waste electronic wiring board.
5. functional mesoporous molecular sieve as claimed in claim 3 is characterized in that the molecular sieve or year golden molecular sieve that adopt the cleaning of 5M hydrochloric acid to be loaded with platinum ion and/or palladium ion in the application of reclaiming in the noble metal from the waste electronic wiring board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101098333A CN102019167B (en) | 2009-09-14 | 2010-01-21 | Functionalized mesoporous molecular sieve and application of functionalized mesoporous molecular sieve in recovering noble metal |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910152465.8 | 2009-09-14 | ||
| CN200910152465 | 2009-09-14 | ||
| CN2010101098333A CN102019167B (en) | 2009-09-14 | 2010-01-21 | Functionalized mesoporous molecular sieve and application of functionalized mesoporous molecular sieve in recovering noble metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102019167A true CN102019167A (en) | 2011-04-20 |
| CN102019167B CN102019167B (en) | 2013-11-13 |
Family
ID=43861195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101098333A Expired - Fee Related CN102019167B (en) | 2009-09-14 | 2010-01-21 | Functionalized mesoporous molecular sieve and application of functionalized mesoporous molecular sieve in recovering noble metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102019167B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112917A (en) * | 2013-01-19 | 2013-05-22 | 桂林理工大学 | Method for purifying lead-bearing wastewater |
| CN106378117A (en) * | 2016-09-14 | 2017-02-08 | 南昌大学 | Preparation method of mesoporous material and application of mesoporous material in low concentration rare earth ion enrichment and recovery |
| CN106984364A (en) * | 2016-01-20 | 2017-07-28 | 中国科学院大连化学物理研究所 | Application of the SAPO molecular sieve analog original powder in separated/extracted metal ion |
| CN112299437A (en) * | 2019-07-31 | 2021-02-02 | 中国石油化工股份有限公司 | Sulfydryl functionalized SBA molecular sieve raw powder, molecular sieve, and preparation methods and applications thereof |
| CN113698031A (en) * | 2021-08-10 | 2021-11-26 | 广西贵港市蓝月亮水处理环保科技有限公司 | Method and equipment for recovering precious metals from comprehensive wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935994A (en) * | 2006-08-23 | 2007-03-28 | 宁夏大学 | Organic group functionized mesoporous molecular sieve enzyme immobilized carrier, and its preparing method |
-
2010
- 2010-01-21 CN CN2010101098333A patent/CN102019167B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935994A (en) * | 2006-08-23 | 2007-03-28 | 宁夏大学 | Organic group functionized mesoporous molecular sieve enzyme immobilized carrier, and its preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 张一平等: "介孔分子筛SBA-15表面的胺基功能化", 《石油学报（石油加工）》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112917A (en) * | 2013-01-19 | 2013-05-22 | 桂林理工大学 | Method for purifying lead-bearing wastewater |
| CN106984364A (en) * | 2016-01-20 | 2017-07-28 | 中国科学院大连化学物理研究所 | Application of the SAPO molecular sieve analog original powder in separated/extracted metal ion |
| CN106378117A (en) * | 2016-09-14 | 2017-02-08 | 南昌大学 | Preparation method of mesoporous material and application of mesoporous material in low concentration rare earth ion enrichment and recovery |
| CN106378117B (en) * | 2016-09-14 | 2019-04-12 | 南昌大学 | A kind of preparation method of mesoporous material and the application in the recycling of low concentration of rare earth ion enrichment |
| CN112299437A (en) * | 2019-07-31 | 2021-02-02 | 中国石油化工股份有限公司 | Sulfydryl functionalized SBA molecular sieve raw powder, molecular sieve, and preparation methods and applications thereof |
| CN112299437B (en) * | 2019-07-31 | 2022-08-19 | 中国石油化工股份有限公司 | Sulfydryl functionalized SBA molecular sieve raw powder, molecular sieve, and preparation methods and applications thereof |
| CN113698031A (en) * | 2021-08-10 | 2021-11-26 | 广西贵港市蓝月亮水处理环保科技有限公司 | Method and equipment for recovering precious metals from comprehensive wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102019167B (en) | 2013-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Rapid capture of trace precious metals by amyloid-like protein membrane with high adsorption capacity and selectivity | |
| CN102019167B (en) | Functionalized mesoporous molecular sieve and application of functionalized mesoporous molecular sieve in recovering noble metal | |
| CN102277497B (en) | Method of reclaiming gold, palladium, platinum and silver from waste circuit board | |
| CN104785212B (en) | A kind of biomass adsorbent, preparation method and its usage | |
| CN109797281B (en) | Sulfide ore precious metal recovery process based on thiosulfate leaching method | |
| CN109652647B (en) | Process for recovering noble metals from molybdenum disulfide based on thiosulfate leaching method | |
| CN110368905A (en) | A kind of sulfydryl amine type functional silica gel material and its application | |
| CN103586001A (en) | Hydroximic acid functionalized polymer/inorganic composite chelating adsorption material and preparation method thereof | |
| CN109706315B (en) | Method for adsorbing noble metal complex ions in thiosulfate leaching solution by using molybdenum disulfide | |
| CN102021333B (en) | Method to purify precious metals from gold ore using functional mesoporous molecular sieve | |
| Bai et al. | Highly efficiency and selective recovery of gold using magnetic covalent organic framework through synergistic adsorption and reduction | |
| CN109652658B (en) | Method for recovering noble metal complex ions from thiosulfate leaching solution by utilizing sulfide ore | |
| CN107519948B (en) | Composite amino weakly-alkaline anion exchange resin and method for recovering rhenium from arsenic sulfide slag leachate | |
| CN109926028B (en) | Thiourea imprinted resin, preparation method thereof and application thereof in gold adsorption | |
| Mohebbi et al. | Ion exchange resin technology in recovery of precious and noble metals | |
| CN102560120B (en) | Method for extracting gold from electronic waste leaching solution by using garlic wastes | |
| CN110607450A (en) | Method for recovering palladium in printed circuit board by selective leaching precipitation | |
| CN104651615A (en) | Method for recovering silver and palladium from waste | |
| CN104789774B (en) | It is a kind of to utilize reduction and method golden in the adsorbing coupled selective recovery aqueous solution | |
| CN109852815B (en) | Method for recovering noble metal complex ions from thiosulfate leaching solution by utilizing molybdenum disulfide | |
| Harumi et al. | Recovery of Au (III) from printed circuit board waste by chitosan/SiO2 coated on iron sand magnetic material | |
| CN109610166B (en) | Chelate fiber, preparation method thereof and application thereof in preparing Au in electronic waste3+Application of separation and enrichment | |
| JP2012041593A (en) | Method for recovering platinum group element | |
| CN105080496A (en) | Preparation method for modified activated carbon for removing Co and Cu | |
| Zhang et al. | A green process for copper recovery from waste printed circuit boards |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131113 Termination date: 20150121 |
|
| EXPY | Termination of patent right or utility model |