CN102019167B - 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
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- CN102019167B CN102019167B CN2010101098333A CN201010109833A CN102019167B CN 102019167 B CN102019167 B CN 102019167B CN 2010101098333 A CN2010101098333 A CN 2010101098333A CN 201010109833 A CN201010109833 A CN 201010109833A CN 102019167 B CN102019167 B CN 102019167B
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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 at noble metal from the waste electronic wiring board, reclaims as the application of the noble metals such as gold, palladium, platinum.
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, are tens times of natural mineral reserve even hundred times.Wherein comprise 3～8% gold, 0.1～1% platinum and palladium, also have the metals such as copper that content do not wait, tin, aluminium, nickel, lead certainly.From the content of the noble metals such as gold, platinum and palladium, reclaim noble metal and have very large economic benefit from discarded electronic circuit board, 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) has the Nano-function thin films that is arranged with ordered meso-porous structure, its duct size homogeneous, aperture is adjustable in the 2-50nm scope, higher specific area is arranged, and its BET specific area generally can reach 1000m
2/ g left and right.These characteristics make mesopore molecular sieve, in fields such as macromolecules adsorption, catalytic reaction, medicament transport, good application prospect 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.
For above-mentioned technical problem, Research Thinking of the present invention is: take full advantage of the large advantages of mesopore molecular sieve specific area such as SBA-15, MCM-41, by some absorption precious metal ion functional groups in grafting on 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, be that mesopore molecular sieve is placed in the dry toluene that contains 0.1～0.5mol/L aminopropane or propanethiol and refluxed 12～24 hours in 100～120 ℃, then filtration and dry with evaporation toluene at 150～180 ℃ of temperature, obtain amido or mercapto-functionalized mesopore molecular sieve.
Described silicon is the 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 the noble metals such as gold, platinum and palladium from the waste electronic wiring board.
For 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 in acid solution, and the characteristics of not adsorbing other metal ions under certain condition, effectively with precious metal ion and common metal ion isolation; , by the pH value of regulator solution, make the precious metal ion desorption that is adsorbed on molecular sieve simultaneously, realize the enrichment of precious metal ion and reactivating of molecular sieve.
The technical scheme that reclaims the 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 palladium ion in gained dissolving metal liquid;
The pH value of (b) regulating dissolving metal liquid, to 1 left and right, is put into dissolving metal liquid with functional mesoporous molecular sieve, at room temperature stirs 8～12 hours, filters the molecular sieve and the filtrate A that obtain being loaded with accordingly platinum ion and/or palladium ion; The functional mesoporous molecular sieve that the application makes is 1 left and right at pH, all can adsorb by high selectivity for platinum ion and palladium ion, gold ion and other metal ions continue to stay in filtrate A, therefore, according to the difference of precious metal ion composition in metallic solution, obtain being loaded with accordingly the molecular sieve of platinum ion or palladium ion or platinum ion and palladium ion.
(c) clean with 3～6M hydrochloric acid (preferred 5M hydrochloric acid) molecular sieve that is loaded with platinum ion and/or palladium ion, filter and obtain platinum chloride and/or palladium chloride solution and the functional mesoporous molecular sieve that reactivates;
(d) regulate the pH value of filtrate A to 2.5 left and right, functional mesoporous molecular sieve is put into filtrate A, at room temperature stirred 8～12 hours, filtration obtains carrying golden molecular sieve, clean and carry 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, can selective absorption gold ion, other metal ions continue to stay in 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, then obtaining take glass fibre, resin with the High-pressure Static Selector separation is main metal dust as main non-metal powder with copper, tin, lead, gold, platinum, palladium (, about platinum and palladium, may only contain platinum in some electronic circuit boards or only contain palladium) etc.
In the scheme of above-mentioned recovery noble metal, the described strong acid of step (a), in order to the dissolution of metals powder, preferably uses nitration mixture or the chloroazotic acid of the volume ratio red fuming nitric acid (RFNA) of 2: 1 and concentrated hydrochloric acid.Regulate the pH value in step (b) and step (d) and can use the 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 process by 3～6M hydrochloric acid solution, preferably by the 5M hydrochloric acid solution, process, can make the noble metal desorption that is adsorbed on molecular sieve, enter in 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 can make corresponding noble metal platinum and palladium by existing techniques such as electrolysis; When obtain be the mixed solution of palladium bichloride and platinum chloride the time, can obtain respectively palladium and platinum by the difference of controlling current potential in electrolytic process.Be 99.99% gold and chlorogold solution can adopt the hydrometallurgical technology electrolysis to obtain purity.
In addition, the functional mesoporous molecular sieve that makes due to the present invention has its adsorption capacity for precious metal ion under different condition, those skilled in the art in actual mechanical process, can determine according to the adsorption capacity of the precious metal ion content in pulp slurry and functional mesoporous molecular sieve both usage ratio.
Compared with prior art, the present invention adopts the functional mesoporous molecular sieve of energy selective absorption noble metal to reclaim noble metal, and technique is simple, and the acidity of only adjusting simply solution can reach the purpose of precious metal ion separation, parsing and enrichment; The adsorption efficiency of functional mesoporous molecular sieve is high, and the efficiency of its ADSORPTION OF GOLD ion reaches more than 98%, and the efficiency 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 present invention three.
Five, the specific embodiment
Below with specific embodiment, technical scheme of the present invention is described further, but protection scope of the present invention is not limited to this:
Embodiment one:
1, the grafting of functional group
2.5g MCM-41 powder is placed in and contains 0.1mol/L aminopropane (C
3H
7NH
2) in the dry toluene of 250 milliliters, refluxed 18 hours at 120 ℃ of temperature, grafting functional group-NH on molecular sieve
2, then filter and mention the MCM-41 powder, and this powder drying at 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 is in 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.Then clean with 5M HCl solution the molecular sieve that is loaded with precious metal ion, obtain only containing PdCl
3Solution 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 after 2 hours and filter the molecular sieve that is loaded with gold ion, measure the content of GOLD FROM PLATING SOLUTION, palladium ion.And clean the molecular sieve that is 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 is in 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-the SH group is on the molecular sieve surface in grafting, also successful grafting on the mesoporous inwall of molecular sieve, make the internal diameter of mesopore molecular sieve diminish, as in grafting-NH
2After group, internal diameter reduces to 2.92nm from 3.09nm, and like this, before and after the grafting functional group, the specific area of molecular sieve reduces to some extent, 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 have the ability of selective stronger efficient adsorption noble metal in acid solution.Can see NH from the adsorption test result
2-MCM-41 molecular sieve almost can adsorbent solution in all precious metal ions, in solution, 100% gold ion and 99.2% palladium ion are adsorbed; And simply the pH of solution is adjusted to 2.5 from 1.0, just can realize preferably separating of gold and palladium ion.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, in solution, 99.3% gold ion can effectively be adsorbed and separate with 91.9% palladium ion.
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 and contains 0.1mol/L aminopropane (C
3H
7NH
2) in the dry toluene of 250 milliliters, refluxed 18 hours at 120 ℃ of temperature, grafting functional group-NH on molecular sieve
2, then filter and mention the SBA-15 powder, and this powder drying at 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 after 2 hours to filter out and be loaded with gold and the functional molecular of platinum ion sieve, the content of mensuration GOLD FROM PLATING SOLUTION, platinum ion.Then clean with 5M HCl solution the molecular sieve that is loaded with precious metal ion, obtain only containing PtCl
3Solution 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 after 2 hours and filter the molecular sieve that is loaded with gold ion, measure the content of GOLD FROM PLATING SOLUTION, platinum ion, and clean the molecular sieve that is loaded with gold ion with 5M HCl solution, obtain AuCl
3Solution and molecular sieve, absorption result is in Table 2.Result shows, by the pH value of regulator solution, NH
2-SBA-15 reaches the purpose of separation and Concentration of Gold and platinum.The molecular sieve that 5M HCl solution washes down can recycle.
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 the volume ratio concentrated hydrochloric acid of 1: 2: the solution that contains metal ion that obtains after the red fuming nitric acid (RFNA) dissolving.Contain golden 0.015mol in 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 1.0 left and right, 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 after filtering solution and contain the not lysate of adsorbing 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.Contain in the lysate of adsorbing metal not and there is no platinum ion, platinum ion is described by the absorption of functional molecular sieve and separate, and most of gold ion and other metals are stayed in lysate still.
The lysate pH value that obtains after filtering is adjusted to 2.5 left and right,, through above-mentioned molecular sieve after the 5MHCl cleaning, being reentered in dissolving metal liquid, at room temperature stirred 12 hours, allow the abundant adsorbing metal ions of molecular sieve.Obtain after filtering being loaded with the chlorauride (AuCl of 0.0148mol
3) and the molecular sieve of other metals (Cu and Ni) of trace and contain the not lysate of adsorbing metal, realized like this separating of gold ion and other metal ions.Then, then adopt 5M HCl to clean a year golden functional molecular sieve, obtain chlorogold solution, the functional molecular sieve that obtains after 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, be that mesopore molecular sieve is placed in the dry toluene that contains 0.1～0.5mol/L aminopropane or propanethiol and refluxed 12～24 hours in 100～120 ℃, then filtration and dry at 150～180 ℃ of temperature, obtain amido or mercapto-functionalized mesopore molecular sieve.
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. the application of functional mesoporous molecular sieve as claimed in claim 1 or 2 in reclaim noble metal from the waste electronic wiring board, described noble metal is one or both and the gold in platinum and 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 palladium ion in gained dissolving metal liquid;
(b) regulate 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) be loaded with the molecular sieve of platinum ion and/or palladium ion with 3～6M hydrochloric acid cleaning, filter the functional mesoporous molecular sieve obtain platinum chloride and/or palladium chloride solution and to reactivate;
(d) regulate 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, carry golden molecular sieve with 3～6M hydrochloric acid cleaning, filter the functional mesoporous molecular sieve that obtains chlorogold solution and reactivate.
4. the application of functional mesoporous molecular sieve as claimed in claim 3 in reclaim noble metal from the waste electronic wiring board, is characterized in that the described strong acid of step (a) is the red fuming nitric acid (RFNA) of volume ratio 2:1 and nitration mixture or the chloroazotic acid of concentrated hydrochloric acid.
5. the application of functional mesoporous molecular sieve as claimed in claim 3 in reclaim noble metal from the waste electronic wiring board, is characterized in that the molecular sieve that adopts the 5M hydrochloric acid cleaning to be loaded with platinum ion and/or palladium ion or carry golden molecular sieve.
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| 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 |
| 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 |
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| 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 |
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| Title |
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| 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）》.2006,35-37. * |
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