CN1136595A - Enriching and activating and dissolving method for low grade and difficult treating noble metal materials - Google Patents
Enriching and activating and dissolving method for low grade and difficult treating noble metal materials Download PDFInfo
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- CN1136595A CN1136595A CN 95106124 CN95106124A CN1136595A CN 1136595 A CN1136595 A CN 1136595A CN 95106124 CN95106124 CN 95106124 CN 95106124 A CN95106124 A CN 95106124A CN 1136595 A CN1136595 A CN 1136595A
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Abstract
The present invention relates to an enrichment activating and dissolvingmethod for low-grade and hard-to-treat noble metal materials. Said method includes the following steps: (a) using sulfide contained in raw material or adding sulfide of heavy metal to smelt metal matte, and separating slag; (b) adding matte in aluminium, smelting aluminium to make it alloyed, (c) adding aluminium in dilute acid, dissolving and separating base metal; and (d) separating and removing insoluble sludge in dilute acid, oxidizing medium and dissolving noble metal.
Description
The enrichment active dissolution method of low-grade and difficult treating noble metal materials, the present invention belongs to precious metals metallurgy.
Precious metal Au, Ag, Pt, Pd, Rh, Ir, Os, Ru content in raw material is few and disperse, and its metallurgical process has a series of enrichments, activation, the tediously long process of separation refining.In recent years, the progressively development and application of new technology of solvent extration separation and Extraction precious metal from solution.All precious metals all change solution in the solvent extration requirement concentrate, and character, composition and concentration are adjusted easily.Britain Acker system refinery adopts sodium peroxide scorification (Ep0048103) to grade greater than 50% precious metal concentrate, has changed the state of precious metal by alkali fusion, makes it be easy to dissolving, but the SiO in the raw material
2Form silicate during alkali fusion, form silica gel during leaching, make filtration difficulty.U.S. Pat 4451290 " reclaims the platinum metals " from waste material and residue be to contain precious metal residue and sulfur-bearing leaching slag and flux high-temperature fusion, the copper matte regulus that contains precious metal with generation reaches scum silica frost mutually, unnecessary iron, nickel are removed in oxidation, contact with copper matte regulus with the deposite metal of selecting in copper or nickel, the iron again, to capture precious metal.This method has been invented from contain precious metal waste material or waste residue with sulfonium scorification and the copper method of trapping method in conjunction with enriching noble metals, method is pyrometallurgy, do not relate to the preparation of higher-grade precious metal concentrate and the activation and the dissolving of precious metal, and the precious metal rate of recovery is except that platinum is higher, all the other are not high, and particularly silver and palladium are all lower.
The objective of the invention is at low-grade (＜10%) or the unmanageable material that contains precious metal (Au, Ag, Pt, Pd, Rh, Ir, Os, Ru), the research invention is a kind of also to activate the further enrichment of all precious metals, obtain higher-grade precious metal concentrate, high-efficient simple dissolving again, the method of preparation high density, precious metal solution that foreign matter content is few, the employing that helps next step solvent extraction or other precious metal refining techniques is carried out.
The enrichment active dissolution method of the low-grade and difficult treating noble metal materials of being invented, comprise the smelting metal sulfonium, aluminium alloying, acidleach goes out base metal, acid oxidase medium dissolves precious metal several steps, it is characterized in that: (1) low-grade and unmanageable to contain the base metal sulfide that noble metal materials utilizes it to contain, perhaps measure and add iron when not enough, nickel, in copper and other heavy non-ferrous metal sulfide a kind of or several, its ratio is a precious metal: base metal (weight ratio)=1: 1-25, the adding fusing point is the slag making material covering that 550-1000 ℃ sodium boron glass slag maybe can form the sodium boron glass, melting in clay or plumbago crucible, temperature is 900-1300 ℃, soaking time 0.5-1.5 hour, precious metal captures in sulfonium phase or metallographic phase, slag making thing such as silicon in the material, sodium boron glass covering slags such as calcium formation fusing point is sodium-boron-silex glass body slag of 790-850 ℃, sulfonium separates with slag, slag multiplexing one is to secondary, precious metal can be reduced to about 30g/t in the slag, precious metal direct yield＞99.6% in the sulfonium; (2) with (1) gained enrichment the sulfonium of precious metal attach aluminium, sulfonium: aluminium (weight ratio)=1: 0.5-3, in clay or plumbago crucible, temperature 1000-1200 ℃, carry out smelting aluminium alloyization, soaking time 10-30 minute; (3) with (2) step gained Al alloy block heating for dissolving base metal in 1-4mol dilute hydrochloric acid or dilute sulphuric acid, keep aluminium and base-metal ion total concn＜150g/l in the solution, temperature＞90 ℃, solid-liquid separation, filtrate does not contain precious metal, can dump or incorporate into the base metal recovery system, filter residue is the noble metal active concentrate of grade＞50%; (4) (3) gained noble metal active concentrate is dissolved whole precious metals with the hydrochloric acid oxidizer, perhaps initial oxidation fractionation by distillation osmium, ruthenium, dissolve other precious metal with the hydrochloric acid oxidizer again, solution acidity is 4-8mol, oxygenant is to choose any one kind of them in chlorine or the aqueous hydrogen peroxide solution, temperature is 80-100 ℃, dissolution time 2-5 hour, precious metal dissolving rate is respectively: Au 99.9%, and Pt 99.9%, Pd 99.9%, Rh 99.8%, and Ir 99.9%, and Os 99.6%, about Ru 99.6%, the insoluble quantity of slag seldom, bullion content is (1%) seldom, can incorporate the following batch of melting into and use.
Advantage of the present invention is: 1, the treatable material subject range of institute is wide, precious metal grade 0.1-20%, precious metal: base metal=1: 1-25, SiO
2, Al
2O
3Deng the higher material of slag making thing content, difficult material all can be handled, and 2, at the activation precious metal, when making it be converted into easy dissolved state, further separated SiO
2, Al
2O
3And base metal.3, precious metal concentrate grade height, active good, precious metal dissolving rate and metal recovery rate height, 4 technological processs are easy, and dissolution process is rapid.
Embodiment
Example 1, alkali fusion distillation osmium, ruthenium and HCl/Cl
2Dissolved undissolved residue concentration of precious metal thing 143.5g, composition are (%): Au 0.275 Pt 5.57Pd 0.925 Rh 0.377 Ir 1.35 O50.075 Ru0.378, and the base metal summation is less than 0.4%.
(1) adds Ni
3S
220g, FeS 23g mixes with residue, uses 60g SiO
2, 75g B
2O
3, 56g Na
2CO
3The slag making thing covers material, in 1250 ℃ of meltings, is incubated 30 minutes in clay crucible, and cooling back slag separates with sulfonium; (2) the 27.6g sulfonium that is obtained adds 45g aluminium in clay crucible, 1150 ℃ of meltings 15 minutes, gets aluminium alloy 71.5g, aluminium slag 4.67g; (3) with aluminium alloy 3molHcl; In temperature＞90 ℃ heating for dissolving, solid-liquid separation; (4) (3) gained solid noble metal concentrate is used 6mol Hcl+ hydroperoxide dissolution, temperature is the water boiling temperature, dissolves 10 minutes, and concentrate is all molten intact.
The precious metal trend, dissolution rate such as table 1:
Apportionment ratio % 95.5 97.4 95.0 97.0 98.9 88.4 95.8 metal balance % 100 100 100 100 100 100 100 examples 2 in dispersion rate % 1.5 1.4 1.4 1.47 0.77 5.6 2.3 your liquid in the dispersion rate % 3.1 1.2 3.7 1.6 0.30 5.98 1.89 aluminium slags in table 1 title Au Pt Pd Rh Ir Os Ru slag composition g/t 49.2 390 200 35 23 25.9 41.6 aluminium slag ingredient % 0.125 2.37 0.409 0.17 0.32 0.128 0.2662 hydrochloric acid leachate composition g/l trace trace trace trace trace trace trace precious metal solution concentration g/l 0.92 18.98 3.07 1.28 4.6 7 0.231 1.269 slag
Certain concentration of precious metal thing 3780g of factory, composition is (%): Au 0.113Pt 0.094 Pd 0.076 Rh 0.0037 Ir 0.0148Os 0.00872 Ru 0.0054 Cu 4.76 Ni 4.19Fe 10.21 SiO
211.1 Al
2O
3＜1 S 14.11CaO 12.52 MgO 1.39
∑ Pt+Au=0.3156% wherein, base metal 19.16%, high and low ratio 1: 60, slag making thing are 26.01%.
(1) adds SiO
21210g, borax 1512g, Na
2CO
31134g slag making material is covered on the material, and in clay crucible, melting is 0.5 hour under 1250 ℃ of temperature, and cooling back slag sulfonium separates, the heavy 2480g of slag, the heavy 418.1g of sulfonium.
(2) in sulfonium: the ratio of aluminium=1: 1.5, sulfonium and aluminium mixed add in the clay crucible, the middle frequency furnace heating, in 1150 ℃ of temperature melting reactions 10 minutes, aluminium alloy 870g.
(3) aluminium alloy after ℃ heating for dissolving of temperature＞90, filters washing, drying, aluminium slag dry weight 31.5g through dilute sulphuric acid (concentration 3mol)
(4) aluminium slag (precious metal concentrate) initial oxidation fractionation by distillation Os, Ru, again with the logical Cl of 8mol HCl
2Oxidation, dissolved 1 hour temperature＞80 ℃, filter precious metal solution 587.5ml, insoluble slag dry weight 1.51g, high and low ratio is 14: 1 in the solution.
Apportionment ratio % in 99.4 98.5 99.12 96.4 99.14 0.93 1.2 apportionment ratio %Os, Ru absorption liquid // ///94.7 83.2 in the 0.028 0.08 0.05 0.2 0.2 0.42 0.39 residual rate % precious metal solution in the dispersion rate 0.13 0.15 0.15 0.1 0.08 0.37 5.8 final insoluble slag in the dispersion rate 0.44 1.2 0.67 0.76 0.29 1.6 2.1 aluminium slag in the concentration g/l slag in concentration g/l 7.22 6.06 4.84 0.23 0.946 0.0052 0.0216Os, Ru absorption liquid // ///0.34 0.123 in content g/t 798.95 1,990 1,010 224 752.7 914.5 562.6 your liquid in content g/final insoluble slag of l trace trace trace trace trace trace trace in content g/t 180 168 137 4.4 15.0 390 380 aluminium slag lysates in content g/t 7.5 17.7 7.7 4.3 6.62 2.15 2.14 aluminium slags in noble metal trend and dissolution rate such as the table 2 table 2 title Au Pt Pd Rh Ir Os Ru slag
Precious metal dissolving rate 99.97 99.92 99.95 99.8 99.8 99.58
*99.61
*(steam rate)
*% metal balance % 100 100 100 100 100 100 100
Example 3 certain noble metal materials 3605g of factory, composition is (%): Au 1.46Pt 3.58 Pd 1.92 Rh 0.16 Ir 0.149 Os 0.159 Ru 0.32 Cu 9.64 Ni 7.98 Fe 1.48 S 33.04 SiO
28.81 CaO 1.78 Al
2O
30.66, Au+ ∑ Pt=7.748% wherein, base metal=19.1%, high and low ratio=1: 2.5, slag making thing=11.25%, (1) adds 361g SiO
2, 361g borax, 289g Na
2CO
3After mixing, the slag making thing covers on the material, melting 1.5 hours under 1250 ℃ of temperature in clay crucible, and the layering melt topples over slagging or cooling back slag sulfonium separates, the heavy 1250g of slag, the heavy 1455.7g of sulfonium.
(2) in sulfonium: aluminium=1: 1.5 ratio, added in the clay crucible under 1150 ℃ of temperature melting reaction 10 minutes, aluminium alloy weigh 3091.5.
(3) aluminium alloy is with 3mol dissolving with hydrochloric acid base metal, temperature＞90 ℃, the solution that does not contain precious metal is discarded, aluminium slag dry weight 17.2g.
(4) lead to cl with 8molHcl again behind the distillation of aluminium slag (precious metal concentrate) initial oxidation Os, the Ru
2Heating for dissolving precious metal 1.5 hours, temperature＞80 ℃, filtering the precious metal solution volume is 2500ml, and the filter residue dry weight is 13.1g, and high and low ratio is 12.6: 1 in the solution.
33 Au Pt Pd Rh Ir Os Rug/t 5.3 6.3 3.8 4.0 2.93 1.35 1.86g/t 1870 4102 5333 213 173 30 80g/l g/l 651 1965 1058 5000 415.7 376.1 784.9g/l 21.06 51.67 27.65 2.27 2.12 0.95 2.63 Os、Ru / / / / / 1.24 1.81g/l％ 0.013 0.006 0.007 0.087 0.068 0.030 0.020％ 0.061 0.055 0.13 0.064 0.056 0.009 0.012 0.016 0.02 0.02 1.1 0.1 0.086 0.09％ 99.89 99.92 99.8 98.7 99.77 41.42 57.35％Os、Ru / / / / / 58.46 42.55％ 99.98 99.98 99.98 98.9 99.9 99.9*99.9
*(steam rate)
*% metal balance % 100 100 100 100 100 100 100
Claims (1)
1, the enrichment active dissolution method of low-grade and difficult treating noble metal materials comprises that smelting metal sulfonium, aluminium alloying, acidleach go out base metal, acid oxidase medium dissolves precious metal several steps, is characterized in that:
1.1 low-grade and difficult treating noble metal materials utilizes its base metal sulfide that contains, or interpolation iron, nickel, in copper and other heavy non-ferrous metal sulfide a kind of or several, maybe can form melting under the covering of slag making material of sodium boron glass slag at sodium boron glass slag, concentration of precious metal is in the metal sulfonium, slag making thing in the material and sodium boron glass form sodium borosilicate glass slag, sulfonium separates with slag, actual conditions is: precious metal: base metal (weight ratio)=1: 1-25, sodium boron glass slag temperature of fusion is 550 ℃-1000 ℃, melting in clay or plumbago crucible, smelting temperature is 900 ℃-1300 ℃, and soaking time 0.5-1.5 hour, slag multiplexing was to secondary;
1.2 being added the aluminium melting, 1.1 gained metal sulfoniums carry out aluminium alloying, sulfonium: aluminium (weight ratio)=1: 0.5-3,, soaking time 10-30 minute, carry out in clay or plumbago crucible by temperature 1000-1200 ℃;
1.3 with 1.2 gained Al alloy blocks, leach base metal with dilute hydrochloric acid or dilute sulphuric acid, solution acidity is 1-4mol, aluminium and base-metal ion total concn＜150g/l in the solution, temperature＞90 ℃, solid-liquid separation;
1.4 1.3 gained solids (concentration of precious metal thing) are dissolved whole precious metals with the hydrochloric acid oxidizer, perhaps initial oxidation fractionation by distillation osmium, ruthenium, dissolve other precious metal with the hydrochloric acid oxidizer again, solution acidity is 4-8mol, oxygenant is to choose any one kind of them in chlorine or the aqueous hydrogen peroxide solution, temperature is 80-100 ℃, dissolution time 2-5 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95106124A CN1039136C (en) | 1995-05-24 | 1995-05-24 | Enriching and activating and dissolving method for low grade and difficult treating noble metal materials |
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|---|---|---|---|
| CN95106124A CN1039136C (en) | 1995-05-24 | 1995-05-24 | Enriching and activating and dissolving method for low grade and difficult treating noble metal materials |
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|---|---|
| CN1136595A true CN1136595A (en) | 1996-11-27 |
| CN1039136C CN1039136C (en) | 1998-07-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95106124A Expired - Fee Related CN1039136C (en) | 1995-05-24 | 1995-05-24 | Enriching and activating and dissolving method for low grade and difficult treating noble metal materials |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212704A (en) * | 2011-05-23 | 2011-10-12 | 贵研铂业股份有限公司 | Dissolution method of noble metal material |
| CN102962446A (en) * | 2012-11-13 | 2013-03-13 | 中国科学院长春应用化学研究所 | Method for activating noble metal nano particles by liquid phase dissolving |
| CN103526040A (en) * | 2013-10-11 | 2014-01-22 | 金川集团股份有限公司 | Process for removing base metals in platinum group metal containing material |
| CN105296759A (en) * | 2015-11-18 | 2016-02-03 | 金川集团股份有限公司 | Method for selectively separating copper and nickel from platinum group metal feed liquid |
| CN109321753A (en) * | 2018-11-27 | 2019-02-12 | 贵研资源（易门）有限公司 | Fail palladium catalyst green reclaim method |
| CN110846505A (en) * | 2019-11-21 | 2020-02-28 | 云龙县铂翠贵金属科技有限公司 | Method for recovering platinum group metal from VOCs (volatile organic compounds) waste catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3279625D1 (en) * | 1981-09-16 | 1989-05-24 | Matthey Rustenburg Refines | Recovery of platinum group metals from scrap and residues |
| JPS58151434A (en) * | 1982-03-02 | 1983-09-08 | Shoei Kagaku Kogyo Kk | Extracting method of noble metal |
-
1995
- 1995-05-24 CN CN95106124A patent/CN1039136C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212704A (en) * | 2011-05-23 | 2011-10-12 | 贵研铂业股份有限公司 | Dissolution method of noble metal material |
| CN102962446A (en) * | 2012-11-13 | 2013-03-13 | 中国科学院长春应用化学研究所 | Method for activating noble metal nano particles by liquid phase dissolving |
| CN103526040A (en) * | 2013-10-11 | 2014-01-22 | 金川集团股份有限公司 | Process for removing base metals in platinum group metal containing material |
| CN103526040B (en) * | 2013-10-11 | 2015-08-12 | 金川集团股份有限公司 | A kind of technique removing base metal from platinum group metalliferous material |
| CN105296759A (en) * | 2015-11-18 | 2016-02-03 | 金川集团股份有限公司 | Method for selectively separating copper and nickel from platinum group metal feed liquid |
| CN109321753A (en) * | 2018-11-27 | 2019-02-12 | 贵研资源（易门）有限公司 | Fail palladium catalyst green reclaim method |
| CN110846505A (en) * | 2019-11-21 | 2020-02-28 | 云龙县铂翠贵金属科技有限公司 | Method for recovering platinum group metal from VOCs (volatile organic compounds) waste catalyst |
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| Publication number | Publication date |
|---|---|
| CN1039136C (en) | 1998-07-15 |
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Applicant after: Kunming Institute of Precious Metals Applicant after: Jinchuan Nonferrous Metal Co. Applicant before: Kunming Noble Metal Inst., China Nonferrous Metal Industry General Co. Applicant before: N/A |
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