CN102797028A - Gold stripping composition and using method thereof - Google Patents
Gold stripping composition and using method thereof Download PDFInfo
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- CN102797028A CN102797028A CN2011101352606A CN201110135260A CN102797028A CN 102797028 A CN102797028 A CN 102797028A CN 2011101352606 A CN2011101352606 A CN 2011101352606A CN 201110135260 A CN201110135260 A CN 201110135260A CN 102797028 A CN102797028 A CN 102797028A
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Abstract
The invention relates to a gold stripping composition and a using method thereof. The gold stripping composition provided by the invention is formed by stripping gold from a base material; the composition comprises one or more gold stripping compounds and a conduction assisting compound, wherein the gold stripping compounds can from covalent bonding with gold, thus the gold on the base material is stripped off; and through the effects of the conduction assisting compound, voltage can be lowered and the gold stripping can be completed without causing damage to the base material, wherein the composition does not contain any cyanide. The invention also provides a using method of the gold stripping composition. According to the conventional gold stripping method, relative risk is caused to operating personnel, and the waste liquid during the process is troublesome to treat, additionally the base material can be damaged, and both the gold stripping speed and gold dissolving quantity have room for improvement. In view of the issue, the invention tries to provide a gold stripping technology without cyanide, not only can the gold be recovered effectively, multiple problems encountered by the prior art can be prevented.
Description
Technical field
The present invention is relevant for the golden constituent of a kind of stripping, the particularly relevant stripping gold constituent that gold is divested from the base material with and method of use.
Background technology
Prosperity and development along with electronic industry; Electronic waste reclaims industry and also arises at the historic moment; Particularly along with the former material price of the recent metal liter that significantly rises; Make the recovery of metallic scrap receive bigger attention, and numerous dealer also drop into more capital, is devoted to promote the efficient of salvage material and the purity of material.Wherein, with the recovery of noble metal, similarly be gold-plated printed substrate, golden finger, flexible base plate, lead frame, and spare part etc., all can see through reclaim technology with golden waste material again row recycle.
In traditional technical field; Because gold (Gold) is the high noble metal of a kind of chemicalstability; It is not easy to be corroded or dissolve by any acid, basic soln; Therefore habitual tradition stripping gold (or claiming to dissolve gold) technology all is to use chloroazotic acid or prussiate mostly, divests gold-plated and reclaims.
Just use chloroazotic acid to divest gold-plated technology because the allotment of chloroazotic acid (aqua regia) is very easy to, and can dissolve most metallic substance, therefore in conventional techniques by a large amount of employings.But on the other hand, because the very corrosive of chloroazotic acid, as far as operator, its potentially dangerous is also quite big, therefore often will give special heed in the protection.
As for, with regard to the technology of using prussiate (cyanide) stripping gold, using the cyanide waste liquor that contains that prussiate produced, wastewater flow rate is few, cyanide content is high, and contains micro heavy.The about 500 times of ability of waste liquid dilution are earlier handled, and increase water consumption and cost, and contained micro-noble metal will blend together mud and can't reclaim simultaneously.Be stressed that especially; In the treatment stage of the stripping gold, easy generation has volatility and the toxic prussiate of tool, can stop the exchange of human tissue cell and oxygen during contact; Cause necrocytosis; Harm to heart and brain is very big, belongs to restrictive highly toxic substance, therefore careless slightlyly will endanger operator.
Except above-mentioned harm to personnel; The chemical stripping method that with chloroazotic acid stripping gold or with the prussiate is master all can be damaged ground, and especially chloroazotic acid can corrode ground fully, so can't process again for the gold-plated defective products of continuous electroplating terminal; Can only reclaim gold, ground then lost efficacy because of infringement.
In addition, and use above-mentioned both chemical substances stripping gold, it shells the golden speed space that all has greatly improved, and is slower with prussiate especially; And above-mentioned both chemical substances are shelled the neither height of molten gold amount of golden gained, also are problems that remains to be improved.
Because for operator, all there is suitable danger in the golden mode of existing stripping, and the liquid waste disposal in the process adds and can injure ground that shelling golden speed and dissolving golden amount all has room for improvement also than trouble.In view of this, the present invention attempts providing a kind of stripping technology for gold of cyanide-free, except can efficient recovery gold, and the variety of problems that can avoid above-mentioned prior art to run into.
Summary of the invention
For solving the problems of the technologies described above, the purpose of this invention is to provide the golden constituent of a kind of stripping.
Another object of the present invention provides a kind of stripping gold constituent that gold is divested from the base material.
Another object of the present invention provides a kind of method of use of the stripping gold constituent that gold is divested from the base material.
At first, the invention provides a kind of stripping gold constituent that gold is divested from the base material, this constituent comprises one or more stripping gold compounds, and wherein this stripping gold compound can form covalent linkage with gold and ties, thereby the gold on the base material is divested; And assistant director of a film or play's electric compound, through the effect of this assistant director of a film or play's electric compound, can reduce voltage and not hinder the completion stripping gold of base material, wherein this constituent does not comprise any prussiate.
In above-mentioned constituent provided by the invention, preferably, said stripping gold compound comprises monothio urea (Thiocarbamide).
In above-mentioned constituent provided by the invention, preferably, said stripping gold compound comprises vitriol with alkyl, have the compound of pyridine-sulfonic acid and have in the compound of nitrilotriacetic one or more.
In above-mentioned constituent provided by the invention, preferably, said stripping gold compound comprises one or more in sulphite and the Sulfates.
In above-mentioned constituent provided by the invention, preferably, said assistant director of a film or play's electric compound be selected from Citrate trianion, oxalate, malate one of them.
In above-mentioned constituent provided by the invention, preferably, said assistant director of a film or play's electric compound be selected from sodium-chlor, Repone K, boric acid, sodium hydroxide and Pottasium Hydroxide one of them.
In above-mentioned constituent provided by the invention, preferably, said assistant director of a film or play's electric compound is a phosphoric acid salt, comprises in potassium hydrogenphosphate and the potassium primary phosphate one or more.
The present invention also provide a kind of on base material, remove gold-plated working method, comprise the golden constituent of stripping is dissolved in water and injects electrolyzer; Auriferous base material is placed in this electrolyzer, and this substrate is contacted with anode; Apply voltage 0.1-4 volt and carry out electrolysis stripping gold; Wherein, shell in the golden process, stir the stripping gold liquid in this electrolyzer, reach best so that shell golden effect in electrolysis.
In aforesaid operations method provided by the invention, preferably, operating temperature range is approximately 20-70 ℃.
In aforesaid operations method provided by the invention, preferably, the Baume of operation (° Be) value is 0.5-10.
The golden constituent of stripping provided by the present invention can be shelled gold fast, does not hinder base material, also can not produce the Toxic waste of contaminate environment, thereby efficient recovery is golden.
Embodiment
About constituent of the present invention and method of use thereof, can further be understood through following detailed Description Of The Invention.
The present invention provides a kind of constituent that gold is divested from the base material, and wherein, this constituent comprises one or more stripping gold compounds, and assistant director of a film or play's electric compound; Wherein, this stripping gold compound can form covalent linkage knot with gold, thereby the gold on the base material is divested, and adds the effect through this assistant director of a film or play's electric compound, can reduce voltage and not hinder the completion stripping gold of base material, and wherein this constituent does not comprise any prussiate.
In one embodiment, stripping gold compound of the present invention comprises monothio urea (Thiocarbamide).Certainly the stripping gold compound also can further comprise vitriol with alkyl, has the compound of pyridine-sulfonic acid and have in the compound of nitrilotriacetic one or more.
In another embodiment, the stripping gold compound also can be selected from the compound of sulphite, Sulfates, persulfuric acid salt, furtherly, can adopt ferrous sulfate (FeSO
4).Certainly also can comprise organic sulfonic acid, for example sulfonic acid such as methanesulfonic, ethane sulfonic acid, propane sulfonic acid.In addition, also can select suitable compound for use to different base materials, such as the compound that contains oil of mirbane, the for example an alkali metal salt and the alkaline earth salt of oil of mirbane carboxylic acid, oil of mirbane carboxylic acid.
In addition, in one embodiment of this invention, assistant director of a film or play's electric compound be selected from Citrate trianion, oxalate, malate one of them.With the Citrate trianion is example, can further select citric acid tri potassium (Tripotassium citrate monohydrate).Certainly also can be selected from boric acid, sodium hydroxide and Pottasium Hydroxide one of them.
Except above-claimed cpd, in a preferred embodiment, assistant director of a film or play's electric compound is selected from sodium sulfate, ammonium sulfate, vitriolate of tartar, sodium-chlor, ammonium chloride, Repone K, an ammonium nitrate, saltpetre, SODIUMNITRATE.And in another preferred embodiment, assistant director of a film or play's electric compound is a phosphoric acid salt, comprises potassium hydrogenphosphate, potassium primary phosphate.
Be noted that constituent of the present invention especially, do not comprise lead (Pb), cadmium (Cd), mercury (Hg), sexavalent chrome (Cr
6+) and bromine (Br) etc. can cause environmental pollution or contain the chemical element of toxin, therefore can not use compounds such as chromic salt yet.In addition, also chemical substance such as sulfur acid or hydrochloric acid not of constituent of the present invention.
In one embodiment, constituent of the present invention is made up of following compounds, comprises thio urea (Thiocarbamide), has the vitriol of alkyl, has the compound of pyridine-sulfonic acid, has the compound and the citric acid salt of nitrilotriacetic.Wherein, the vitriol that has an alkyl is sulfuric acid list ester sodium salt in the ninth of the ten Heavenly Stems (sodium stearyl sulfate); Compound with pyridine-sulfonic acid then is pyridine-3-sulphonic acid (Pyridine-3-sulfonic acid); Compound with pyridine-sulfonic acid is pyridine-3-sulphonic acid (Pyridine-3-sulfonic acid); Compound with nitrilotriacetic then is NTA (Nitrilotriacetic acid); Citric acid salt then is to select citric acid tri potassium (Tripotassium citrate monohydrate).
The invention provides a kind of on base material, remove gold-plated working method, working method comprises above-mentioned constituent is dissolved in water and injects an electrolyzer; Auriferous base material is placed in this electrolyzer, and this substrate is contacted with anode; Apply voltage 0.1-4 volt and carry out electrolysis stripping gold; Wherein, shell in the golden process, stir the stripping gold liquid in this electrolyzer, reach best so that shell golden effect in electrolysis.
Above-mentioned working method, its operating temperature range are approximately 20-70 ℃.Cathode material can be selected from stainless steel, titanium or titanium alloy.Baume (° Be) value is 0.5-10.And this substrate comprises metals such as layer of copper, nickel, aluminium or silver, and said gold be plating on it.Wherein substrate possibly be objects such as useless electric power connector terminal or PCB.
In the stripping gold liquid step in stirring this electrolyzer, the mode that available drum rotates stirs.Wherein, the stirring that strengthens tank liquor can increase the reactivity of stripping gold, and tank liquor circulating line capable of using gos deep into bottom land, and increases the filtration unit impurity screening, is stopped up by impurity to prevent circulation pore, influences mixing effect.
Electrolysis that the present invention utilized stripping gold is a kind of electrochemical process, through the external world electric energy is provided, and the terminal that contains gold plate on the anode is dissociated and is dissolved in the electrolytic solution, reaches the effect of gold plate strip.
Electrolytic deplating process and electroplating process just in time are opposite, strip be metal plating as anode, lose electronics and become the process of metals ion from piece surface:
Electroplate: M
N++ ne → M
Strip: M-ne → M
N+
Mn+ in the reaction formula representes the metals ion of n valency, and ne representes n electronic number, and M then is the metal that ortho states is gone back in representative.
The gold concentration test
To substrate, the gold concentration analysis behind the especially gold-plated tankage stripping gold has following mode reference, can effectively grasp the situation of golden yield.
One, instrumental method (Atomic Absorption Spectroscopy AAS)
Elder generation's preparation reference liquid is also got 0.5ml and is shelled golden liquid, adds pure water and is diluted to 500ml, utilizes the Atomic Absorption Spectroscopy AAS schedule of operation to analyze again.
Two, burn golden weighting method
(1) gets 10ml and shell golden tank liquor amount in Erlenmeyer flask
(2) add the 50ml vitriol oil and tank liquor is heated to Vandyke brown
(3) add 10ml concentrated nitric acid and tank liquor is heated to transparent clarification
(4) add 150ml pure water and be heated to boiling
(5) filter paper filtering
(6) place crucible also to dryout with 900 ℃
(7) weigh and calculate the crucible weight difference (Δ W) before and after dryouting
(8) calculate: Au [g/L]=(the stripping gold tank liquor amount that Δ W/ is got) x100
The test of heavy industry sample reliability
The corrosion resistant test of Gold plated Layer then is according to electronic industries alliance EIA-364-26B, uses 5% neutral brine (pH6.5-7.2), 35 ± 1 ℃ of following spray reaction 24hr of temperature; And, using 70 ± 1% nitric acid according to EIA-364-53, temperature 23+2 ℃, humidity is reacted 75mins less than 60%.And the low power contact impedance of Gold plated Layer (Low Level Contact Resistance then is according to EIA-364-23 LLCR), open circuit voltage 20mV max., test current 100mA.And the no slicker solder stove of gold-plated sample dipping measured the wettability equilibrium (wetting balance) of its coating.The test of wettability equilibrium is according to U.S. army mark standard MIL-STD-833E, 245 ± 3 ℃ of furnace temperature of test, impregnating depth is 2mm, the immersion time is 5s, immerse with the speed of leaving be 2mm/s, no slicker solder stove is the Sn-3.0Ag-0.5Cu system.
Use constituent of the present invention, carry out the gold-plated operation of heavy industry through stripping Jin Houzai, relevant reliability test all passing through really examination criteria to the gold-plated unusual terminal of junctor.
The resin cation(R.C.) recovery system uses
But the gold ion that the cation type resin active adsorption is positively charged.When the golden tank liquor of stripping when yellowing is muddy gradually by transparent clarification, expression gold ion concentration raises, and gold ion is reclaimed in resin cation(R.C.) tower circulation therefore capable of using, lets the golden liquid of stripping become clarification by muddiness, prolongs the digestion time of the golden electrolytic solution of stripping.
The golden compsn of stripping of the present invention, it is fast that it shells golden speed, can divest gold plate effectively completely, especially added assistant director of a film or play's electric compound, strengthens the conducting of energising after-current, can reduce required voltage, so can not hinder base material (like copper or nickel) behind the stripping gold.
Through constituent of the present invention; The cyanide-free stripping technology for gold of setting up of success substitutes the normal prussiate system that uses of original plating industry; And utilize electrolytic mode rapidly Gold plated Layer on the bonder terminal to be divested; Can be used for the recovery that gold-plated unusual terminal carries out heavy industry operation or terminal tankage gold, reach circulation (recovery) purpose.
And, constituent of the present invention, the harm that has solved existing prussiate and chloroazotic acid fully comprises producing waste water or other waste that is difficult to handle recovery, also can be to user or environment generation injury, the environmental protection again of safety very.
Though the present invention illustrates as above with preferred embodiments, so it is not only to terminate in the foregoing description that in order to limit spirit of the present invention with the invention entity.Be with, the modification of in not breaking away from spirit of the present invention and scope, being done all should be included in the following claim.
Claims (10)
1. constituent that gold is divested from the base material, this constituent comprises:
One or more shell gold compound, and wherein, this stripping gold compound can form the covalent linkage knot with gold, thereby the gold on the base material is divested; And
One assistant director of a film or play's electric compound through the effect of this assistant director of a film or play's electric compound, can reduce voltage and not hinder the completion stripping gold of base material, and wherein, this constituent does not comprise any prussiate.
2. constituent as claimed in claim 1, wherein, said stripping gold compound comprises monothio urea.
3. constituent as claimed in claim 1, wherein, said stripping gold compound comprises vitriol with alkyl, have the compound of pyridine-sulfonic acid and have in the compound of nitrilotriacetic one or more.
4. constituent as claimed in claim 1, wherein, said stripping gold compound comprises one or more in sulphite and the Sulfates.
5. constituent as claimed in claim 1, wherein, said assistant director of a film or play's electric compound be selected from Citrate trianion, oxalate, malate one of them.
6. constituent as claimed in claim 1, wherein, said assistant director of a film or play's electric compound be selected from sodium-chlor, Repone K, boric acid, sodium hydroxide and Pottasium Hydroxide one of them.
7. constituent as claimed in claim 1, wherein, said assistant director of a film or play's electric compound is a phosphoric acid salt, comprises in potassium hydrogenphosphate and the potassium primary phosphate one or more.
One kind on base material, remove gold-plated working method, comprising:
Each described constituent of claim 1-7 is dissolved in water and injects an electrolyzer;
One auriferous base material is placed in the said electrolyzer, and this substrate is contacted with anode;
Apply voltage 0.1-4 volt and carry out electrolysis stripping gold;
Wherein, shell in the golden process, stir the stripping gold liquid in the said electrolyzer, reach best so that shell golden effect in electrolysis.
9. the described method of claim 8, wherein, service temperature is 20-70 ℃.
10. the described method of claim 8, wherein, the Baume value of operation is 0.5-10.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110135260.6A CN102797028B (en) | 2011-05-24 | 2011-05-24 | Shell golden constituent and using method |
| HK13105951.1A HK1178222A1 (en) | 2011-05-24 | 2013-05-21 | Gold stripping composition and using method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110135260.6A CN102797028B (en) | 2011-05-24 | 2011-05-24 | Shell golden constituent and using method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102797028A true CN102797028A (en) | 2012-11-28 |
| CN102797028B CN102797028B (en) | 2016-01-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110135260.6A Active CN102797028B (en) | 2011-05-24 | 2011-05-24 | Shell golden constituent and using method |
Country Status (2)
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| CN (1) | CN102797028B (en) |
| HK (1) | HK1178222A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104005030A (en) * | 2013-02-22 | 2014-08-27 | 优胜奈米科技有限公司 | Metal stripping additive, composition containing the same and method for stripping metal |
| CN104294273A (en) * | 2014-11-08 | 2015-01-21 | 汕头超声印制板（二厂）有限公司 | Non-toxic gold stripping liquid and method for detecting printed circuit board through non-toxic gold stripping liquid |
| CN109913881A (en) * | 2017-12-13 | 2019-06-21 | 鹏鼎控股(深圳)股份有限公司 | It shells golden liquid and component shells golden method |
| CN111663041A (en) * | 2019-03-05 | 2020-09-15 | 优胜奈米科技有限公司 | Lithium cobalt stripping additive and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220501A (en) * | 2007-01-12 | 2008-07-16 | 金益鼎企业股份有限公司 | Precious metal containing matter recycling system and method |
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2011
- 2011-05-24 CN CN201110135260.6A patent/CN102797028B/en active Active
-
2013
- 2013-05-21 HK HK13105951.1A patent/HK1178222A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220501A (en) * | 2007-01-12 | 2008-07-16 | 金益鼎企业股份有限公司 | Precious metal containing matter recycling system and method |
Non-Patent Citations (2)
| Title |
|---|
| J.C.LIN等: "Electrochemical stripping of gold from Au-Ni-Cu electronic connector scrap in an aqueous solution of thiourea", 《JOURNAL OF APPLIED ELECTROCHEMISTRY》 * |
| 杨玉芬等: "废印刷线路板中稀贵金属的回收现状", 《稀有金属》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104005030A (en) * | 2013-02-22 | 2014-08-27 | 优胜奈米科技有限公司 | Metal stripping additive, composition containing the same and method for stripping metal |
| CN104294273A (en) * | 2014-11-08 | 2015-01-21 | 汕头超声印制板（二厂）有限公司 | Non-toxic gold stripping liquid and method for detecting printed circuit board through non-toxic gold stripping liquid |
| CN109913881A (en) * | 2017-12-13 | 2019-06-21 | 鹏鼎控股(深圳)股份有限公司 | It shells golden liquid and component shells golden method |
| CN111663041A (en) * | 2019-03-05 | 2020-09-15 | 优胜奈米科技有限公司 | Lithium cobalt stripping additive and application thereof |
| CN111663041B (en) * | 2019-03-05 | 2022-05-06 | 优胜奈米科技有限公司 | Lithium cobalt stripping additive and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1178222A1 (en) | 2013-09-06 |
| CN102797028B (en) | 2016-01-06 |
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