CN102797028B - Shell golden constituent and using method - Google Patents
Shell golden constituent and using method Download PDFInfo
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- CN102797028B CN102797028B CN201110135260.6A CN201110135260A CN102797028B CN 102797028 B CN102797028 B CN 102797028B CN 201110135260 A CN201110135260 A CN 201110135260A CN 102797028 B CN102797028 B CN 102797028B
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Abstract
The present invention relates to the golden constituent of a kind of stripping and using method.The golden constituent of stripping provided by the invention is a kind of stripping gold constituent divested by gold from base material, and this constituent comprises one or more stripping gold compound, and assistant director of a film or play's electric compound; Wherein, this stripping gold compound can form covalently bonded with gold, thus is divested by the gold on base material, and by the effect of this assistant director of a film or play's electric compound, can reduce voltage and not hinder completing of base material and shell gold, wherein, this constituent does not comprise any prussiate.Present invention also offers the using method of above-mentioned stripping gold constituent.Due to the golden mode of existing stripping, for operator, all there is suitable danger, and the liquid waste disposal in process also comparatively bothers, adds and can injure ground, shell golden speed and molten gold amount all have room for improvement.In view of this, the present invention attempts providing a kind of stripping technology for gold of cyanide-free, except except efficient recovery gold, and can avoiding the variety of problems that above-mentioned prior art runs into.
Description
Technical field
The present invention has and shells golden constituent about one, particularly about the stripping gold constituent that divested by gold from base material and its using method.
Background technology
Along with prosperity and the development of electronic industry, electronic waste reclaims industry and also arises at the historic moment, particularly along with recent metal raw material price significantly rises liter, the recovery of metallic scrap is made to be subject to larger attention, and numerous dealer also drops into more capital, be devoted to promote the efficiency of salvage material and the purity of material.Wherein, with the recovery of noble metal, similarly be gold-plated printed circuit board (PCB), golden finger, flexible base plate, lead frame and spare part etc., all can pass through recovery process by the row recycling again of golden waste material.
In traditional technical field, because gold (Gold) is the high noble metal of a kind of chemical stability, its be not easy by any acid, basic solution corrode or dissolve, therefore usual tradition stripping gold (or claiming molten gold) technology is all use chloroazotic acid or prussiate mostly, divests gold-plated and is reclaimed.
Just use chloroazotic acid to divest gold-plated technology, because the allotment of chloroazotic acid (aquaregia) is very easy to, and most metallic substance can be dissolved, therefore in conventional techniques by a large amount of employings.But on the other hand, because the corrodibility of chloroazotic acid is extremely strong, for operator, its potentially dangerous is also quite large, therefore protection often will give special heed to.
As for, with regard to using the technology of prussiate (cyanide) stripping gold, what use prussiate to produce contains cyanide waste liquor, and wastewater flow rate is few, cyanide content is high, and containing micro heavy.Waste liquid first must dilute about 500 times of ability process, increases water consumption and cost, and contained micro-noble metal will blend together mud and cannot reclaim simultaneously.Be stressed that especially, in shelling gold treatment stage, easy generation has volatility and the prussiate of tool toxicity, the exchange of human tissue cell and oxygen can be stoped during contact, cause necrocytosis, very large to the harm of heart and brain, belong to restrictive highly toxic substance, therefore careless slightlyly will endanger operator.
Except above-mentioned to except the harm of personnel, all can damage ground with chloroazotic acid stripping gold or the chemical stripping method based on prussiate, especially ground can corrode by chloroazotic acid completely, and the gold-plated defective products therefore for continuous electroplating terminal cannot be processed again, can only gold recovering, ground then lost efficacy because of infringement.
In addition, and use both chemical substances above-mentioned stripping gold, it is shelled golden speed and all to have greatly improved space, especially slower with prussiate; And the molten gold amount that both chemical substances above-mentioned shell golden gained is neither high, it is also a problem to be improved.
Due to the golden mode of existing stripping, for operator, all there is suitable danger, and the liquid waste disposal in process also comparatively bothers, adds and can injure ground, shell golden speed and molten gold amount all have room for improvement.In view of this, the present invention attempts providing a kind of stripping technology for gold of cyanide-free, except except efficient recovery gold, and can avoiding the variety of problems that above-mentioned prior art runs into.
Summary of the invention
For solving the problems of the technologies described above, the object of this invention is to provide the golden constituent of a kind of stripping.
Another object of the present invention is to provide a kind of stripping gold constituent divested by gold from base material.
Another object of the present invention is to provide a kind of using method of the stripping gold constituent divested by gold from base material.
First, the invention provides a kind of stripping gold constituent divested by gold from base material, this constituent comprises one or more stripping gold compounds, and wherein this stripping gold compound can form covalently bonded with gold, thus is divested by the gold on base material; And assistant director of a film or play's electric compound, by the effect of this assistant director of a film or play's electric compound, can reduce voltage and not hinder completing of base material and shell gold, wherein this constituent does not comprise any prussiate.
In above-mentioned constituent provided by the invention, preferably, described stripping gold compound comprises monothio urea (Thiocarbamide).
In above-mentioned constituent provided by the invention, preferably, described stripping gold compound comprise the vitriol with alkyl, the compound with pyridine-sulfonic acid and have in the compound of nitrilotriacetic one or more.
In above-mentioned constituent provided by the invention, preferably, described stripping gold compound comprises one or more in sulphite and Sulfates.
In above-mentioned constituent provided by the invention, preferably, described 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, described assistant director of a film or play's electric compound be selected from sodium-chlor, Repone K, boric acid, sodium hydroxide and potassium hydroxide one of them.
In above-mentioned constituent provided by the invention, preferably, described assistant director of a film or play's electric compound is phosphoric acid salt, comprises one or more in dipotassium hydrogen phosphate and potassium primary phosphate.
Present invention also offers and a kind ofly on base material, remove gold-plated working method, comprise and golden for stripping constituent is dissolved in water and injects electrolyzer; Base material containing gold is placed in this electrolyzer, and makes this substrate and positive contact; Apply voltage 0.1-4 volt and carry out electrolysis stripping gold; Wherein, shell in golden process in electrolysis, stir the stripping gold liquid in this electrolyzer, reach best to make stripping gold effect.
In aforesaid operations method provided by the invention, preferably, operating temperature range is approximately 20-70 DEG C.
In aforesaid operations method provided by the invention, preferably, Baume (° Be) value of operation is 0.5-10.
The golden constituent of stripping provided by the present invention can shell gold fast, does not hinder base material, also can not produce the Toxic waste of contaminate environment, thus efficient gold recovering.
Embodiment
About constituent of the present invention and using method thereof, by following detailed Description Of The Invention, can be further understood.
The invention provides a kind of constituent divested by gold from base material, 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 covalently bonded with gold, thus is divested by the gold on base material, adds the effect by this assistant director of a film or play's electric compound, and can reduce voltage and not hinder completing of base material and shell gold, wherein this constituent does not comprise any prussiate.
In one embodiment, stripping gold compound of the present invention comprises monothio urea (Thiocarbamide).Certain stripping gold compound also can comprise further the vitriol with alkyl, the compound with pyridine-sulfonic acid and have in the compound of nitrilotriacetic one or more.
In another embodiment, 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 organic sulfonic acid can be comprised, the sulfonic acid such as such as methanesulfonic, ethane sulfonic acid, propane sulfonic acid.In addition, also suitable compound can be selected for different base materials, the compound such as containing oil of mirbane, an alkali metal salt of such as oil of mirbane carboxylic acid, oil of mirbane carboxylic acid and alkaline earth salt.
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.For Citrate trianion, citric acid tri potassium (Tripotassiumcitratemonohydrate) can be selected further.Certainly also can be selected from boric acid, sodium hydroxide and potassium 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, potassium sulfate, sodium-chlor, ammonium chloride, Repone K, ammonium nitrate, saltpetre, SODIUMNITRATE.And in a further preferred embodiment, assistant director of a film or play's electric compound is phosphoric acid salt, comprise dipotassium hydrogen phosphate, 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 the chemical element containing toxin, therefore also can not use the compounds such as chromic salt.In addition, the constituent of the present invention also not chemical substance such as sulfur acid or hydrochloric acid.
In one embodiment, constituent of the present invention is made up of following compounds, comprises thio urea (Thiocarbamide), has the vitriol of alkyl, have the compound of pyridine-sulfonic acid, has compound and the citric acid salt of nitrilotriacetic.Wherein, there is vitriol system sulfuric acid list ester sodium salt in the ninth of the ten Heavenly Stems (sodium stearyl sulfate) of alkyl; The compound with pyridine-sulfonic acid is then pyridine-3-sulphonic acid (Pyridine-3-sulfonicacid); The compound with pyridine-sulfonic acid is pyridine-3-sulphonic acid (Pyridine-3-sulfonicacid); The compound with nitrilotriacetic is then nitrilotriacetic acid(NTA) (Nitrilotriaceticacid); Citric acid salt is then select citric acid tri potassium (Tripotassiumcitratemonohydrate).
The invention provides and a kind ofly on base material, remove gold-plated working method, working method comprises and to be dissolved in water by above-mentioned constituent and to inject an electrolyzer; Base material containing gold is placed in this electrolyzer, and makes this substrate and positive contact; Apply voltage 0.1-4 volt and carry out electrolysis stripping gold; Wherein, shell in golden process in electrolysis, stir the stripping gold liquid in this electrolyzer, reach best to make stripping gold effect.
Above-mentioned working method, its operating temperature range is approximately 20-70 DEG C.Cathode material can be selected from stainless steel, titanium or titanium alloy.Baume (° Be) value is 0.5-10.And this substrate comprises the metals such as one deck copper, nickel, aluminium or silver, and described gold be plating thereon.Wherein substrate may be the useless object such as electronic connector terminal or PCB.
Stirring in the gold of the stripping in this electrolyzer liquid step, the mode that available drum rotates stirs.Wherein, the stirring strengthening tank liquor can increase the reactivity of stripping gold, tank liquor circulating line can be utilized to go deep into bottom land, and increase filtration devices impurity, to prevent circulation pore from being blocked by impurity, affect mixing effect.
The electrolysis stripping gold that the present invention utilizes, is a kind of electrochemical process, provides electric energy by the external world, make the terminal containing gold plate on anode carry out dissociating and be dissolved in electrolytic solution, reach the effect of gold plate strip.
Electrolytic deplating process and electroplating process are just in time contrary, strip be metal plating as anode, lose electronics from piece surface and become the process of metal ion:
Plating: M
n++ ne → M
Strip: M-ne → M
n+
Mn+ in reaction formula represents the metal ion of n valency, and ne represents n electronic number, and M is then the metal representing reduction-state.
Gold concentration is tested
For substrate, the gold concentration analysis after especially gold-plated tankage stripping gold, has with under type reference, effectively can grasp the situation of golden yield.
One, instrumental method (Atomic Absorption Spectroscopy AAS)
First prepare reference liquid and get 0.5ml and shell golden liquid, add pure water and be diluted to 500ml, recycling Atomic Absorption Spectroscopy AAS schedule of operation is analyzed.
Two, golden weighting method is burnt
(1) get 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) be placed in crucible and dryout with 900 DEG C
(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/ gets) x100
Heavy industry sample reliability is tested
The corrosion resistant test of Gold plated Layer is then according to electronic industries alliance EIA-364-26B, uses the neutral brine (pH6.5-7.2) of 5%, spray reaction 24hr at temperature 35 ± 1 DEG C; And according to EIA-364-53, use the nitric acid of 70 ± 1%, temperature 23+2 DEG C, humidity is less than 60%, reaction 75mins.And the low power contact impedance (LowLevelContactResistance, LLCR) of Gold plated Layer is then according to EIA-364-23, open circuit voltage 20mVmax., test current 100mA.And gold-plated sample dipping is measured the wettability equilibrium (wettingbalance) of its coating without slicker solder stove.The test of wettability equilibrium is according to U.S. army mark specification MIL-STD-833E, and test furnace temperature 245 ± 3 DEG C, impregnating depth is 2mm, and the immersion time is 5s, and immersing with the speed left is 2mm/s, is Sn-3.0Ag-0.5Cu system without slicker solder stove.
Use constituent of the present invention, carry out the gold-plated operation of heavy industry for the gold-plated abnormal terminal of junctor through stripping Jin Houzai, relevant reliability test all passes through examination criteria really.
Resin cation (R.C.) recovery system uses
Cation type resin can the positively charged gold ion of active adsorption.When yellowing is muddy gradually by transparent clarification for the golden tank liquor of stripping, represents that gold ion concentration raises, therefore can utilize resin cation (R.C.) tower circulation and stress gold ion, allow the golden liquid of stripping by muddiness change clarification, extend the digestion time of stripping Gold electrolysis liquid.
The golden composition of stripping of the present invention, it is fast that it shells golden speed, can divest gold plate effectively completely, especially add 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 (as copper or nickel) after stripping gold.
By constituent of the present invention, successfully set up cyanide-free stripping technology for gold and carry out the prussiate system that alternative original plating industry often uses, and utilize the mode of electrolysis Gold plated Layer on bonder terminal to be divested rapidly, can be used for the recovery that gold-plated abnormal terminal carries out heavy industry operation or terminal tankage gold, reach circulation (recovery) object.
And constituent of the present invention, completely solves the harm of existing prussiate and chloroazotic acid, comprise the waste water or other waste that can not produce and be difficult to process recovery, also can not produce injury to user or environment, safety environmental protection again very.
Though the present invention illustrates as above with preferred embodiments, so itself and be not used to limit spirit of the present invention and invention entity only terminate in above-described embodiment you.Therefore not departing from the amendment done in spirit of the present invention and scope, all should be included in following claim.
Claims (7)
1. the constituent from base material, gold divested, this base material is a substrate comprising copper or nickel coating, and this comprises on the substrate of copper or nickel, at least partially nickel coating has golden film coating formed thereon, and this constituent comprises:
One or more shell gold compound, wherein, this stripping gold compound can form covalently bonded with gold, thus is divested by the gold on base material, this stripping gold compound comprise the vitriol with alkyl, the compound with pyridine-sulfonic acid and have in the compound of nitrilotriacetic one or more; And
One assistant director of a film or play's electric compound, by the effect of this assistant director of a film or play's electric compound, can voltage be reduced and not hinder completing of base material and shell gold, wherein, this constituent does not comprise any one in any prussiate, sulfuric acid, hydrochloric acid, chromic salt, divests rear injury copper or nickel coating to avoid gold.
2. constituent as claimed in claim 1, wherein, described assistant director of a film or play's electric compound be selected from Citrate trianion, oxalate, malate one of them.
3. constituent as claimed in claim 1, wherein, described assistant director of a film or play's electric compound be selected from sodium-chlor, Repone K, boric acid, sodium hydroxide and potassium hydroxide one of them.
4. constituent as claimed in claim 1, wherein, described assistant director of a film or play's electric compound is phosphoric acid salt, comprises one or more in dipotassium hydrogen phosphate and potassium primary phosphate.
5. on base material, remove a gold-plated working method, this base material is a substrate comprising layers of copper or nickel coating, at least partially layers of copper or nickel coating has golden film coating formed thereon, comprising:
One electrolyzer is provided, this electrolyzer comprises the electrolytic solution of the constituent composition described in any one of claim 1-4, wherein this stripping gold compound can form covalently bonded with gold, this assistant director of a film or play's electric compound can reduce electrolysis voltage, this constituent does not comprise any prussiate, also any one not in sulfur acid, hydrochloric acid, chromic salt, divests rear injury copper or nickel coating to avoid gold;
The described base material containing gold is placed in described electrolyzer, and makes this substrate jointed anode;
Apply direct current and determine voltage 0.1-4 volt to carry out electrolysis stripping gold;
Wherein, shell in golden process in electrolysis, stir the stripping gold liquid in described electrolyzer, reach best to make stripping gold effect.
6. method according to claim 5, wherein, service temperature is 20-70 DEG C.
7. method according to claim 5, 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 CN102797028A (en) | 2012-11-28 |
| CN102797028B true CN102797028B (en) | 2016-01-06 |
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| CN201110135260.6A Active CN102797028B (en) | 2011-05-24 | 2011-05-24 | Shell golden constituent and using method |
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| CN (1) | CN102797028B (en) |
| HK (1) | HK1178222A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI471457B (en) * | 2013-02-22 | 2015-02-01 | Uwin Nanotech Co Ltd | Metal stripping additive, composition containing the same, and method for stripping metal by using the composition |
| CN104294273B (en) * | 2014-11-08 | 2016-09-21 | 汕头超声印制板（二厂）有限公司 | A kind of nontoxic stripping gold liquid and the method being applied to printed circuit board detection thereof |
| 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 |
| 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 |
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 |
-
2011
- 2011-05-24 CN CN201110135260.6A patent/CN102797028B/en active Active
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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 |
|---|
| Electrochemical stripping of gold from Au-Ni-Cu electronic connector scrap in an aqueous solution of thiourea;J.C.LIN等;《JOURNAL OF APPLIED ELECTROCHEMISTRY》;19941231;第24卷;第2节实验部分、第3.1节pH对剥金的影响和第3.2节硫脲浓度对剥金的影响 * |
| 废印刷线路板中稀贵金属的回收现状;杨玉芬等;《稀有金属》;20040831;第28卷(第4期);第2.2.2节电化学提纯金 * |
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| Publication number | Publication date |
|---|---|
| CN102797028A (en) | 2012-11-28 |
| HK1178222A1 (en) | 2013-09-06 |
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