CN102795732A - Method for recycling gold and cyanides in surface treatment wet-process cleaning solution - Google Patents
Method for recycling gold and cyanides in surface treatment wet-process cleaning solution Download PDFInfo
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- CN102795732A CN102795732A CN2012102736167A CN201210273616A CN102795732A CN 102795732 A CN102795732 A CN 102795732A CN 2012102736167 A CN2012102736167 A CN 2012102736167A CN 201210273616 A CN201210273616 A CN 201210273616A CN 102795732 A CN102795732 A CN 102795732A
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Abstract
The invention relates to a method for recycling gold and cyanides in a surface treatment wet-process cleaning solution, which comprises the following steps: filtering a plating solution or cleaning solution with a carbon fiber filter; carrying out electrodeposition treatment to precipitate gold and heavy metals to form a metal mixture, and carrying out separation treatment with a separating unit to adsorb residual gold; reacting white lime with boric acid to form a calcium borate precipitate, separating the calcium borate precipitate and citric acid with a nano filter membrane to form a regenerative solution, and storing the regenerative solution in a regenerative solution storage tank; dissolving gold in the metal mixture by using the regenerative solution, thereby forming a gold-containing solution; and separating the gold-containing solution with a reverse osmosis module to obtain an osmotic solution which osmoses through the reverse osmosis membrane and an unosmotic concentrated solution, wherein the osmotic solution is sent back to the regenerative solution storage tank. Therefore, the method provided by the invention can implement the goal of recycling gold by using the concentrated solution containing high-concentration gold potassium cyanide.
Description
Technical field
The present invention be more particularly directed to a kind of being used for carries out the golden recovery method in the surface treatment wet process that resource reclaims to electroless plating liquid or the contained gold of scavenging solution.
Background technology
In the general surface treatment process of Electroless plating or chemical gilding; Because plating bath need use boric acid or dimethylamine borane (Dimethyl amine-borate; DMAB) be used as reductive agent; Mat is oxidized to borate misfit thing (borate complex) and the gold in the gold potassium cyanide is reduced into metallic state gold and separates out, and therefore needs constantly to replenish gold potassium cyanide, to keep the quality of Gold plated Layer.In addition, the pH value of plating bath can change along with the carrying out of processing procedure, therefore, also needs adding citric acid and Pottasium Hydroxide to be used as soda acid buffered soln, and in order to regulating extremely required scope of pH value, and above-mentioned characteristic can determine the use life time of plating bath.Yet, can not work as the gold that still contains suitable concentration in the discarded plating bath that plating bath uses, need recycle, to reduce manufacturing cost.
Need quite complicated recovery system owing to from plating bath, reclaim gold, so gold-plated dealer is sold to recovery manufacturer with plating bath to handle.
In surface treatment process, often need carry out clean to the plating piece that forms Gold plated Layer, use and remove residual plating bath on the plating piece surface; Avoid polluting or influencing next fabrication process; And generally be to be used as scavenging solution with deionized water, therefore, the scavenging solution after the cleaning can contain a spot of gold.Under the situation of market price of gold continuous rise, the gold that reclaims in the scavenging solution obtains the industry attention gradually, can use resin to reclaim with suction type.
Yet; The shortcoming of prior art is; The recovery system of gold is costliness and complicated operation not only, thus do not combine original gold-plated equipment, such as the coating bath body; Make manufacturing cost further to reduce; And the waste liquid that is produced in the gold-plated processing procedure may contain prussiate, borate misfit thing, alcohol acid (hydroxyl acid) misfit thing (such as Citrate trianion misfit thing, phosphoric acid salt misfit thing), and under the new line of environmental consciousness and relevant decree strict day by day, the dealer must have the ability of site disposal.Therefore, the recycle method of gold and prussiate can be integrated into the recovery of gold original gold-plated equipment in a kind of surface treatment wet process scavenging solution of needs, and outer processing of need not entrusting uses solving above-mentioned prior art problems.
Summary of the invention
The recycle method of main purpose of the present invention gold and prussiate in a kind of surface treatment wet process scavenging solution is provided; Especially to the gold that is comprised in plating bath in the surface treatment process or the scavenging solution; And plating bath or scavenging solution further comprise solid impurity, organic impurities, boric acid, Hydrocerol A, Potssium Cyanide, Pottasium Hydroxide, beavy metal impurity, and method of the present invention comprises the steps:
Containing the collection and treatment of gold paste liquid, is to utilize carbon fiber filter to filter solid impurity in plating bath or the scavenging solution and the organic impurities that dissolves, and forms filtered liq;
The gold separating treatment; Be to utilize electrodeposition process that the gold in the filtered liq and heavy metal are separated out with the form of metallic state and form the metal mixture that comprises metallic state gold and metallic state heavy metal; And utilize separating unit to carry out separating treatment to adsorb remaining gold, use the not auriferous parting liquid of formation;
The lime borate separating treatment; Be to utilize calcium groove with white lime; Make the boric acid in the parting liquid form the lime borate throw out; And utilize lime borate throw out and the Hydrocerol A in the nano-filtration membrane separating calcium groove, use the regeneration soln that forms boronic acid containing not and only contain Potssium Cyanide and Pottasium Hydroxide, and regeneration soln further injects the regeneration soln storage tanks;
The gold dissolution process is the metallic state gold of regeneration soln to be comprised in the dissolution of metals mixture that utilizes in the regeneration soln storage tanks, uses separating beavy metal, forms gold-containing solution; And,
The reverse osmosis separating treatment; Be utilize tool reverse osmosis membrane and high pressure pumping the reverse osmosis module; Gold-containing solution is separated into penetrating fluid that penetrates reverse osmosis membrane and the liquid concentrator that does not permeate; Wherein penetrating fluid comprises Potssium Cyanide and Pottasium Hydroxide, and it is recycled to the regeneration soln storage tanks, and liquid concentrator comprises gold potassium cyanide.
Therefore, method of the present invention produces the liquid concentrator with high density gold potassium cyanide, can be in order to being deployed into required plating bath, thereby realize reclaiming the purpose of gold, and reach the target of zero release and zero mud.
Description of drawings
Fig. 1 is the treatment scheme synoptic diagram of the recycle method of gold and prussiate in the surface treatment wet process scavenging solution of the present invention;
Fig. 2 is the system architecture synoptic diagram of recycle method of the present invention;
More than each figure shown in the indicated assembly of symbol be respectively:
10 carbon fiber filters; 20 galvanic deposit unit; 22 separating units; 30 calcium grooves; 32 nano-filtration membrane; 40 regeneration soln storage tankss; 50 lixators; 60 reverse osmosis modules; L1 plating bath or scavenging solution; The L2 filtered liq; The L3 parting liquid; The L4 regeneration soln; L5 store regenerated solution; The L6 gold-containing solution; The L7 liquid concentrator; The L8 penetrating fluid; The MX1 metal mixture; The MX2 filtering mixt; S10 contains the collection and treatment of gold paste liquid; S20 gold separating treatment; S30 lime borate separating treatment; S40 gold dissolution process; S50 reverse osmosis separating treatment.
Embodiment
Below cooperate graphic and component symbol is done more detailed explanation to embodiment of the present invention, have the knack of this art and after studying this specification sheets carefully, can implement according to this in order to do making.
Consult Fig. 1; The recycle method of gold and prussiate comprises step S10, S20, S30, S40 and S50 in the surface treatment wet process scavenging solution of the present invention; In order to contain the collection and treatment of gold paste liquid, golden separating treatment, lime borate separating treatment, golden dissolution process and reverse osmosis separating treatment respectively; Use and reclaim the gold that is comprised in plating bath in the surface treatment process or the scavenging solution; Wherein plating bath or scavenging solution can further comprise any one in solid impurity, organic impurities, boric acid, Hydrocerol A, Potssium Cyanide, Pottasium Hydroxide and the beavy metal impurity at least, and beavy metal impurity can comprise nickel or cobalt.
Simultaneously, the characteristics for clear bright the inventive method please cooperate and consult Fig. 2, the system architecture synoptic diagram of recycle method of the present invention.
At first; The recovery method of gold is to be begun to contain the collection and treatment of gold paste liquid by step S10 in the surface treatment process of the present invention; Mainly be to utilize carbon fiber filter 10 to filter solid impurity among plating bath or this scavenging solution L1 and the organic impurities that dissolves; Use forming filtered liq L2, wherein carbon fiber filter 10 has the thomel (not shown).
Then in step S20, carry out golden separating treatment; Mainly comprise electrodeposition process and separating treatment; Wherein electrodeposition process is to utilize galvanic deposit unit 20 mat electric power that the gold that is comprised among the filtered liq L2 and heavy metal are reduced into the form of metallic state and separate out; Thereby form the metal mixture MX1 that comprises metallic state gold and metallic state heavy metal, and separating treatment is to utilize the remaining gold of separating unit 22 absorption, and separating unit 22 can comprise resin; Use the not auriferous parting liquid L3 of formation, that is utilize electrodeposition process and adsorption treatment and separate all golden compositions fully.
In step S30, carry out the lime borate separating treatment; Be to comprise precipitation process and nanofiltration processing; Wherein precipitation process is that utilization has the calcium groove 30 of white lime (Ca (OH) 2) and makes the boric acid among the parting liquid L3 form the lime borate throw out; And the nanofiltration processing is to utilize nano-filtration membrane 32 with lime borate throw out and Hydrocerol A in the separating calcium groove 30; Formation comprises the filtering mixt MX2 of lime borate throw out and Hydrocerol A, and forms boronic acid containing not and only contain the regeneration soln L4 of Potssium Cyanide and Pottasium Hydroxide, and regeneration soln L4 further injects regeneration soln storage tanks 40 to form store regenerated solution L5.
Then get into step S40 to carry out golden dissolution process; Be the metallic state gold of store regenerated solution L5 that in lixator 50, utilizes in the regeneration soln storage tanks 40 to be comprised among the dissolution of metals mixture M X2; Thereby the realization separating beavy metal, form the gold-containing solution L6 that does not contain heavy metal.
At last; In step S50, carry out the reverse osmosis separating treatment, be the reverse osmosis module 60 of utilizing tool reverse osmosis membrane (not shown) and HPP (not shown), and gold-containing solution L6 is separated into liquid concentrator L7 that does not penetrate reverse osmosis membrane and the penetrating fluid L8 that penetrates reverse osmosis membrane; Wherein liquid concentrator L7 comprises gold potassium cyanide; And penetrating fluid L8 comprises Potssium Cyanide and Pottasium Hydroxide, is to be recycled to regeneration soln storage tanks 40, uses the circulating path that forms sealing.
Above-mentioned reverse osmosis membrane can be made up of polyimide (Polyimide) the spiral weaved film of nano molecular level.
In addition; For the filtered liq L2 that is produced among the further filtration step S10, can further use the two channels screen cloth to handle, be the filtered liq L2 that utilizes two channels screen cloth module (not shown) filtration step S10; Again and then the golden separating treatment of subsequent step S20 is provided; And two channels screen cloth module comprises two groups screen cloth and pump, and wherein the screen cloth of each group and pump form independently passage, and pump can extract filtered liq L2 and filter through screen cloth.Because two groups screen cloth and pumps are independent operations, therefore can avoid wherein one group of screen cloth and pump to lose efficacy because of unexpected situation makes integrated operation, improve the operational reliability of practice.
Characteristics of the present invention are to utilize and contain the collection and treatment of gold paste liquid, golden separating treatment, lime borate separating treatment, golden dissolution process and reverse osmosis separating treatment; Golden composition in order to plating bath or scavenging solution comprised in the surface treatment process that will comprise Electroless plating or chemical gilding reclaims, utilizes; Produce the liquid concentrator of tool high density gold potassium cyanide; Can be used as fresh plating bath and supply the electroless plating processing procedure to use, especially be fit to connect original coating bath and operate together, and do not need to handle outside the extra committee; Reduce whole cost, and improve operation efficiency.
Another characteristics of the present invention are that the filtering mixt that the lime borate separating treatment is produced comprises lime borate throw out and Hydrocerol A, can utilize through simple cleaning again, further improve resource and reclaim effect, realize subtracting target useless, zero release.
The above only is used to explain preferred embodiment of the present invention, is not that the present invention is done any pro forma restriction, everyly does relevant any modification of the present invention or change following of identical invention spirit, includes within rights protection scope of the present invention.
Claims (4)
1. the recycle method of gold and prussiate in the surface treatment wet process scavenging solution; It is the gold that is comprised in order in plating bath or the scavenging solution in the recovery surface treatment process; And this plating bath or this scavenging solution comprise in solid impurity, organic impurities, boric acid, Hydrocerol A, Potssium Cyanide, Pottasium Hydroxide and the beavy metal impurity any one at least; It is characterized in that this recycle method comprises following treatment step:
Containing the collection and treatment of gold paste liquid, is to utilize a carbon fiber filter to filter solid impurity in plating bath or the scavenging solution and the organic impurities that dissolves, and uses the formation filtered liq;
Carry out golden separating treatment; Be to utilize a galvanic deposit unit mat electric power to carry out electrodeposition process; And the gold in the filtered liq and heavy metal are reduced into metallic state and separate out; Formation comprises the metal mixture of metallic state gold and metallic state heavy metal, and utilizes a separating unit to carry out separating treatment, forms not auriferous parting liquid;
Carry out the lime borate separating treatment; Be to utilize a calcium groove, make the boric acid in the parting liquid form the lime borate throw out, and utilize nano-filtration membrane with lime borate throw out and Hydrocerol A in the separating calcium groove with white lime; Formation comprises the filtering mixt of lime borate throw out and Hydrocerol A; And form boronic acid containing not and only contain the regeneration soln of Potssium Cyanide and Pottasium Hydroxide, and regeneration soln further injects a regeneration solution storage and deposits groove, forms store regenerated solution;
Carrying out golden dissolution process, is in a lixator, utilizes the store regenerated solution in the regeneration soln storage tanks golden to dissolve the metallic state that is comprised in this metal mixture, uses and separates this heavy metal, forms gold-containing solution; And
Carry out the reverse osmosis separating treatment; It is a reverse osmosis module of utilizing tool reverse osmosis membrane and high pressure pumping; This gold-containing solution is separated into the penetrating fluid that penetrates reverse osmosis membrane reach the liquid concentrator that does not penetrate this reverse osmosis membrane; Wherein penetrating fluid comprises Potssium Cyanide and Pottasium Hydroxide, is recycled to the regeneration soln storage tanks, and wherein liquid concentrator comprises gold potassium cyanide.
2. the recycle method of gold and prussiate is characterized in that described beavy metal impurity comprises nickel or cobalt in the surface treatment wet process scavenging solution according to claim 1.
3. the recycle method of gold and prussiate is characterized in that in the surface treatment wet process scavenging solution according to claim 1, and described reverse osmosis membrane is to be made up of the polyimide of nano molecular level (Polyimide) spiral weaved film.
4. the recycle method of gold and prussiate in the surface treatment wet process scavenging solution according to claim 1; It is characterized in that; This recycle method further comprises uses the two channels screen cloth to handle; Be to utilize a two channels screen cloth module further to filter this to contain the filtered liq that is produced in the collection and treatment of gold paste liquid, using confession should the gold separating treatment, and this two channels screen cloth module comprises two groups of screen clothes and pumping; And the screen cloth of each group and pumping form independently passage, and this pumping is extracted filtered liq and passed through screen cloth.
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| CN201210273616.7A CN102795732B (en) | 2012-08-02 | 2012-08-02 | Method for recycling gold and cyanides in surface treatment wet-process cleaning solution |
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| CN102795732B CN102795732B (en) | 2014-04-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498546A (en) * | 2019-07-03 | 2019-11-26 | 上悦（上海）印刷有限公司 | The sewage treatment circulatory system and its method |
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| JP2003147444A (en) * | 2001-11-09 | 2003-05-21 | Nippon Parkerizing Co Ltd | Method for recovering valuable metal from metal cyanide-containing solution |
| JP4283870B1 (en) * | 2008-03-10 | 2009-06-24 | アサヒプリテック株式会社 | Metal Au recovery method |
| CN101649395A (en) * | 2009-07-17 | 2010-02-17 | 广东奥美特集团有限公司 | Method for extracting gold and recycling cyanide from cyanide-containing wastewater |
| CN102311181A (en) * | 2010-07-07 | 2012-01-11 | 刘春喜 | Embrane method and acidifying combined treatment reuse cyanide barren solution technology and method |
| CN102452703A (en) * | 2010-10-27 | 2012-05-16 | 王辉 | Method for recovering resources from gold mine cyanide barren solution |
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- 2012-08-02 CN CN201210273616.7A patent/CN102795732B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147444A (en) * | 2001-11-09 | 2003-05-21 | Nippon Parkerizing Co Ltd | Method for recovering valuable metal from metal cyanide-containing solution |
| JP4283870B1 (en) * | 2008-03-10 | 2009-06-24 | アサヒプリテック株式会社 | Metal Au recovery method |
| CN101649395A (en) * | 2009-07-17 | 2010-02-17 | 广东奥美特集团有限公司 | Method for extracting gold and recycling cyanide from cyanide-containing wastewater |
| CN102311181A (en) * | 2010-07-07 | 2012-01-11 | 刘春喜 | Embrane method and acidifying combined treatment reuse cyanide barren solution technology and method |
| CN102452703A (en) * | 2010-10-27 | 2012-05-16 | 王辉 | Method for recovering resources from gold mine cyanide barren solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110498546A (en) * | 2019-07-03 | 2019-11-26 | 上悦（上海）印刷有限公司 | The sewage treatment circulatory system and its method |
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