CN102560499A - Device for recycling printed circuit board acidic etching solution - Google Patents

Device for recycling printed circuit board acidic etching solution Download PDF

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Publication number
CN102560499A
CN102560499A CN2012100238059A CN201210023805A CN102560499A CN 102560499 A CN102560499 A CN 102560499A CN 2012100238059 A CN2012100238059 A CN 2012100238059A CN 201210023805 A CN201210023805 A CN 201210023805A CN 102560499 A CN102560499 A CN 102560499A
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China
Prior art keywords
etching
etching solution
circuit board
printed circuit
regeneration device
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Pending
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CN2012100238059A
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Chinese (zh)
Inventor
何世武
吴超
王大定
崔磊
李建光
李明军
王丹
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KUNSHAN JIECHI ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT CO LTD
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KUNSHAN JIECHI ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT CO LTD
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Application filed by KUNSHAN JIECHI ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT CO LTD filed Critical KUNSHAN JIECHI ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT CO LTD
Priority to CN2012100238059A priority Critical patent/CN102560499A/en
Publication of CN102560499A publication Critical patent/CN102560499A/en
Pending legal-status Critical Current

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Abstract

The invention provides a device for recycling printed circuit board acidic etching solution, which comprises a waste etching solution storage tank, a composite membrane electrolytic cell, an etching solution overflow tank, a jet flow absorption tank, a jet aerator, a pipeline and a waste solution pump. The composite membrane electrolytic cell is divided into a cathode chamber and an anode chamber though the composite membrane; the etching solution storage tank is connected with the cathode chamber and communicated with an etching cylinder of the production line; the etching solution overflow tank is connected with the anode chamber and communicated with the etching cylinder of the production line; an air inlet of the jet aerator is connected with an air outlet of the anode chamber, and the jet flow absorption tank is connected with the jet aerator and communicated and circulated with the etching cylinder of the production line. In the invention, elementary copper is dissolved out at the cathode by adopting the electrolysis principle so as to reduce the content of copper ions in the waste etching solution; and cuprous ions in the etching solution overflow tank and the anode chamber are oxidized by chlorine produced by anodic electrolysis. In the invention, no pollutants are discharged in the recycling process so that economic benefit is realized, and multilayer interests such as environment protection and material recycling are also attained.

Description

A kind of printed circuit board acidic etching liquid cyclic regeneration device
Technical field
The present invention is applicable to printed circuit board etching technique field, relates in particular to a kind of printed circuit board acidic etching liquid cyclic regeneration device.
Background technology
The World PCB industry production value accounts for more than 1/4th of the electronic component industry gross output value, is the maximum industry of proportion in each electronic component segmentation industry, and industry size reaches 40,000,000,000 dollars.Simultaneously, because its unique status in the electronics basic industry has become most active industry in the contemporary electronic component industry.
Etching is as the important process in the PCB processing procedure, and acidic etching liquid is widely used because have that lateral erosion is little, speed is easy to control and be prone to characteristics such as regeneration.In etching process, Cu 2+Generate Cu with the Cu effect +, along with the carrying out of etching reaction, Cu +Quantity is more and more, Cu 2+Reduce, the etching solution etch capabilities descends very soon, for keeping stablizing etch capabilities, needs to add oxygenant and makes Cu +Be converted into Cu as early as possible 2+Simultaneously as the interior Cu of etching cylinder 2+When concentration reaches certain numerical value or the solution of etching cylinder when surpassing certain volume, need timely exclusive segment etching solution to guarantee the normal operation of etching work procedure, this discharge etching solution is referred to as etching waste liquor.
Pollute and reach certain economic benefits for environment is reduced, most of method of cyclic regeneration of using replaces directly handling before the method that reclaims copper, and because technological immature extensively not sending out is used, the method for reprocessing cycle is following at present:
1, extraction electrodip process: this method is mixed acidic etching waste liquid with extraction agent mutually; Extraction agent is extracted the cupric ion in the etching solution; After the sulfuric acid back extraction, obtain copper-bath, obtain elemental copper after the electrolysis, and the etching solution that is lowered behind the cupric ion returns the etching line use through allotment.This method needs to regulate pH value to just just extraction of 1-2 with ammoniacal liquor when extraction; And the non-constant of acidic extractant extracting power, it is slow that cupric ion reduces, and carries extraction agent in the etching solution easily secretly; Can increment at the process liquid medicine of regulating pH value, and disadvantage such as oxygenant can't be provided.
2, electrolysis with ion-exchange film method of reproduction: this method is with anionic membrane negative electrode and anode to be separated, and the principle of ion migration makes cl ions move to anode when utilizing electrolysis, thereby anolyte and the circulation of etching cylinder reach the regeneration of Red copper oxide ion.But this method energy consumption in the process of electrolytic regeneration is big, the cost height and the cracky of ionic membrane, and the chlorine of generation can not reclaim, and not only causes the waste of drawing resource but also pollute the draw ring border.
3, oxalate precipitation method: this method is with the reaction of the cupric ion in oxalic acid and the acidic etching liquid, the etching solution reuse behind the reduction cupric ion.But this method can only reclaim hydrochloric acid, improves the volumetric molar concentration of hydrochloric acid, can't the regenerated acidic etching in required oxygenant, use repeatedly the back easily can increment and impurity increase.
Summary of the invention
The present invention provides a kind of printed circuit board acidic etching liquid cyclic regeneration device; In its when operation device, not only can continuous and automatic, can effectively solve the technical problem of acidic etching liquid regeneration extra interpolation oxygenant of needs and reprocessing cycle simultaneously.
The object of the invention is realized through following technical scheme:
A kind of printed circuit board acidic etching liquid cyclic regeneration device; Comprise etching waste liquor storage tanks, composite diaphragm electrolyzer, etching solution overflow groove, jet absorption cell, ejector, pipeline and waste drains pump, said composite diaphragm electrolyzer is divided into cathode compartment and anolyte compartment through composite diaphragm:
Said etching waste liquor storage tanks links to each other with cathode compartment and communicates with production line etching cylinder 8;
Said etching solution overflow groove links to each other with the anolyte compartment, and communicates with production line etching cylinder through pipeline and waste drains pump;
The inlet mouth of said ejector links to each other with the venting port of said anolyte compartment, and said jet absorption cell links to each other with ejector and communicates and circulate with production line etching cylinder.
Preferably, link to each other with waste drains pump through pipeline between said etching waste liquor storage tanks, composite diaphragm electrolyzer, etching solution overflow groove, jet absorption cell, ejector and the production line etching cylinder.
Preferably, be placed with no coating metal titanium plate in the said cathode compartment, and link to each other with the negative pole of direct supply; Be placed with the conduction titanium anode plate of noble coatings such as scribbling ruthenium, rhodium, iridium in the said anolyte compartment, and link to each other with the positive pole of direct supply.
Preferably, can be divided into several cathode compartments and anolyte compartment in the said composite diaphragm electrolyzer, also a plurality of composite diaphragm electrolyzer parallel connections or series connection.
Preferably, the water-in of said ejector links to each other with the bottom of jet absorption cell, and the water outlet of ejector links to each other with the top of jet absorption cell.
Preferably, said acidic etching liquid cyclic regeneration device also comprises emission-control equipment, and this emission-control equipment is connected with the top vent of cathode compartment, etching solution overflow groove and jet absorption cell respectively; Said emission-control equipment also comprises the alkali lye spray equipment.
Utilize electrolysis principle to separate out elemental copper through this acidic etching liquid cyclic regeneration device at negative electrode; And generation acidic etching liquid; Acidic etching liquid flows into the anolyte compartment through composite diaphragm from cathode compartment; The strong oxidizer chlorine that in the anolyte compartment, utilizes the cl ions electrolysis principle to produce, the cuprous ion in the oxide etch waste liquid.
Compared with prior art, the advantage of technical scheme of the present invention is:
A kind of printed circuit board acidic etching liquid cyclic regeneration device of the present invention; Utilize electrolysis principle to separate out elemental copper at negative electrode; Reduce the copper ion concentration in the etching waste liquor, and utilized the cl ions electrolysis principle to produce strong oxidizer chlorine, the cuprous ion in the oxide etch waste liquid; Both solved and added oxygenant in the prior art extraly and come Red copper oxide ionic technical problem; Reduce manufacturing cost, and do not added impurity in the regenerated etching solution, guaranteed the consistence of regenerated etching solution and fresh etching solution; Simultaneously can also reclaim the very high cathode copper of purity, and not have discharge of wastewater, realize etching work procedure cleaner production .
Description of drawings
Fig. 1 is the structural representation of a kind of printed circuit board acidic etching liquid cyclic regeneration device of the present invention.
Fig. 2 is the schematic flow sheet of a kind of printed circuit board acidic etching liquid cyclic regeneration device of the present invention.
Label declaration among the figure: 1, etching waste liquor storage tanks, 2, the composite diaphragm electrolyzer, 3, the etching solution overflow groove, 4, the jet absorption cell, 5, ejector, 6, pipeline, 7, waste drains pump, 8, production line etching cylinder,
2.1, cathode can, 2.2, anode slot.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Consult Fig. 1; A kind of printed circuit board acidic etching liquid of the present invention cyclic regeneration device; Comprise etching waste liquor storage tanks 1, composite diaphragm electrolyzer 2, etching solution overflow groove 3, jet absorption cell 4, ejector 5, pipeline 6 and waste drains pump 7 etc., composite diaphragm electrolyzer 2 is made up of with anolyte compartment 2.2 cathode compartment 2.1.
Separate mutually by composite diaphragm in the middle of cathode compartment 2.1 and the anolyte compartment 2.2, and be placed with no coating metal titanium plate in the said cathode compartment 2.1 and link to each other with the negative pole of direct supply; Be placed with the conduction titanium anode plate of noble coatings such as scribbling ruthenium, rhodium, iridium in the anolyte compartment 2.2, and link to each other with the positive pole of direct supply.
Contain cupric ion in the printed circuit board acidic etching liquid, and bivalent cupric ion plays a major role to etching; Along with the carrying out that produces, bivalent cupric ion can reduce gradually in the etching solution in process of production, and cuprous ion increases gradually, and this makes the etch capabilities of etching solution reduce greatly, becomes waste liquid.Contain a large amount of bivalent cupric ions and a certain amount of cuprous ion in the waste liquid, and the cupric ion total amount surpasses certain numerical value, no longer possessed etch capabilities.
Printed circuit board acidic etching liquid cyclic regeneration device provided by the invention; Etching waste liquor storage tanks 1 and production line etching cylinder 8 are connected; Store the etching waste liquor in the production line etching cylinder 8, and with this etching waste liquor through providing to cathode compartment 2.1 under waste drains pump 7 effects.Reduction reaction takes place in cathode compartment 2.1 at etching waste liquor under the effect of electric current; Its cupric ion is reduced into elemental copper; Flow to anolyte compartment 2.2 through composite diaphragm then, and same under the effect of electric current etching solution oxidizing reactions take place in above-mentioned anolyte compartment 2.2, its ORP redox potential raises.The etching solution that reduces cupric ion and rising ORP redox potential has had new activity again; Its logical overflow spout flows in the above-mentioned etching solution overflow groove 3; After production line etching cylinder inner control system sends the too high signal of proportion by in the said waste drains pump 7 suction production line etching cylinders 8; Stop after sending signal once more, unnecessary liquid medicine just flows out to the above-mentioned etching waste liquor storage cylinder 1 from riser in the production line etching cylinder 8 and add behind the regenerated liquid.And the purpose that the regenerated liquid in the said etching solution overflow groove 3 adds is to reduce the proportion in the production line etching cylinder 8 and improves ORP redox potential in the part cylinder.
Further, cathode compartment 2.1 is connected with etching waste liquor storage tanks 1, and this etching waste liquor is separated out elemental copper after getting into cathode compartment 2.1 on negative plate, and concrete reaction formula is expressed as: Cu 2++ 2e=Cu greatly reduces the copper ion concentration in the etching waste liquor, owing to intake and the water outlet liquid level difference, etching solution migrates in the anolyte compartment 2.2 then, and under galvanic action, the anodic cl ions loses electronics, generates chlorine, and concrete reaction formula is expressed as: 2Cl --2e=Cl 2, because the strong oxidation of chlorine is oxidized to bivalent cupric ion with the cuprous ion in the anolyte compartment, concrete reaction formula is expressed as: Cl 2+ 2CuCl=2CuCl 2Thereby, realized the regeneration of copper ions acidic etching liquid.
Will produce 1mol chlorine owing to produce 1mol copper in the electrolytic process; Though the Red copper oxide ion has consumed a part in above-mentioned anolyte compartment 2.2; But also have a large amount of chlorine in anolyte compartment 2.2, to overflow, the present invention is the purpose that reaches holomorphosis, after etching waste liquor regeneration; The unnecessary chlorine that produces is anti-through the etching solution in the following and above-mentioned jet absorption cell 4 of the effect of ejector 5, and specifically reaction formula is expressed as: Cl 2+ 2CuCl=2CuCl 2The inlet mouth of ejector 5 links to each other with the venting port of anolyte compartment 2.2, and the water-in jet of ejector 5 absorbs cylinder 4 bottoms and links to each other, and its water outlet absorbs cylinder 4 tops with jet and links to each other.And the acidic etching liquid pump circulation in etching solution in the jet absorption cell 4 and the production line etching cylinder 8 makes the cuprous ion in its etching cylinder be oxidized to bivalent cupric ion, guarantees that acidic etching liquid has enough etch activity.
This printed circuit board acidic etching liquid cyclic regeneration device also comprises an emission-control equipment; This emission-control equipment is connected with cathode compartment 2.1, etching solution overflow groove 3, jet absorption cell 4 top vent respectively; Collect the waste gas (chlorine and hydrogenchloride) in cathode compartment 2.1, etching solution overflow groove 3, the jet absorption cell 4; In emission-control equipment, comprise an alkali lye feeding mechanism, this aqueous alkali feeding mechanism provides alkaline solution; Utilize strong base solution and above-mentioned waste gas to carry out neutralization reaction, thereby realize the qualified discharge of waste gas.And this alkali lye feeding mechanism is the aqueous alkali spray equipment.Alkaline solution is restriction not, can be sodium hydroxide, calcium hydroxide etc.
Consult Fig. 2; The flow process signal of a kind of printed circuit board acidic etching liquid cyclic regeneration device of the present invention: printed circuit board acidic etching liquid cyclic regeneration device of the present invention; Utilize electrolysis principle to separate out elemental copper at negative electrode; Reduce the content of cupric ion in the etching waste liquor, thereby reach the purpose of etching waste liquor reprocessing cycle; Utilize electrolysis principle to produce strong oxidizer chlorine; Come the cuprous ion in the oxide etch waste liquid; Solved and added oxygenant in the prior art extraly and come Red copper oxide ionic technical problem; Reduce production cost, and do not added impurity in the regenerated etching solution, guaranteed the consistence of regenerated etching solution and fresh etching solution.
The chlorine that the fluidic device assurance electrolysis of regenerating unit of the present invention produces does not directly discharge but is back in the production line etching cylinder, has improved the utilization ratio of chlorine on the one hand, has also reduced the exhaust gas discharging amount on the other hand, reduces environmental pollution.
The emission-control equipment of regeneration system rapidly of the present invention, waste gas that this regeneration system rapidly is produced such as chlorine, hydrogen chloride gas carry out neutralizing treatment, have guaranteed the zero release of waste gas, have realized environmental protection requirement.
The foregoing description just is to let the one of ordinary skilled in the art can understand content of the present invention and enforcement according to this in order technical conceive of the present invention and characteristics to be described, to be its objective is, can not limit protection scope of the present invention with this.The variation or the modification of every equivalence that the essence of content has been done according to the present invention all should be encompassed in protection scope of the present invention.

Claims (8)

1. printed circuit board acidic etching liquid cyclic regeneration device; It is characterized in that; This acidic etching liquid cyclic regeneration device comprises etching waste liquor storage tanks (1), composite diaphragm electrolyzer (2), etching solution overflow groove (3), jet absorption cell (4), ejector (5), pipeline (6) and waste drains pump (7), and said composite diaphragm electrolyzer (2) is divided into cathode compartment (2.1) and anolyte compartment (2.2) through composite diaphragm:
Said etching waste liquor storage tanks (1) links to each other with cathode compartment (2.1) and communicates with production line etching cylinder (8);
Said etching solution overflow groove (3) links to each other with anolyte compartment (2.2), and communicates with production line etching cylinder (8) through pipeline (6) and waste drains pump (7);
The inlet mouth of said ejector (5) links to each other with the venting port of said anolyte compartment (2.2), and said jet absorption cell (4) links to each other with ejector (5) and communicates and circulate with production line etching cylinder (8).
2. printed circuit board acidic etching liquid cyclic regeneration device according to claim 1; It is characterized in that, link to each other with waste drains pump (7) through pipeline (6) between said etching waste liquor storage tanks (1), composite diaphragm electrolyzer (2), etching solution overflow groove (3), jet absorption cell (4), ejector (5) and the production line etching cylinder (8).
3. printed circuit board acidic etching liquid cyclic regeneration device according to claim 1 is characterized in that, is placed with no coating metal titanium plate in the said cathode compartment (2.1), and links to each other with the negative pole of direct supply.
4. printed circuit board acidic etching liquid cyclic regeneration device according to claim 1 is characterized in that, is placed with the conduction titanium anode plate of noble coatings such as scribbling ruthenium, rhodium, iridium in said anolyte compartment (2.2), and links to each other with the positive pole of direct supply.
5. printed circuit board acidic etching liquid cyclic regeneration device according to claim 1; It is characterized in that; Can be divided into several cathode compartments (2.1) and anolyte compartment (2.2) in the said composite diaphragm electrolyzer (2), also a plurality of composite diaphragm electrolyzers (2) parallel connection or series connection.
6. printed circuit board acidic etching liquid cyclic regeneration device according to claim 1; It is characterized in that; The water-in of said ejector (5) links to each other with the bottom of jet absorption cell (4), and the water outlet of ejector (5) links to each other with the top of jet absorption cell (4).
7. printed circuit board acidic etching liquid cyclic regeneration device according to claim 1; It is characterized in that; Said acidic etching liquid cyclic regeneration device also comprises emission-control equipment, this emission-control equipment respectively and the top vent of cathode compartment (2.1), etching solution overflow groove (3) and jet absorption cell (4) be connected.
8. printed circuit board acidic etching liquid cyclic regeneration device according to claim 7 is characterized in that said emission-control equipment also comprises the alkali lye spray equipment.
CN2012100238059A 2012-02-03 2012-02-03 Device for recycling printed circuit board acidic etching solution Pending CN102560499A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105039989A (en) * 2015-06-26 2015-11-11 无锡市瑞思科环保科技有限公司 Electrodeposition decoppering and regenerating method of waste copper-bearing etching liquor of acidic chlorination system
CN105177584A (en) * 2015-09-09 2015-12-23 成都虹华环保科技股份有限公司 Acidic waste etching solution cyclic regeneration system with regenerated liquid treatment function
CN107555695A (en) * 2017-10-27 2018-01-09 深圳市洁驰科技有限公司 A kind of Zero discharging system and processing method of acid etching regenerated liquid
CN109881216A (en) * 2019-04-12 2019-06-14 深圳市泓达环境科技有限公司 A kind of acidic electrolysis slot and the electrolysis producing line using it
CN112095121A (en) * 2019-06-17 2020-12-18 昆山卫司特环保设备有限公司 Method and device for regenerating and recycling waste copper liquid of printed circuit board
CN113493915A (en) * 2020-04-01 2021-10-12 健鼎(湖北)电子有限公司 Regeneration method and system of acidic etching waste liquid
CN115572975A (en) * 2022-10-13 2023-01-06 深圳市中冠环保科技有限公司 Method and device for recycling copper chloride hydrochloride etching waste liquid

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CN1896324A (en) * 2006-06-29 2007-01-17 李海涛 Extraction of copper from waste etching liquid in chloride system circuit board
CN2861181Y (en) * 2005-11-25 2007-01-24 叶建均 Regeneration and copper recovery device for copper chloride acid etching liquid
CN201834972U (en) * 2010-10-19 2011-05-18 深圳市洁驰科技有限公司 Regeneration system of acid etching liquid containing copper ions
CN202492580U (en) * 2012-02-03 2012-10-17 昆山市洁驰环保科技发展有限公司 Acid etching liquid recycling device of PCB (Printed Circuit Board)

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Publication number Priority date Publication date Assignee Title
CN2861181Y (en) * 2005-11-25 2007-01-24 叶建均 Regeneration and copper recovery device for copper chloride acid etching liquid
CN1896324A (en) * 2006-06-29 2007-01-17 李海涛 Extraction of copper from waste etching liquid in chloride system circuit board
CN201834972U (en) * 2010-10-19 2011-05-18 深圳市洁驰科技有限公司 Regeneration system of acid etching liquid containing copper ions
CN202492580U (en) * 2012-02-03 2012-10-17 昆山市洁驰环保科技发展有限公司 Acid etching liquid recycling device of PCB (Printed Circuit Board)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105039989A (en) * 2015-06-26 2015-11-11 无锡市瑞思科环保科技有限公司 Electrodeposition decoppering and regenerating method of waste copper-bearing etching liquor of acidic chlorination system
CN105039989B (en) * 2015-06-26 2017-10-17 无锡市瑞思科环保科技有限公司 A kind of acid chlorization system copper-containing etching waste solution electrodeposition decopper(ing) and regeneration method
CN105177584A (en) * 2015-09-09 2015-12-23 成都虹华环保科技股份有限公司 Acidic waste etching solution cyclic regeneration system with regenerated liquid treatment function
CN107555695A (en) * 2017-10-27 2018-01-09 深圳市洁驰科技有限公司 A kind of Zero discharging system and processing method of acid etching regenerated liquid
CN109881216A (en) * 2019-04-12 2019-06-14 深圳市泓达环境科技有限公司 A kind of acidic electrolysis slot and the electrolysis producing line using it
CN109881216B (en) * 2019-04-12 2023-11-28 株洲稷维环境科技有限公司 Acid electrolytic tank and electrolytic production line using same
CN112095121A (en) * 2019-06-17 2020-12-18 昆山卫司特环保设备有限公司 Method and device for regenerating and recycling waste copper liquid of printed circuit board
CN112095121B (en) * 2019-06-17 2023-05-09 昆山卫司特环保设备有限公司 Method and device for regenerating and recycling waste copper liquid of printed circuit board
CN113493915A (en) * 2020-04-01 2021-10-12 健鼎(湖北)电子有限公司 Regeneration method and system of acidic etching waste liquid
CN115572975A (en) * 2022-10-13 2023-01-06 深圳市中冠环保科技有限公司 Method and device for recycling copper chloride hydrochloride etching waste liquid
CN115572975B (en) * 2022-10-13 2024-08-20 中境源科技(深圳)有限公司 Method and device for recycling hydrochloric acid copper chloride etching waste liquid

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Application publication date: 20120711