CN1288075A - Circulation and regeneration technology for non-fluoride type etching agent - Google Patents
Circulation and regeneration technology for non-fluoride type etching agent Download PDFInfo
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- CN1288075A CN1288075A CN 00113699 CN00113699A CN1288075A CN 1288075 A CN1288075 A CN 1288075A CN 00113699 CN00113699 CN 00113699 CN 00113699 A CN00113699 A CN 00113699A CN 1288075 A CN1288075 A CN 1288075A
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Abstract
A cyclic regeneration technology for non-fluoride detining agent of PCB includes removing Pb, Sn and Cu from used detinning liquid and adding active components to obtain regenerated detinning agent for cyclic use. Its advantages are reducing environmental pollution, low cost and use of waste.
Description
The present invention relates to a kind ofly scrap the regeneration of moving back the agent of (weldering) tin and recycle technology.
The operation that produces the waste liquid maximum in printed circuit board (PCB) enterprise is the etching agent waste liquid, etching agent be a kind of to plumbous, tin and alloy thereof have certain dissolving capacity (general 〉=100g (Pb/Sn)/L) and dissolution rate (and insert dissolve in dissolution time be less than 3 minutes, spray time is less than 2 minutes), but to the very slow solution of the reaction of copper, in etching agent solution molten slicker solder (alloy) amount more (〉=100g/L), when molten slicker solder (alloy) speed is very slow or copper corrosion when becoming very violent, product then faces and scraps.To early stage fluoroborate-superoxide etching agent system, the American has studied to scrap in the liquid to this class and has added potassium ion and make molten tin complex ion form deposited salt, and the solution after the filtration is by adding the method (USP4673521) that fluorochemical is reused.But for non-fluoride type etching agent (USP4713144), as contain nitric acid, sulfuric acid, hydrochloric acid or other organic acid are (as amino acid, EDTA, organic sulfonic acid etc.) etching agent, though since nineteen nineties, become the first-selected type (it is non-fluoride type etching agent that the PCB enterprise more than 95% uses the latter) of backstep welding tin operation in the PCB enterprise, after being scrapped, such etching agent solution regenerates and the technology of recycle, cause such waste liquid to be entered in water drain or the river direct or disguisedly, because heavy metal (Pb-Sn-Cu) content in the waste liquid generally is higher than 100g/L, and wherein contain nitric acid and nitrate, various organism etc., thereby water resources and ecotope caused very serious pollution.A small amount of waste liquid has been extracted valuable metal earlier by the people, but the amount of nitric acid and iron nitrate, organism etc. does not reduce in the remaining afterwards raffinate, and still contains a certain amount of slicker solder, and such waste liquid still pollutes environment after discharging.
The purpose of this invention is to provide a kind of technology to the spent solution regeneration recycle behind the etching agent backstep welding tin.
The objective of the invention is to realize by following approach: a kind of non-fluoride type etching agent circulation and regeneration technology is characterized in that; To moving back that nonfluorinated type etching agent waste liquid behind the tin precipitates or solvent extraction or ion-exchange or absorption or membrane sepn are handled, separation of lead, tin, copper from waste liquid, restock combines the effective constituent of nonfluorinated type etching agent.Add precipitation agent the nonfluorinated type etching agent waste liquid that moves back behind the tin carried out precipitation process, precipitation agent for contain-OH,
-SH ,-compound of S-and halide-ions, one or more.But to moving back non-fluoride type etching agent waste liquid also carrying out hydrolyzing and precipitating or chemical reduction precipitation or the electrochemical reduction depositing treatment behind the tin.The effective constituent that combines non-fluoride type etching agent of restock is acid (mineral acid and organic acid), promotor (rate accelerating material(RAM)), copper inhibitor, tensio-active agent, oxynitride inhibitor, heavy metal complexing agent.Mineral acid comprises thionamic acid, and organic acid comprises and contains carboxylic acid group-COOH and sulfonic group-SO
3The organic acid of H as naphthene sulfonic acid, phenylformic acid, trifluoroacetic acid, Succinic Acid, citric acid, gluconic acid, methylsulphonic acid, can be one or more organic acid mixtures during use.Promotor (rate accelerating material(RAM)) comprises various oxygenants, pro-oxidant and acid, as superoxide, peroxycarboxylic acid, Mono Chloro Acetic Acid, can be the mixture of one or more promotor during use.Copper inhibitor comprises nitrogen-containing heterocycle compound, citric acid, phosphoric acid, hexamethylenetetramine, thiocyanide, triazole compound and their mixture.Heavy metal complex is to form the material of stablizing complex ion with lead, tin, copper, as ethylenediamine tetraacetic acid (EDTA), halogen ion, aminocarboxylic acid and their mixture.The oxynitride inhibitor is various ammonium salts and urea.
The present invention is by carrying out recycling utilization to the waste liquid behind the etching agent backstep welding tin, has following technique effect, the one, environmental benefit, by the waste liquid behind the etching agent backstep welding tin is carried out recycling utilization, make and cause the PCB enterprise of very big pollution to move back the zero release that the tin operation has realized waste water environment, solved the problem of source of pollution, the 2nd, economic benefit, the separation of the slicker solder copper in the waste liquid, both avoided pollution to environment, increased a considerable byproduct income again, to separating the waste liquid restock active principle of slicker solder copper, recycle reduces to use and opens cylinder etching agent raw material 2/3, make the cost of producing etching agent descend 2/3, have tangible economic benefit and competitive edge.
The invention will be further described below in conjunction with embodiment:
Embodiment 1
Guangdong circuit board plant backstep welding tin waste liquid contains free nitric acid 13.5% (W/V) after measured, and stanniferous copper is respectively 2.8 grams per liters, 96 grams per liters.Get 1 liter of this waste liquid (proportion about 1.38), boiled 1 hour, sedimentation and filtration, filtered liquid extracts with organic solvent (Lix983 of HENKEL company), water tin copper content after measured is respectively 2 grams per liters and 0.8 grams per liter, and volume is 860 milliliters, to wherein adding 48.5 milliliter of 68% nitric acid, 12 gram iron nitrates (technical grade), 2 gram dodecyl sodium sulfonates, 35 milliliters of methylsulphonic acids (70% technical grade), 5 gram ethylenediamine tetraacetic acid (EDTA)s, 1 gram Ammonium bicarbonate food grade, 10 milliliters of copper inhibitors (contain mercapto benzothiazole 8%, the ethanol-water solution that contains hexamethylenetetramine 5%), be chilled to 938 milliliters of room temperature gained solution after the mixing, proportion 1.26, moving back tin test (dip bath processes) shows, the tin speed of moving back of this regenerated liquid is≤73 seconds, and moving back the tin capacity is 163 grams per liters, 3 minutes insoluble coppers, plate face light is clean and tidy behind the backstep welding tin, and is identical with the application performance of newly opening the cylinder etching agent.
Embodiment 2
Hunan circuit board plant backstep welding tin waste liquid, contain free nitric acid 14.1% (W/V), slicker solder copper content is respectively 34.3 grams per liters, 67.1 grams per liter, 4.8 grams per liter, iron 2.9% (W/V) is got 1 liter of this waste liquid, after underpressure distillation (100 mmhg) goes out nitric acid 118 grams, filter, through adding 15 gram industrial sulphuric acids (96%) behind the Zeo-karb, 2.5 restrain ammonium sulfate and 1.5 gram sodium n-butyl-xanthates in the filtrate, feed 1 gram hydrogen sulfide again, boil after-filtration, filtrate contains slicker solder copper and is respectively 0.9 grams per liter, 1.2 grams per liter, 0.7 grams per liter is refunded the nitric acid that steams, replenish 37 milliliter of 68% industrial nitric acid, 15 gram industrial nitric acid iron, 30 milliliters of technical grade 70% methylsulphonic acids, 10 gram thionamic acids, 5 gram glycine, 6 gram Mono Chloro Acetic Acids, 1.5 gram imidazoles, 0.5 gram hexamethylenetetramine, be chilled to room temperature behind the mixing, get 916 milliliters of solution, proportion 1.27 moves back tin test (dip bath processes) and shows, the tin speed of moving back of this regenerated liquid is≤76 seconds, moves back tin capacity 154 grams per liters; Copper not in 3 minutes, plate face light is clean and tidy behind the backstep welding tin, and is identical with the application performance of newly opening the cylinder etching agent.
Embodiment 3
Zhejiang circuit board plant backstep welding tin waste liquid, contain free nitric acid 12.6% (W/V) after measured, slicker solder copper iron level is respectively 36 grams per liters, 66 grams per liters, 4.1 grams per liter, 3.1% (W/V), get 1 liter of this waste liquid, boiled under the normal pressure 1 hour, be chilled to the room temperature after-filtration, filtrate is dropped into 20 gram industrial sulphuric acid ammoniums, be chilled to zero degree after precipitation finishes and feed 5ML1% polyacrylamide (M=160 ten thousand) clarification, clear liquid slicker solder copper content after measured is respectively 0.7 grams per liter, 1.3 grams per liters, 0.5 grams per liter, replenish the 50ML68% industrial nitric acid, 15 gram industrial nitric acid iron, the polyoxyethylene glycol of 3 gram M=400,40 gram tosic acid, 4 gram sarkosines, 1.5 the gram volatile salt, 2.5 gram triazoles are chilled to room temperature behind the mixing, 912 milliliters of gained solution, proportion 1.25 moves back tin test (dip bath processes) and shows, the tin speed of moving back of this regenerated liquid is≤78 seconds, moving back the tin capacity is 151 grams per liters, insoluble copper in 3 minutes, plate face light is clean and tidy behind the backstep welding tin, and is identical with the application performance of newly opening the cylinder etching agent.
Claims (9)
1, a kind of non-fluoride type etching agent circulation and regeneration technology is characterized in that; To moving back that nonfluorinated type etching agent waste liquid behind the tin precipitates or solvent extraction or ion-exchange or absorption or membrane sepn are handled, separation of lead, tin, copper from waste liquid, restock combines the effective constituent of nonfluorinated type etching agent.
2, non-fluoride type etching agent circulation and regeneration technology according to claim 1 is characterized in that; Add precipitation agent the nonfluorinated type etching agent waste liquid that moves back behind the tin carried out precipitation process, precipitation agent for contain-OH,
-SH ,-compound of S-and halide-ions, one or more.
3, non-fluoride type etching agent circulation and regeneration technology according to claim 1 is characterized in that; To moving back nonfluorinated type etching agent waste liquid carrying out hydrolyzing and precipitating or chemical reduction precipitation or the electrochemical reduction depositing treatment behind the tin
4, non-fluoride type etching agent circulation and regeneration technology according to claim 1 is characterized in that; The effective constituent that combines non-fluoride type etching agent of restock is acid (mineral acid and organic acid), promotor (rate accelerating material(RAM)), copper inhibitor, tensio-active agent, oxynitride inhibitor, heavy metal complexing agent.
5, non-fluoride type etching agent circulation and regeneration technology according to claim 4 is characterized in that; Mineral acid comprises thionamic acid, and organic acid comprises and contains carboxylic acid group-COOH and sulfonic group-SO
3The organic acid of H as naphthene sulfonic acid, phenylformic acid, trifluoroacetic acid, Succinic Acid, citric acid, gluconic acid, methylsulphonic acid, can be one or more organic acid mixtures during use.
6, non-fluoride type etching agent circulation and regeneration technology according to claim 4 is characterized in that; Promotor (rate accelerating material(RAM)) comprises various oxygenants, pro-oxidant and acid, as superoxide, peroxycarboxylic acid, Mono Chloro Acetic Acid, can be one or more organic acid mixtures during use.
7, non-fluoride type etching agent circulation and regeneration technology according to claim 4 is characterized in that; Copper inhibitor comprises nitrogen-containing heterocycle compound, citric acid, phosphoric acid, hexamethylenetetramine, thiocyanide, triazole compound and their mixture.
8, non-fluoride type etching agent circulation and regeneration technology according to claim 4 is characterized in that; Heavy metal complex is to form the material of stablizing complex ion with lead, tin, copper, as ethylenediamine tetraacetic acid (EDTA), halogen ion, aminocarboxylic acid and their mixture.
9, non-fluoride type etching agent circulation and regeneration technology according to claim 4 is characterized in that; The oxynitride inhibitor is various ammonium salts and urea.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113699 CN1288075A (en) | 2000-09-21 | 2000-09-21 | Circulation and regeneration technology for non-fluoride type etching agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113699 CN1288075A (en) | 2000-09-21 | 2000-09-21 | Circulation and regeneration technology for non-fluoride type etching agent |
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| CN1288075A true CN1288075A (en) | 2001-03-21 |
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| CN 00113699 Pending CN1288075A (en) | 2000-09-21 | 2000-09-21 | Circulation and regeneration technology for non-fluoride type etching agent |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523947A (en) * | 2013-08-26 | 2014-01-22 | 赣州聚环科技有限公司 | Solder removing waste liquid regeneration treatment method |
| CN105297020A (en) * | 2014-06-25 | 2016-02-03 | 优胜奈米科技有限公司 | Tin stripping additive and application thereof |
| CN107059008A (en) * | 2017-01-11 | 2017-08-18 | 长江大学 | One kind is used to strip scolding tin material tin stripping liquid and preparation method thereof on discarded PCB |
| CN107557801A (en) * | 2017-07-21 | 2018-01-09 | 深圳市祺鑫天正环保科技有限公司 | The processing method of tin removal waste liquor |
| CN110408935A (en) * | 2018-04-27 | 2019-11-05 | 惠州市鸿宇泰科技有限公司 | A kind of recycling auxiliary agent of tin removal waste liquor and the method for resource of tin removal waste liquor |
| CN114232030A (en) * | 2021-12-23 | 2022-03-25 | 广东鑫菱环境科技有限公司 | PCB methanesulfonic acid tin stripping waste liquid recycling method and application thereof |
-
2000
- 2000-09-21 CN CN 00113699 patent/CN1288075A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523947A (en) * | 2013-08-26 | 2014-01-22 | 赣州聚环科技有限公司 | Solder removing waste liquid regeneration treatment method |
| CN105297020A (en) * | 2014-06-25 | 2016-02-03 | 优胜奈米科技有限公司 | Tin stripping additive and application thereof |
| CN105297020B (en) * | 2014-06-25 | 2021-06-25 | 优胜奈米科技有限公司 | Tin stripping additive and application thereof |
| CN107059008A (en) * | 2017-01-11 | 2017-08-18 | 长江大学 | One kind is used to strip scolding tin material tin stripping liquid and preparation method thereof on discarded PCB |
| CN107557801A (en) * | 2017-07-21 | 2018-01-09 | 深圳市祺鑫天正环保科技有限公司 | The processing method of tin removal waste liquor |
| CN110408935A (en) * | 2018-04-27 | 2019-11-05 | 惠州市鸿宇泰科技有限公司 | A kind of recycling auxiliary agent of tin removal waste liquor and the method for resource of tin removal waste liquor |
| CN114232030A (en) * | 2021-12-23 | 2022-03-25 | 广东鑫菱环境科技有限公司 | PCB methanesulfonic acid tin stripping waste liquid recycling method and application thereof |
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