CN101215062A - Method and system for reclaiming valuable resource in acidic etching waste liquid - Google Patents
Method and system for reclaiming valuable resource in acidic etching waste liquid Download PDFInfo
- Publication number
- CN101215062A CN101215062A CNA2007100327988A CN200710032798A CN101215062A CN 101215062 A CN101215062 A CN 101215062A CN A2007100327988 A CNA2007100327988 A CN A2007100327988A CN 200710032798 A CN200710032798 A CN 200710032798A CN 101215062 A CN101215062 A CN 101215062A
- Authority
- CN
- China
- Prior art keywords
- etching waste
- waste liquor
- pipeline
- links
- recycling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
Provided are system of value resource in acidic corrosion waste fluid and a recycling method. The recycling method of the invention includes the following steps that adding oxidation agent and concentrated sulfuric acid into the corrosion waste fluid, pre-heating and heating the corrosion waste fluid, evaporating out water vapor and hydrogen chloride under negative pressure and recycling hydrochloric acid, the residue separates hydric sulphate from blue copperas crystal via centrifugal filtration and recycle hydric sulphate, washing blue copperas crystal by blue copperas crystal solution and absolute ethyl alcohol and recycling blue copperas. The recycling system comprises an oxidation ditch, a dosage bunker, a pre-heater, a heat booster, an evaporation tank, a filter, a cooler, a spraying and absorbing device and the like. The recycling method of the invention increases the recovery rate of metal copper and hydrogen chloride, with both recovery rates more than 99%. The method can employ scheme of batch operation or continuous recycling, which is adapted for industry utilization.
Description
Technical field
The present invention relates to the recovery method and the recovery system of valuable resource in a kind of acidic industrial effluent, the recovery method and the recovery system of valuable resource in particularly a kind of acidic etching waste liquid.
Background technology
Acidic etching waste liquid is the trade effluent that produces in a kind of internal layer circuit graphic making process of multilayer board, and main component is Cu
2+, H
+, CuCl, [CuCl
3]
2-[CuCl
4]
2-, the content of copper is 120～160g/L, density is 1.2～1.4g/mL.China is the big producing country that is only second to the printed board of Japan, and the copper of the copper-clad plate form that is consumed has accounted for 30% of the whole nation.In the etching process of printed board, the copper in the copper-clad plate more than 60%～70% is etched and enter in the etching solution, therefore produces a large amount of high density copper-containing acid waste waters.As discharging of waste liquid, a large amount of acidic etching waste liquids is contaminate environment seriously, and causes the huge waste of resource, therefore, efficiently, economical and contamination-freely realize the recovery of valuable resource in the acidic etching waste liquid will having significant environmental benefit and economic benefit.
At present, in the acidic etching waste liquid of public publish the recovery method of valuable resource mainly contain neutralisation, electrolytic process and simple distillation.
Neutralisation (Jiang Shaowang: utilize the printed board acid etching waste liquor to produce copper sulfate, " aerospace processing ", 1995 (1): 21～22), promptly add an amount of alkaline solution and heating, make the cupric ion in the etching waste liquor be converted into the cupric oxide precipitation, in precipitation, add dilute sulphuric acid, get copper sulfate through crystallization.This method copper recovery is low, only is 85%, and the purity of copper sulfate is 70%, still has the copper-containing wastewater discharging.
Electrolytic process (U.S. Pat P 4051001, China Patent No. ZL 200520067901.9, Chinese patent publication number CN 1896324A) is divided into conventional electrolysis method and membrane electrolysis again.The conventional electrolysis method is because of chlorion generation oxidizing reaction in the anolyte, and anode surface has a large amount of chlorine to generate.Although can draw gas by conduit, perhaps inside and outside groove, carry out chemical absorption, be difficult to avoid the effusion of chlorine.Membrane electrolysis still is in the laboratory study stage because of being subjected to the restriction of ion-exchange membrane preparation technology.In addition, electrolytic process can't obtain fine and close copper coin, is mingled with morely in the gained copper, and commercial value is low.
Simple distillation (Chinese patent publication number CN1824835A) is about to distill in the sulfuric acid adding etching waste liquor, reclaim through condensation and obtain hydrochloric acid, and the raffinate after the distillation then is dissolved in water, and crystallisation by cooling gets copper sulfate crystal.This method can not discharge the cuprous ion that is the complex compound form, and the rate of recovery of copper is lower.In addition, the add-on of the vitriol oil is by cupric ion, and is excessive 5%～15%, and excess sulfuric acid is less, is difficult to displace fully the hydrogenchloride in the distillation etching waste liquor.Since be air distillation, temperature required higher in the distillation later stage.
Summary of the invention
At the deficiencies in the prior art, first purpose of the present invention provides a kind of raising metallic copper and the hydrogenchloride rate of recovery, is applicable to the recovery method of the acidic etching waste liquid of industrial application.
Another object of the present invention provides a kind of recovery system that realizes its recovery method as resource in the above-mentioned acidic etching waste liquid.
Recovery method of the present invention may further comprise the steps successively:
1. under agitation condition, in acidic etching waste liquid, add oxygenant, make etching waste liquor transparent;
2. V by volume
Etching waste liquor: V
Sulfuric acid=1: 0.15～0.60, stir down with dosing in the vitriol oil adding etching waste liquor of 98wt%;
3. the etching waste liquor of the above-mentioned adding vitriol oil of preheating;
4. be that 100～140 ℃ saturated vapor heats above-mentioned etching waste liquor with temperature;
5. under 80～130 ℃ and negative pressure, evaporate, evaporate water vapor and hydrogenchloride;
6. resistates separates sulfuric acid through centrifuging with copper sulfate crystal, with copper/saturated copper sulphate solution, absolute ethanol washing copper sulfate crystal.
Described oxygenant is air or 30% hydrogen peroxide.
Comprise CuCl, H in the acidic etching waste liquid
2CuCl
3If, do not carry out oxidation pre-treatment, white CuCl precipitation then appears in evaporative process, and the rate of recovery of copper and the purity of copper sulfate all have reduction.Adding oxygenant in the etching waste liquor, to carry out pretreated purpose be to make the cuprous ion that is the complex compound form in the etching waste liquor be converted into the cupric ion of divalence, thereby reduce the cupric ion of complex compound form in the etching waste liquor, to improve the rate of recovery of metallic copper.
The purpose that adds the vitriol oil (density 1.84g/mL) is to change the chlorion in the copper chlorine title complex in the etching waste liquor into hydrogenchloride, and collaborative copper sulfate promotes separating out of hydrogenchloride and separates out because of salting-out effect promotes the crystallization of copper sulfate.Evidence, the sulfuric acid add-on is excessive less, is difficult to displace fully the hydrogenchloride in the distillation etching waste liquor, so, strengthened the vitriolic consumption.Because the vitriol oil has bigger solution heat,, vitriolic wants slowly intermittently to add in case of necessity so adding.In addition, the vitriol oil adds the temperature that can improve etching waste liquor, saves a part of heat input.In fact, sulfuric acid has three effects: 1. metathesis is about to cupric chloride and is converted into copper sulfate; 2. change HCl-H
2The azeotropic point of O system promptly promotes the volatilization of hydrogenchloride; And, promote copper sulfate crystallization from solution to separate out 3. because of salting-out effect (common-ion effcet).Sulfuric acid add-on of the present invention is by cupric ion, and excessive 45%～480%.
The medium of the etching waste liquor of the above-mentioned adding vitriol oil of preheating is the water vapor of etching waste liquor evaporation formation and the mixture of hydrogenchloride, and temperature is 80～130 ℃.
Test-results shows that the gas phase that forms in the evaporation is formed relevant with evaporation process.Early stage, gas phase was mainly water vapor, and heat is higher, is used for the preheating etching waste liquor, can save heat energy.The gas phase in later stage is the mixture of hydrogenchloride and water vapor, can obtain the hydrochloric acid of 22wt%～28wt% after the condensation, the unabsorbed hydrogenchloride of non-condensable gases and minute quantity, i.e. tail gas, absorption capable of circulation.
Owing to adopt negative pressure evaporation, no hydrogenchloride is overflowed in the removal process.
The resistates that evaporates behind water vapor and the hydrogenchloride contains sulfuric acid and copper sulfate.Resistates separates sulfuric acid and copper sulfate crystal through centrifuging.The sulfuric acid that obtains can be used for handling next batch etching waste liquor, recycle.Copper sulfate crystal is with copper/saturated copper sulphate solution, absolute ethanol washing, to remove the impurity of surface adsorption.
Solids is cupric sulfate crystals CuSO
4.xH
2O (wherein x is 1,3 and 5).Usually, what of crystal water in the cupric sulfate crystals free vitriolic amount, vaporization temperature etc. determined in the etching waste liquor.If the copper sulfate that reclaims is used to prepare cathode plate, then Zui You selection is CuSO
4.5H
2O.In case of necessity, use water dissolution, the mixture of the above-mentioned cupric sulfate crystals of recrystallization obtains CuSO
4.5H
2O.
Recovery method of the present invention, the rate of recovery of copper and hydrochloric acid all is higher than 99%.This method can adopt batch-type to implement, if increase device, also can adopt the recovery method of continous way.
Be used to realize that the system of recovery method of the present invention comprises as lower device:
An oxidation trough 1 is used to hold etching waste liquor and to the oxidation pre-treatment of etching waste liquor, it is equipped with the inlet of a gas inlet or hydrogen peroxide;
A dosing vessel 4 links to each other with oxidation trough with valve 3 by pipeline 2, is used to hold the etching waste liquor through oxidation pre-treatment, and it is equipped with a sulfuric acid inlet and meter, whipping appts;
A preheater 22 links to each other with dosing vessel 4 with acid proof pump 6 by pipeline 5, is used for the preheating of etching waste liquor;
A well heater 15 links to each other with preheater 22 with acid proof pump 11 by pipeline 21, is used for heating and has mixed the vitriolic etching waste liquor;
An evaporating pot 16 links to each other with well heater 15 with valve 19 by pipeline 20, is used for negative pressure evaporation;
A filter 12 links to each other with evaporating pot 16 with valve 13 by pipeline 14, is used for separating the sulfuric acid and the copper sulfate crystal of the resistates after the evaporation;
A condenser 8 by pipeline 17 and valve 18, links to each other with evaporating pot 16 with pipeline 7 through preheater 22, is used for the condensation of water vapor and hydrogenchloride;
An injection resorber 10 links to each other with condenser 8 by pipeline 9, is used to produce subnormal ambient and absorbs fail the tail gas of condensation, and the use of spraying resorber 10 helps the absorption of negative pressure evaporation and tail gas.
Fig. 1 is the recovery method schema of valuable resource in the acidic etching waste liquid of the present invention.
Fig. 2 is the recovery system of valuable resource in the acidic etching waste liquid of the present invention.
In conjunction with Fig. 1, Fig. 2 recovery method of the present invention and recovery system are specified: be acid The etching waste liquor of property is inserted oxidation trough 1, and this groove is the column type plastic channel. Blast air or add dioxygen Water becomes transparent etching waste liquor after making its oxidation. This transparent etching waste liquor enters batching through pipeline 2 Groove 4, dosage bunker 4 also are the column type plastic channel, its top be equipped with a sulfuric acid entrance and meter, Agitating device. Meter is in order to control the proportioning of etching waste liquor and the concentrated sulfuric acid. In the mistake that adds the concentrated sulfuric acid In the journey, agitating device fully stirs etching waste liquor, to avoid localized hyperthermia. Etching through sulfuric acid acidation Waste liquid pumps into preheater 22 through pipeline 5 and acid-proof pump 6, produce with evaporator 16 80～130 ℃ Water vapour and hydrogen chloride generation heat exchange, the etching waste liquor temperature increase. Etching waste liquor after the preheating is through pipe Road 21 and acid-proof pump 11 pump in the heater 15, with temperature be 100～140 ℃ saturated vapor Carry out heat exchange, enter evaporator 16 by pressure differential then, carry out negative pressure evaporation. Evaporator 16 The water vapour and the hydrogen chloride that produce are introduced into preheater 22, heat are passed to etching waste liquor, then Enter condenser 8 and carry out heat exchange with cooling water, obtain hydrochloric acid after the condensation. " bearing in the evaporator 16 Press " be that condensation and Jet absorber 10 by water vapour and hydrogen chloride causes, pressure is about 0.05～0.08MPa. Tail gas is then absorbed by Jet absorber 10 circulations. The remnants that evaporator 16 produces Thing enters filter 12, the sulfuric acid of separated free and copper sulfate crystal.
Can select graphite or graphite modified plastics is the material of preheater. The effect of preheating is to utilize Waste heat improves the flowability of etching waste liquor, reduces simultaneously the cooling energy consumption. All connecting pipe all adopts anti-The carbon steel lining plastic matter pipeline of corrosion.
Embodiment
With following embodiment valuable resource recovery method of the present invention is described in detail.
Embodiment 1
2000L etching waste liquor (with content 9.2wt%, cl content 14.5wt%, density 1.3g/mL), under agitation condition, blasting air, to carry out oxidation transparent until solution.The vitriol oil of 400L 98wt% is mixed with etching waste liquor after the oxide treatment, and constantly stir, form etching waste liquor.With 0.07MPa saturated vapor heating etching waste liquor, carry out negative pressure evaporation then, pressure is 0.06MPa, discharges resistates, and filters, and then to the copper sulfate crystal copper/saturated copper sulphate aqueous solution, absolute ethanol washing, obtains CuSO
4.5H
2O 939.1Kg, purity is that 99%. rate of recovery are 99.5%.The water vapor and the hydrogenchloride that produce obtain the hydrochloric acid 1542.7Kg of 25wt% after the condensation, the rate of recovery is 99.5%.
2500L under agitation condition, adds 30% hydrogen peroxide with the etching waste liquor of embodiment 1, and is transparent until solution.The vitriol oil of 750L 95wt% is mixed with above-mentioned solution, and constantly stir.With 0.08MPa saturated vapor heating etching waste liquor, carry out negative pressure evaporation then, discharge resistates, obtain CuSO after filtration
4.3H
2O and CuSO
4.5H
2The mixture 1092.6Kg of O, the rate of recovery is 99.2%.Obtain the hydrochloric acid of 1848.6Kg 26wt% after water vapor that produces and the hydrogen chloride condensed, the rate of recovery is 99.2%.
Embodiment 3
Under agitation condition, blast air to 300L with the etching waste liquor of embodiment 1 and carry out oxide treatment, transparent until solution.The vitriol oil of 120L 98% is mixed with above-mentioned clear solution, and constantly stir.With 0.08MPa saturated vapor heating etching waste liquor, carry out negative pressure evaporation then, discharge resistates, obtain copper sulfate crystal after filtration, then, carry out purification process with the copper/saturated copper sulphate aqueous solution, absolute ethanol washing, get 140.3Kg CuSO
4.5
H2O, purity is 99.2%, the rate of recovery is 99.3%.The water vapor and the hydrogenchloride that produce obtain the hydrochloric acid 224.4Kg of 25wt% after the condensation, the rate of recovery is 99.2%.
Claims (3)
1. the recovery method of valuable resource in the acidic etching waste liquid is characterized in that may further comprise the steps successively:
1. under agitation condition, in etching waste liquor, add oxygenant, make solution transparent;
2. V by volume
Etching waste liquor: V
Sulfuric acid=1: 0.15～0.60, stir down with dosing in the vitriol oil adding etching waste liquor of 98wt%;
3. the etching waste liquor of the above-mentioned adding vitriol oil of preheating;
4. be that 100～140 ℃ saturated vapor heats above-mentioned etching waste liquor with temperature;
5. under 80～130 ℃ and negative pressure, evaporate, evaporate water vapor and hydrogenchloride;
6. resistates separates sulfuric acid through centrifuging with copper sulfate crystal, with copper/saturated copper sulphate solution, absolute ethanol washing copper sulfate crystal.
2. the recovery method of valuable resource in the acidic etching waste liquid according to claim 1 is characterized in that described oxygenant is air or 30% hydrogen peroxide.
3. be used to realize that the system of the described recovery method of claim 1 comprises with lower device:
An oxidation trough (1) is used to hold etching waste liquor and to the oxidation pre-treatment of etching waste liquor, it is equipped with the inlet of a gas inlet or hydrogen peroxide;
A dosing vessel (4) links to each other with oxidation trough with valve (3) by pipeline (2), is used to hold the etching waste liquor through oxidation pre-treatment, and it is equipped with a sulfuric acid inlet and meter, whipping appts;
A preheater (22) links to each other with dosing vessel (4) with acid proof pump (6) by pipeline (5), is used for the preheating of etching waste liquor;
A well heater (15) links to each other with preheater (22) with acid proof pump (11) by pipeline (21), is used for heating and has mixed the vitriolic etching waste liquor;
An evaporating pot (16) links to each other with well heater (15) with valve (19) by pipeline (20), is used for negative pressure evaporation;
A filter (12) links to each other with evaporating pot (16) with valve (13) by pipeline (14), is used for separating the sulfuric acid and the copper sulfate crystal of the resistates after the evaporation;
A condenser (8), by pipeline (17) and valve (18), through preheater (22), pipeline (7) links to each other with evaporating pot (16), is used for the condensation of water vapor and hydrogenchloride;
An injection resorber (10) links to each other with condenser (8) by pipeline (9), is used to produce subnormal ambient and absorbs fail the tail gas of condensation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710032798A CN100593041C (en) | 2007-12-26 | 2007-12-26 | Method and system for reclaiming valuable resource in acidic etching waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710032798A CN100593041C (en) | 2007-12-26 | 2007-12-26 | Method and system for reclaiming valuable resource in acidic etching waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101215062A true CN101215062A (en) | 2008-07-09 |
| CN100593041C CN100593041C (en) | 2010-03-03 |
Family
ID=39621583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710032798A Expired - Fee Related CN100593041C (en) | 2007-12-26 | 2007-12-26 | Method and system for reclaiming valuable resource in acidic etching waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100593041C (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010009611A1 (en) * | 2008-07-21 | 2010-01-28 | 深圳市危险废物处理站有限公司 | Method for removing arsenic and iron from acidic waste solution generated during etching of printed circuit boards |
| CN101792220A (en) * | 2010-03-16 | 2010-08-04 | 杭州电子科技大学 | Comprehensive treatment method of acidic etching waste liquid |
| CN101935121A (en) * | 2010-09-02 | 2011-01-05 | 昆山联鼎环保科技有限公司 | Process for recycling alkali waste etching liquid |
| CN102107978A (en) * | 2010-12-23 | 2011-06-29 | 惠州市奥美特环境科技有限公司 | Method for resource utilization and innocent treatment of etching waste liquid containing copper in circuit board industry |
| CN102198962A (en) * | 2011-03-21 | 2011-09-28 | 福州裕龙环保开发有限公司 | Process for treating PCB production wastewater |
| CN104016402A (en) * | 2014-06-13 | 2014-09-03 | 金悦通电子（翁源）有限公司 | Copper sulfate extracting method of micro-etching waste liquor and system thereof |
| CN104085911A (en) * | 2014-06-28 | 2014-10-08 | 南通久信石墨科技开发有限公司 | Process device for generating copper sulfate by replacing copper etchant |
| WO2015150448A1 (en) * | 2014-04-01 | 2015-10-08 | Sigma Engineering Ab | Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent |
| CN105540975A (en) * | 2015-12-30 | 2016-05-04 | 北京赛科康仑环保科技有限公司 | Recycling method and system of PCB (printed circuit board) etching waste liquid |
| CN105671554A (en) * | 2016-03-17 | 2016-06-15 | 惠州市星之光科技有限公司 | Electrolytic low-content copper ion recovery device |
| CN107099802A (en) * | 2017-06-16 | 2017-08-29 | 深圳市新锐思环保科技有限公司 | A kind of novel acid etching solution resource recycling method and recycling system |
| CN107354461A (en) * | 2017-09-13 | 2017-11-17 | 田成 | A kind of printed circuit board acidic etching waste liquor process for regenerating, recovering and reutilizing |
| CN107385445A (en) * | 2017-07-27 | 2017-11-24 | 四会富士电子科技有限公司 | A kind of method that circuitboard etching waste liquid recycles |
| CN107419272A (en) * | 2017-09-14 | 2017-12-01 | 江苏泰特联合环保科技有限公司 | A kind of technique and device that hydrochloric acid and Preparation of Cupric Sulfate are reclaimed from acidic etching waste liquid |
| CN111170276A (en) * | 2020-01-16 | 2020-05-19 | 四川永祥新能源有限公司 | Hydrochloric acid analysis method |
| CN113694552A (en) * | 2020-05-22 | 2021-11-26 | 江西理工大学 | Method and system for removing fluorine and/or chlorine from sulfate solution by flash evaporation |
| CN113737184A (en) * | 2021-11-04 | 2021-12-03 | 清大国华环境集团股份有限公司 | Copper-containing etching waste liquid recovery device and copper-containing etching waste liquid recovery method |
| CN114177638A (en) * | 2021-12-28 | 2022-03-15 | 东莞市恒建环保科技有限公司 | Single-steaming treatment process for copper sulfate mother liquor |
| CN114561669A (en) * | 2022-03-03 | 2022-05-31 | 无锡中天固废处置有限公司 | Method for recycling acidic copper-containing ammonium-containing etching waste liquid |
| CN116443916A (en) * | 2023-04-28 | 2023-07-18 | 常州大学 | Method for preparing copper sulfate by combining PCB etching waste liquid |
-
2007
- 2007-12-26 CN CN200710032798A patent/CN100593041C/en not_active Expired - Fee Related
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010009611A1 (en) * | 2008-07-21 | 2010-01-28 | 深圳市危险废物处理站有限公司 | Method for removing arsenic and iron from acidic waste solution generated during etching of printed circuit boards |
| CN101792220A (en) * | 2010-03-16 | 2010-08-04 | 杭州电子科技大学 | Comprehensive treatment method of acidic etching waste liquid |
| CN101935121A (en) * | 2010-09-02 | 2011-01-05 | 昆山联鼎环保科技有限公司 | Process for recycling alkali waste etching liquid |
| CN102107978A (en) * | 2010-12-23 | 2011-06-29 | 惠州市奥美特环境科技有限公司 | Method for resource utilization and innocent treatment of etching waste liquid containing copper in circuit board industry |
| CN102107978B (en) * | 2010-12-23 | 2012-07-18 | 惠州Tcl环境科技有限公司 | Method for resource utilization and innocent treatment of etching waste liquid containing copper in circuit board industry |
| CN102198962A (en) * | 2011-03-21 | 2011-09-28 | 福州裕龙环保开发有限公司 | Process for treating PCB production wastewater |
| WO2015150448A1 (en) * | 2014-04-01 | 2015-10-08 | Sigma Engineering Ab | Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent |
| CN106661738A (en) * | 2014-04-01 | 2017-05-10 | 西格玛工程集团 | Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent |
| TWI747804B (en) * | 2014-04-01 | 2021-12-01 | 瑞典商席克馬工程有限公司 | Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent |
| CN106661738B (en) * | 2014-04-01 | 2019-11-19 | 西格玛工程集团 | By using oxygen and/or air as oxidant the copper oxide in copper etching solution |
| US9920434B2 (en) | 2014-04-01 | 2018-03-20 | Sigma Engineering Ab | Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent |
| CN104016402A (en) * | 2014-06-13 | 2014-09-03 | 金悦通电子（翁源）有限公司 | Copper sulfate extracting method of micro-etching waste liquor and system thereof |
| CN104085911A (en) * | 2014-06-28 | 2014-10-08 | 南通久信石墨科技开发有限公司 | Process device for generating copper sulfate by replacing copper etchant |
| CN105540975A (en) * | 2015-12-30 | 2016-05-04 | 北京赛科康仑环保科技有限公司 | Recycling method and system of PCB (printed circuit board) etching waste liquid |
| CN105671554B (en) * | 2016-03-17 | 2018-08-17 | 惠州市星之光科技有限公司 | A kind of electrolysis low content copper ion retracting device |
| CN105671554A (en) * | 2016-03-17 | 2016-06-15 | 惠州市星之光科技有限公司 | Electrolytic low-content copper ion recovery device |
| CN107099802A (en) * | 2017-06-16 | 2017-08-29 | 深圳市新锐思环保科技有限公司 | A kind of novel acid etching solution resource recycling method and recycling system |
| CN107385445A (en) * | 2017-07-27 | 2017-11-24 | 四会富士电子科技有限公司 | A kind of method that circuitboard etching waste liquid recycles |
| CN107354461A (en) * | 2017-09-13 | 2017-11-17 | 田成 | A kind of printed circuit board acidic etching waste liquor process for regenerating, recovering and reutilizing |
| CN107419272B (en) * | 2017-09-14 | 2019-11-12 | 江苏泰特联合环保科技有限公司 | A kind of technique and device recycling hydrochloric acid and Preparation of Cupric Sulfate from acidic etching waste liquid |
| CN107419272A (en) * | 2017-09-14 | 2017-12-01 | 江苏泰特联合环保科技有限公司 | A kind of technique and device that hydrochloric acid and Preparation of Cupric Sulfate are reclaimed from acidic etching waste liquid |
| CN111170276A (en) * | 2020-01-16 | 2020-05-19 | 四川永祥新能源有限公司 | Hydrochloric acid analysis method |
| CN113694552A (en) * | 2020-05-22 | 2021-11-26 | 江西理工大学 | Method and system for removing fluorine and/or chlorine from sulfate solution by flash evaporation |
| CN113694552B (en) * | 2020-05-22 | 2023-01-17 | 江西理工大学 | Method and system for removing fluorine and/or chlorine from sulfate solution by flash evaporation |
| CN113737184A (en) * | 2021-11-04 | 2021-12-03 | 清大国华环境集团股份有限公司 | Copper-containing etching waste liquid recovery device and copper-containing etching waste liquid recovery method |
| CN114177638A (en) * | 2021-12-28 | 2022-03-15 | 东莞市恒建环保科技有限公司 | Single-steaming treatment process for copper sulfate mother liquor |
| CN114561669A (en) * | 2022-03-03 | 2022-05-31 | 无锡中天固废处置有限公司 | Method for recycling acidic copper-containing ammonium-containing etching waste liquid |
| WO2023165021A1 (en) * | 2022-03-03 | 2023-09-07 | 无锡中天固废处置有限公司 | Method for recycling acidic copper-containing and ammonium-containing waste etching solution |
| CN116443916A (en) * | 2023-04-28 | 2023-07-18 | 常州大学 | Method for preparing copper sulfate by combining PCB etching waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100593041C (en) | 2010-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100593041C (en) | Method and system for reclaiming valuable resource in acidic etching waste liquid | |
| CN104326612B (en) | A kind of method and system reclaiming salt from Waste Water Treatment | |
| CN105217870B (en) | Reinforcing rubber accelerating agent wastewater preprocessing process | |
| CN104609633A (en) | Method and device for utilizing sewage containing ammonia and sodium | |
| CN110656248B (en) | Extraction system for separating magnesium from magnesium-containing brine by using secondary amide/alkyl alcohol composite solvent to extract lithium and boron, extraction method and application thereof | |
| CN106185810B (en) | A kind of joint disposal technique of acidic copper chloride waste etching solution | |
| CN103803753A (en) | Comprehensive recovery treatment method for H acid industrial waste water | |
| CN104876383A (en) | Method for preparing ammonia water and calcium chloride solution through decomposition recovery of ammonium chloride waste liquor | |
| WO2021088285A1 (en) | Extraction system and extraction method for extracting lithium and boron by separating calcium from calcium-containing brine with secondary amide/alkyl alcohol composite solvent, and use of extraction method | |
| CN100467671C (en) | Method for recovering hydrochloric acid and copper sulfate from acidic etching liquid | |
| CN105923877A (en) | Wastewater treatment process for wet-process chromium metallurgy | |
| CN105540975B (en) | A kind of recycling processing method and its system of PCB circuit board etching waste liquor | |
| CN110127925A (en) | A method of by the produced mixed salt recycling of waste acid treatment | |
| CN111573942A (en) | Method for recycling copper-nickel electroplating waste liquid | |
| CN109468465B (en) | Process for recovering metal copper and nickel salt from waste ABS electroplated part | |
| CN108505043B (en) | Method for regenerating and recycling PCB (printed Circuit Board) acidic etching waste liquid | |
| CN204310904U (en) | A kind of system reclaiming salt from Waste Water Treatment | |
| CN106698790A (en) | Comprehensive recycling method for graphite production wastewater | |
| CN102199704B (en) | Recycling use method of sodium chloride or sodium sulfate in hydrometallurgy | |
| Guo et al. | Recovery of copper from printed circuit board (PCB) acidic etching wastewater: Ammonia regulates the crystallization of high valued copper salt | |
| CN106517255B (en) | A kind of device and method for reducing Mg/Li ratio in old halogen | |
| Ni et al. | An extraction and precipitation process for the removal of Ca and Mg from ammonium sulfate rare earth wastewaters | |
| CN114314637A (en) | Method for preparing high-purity copper sulfate from acidic copper chloride etching waste liquid | |
| CN105177622B (en) | A kind of energy-saving electrolytic manganese production new technique | |
| CN104692447B (en) | Etching waste liquor and wiring board mud are processed the method for preparing basic copper chloride simultaneously |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| DD01 | Delivery of document by public notice |
Addressee: Hao Yu Document name: Notification to Pay the Fees |
|
| DD01 | Delivery of document by public notice |
Addressee: Hao Yu Document name: Notification of Termination of Patent Right |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100303 Termination date: 20121226 |