CN103602988A - Resourceful treatment and cyclic utilization method of PCB circuit board waste etching liquid - Google Patents
Resourceful treatment and cyclic utilization method of PCB circuit board waste etching liquid Download PDFInfo
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Abstract
The invention relates to a resourceful treatment and cyclic utilization method of PCB circuit board waste etching liquid. The resourceful treatment and cyclic utilization method comprises following steps: an alkali source is added into the waste etching liquid so as to promote decomposition of cuprammouium complex ions in the waste etching liquid, and transfer free ammonium ions into molecular state ammonia; waste water generated by the hybrid reaction is delivered into a deamination reaction tower, further decomposition of cuprammouium complex ions is realized in the deamination reaction tower, and free ammonia molecules in the waste water is exhausted via the top of the deamination reaction tower in gaseous state, is delivered into an ammonia absorption tower, is absorbed by concentrated hydrochloric acid, and is transferred into ammonium chloride solution so as to realize ammonium/ammonia resource recovery; and copper ions in the waste water is transferred into copper compounds to precipitate and realize recovery. According to the resourceful treatment and cyclic utilization method of PCB circuit board waste etching liquid, ammonia-nitrogen removal rate and ammonia recovery rate are both above 99.9%; copper recovery rate is more than 95%; coupling of ammonia recovery process and ammonium chloride synthetic process is realized; recoveries of ammonia/ammonium and copper are realized respectively; the ammonium chloride solution prepared by recycling can be recycled as a new etching solution after supplement of additives and deionized water; and all-component resourceful utilization of circuit board etching ammonia-nitrogen wastewater is realized.
Description
Technical field
The present invention relates to the treatment process of the etching waste liquor containing ammonia and copper that a kind of wiring board course of processing produces, particularly a kind of circuitboard etching waste liquid is carried out with concentrated hydrochloric acid, absorbing the method that produces ammonium chloride again after ammoniacal liquor separation.
Background technology
Along with the high speed development of hyundai electronics information industry, the development of printed circuit board (PCB) industry is very rapid, and at present, China has become world-class printed circuit board manufactured place.Wherein etching work procedure is a part for proportion maximum in PCB Production Flow Chart.Cupric ion in etching solution reaches after finite concentration just as discharging of waste liquid.Etching solution has alkalescence and acid two large classes.In alkaline etching waste liquid for producing, contain a large amount of copper, it is mainly with [Cu (NH
3)
4]
2+form exist, also contain a large amount of ammonia nitrogen etc. simultaneously.Copper content average out to 160g/L wherein, ammonia-nitrogen content is up to 200g/L.This class waste liquid is as caused serious environmental pollution and great economic waste without dealing carefully with utilization.
In recent years, for the recycling of wiring board alkaline etching liquid, investigator both domestic and external does a lot, and has also obtained some achievements.
CN1931720A discloses a kind of method with producing ammonium chloride with waste circuit board etching solution, adopts and directly with acidic etching liquid and alkaline etching liquid neutralisation, obtains mantoquita precipitation-copper oxychloride, then the solution sinking after copper is carried out to evaporative crystallization obtain ammonia chloride crystal.Yet, because acidic etching liquid comprises cupric chloride, hydrochloric acid, sodium-chlor and oxygenant Multiple components, adopt in this way and sink after copper, in solution, contain mentioned component, the purity of the ammonia chloride crystal obtaining after evaporative crystallization is difficult to guarantee.
CN102925704A discloses a kind of method and apparatus of producing cupric oxide and ammoniacal liquor with alkaline copper etching waste liquor, adds sodium hydroxide in alkaline etching liquid, uses reactor water steam-heated cal(l)andria to carry out ammonia still process in 3-4 hour, and reclaims ammoniacal liquor and cupric oxide.The main drawback that this technique exists is that steam consumption is large, product be ammoniacal liquor can not direct reuse to etch process, complex operation step, completes the processing of batch time used long.Due to Heating temperature lower (60～80 ℃), in the waste water after processing, ammonia-nitrogen content is not easy up to standard.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the technical problem to be solved in the present invention is to propose etching waste liquor recycling treatment and the circulation utilization method containing ammonia and copper that a kind of wiring board course of processing produces.The present invention carries out alkaline etching waste liquid for producing with concentrated hydrochloric acid, to absorb and produce ammonium chloride again after ammoniacal liquor separation, has realized the qualified discharge of the complete recycle of circuitboard etching waste liquid and ammonia nitrogen waste water.
For reaching this object, the present invention by the following technical solutions:
The recycling treatment of PCB circuitboard etching waste liquid and a circulation utilization method, described etching waste liquor is alkaline etching liquid, by following steps, processes:
(1) in raw material waste water, add alkali source, make the ammonium salt in waste water change molecular state ammonia into, with react the high temperature deamination water heat exchange that deammoniation tower tower reactor flows out after enter reaction deammoniation tower;
(2) in reaction deammoniation tower, thermal source passes into from tower reactor, and ammonia is separated under hot effect with water, and amino molecule is discharged from tower top with steam-like;
(3) from water, separated ammonia steam enters ammonia absorber by reacting deammoniation tower tower top, and by concentrated hydrochloric acid, is absorbed as ammonium chloride solution in ammonia absorber, realizes the regeneration of etching solution.
The present invention can optionally carry out: (4) high temperature deamination water flows out from reaction deammoniation tower tower reactor, and carries out heat exchange with raw material waste water, obtains low temperature deamination water after cooling, and carrying out solid after solid-liquid separation is copper compound precipitation, and liquid is deamination waste water.
The partial oxidation ammonium solution obtaining in step (3) refluxes as absorption agent, and rest part is as etching solution reuse.
The present invention adds alkali source to promote the cuprammonium complexing ion in water to decompose in etching waste liquor, and free ammonium radical ion is transformed into molecular state ammonia, waste water after hybrid reaction enters reaction deammoniation tower, in reaction deammoniation tower, cuprammonium complexing ion further decomposes, simultaneously the free ammonia molecule in water is discharged from tower top with gaseous state, enters in ammonia absorber by concentrated hydrochloric acid, to be absorbed as ammonium chloride solution and to realize ammonium/ammonia resource and reclaim.Ammonia nitrogen concentration≤15mg/L in the waste water of discharging at the bottom of reaction deammoniation tower tower, cupric ion in waste water forms copper compound precipitation and reclaims, utilize concentrated hydrochloric acid to absorb liberated heat in ammonia process simultaneously and react the required heat of deammoniation tower, realization response pick up the heat for providing.
Raw material waste water and the mixed pH>10 of alkali source that step of the present invention (1) is described, for example 10.2,10.7,11.3,11.5,12,12.5,12.9 etc., preferred pH is 12.Described alkali source is preferably sodium hydroxide and/or calcium hydroxide, more preferably the sodium hydroxide of mass concentration 45%.
The theoretical plate number of the described reaction deammoniation tower of step (2) is at least 6, for example, can select 6, and 10,16,18,26 etc.
Described thermal source is preferably liberated heat in electricity, thermal oil, steam or synthesizing chlorinated ammonium process.The heat that synthesizing chlorinated ammonium process (absorption process) produces can, for reaction deammoniation tower tower reactor is heated, make ammonia separated under heat effect with water.
The described ammonia gauge pressure separated with water of step (2) is-0.09～1.4MPa, for example, can select-0.02MPa 0.1MPa, 0.3MPa, 0.7MPa, 1.1MPa, 1.35MPa etc., further preferred 0.7MPa.
The inside of the described reaction deammoniation tower of step (2), column bottom temperature remains on 70～150 ℃, for example, can select 70.2 ℃, and 76.5 ℃, 85.3 ℃, 90 ℃, 98.7 ℃, 104.2 ℃, 120 ℃, 134.7 ℃, 148.9 ℃ etc., further preferably 90～130 ℃, most preferably 110 ℃.
In isolated ammonia steam described in step (3), the volumn concentration of ammonia is 1～70%, for example, can select 1.5%, 11%, 20%, 25.8%, 34.2%, 40%, 48%, 55.6%, 63%, 68.7% etc., is preferably 20～50%.
The temperature of ammonia steam is 80～145 ℃.
Described concentrated hydrochloric acid is analytical pure, and wherein the quality percentage composition of hydrogenchloride is 5～40%.
The internal layer material of described ammonia absorber is a kind of in graphite, tetrafluoroethylene, poly-difluoroethylene, titanium or composite titanium material.
Ammonia steam described in step (3) absorbs by the spray of concentrated hydrochloric acid, and the temperature of reaction of absorption process is 150～200 ℃, for example 152 ℃, 158.7 ℃, 170 ℃, 173.5 ℃, 179 ℃, 186 ℃, 193 ℃, 199 ℃ etc., is preferably 170 ℃.The heat that absorption process produces heats to the deamination water of reaction deammoniation tower tower reactor by the heat transfer tube in ammonia absorber to boil again, thereby separated under heat effect with water for making to react in deammoniation tower ammonia.
The part that the described ammonium chloride solution of step (3) is back in ammonia absorber is 0.5～5.5 with the volume ratio as etching solution reuse part, for example 0.51,0.57,0.6,1.2,1.8,3,3.7,4.3,4.8 etc., be preferably 1～3.
The pH value of the ammonium chloride solution reclaiming is 4～6, more preferably 5.
The equipment that the high temperature deamination water that step (4) is described and raw material waste water carry out heat exchange is plate-type heat exchanger, shell and tube heat exchanger or spiral tube heat exchanger.
Ammonia nitrogen concentration≤15mg/L in high temperature deamination water described in step (4).
Compare with prior art scheme, the present invention has following beneficial effect:
(1) the present invention passes through to adopt decomplexing deamination recovery technology, the ammonia in separated alkaline etching liquid, and obtain ammonium chloride solution with the ammonia that concentrated hydrochloric acid absorption extraction goes out, realize the direct reuse of etching solution.
(2) the ammonium chloride solution purity that the present invention obtains is high, can meet the service requirements of etch process, and in the discharge waste liquid simultaneously obtaining, ammonia nitrogen concentration meets environmental emission standard requirement completely.
(3) the present invention adopts the copper compound in mechanical separation recycle-water, and resource is reclaimed again in both decontaminations.
(4) in the present invention, the main equipment adopting is reaction deammoniation tower and ammonia absorber, technological process is simple, and energy consumption is low, and especially this ammonia absorber is when utilizing concentrated hydrochloric acid absorbing ammonia ammonium chloride processed, the heat of generation is heated reaction deamination tower reactor, greatly reduce energy consumption.
Accompanying drawing explanation
Fig. 1 reclaims respectively the process flow diagram of ammonium chloride, copper compound the etching waste liquor containing ammonia and copper producing from the wiring board course of processing.
In figure: A-feed preheater; B-reacts deammoniation tower; C-ammonia absorber; D-solid-liquid separator;
1-raw material waste water; 2-alkali source; Waste water after 3-heating; 4-ammonia steam; 5-concentrated hydrochloric acid; 6-product ammonium chloride solution; 7-backflow ammonium chloride solution; 8-deamination water; The 9-steam that boils again; 10-thermal source; 11-high temperature deamination water; 12-low temperature deamination water; 13-copper compound precipitation; 14-deamination waste water.
Below the present invention is described in more detail.But following example is only simple and easy example of the present invention, does not represent or limit the scope of the present invention, and protection scope of the present invention is as the criterion with claims.
Embodiment
Below in conjunction with accompanying drawing and by embodiment, further illustrate technical scheme of the present invention.
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
As shown in Figure 1, a kind of recycling treatment of PCB circuitboard etching waste liquid and circulation utilization method, described etching waste liquor is alkaline etching liquid.To 1 adding alkali source 2 in raw material waste water, make the ammonium salt in waste water change molecular state ammonia into, enter reaction deammoniation tower B with the waste water 3 that reacts high temperature deamination water 11 that deammoniation tower B tower reactor flows out and become after heat exchange after heating in feed preheater A; In reaction deammoniation tower B, thermal source 10 passes into from tower reactor, and ammonia is separated under hot effect with water, and amino molecule is discharged from tower top with steam-like; Ammonia steam 4 separated from water enters ammonia absorber C by reaction deammoniation tower B tower top, and by concentrated hydrochloric acid 5 spray-absorptions, be ammonium chloride solution in ammonia absorber C, wherein, backflow ammonium chloride solution 7 refluxes as absorption agent, product ammonium chloride solution 6 is as etching solution reuse, thereby realizes the regeneration of etching solution.High temperature deamination water 11 flows out from reaction deammoniation tower B tower reactor, and carry out heat exchange with raw material waste water 1 in feed preheater A, and after cooling, obtain low temperature deamination water 12, in solid-liquid separator D, carry out after solid-liquid separation, solid is copper compound precipitation 13, and liquid is deamination waste water 14.The heat that in ammonia absorber C, absorption process produces adds the thermosetting steam 9 that boils again to the deamination water 8 of reaction deammoniation tower B tower reactor by the heat transfer tube in ammonia absorber C, returns to reaction deammoniation tower B.
The internal layer material of described ammonia absorber C is a kind of in graphite, tetrafluoroethylene, poly-difluoroethylene, titanium or composite titanium material.Described feed preheater A is plate-type heat exchanger, shell and tube heat exchanger or spiral tube heat exchanger.
Embodiment 1
The water quality of certain circuitboard etching waste liquid is: ammonia nitrogen concentration 50000mg/L, copper ion concentration 50000mg/L, pH value 9.4.During processing, after being regulated to pH to 11.5 with 45% sodium hydroxide, raw material waste water is transported in the reaction deammoniation tower that is provided with 6 theoretical stages, 70 ℃ of column bottom temperatures, 70 ℃ of tower top temperatures, under the normal atmosphere of gauge pressure-0.9, carry out deamination processing, ammonia quantity in isolated ammonia steam (volumn concentration of ammonia) is 70%, ammonia steam is absorbed as ammonium chloride solution by concentrated hydrochloric acid after entering ammonia absorber, the temperature of reaction of absorption process is 150 ℃, in the ammonium chloride generating, 85% refluxes, and remains 15% as product-collecting.After high temperature deamination water after deamination and raw material wastewater heat exchange, through solid-liquid separation, obtain the water after copper compound and processing.Analysis shows, the water-quality guideline after processing is as follows: ammonia nitrogen concentration 10mg/L, total copper concentration 0.5mg/L, pH value 8.6, the ammonium chloride solution pH value 6 of recovery.
Embodiment 2
The water quality of certain circuitboard etching waste liquid is: ammonia nitrogen concentration 100000mg/L, copper ion concentration 110000mg/L, pH value 9.6.During processing, after being regulated to pH to 11.5 with 45% sodium hydroxide, raw material waste water is transported in the reaction deammoniation tower that is provided with 6 theoretical stages, 90 ℃ of column bottom temperatures, 90 ℃ of tower top temperatures, under 0.1 normal atmosphere of gauge pressure, carry out deamination processing, ammonia quantity in isolated ammonia steam (volumn concentration of ammonia) is 70%, ammonia steam is absorbed as ammonium chloride solution by concentrated hydrochloric acid after entering ammonia absorber, the temperature of reaction of absorption process is 175 ℃, in the ammonium chloride generating, 85% refluxes, and remains 15% as product-collecting.After high temperature deamination water after deamination and raw material wastewater heat exchange, through solid-liquid separation, obtain the water after copper compound and processing.Analysis shows, the water-quality guideline after processing is as follows: ammonia nitrogen concentration 10mg/L, total copper concentration 0.5mg/L, pH value 8.6, the ammonium chloride solution pH value 6 of recovery.
Embodiment 3
The water quality of certain circuitboard etching waste liquid is: ammonia nitrogen concentration 150000mg/L, copper ion concentration 130000mg/L, pH value 9.7.During processing, after being regulated to pH to 12 with 45% sodium hydroxide, raw material waste water is transported in the reaction deammoniation tower that is provided with 16 theoretical stages, 110 ℃ of column bottom temperatures, 100 ℃ of tower top temperatures, carry out deamination processing under 7 normal atmosphere of gauge pressure, ammonia quantity in isolated ammonia steam (volumn concentration of ammonia) 50%, ammonia steam is absorbed as ammonium chloride solution by concentrated hydrochloric acid after entering ammonia absorber, the temperature of reaction of absorption process is 190 ℃, and in the ammonium chloride of generation, 75% refluxes, and remains 25% as product-collecting.After high temperature deamination water after deamination and raw material wastewater heat exchange, through solid-liquid separation, obtain the water after copper compound and processing.Analysis shows, the water-quality guideline after processing is as follows: ammonia nitrogen concentration 12mg/L, total copper concentration 1mg/L, pH value 8.7, the ammonium chloride solution pH value 5 of recovery.
Embodiment 4
The water quality of certain circuitboard etching waste liquid is: ammonia nitrogen concentration 200000mg/L, copper ion concentration 160000mg/L, pH value 9.8.During processing, after being regulated to pH to 12.5 with 45% sodium hydroxide, raw material waste water is transported in the reaction deammoniation tower that is provided with 26 theoretical stages, 130 ℃ of column bottom temperatures, 110 ℃ of tower top temperatures, under 14 normal atmosphere of gauge pressure, carry out deamination processing, ammonia quantity in isolated ammonia steam (volumn concentration of ammonia) 20%, ammonia steam is absorbed as ammonium chloride solution by concentrated hydrochloric acid after entering ammonia absorber, the temperature of reaction of absorption process is 200 ℃, in the ammonium chloride generating, 50% refluxes, and remains 50% as product-collecting.After high temperature deamination water after deamination and raw material wastewater heat exchange, through solid-liquid separation, obtain the water after copper compound and processing.Analysis shows, the water-quality guideline after processing is as follows: ammonia nitrogen concentration 15mg/L, total copper concentration 1mg/L, pH value 8.9, the ammonium chloride solution pH value 4 of recovery.
Embodiment 5
The water quality of certain circuitboard etching waste liquid is: ammonia nitrogen concentration 230000mg/L, copper ion concentration 180000mg/L, pH value 9.9.During processing, after being regulated to pH to 14 with 45% sodium hydroxide, raw material waste water is transported in the reaction deammoniation tower that is provided with 26 theoretical stages, 150 ℃ of column bottom temperatures, 130 ℃ of tower top temperatures, carry out deamination processing under 14 normal atmosphere of gauge pressure, ammonia quantity in isolated ammonia steam (volumn concentration of ammonia) 1%, ammonia steam is absorbed as ammonium chloride solution by concentrated hydrochloric acid after entering ammonia absorber, the temperature of reaction of absorption process is 180 ℃, and in the ammonium chloride of generation, 34% refluxes, and remains 66% as product-collecting.After high temperature deamination water after deamination and raw material wastewater heat exchange, through solid-liquid separation, obtain the water after copper compound and processing.Analysis shows, the water-quality guideline after processing is as follows: ammonia nitrogen concentration 15mg/L, total copper concentration 1mg/L, pH value 9, the ammonium chloride solution pH value 4 of recovery.
The present invention to circuitboard etching waste liquid ammonia nitrogen removal frank and ammonia recovery all more than 99.9%, the rate of recovery >95% of copper, and ammonia is reclaimed and the coupling of ammonium chloride synthesis technique, ammonia/ammonium in waste liquid, copper are reclaimed respectively, after the ammonium chloride solution supplemented by additives of recovery preparation, deionized water, can be used as new etching solution and recycle, realize the total composition recycling that circuit board etching operation produces ammonia nitrogen waste water.Present method flow process is simple, stable, and floor space is little, and processing efficiency is high.
Applicant's statement, the present invention illustrates treatment process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned treatment step, does not mean that the present invention must rely on above-mentioned treatment step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of the selected raw material of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. the recycling treatment of PCB circuitboard etching waste liquid and a circulation utilization method, is characterized in that, described etching waste liquor is alkaline etching liquid, by following steps, processes:
(1) in raw material waste water, add alkali source, make the ammonium salt in waste water change molecular state ammonia into, with react the high temperature deamination water heat exchange that deammoniation tower tower reactor flows out after enter reaction deammoniation tower;
(2) in reaction deammoniation tower, thermal source passes into from tower reactor, and ammonia is separated under hot effect with water, and amino molecule is discharged from tower top with steam-like;
(3) from water, separated ammonia steam enters ammonia absorber by reacting deammoniation tower tower top, and by concentrated hydrochloric acid, is absorbed as ammonium chloride solution in ammonia absorber, realizes the regeneration of etching solution.
2. the method for claim 1, is characterized in that, optionally carries out: (4) high temperature deamination water flows out from reaction deammoniation tower tower reactor, and carry out heat exchange with raw material waste water, after cooling, obtain low temperature deamination water, carrying out solid after solid-liquid separation is copper compound precipitation, and liquid is deamination waste water;
Preferably, the partial oxidation ammonium solution obtaining in step (3) refluxes as absorption agent, and rest part is as etching solution reuse.
3. method as claimed in claim 1 or 2, is characterized in that, raw material waste water and the mixed pH>10 of alkali source that step (1) is described, and preferably pH is 12; Described alkali source is preferably sodium hydroxide and/or calcium hydroxide, the sodium hydroxide that further preferred mass concentration is 45%.
4. the method as described in one of claim 1-3, is characterized in that, the theoretical plate number of the described reaction deammoniation tower of step (2) is at least 6; Described thermal source is preferably liberated heat in electricity, thermal oil, steam or synthesizing chlorinated ammonium process;
Preferably, the described ammonia gauge pressure separated with water of step (2) is-0.09～1.4MPa, further preferred 0.7MPa;
Preferably, the inside of the described reaction deammoniation tower of step (2), column bottom temperature remains on 70～150 ℃, and further preferably 90～130 ℃, most preferably 110 ℃.
5. the method as described in one of claim 1-4, is characterized in that, in the described isolated ammonia steam of step (3), the volumn concentration of ammonia is 1～70%, is preferably 20～50%;
Preferably, the temperature of ammonia steam is 80～145 ℃;
Preferably, described concentrated hydrochloric acid is analytical pure, and wherein the quality percentage composition of hydrogenchloride is 5～40%;
Preferably, the internal layer material of described ammonia absorber is a kind of in graphite, tetrafluoroethylene, poly-difluoroethylene, titanium or composite titanium material.
6. the method as described in one of claim 1-5, is characterized in that, the described ammonia steam of step (3) absorbs by the spray of concentrated hydrochloric acid, and the temperature of reaction of absorption process is 150～200 ℃, is preferably 170 ℃.
7. the method as described in one of claim 1-6, is characterized in that, the part that the described ammonium chloride solution of step (3) is back in ammonia absorber is 0.5～5.5 with the volume ratio as etching solution reuse part, is preferably 1～3;
Preferably, the pH value of the ammonium chloride solution of recovery is 4～6, more preferably 5.
8. the method as described in one of claim 2-7, is characterized in that, the equipment that the high temperature deamination water that step (4) is described and raw material waste water carry out heat exchange is plate-type heat exchanger, shell and tube heat exchanger or spiral tube heat exchanger.
9. the method as described in one of claim 2-8, is characterized in that, ammonia nitrogen concentration≤15mg/L in the described high temperature deamination water of step (4).
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| CN104386874A (en) * | 2014-04-08 | 2015-03-04 | 红板（江西）有限公司 | Processing technology for high-concentration waste liquid in circuit board industry |
| CN106191867A (en) * | 2016-08-25 | 2016-12-07 | 东莞市广华化工有限公司 | A kind of wiring board acidic etching waste liquid resource reusing method |
| CN106336039A (en) * | 2016-09-26 | 2017-01-18 | 大连东泰产业废弃物处理有限公司 | Method of non-noxious treatment of scrapped silicon dioxide etching solution |
| 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 |
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| CN104386874B (en) * | 2014-04-08 | 2016-02-17 | 红板（江西）有限公司 | A kind of wiring board industry high-concentration waste liquor treating process |
| CN104386874A (en) * | 2014-04-08 | 2015-03-04 | 红板（江西）有限公司 | Processing technology for high-concentration waste liquid in circuit board industry |
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| CN106336039A (en) * | 2016-09-26 | 2017-01-18 | 大连东泰产业废弃物处理有限公司 | Method of non-noxious treatment of scrapped silicon dioxide etching solution |
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