CN109368936A - The processing method of copper waste etching solution - Google Patents
The processing method of copper waste etching solution Download PDFInfo
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- CN109368936A CN109368936A CN201811462696.4A CN201811462696A CN109368936A CN 109368936 A CN109368936 A CN 109368936A CN 201811462696 A CN201811462696 A CN 201811462696A CN 109368936 A CN109368936 A CN 109368936A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/323—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 by electrostatic effects or by high-voltage electric fields
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/818—Employing electrical discharges or the generation of a plasma
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The present invention relates to a kind of processing methods of copper waste etching solution, comprising: decomposes copper waste etching solution under the action of load has the solid packing of catalyst, obtains the first waste liquid and the first exhaust gas；The pH to 8~10 for adjusting the first waste liquid obtains the second waste liquid；It distills the second waste liquid to obtain distillate and concentrate；Distillate biochemical treatment is purified liquid and the second exhaust gas；Concentrate burning disposal is obtained into third exhaust gas；And the first exhaust gas, the second exhaust gas and third exhaust gas are handled with waste gas treatment equipment.The processing method of above-mentioned copper waste etching solution can effectively control the decomposition rate of hydrogen peroxide in copper waste etching solution, improve the safety that hydrogen peroxide decomposes, and be discharged in treatment process without foul smell, do not pollute the environment.
Description
Technical field
The present invention relates to photoelectric fields, more particularly to a kind of processing method of copper waste etching solution.
Background technique
Copper etching process in photovoltaic industry liquid crystal manufacturing process is needed using a large amount of copper etchant solution, in the copper etchant solution
Hydrogen peroxide (15%~25%, mass fraction) containing higher concentration.When the concentration of hydrogen peroxide of copper etchant solution is reduced to erosion
Carving after efficiency does not reach requirement just becomes copper waste etching solution, and concentration of hydrogen peroxide is still very high in the copper waste etching solution, content
About 5%~20% (mass fraction) contains a certain amount of copper ion simultaneously.For controllable, the copper etchant solution for guaranteeing etch-rate
It also added a certain amount of organic amine corrosion inhibiter (such as iminodiacetic acid, pentaamino tetrazole) in formula, cause to generate
Copper waste etching solution in contain a certain amount of organic amine.
Above-mentioned copper waste etching solution yield is huge, if but deal with improperly or not in time, hydrogen peroxide can occur acutely to decompose, it deposits
In huge security risk, in addition, the decomposition of organic amine compound can generate unpleasant foul smell, environment is polluted.
Summary of the invention
Based on this, it is necessary to provide the processing method of a kind of safer and more environmentally friendly copper waste etching solution.
A kind of processing method of copper waste etching solution, comprising the following steps:
Copper waste etching solution is decomposed under the action of load has the solid packing of catalyst, obtains the first waste liquid and first useless
Gas, the catalyst are selected from least one of transition metal simple substance and transition metal oxide, and the solid packing is porous
Material；
The pH to 8~10 for adjusting first waste liquid, obtains the second waste liquid；
Second waste liquid is distilled, distillate and concentrate are obtained；
By the distillate through biochemical treatment, it is purified liquid and the second exhaust gas；
By the concentrate burning disposal, third exhaust gas is obtained；And
First exhaust gas, second exhaust gas and the third exhaust gas are handled with waste gas treatment equipment.
The processing method of above-mentioned copper waste etching solution, by the way that copper waste etching solution to be had to the porosu solid filler of catalyst through loading
It decomposes, can effectively control the decomposition rate of hydrogen peroxide, decompose hydrogen peroxide safety and stability, avoid useless because not handling
Liquid, copper ion catalyzing hydrogen peroxide acutely decomposes caused security risk, and hydrogen peroxide removal rate reaches after being catalytically decomposed
90% or more；PH by adjusting the first waste liquid can convert alkalescent waste liquid for the first acid waste liquid, so that subsequent place
It is free from environmental pollution in reason and discharge；The scavenging solution for capableing of safety dumping is obtained after distillate and concentrate are handled respectively and is given up
Gas；The exhaust gas generated in whole process discharges after waste gas treatment equipment is handled, and without obvious peculiar smell, avoids pollution environment.
In one of the embodiments, the transition metal simple substance in Ag, Cu, Cr, Fe, Mn, Pb and Pt at least
It is a kind of；And/or the transition metal oxide is selected from silver oxide, copper oxide, chromium oxide, iron oxide, manganese dioxide and lead oxide
At least one of.
The solid packing is selected from aluminium oxide, silica gel, active carbon, float stone, diatomite, leech in one of the embodiments,
At least one of stone, kaolin, bentonite, wollastonite and sepiolite.
The reaction time that the copper waste etching solution decomposes under the action of the catalyst in one of the embodiments, is
10min~30min.
The catalysis point that load has the solid packing of the catalyst that a sealing is arranged in one of the embodiments,
It solves in device, the speed that the copper waste etching solution flows through the catalytic decomposition device is 50mL/min~150mL/min.
The reagent for adjusting pH is in sodium hydroxide, potassium hydroxide and calcium hydroxide in one of the embodiments,
At least one.
The step of pH value of first waste liquid is adjusted in one of the embodiments, to 8~10, obtains the second waste liquid it
Afterwards, further include the steps that second waste liquid being filtered separation before the step of distilling second waste liquid.
The distillation is vacuum distillation in one of the embodiments,.
The volume ratio of the distillate and second waste liquid is 0.8~0.9: 1.0 in one of the embodiments,.
At in one of the embodiments, by first exhaust gas, second exhaust gas and the third exhaust gas through exhaust gas
The step of managing equipment processing includes: by first exhaust gas, second exhaust gas and the third exhaust gas through plasma apparatus
It decomposes, then handles first exhaust gas, second exhaust gas and the third exhaust gas after decomposition through spray-absorption.
Detailed description of the invention
Fig. 1 is the flow chart of the processing method of the copper waste etching solution of an embodiment.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give preferred embodiment of the invention.But the invention can be realized in many different forms, however it is not limited to herein
Described embodiment.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more saturating
It is thorough comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
Body embodiment purpose, it is not intended that in limitation the present invention.
Referring to Fig. 1, the processing method of the copper waste etching solution of an embodiment can will contain a certain amount of copper ion, mistake
The copper waste etching solution of hydrogen oxide and organic matter carries out safer and environmentally friendly decomposition and processing.
The processing method of above-mentioned copper waste etching solution the following steps are included:
S110: by copper waste etching solution load have the solid packing of catalyst under the action of decompose, obtain the first waste liquid and
First exhaust gas.
Specifically, copper content is 3g/L~5g/L in above-mentioned copper waste etching solution, the mass content of hydrogen peroxide is 5%~
20%, COD (COD) is 50g/L~100g/L.It can also contain comprising other hydrogen peroxide in above-mentioned copper waste etching solution
Measure high waste water.
Specifically, above-mentioned catalyst is selected from least one of transition metal simple substance and transition metal oxide, described solid
Body filler is porous material, useless effectively to control catalyst and copper etching so as to which catalyst to be supported in its pore structure
The contact of liquid.
Further, transition metal simple substance is selected from least one of Ag, Cu, Cr, Fe, Mn, Pb and Pt.Oxo transition metal
Compound is selected from least one of silver oxide, copper oxide, chromium oxide, iron oxide, manganese dioxide and lead oxide.Solid packing is selected from
At least one of aluminium oxide, silica gel, active carbon, float stone, diatomite, vermiculite, kaolin, bentonite, wollastonite and sepiolite.
Further, the reaction time that copper waste etching solution decomposes under the effect of the catalyst is 10min~30min, so that
Hydrogen peroxide sufficiently decomposes, and hydrogen peroxide removal rate reaches 90% or more.
Specifically, the catalytic decomposition that load has the solid packing of catalyst that the sealing with feeding inlet and discharge gate is arranged in
In device, the speed that copper waste etching solution flows through catalytic decomposition device is 50mL/min~150mL/min, so that hydrogen peroxide stabilizers
It decomposes.If hydrogen peroxide decompose it is too fast tank boil-overs would tend to occur or even the phenomenon that explode, and control copper waste etching solution and flow through and urge
The speed for changing decomposer can effectively control contact of the hydrogen peroxide with catalyst, to guarantee the stabilization point of hydrogen peroxide
Solution.Waste liquid is discharged through discharge gate in the first waste liquid generated after decomposition, and the first exhaust gas enters at follow-up equipment under conditions of negative pressure
Reason.
Hydrogen peroxide can generate a certain amount of hydroxyl radical free radical in catalytic decomposition process in above-mentioned copper waste etching solution, with copper
Oxidation reaction occurs for the organic matter in etching waste liquor, therefore can reduce the COD content in waste liquid, but can generate unpleasant gas simultaneously
Taste need to could discharge to avoid pollution environment after follow-up equipment is handled.
S120: the pH to 8~10 of the first waste liquid is adjusted, the second waste liquid is obtained.
Specifically, the reagent for adjusting pH is selected from least one of sodium hydroxide, potassium hydroxide and calcium hydroxide.Further
Ground, the reagent of above-mentioned adjusting pH are solid or aqueous solution.
It specifically, further include the step being separated by filtration after the step of adjusting the first waste liquor PH to 8~10, obtaining the second waste liquid
Suddenly.Copper ion in first waste liquid can be precipitated by the first waste liquid adjusting pH to 8~10, while obtaining the second of alkalinity and giving up
Liquid.Copper is recycled after being separated by filtration.Further, adjust pH after can first by the second waste liquid stewing process for a period of time after again into
Row filtering, so that precipitating is complete.Copper can be recycled to 8~10 one side by adjusting pH, and another aspect alkaline environment can be avoided copper
Fluorine ion in etching waste liquor corrodes equipment.
Further, vacuum filtration or centrifugal filtration are filtered into.
S130: the second waste liquid is distilled, distillate and concentrate are obtained.
Specifically, it distills for vacuum distillation.Vacuum distillation can accelerate the speed of distillation.Further, distillation is to distillating
The volume ratio of liquid and the second waste liquid can stop distilling when being 0.8~0.9: 1.0.
S140: by distillate through biochemical treatment, liquid and the second exhaust gas are purified.
Biochemical processing method is to be mixed waste liquid with microorganism, is decomposed using the intracorporal biological chemistry action of microorganism
Organic matter and certain inorganic toxic materials in waste liquid, make unstable organic matter and inorganic toxic material be converted into a kind of dirt of innocuous substance
Method for treating water.BOD5/ COD is the index of sewage bio-degradable, wherein BOD5For five-day BOD, numerical value is bigger,
It proves that the organic matter contained in water is more, pollutes more serious.COD is COD, and reflection chemically measures in water sample
The amount for the reducing substances for needing to be oxidized, usually with BOD5/ COD=0.3 is the lower limit of sewage bio-degradable.If BOD5/
COD >=0.3, then waste liquid can be by discharging after biochemical treatment.
COD content is low in distillate after distillation for second waste liquid, can direct emission after biochemical treatment.In other implementations
In mode, before distillate carries out biochemical treatment, materializing strategy can also be carried out, so that distillate reaches the index of biochemical treatment.
S150: by concentrate burning disposal, third exhaust gas is obtained.
COD content is high but small in size in concentrate, through conventional burning disposal.
It should be noted that the sequence of step S140 and step S150 are not limited to step S140 preceding, step S150 rear,
It can also be step S140 and step S150 while carrying out or step S150 is preceding, step S140 is rear.
S160: the first exhaust gas, the second exhaust gas and third exhaust gas are handled through waste gas treatment equipment.
Specifically, the step of the first exhaust gas, the second exhaust gas and third exhaust gas being handled through processing equipment includes: that first gives up
Gas, the second exhaust gas and third exhaust gas are decomposed through plasma apparatus, then by the first exhaust gas, the second exhaust gas and the third after decomposition
Exhaust gas is handled through spray-absorption.Further, plasma apparatus is low temperature plasma equipment.Exhaust gas by low temperature etc. from
When daughter equipment, electric field electric discharge generates the pollutant in high energy electron, with exhaust gas and forms active group, by a series of reaction
To achieve the purpose that degradation of contaminant.Have that purification efficiency is high, it is secondary not generate using low temperature plasma equipment processing exhaust gas
The advantages that pollution.
Specifically, the solution of spray-absorption is water, acid solution or lye etc..
The processing method of above-mentioned copper waste etching solution passes through the catalyst by copper waste etching solution through being supported on solid packing point
Solution, can effectively control the decomposition rate of hydrogen peroxide, decompose hydrogen peroxide safety and stability, avoid because not disposing waste liquid,
Copper ion catalyzing hydrogen peroxide acutely decomposes caused security risk, and after being catalytically decomposed hydrogen peroxide removal rate up to 90% with
On.
PH by adjusting the first waste liquid can convert alkalescent waste liquid for the first acid waste liquid, so that subsequent processing
And it is free from environmental pollution in discharge, while can also be recycled copper by filtering.
It substantially reduces the COD total amount of distillate after distilling, can be discharged after biochemical treatment, COD contains in concentrate
Amount is high but small in size, through burning disposal.Second waste liquid is reduced into processing cost by evaporation and concentration.
The first exhaust gas, the second exhaust gas and the third exhaust gas generated in whole process handles heel row through waste gas treatment equipment
It puts, without obvious peculiar smell, avoids pollution environment.
The following are specific embodiment parts:
It should be noted that the content measuring of hydrogen peroxide uses potassium permanganate in copper waste etching solution in following embodiment
The test of titration, COD content uses the method for oxidation of dichromic, BOD5The test of content is using dilution and inocalation method, volatility
The test of content of organics is measured using fixed VOC on-line detector (ZY100-VOC).
Embodiment 1
Copper content is 5.01g/L in the copper waste etching solution to be processed of the present embodiment, and content of hydrogen peroxide is
10.32wt%, COD 78g/L.Specific processing method is as follows:
(1) copper waste etching solution is pumped into the catalytic decomposition device of sealing with the speed of 150mL/min, and etches copper
Catalyst decomposition reaction 10min of the waste liquid through being supported on solid packing, the first waste liquid and the first exhaust gas after being decomposed,
In, catalyst is Ag simple substance, and solid packing is the mixed fillers of porous aluminas and float stone.
(2) sodium hydroxide solution is added into the first waste liquid and adjusts pH to 9.0, obtain the second waste liquid.
(3) it will be transferred to after the filtering of the second waste liquid and be evaporated under reduced pressure to obtain distillate and concentrate in evaporator.Wherein evaporate
The volume ratio of liquid and the second waste liquid is 0.843: 1.0, COD 2.13g/L, BOD out5/ COD be 0.65, distillate through biochemistry at
Obtaining after reason can be with the scavenging solution of direct emission and the second exhaust gas.Concentrate obtains third exhaust gas through burning disposal.
(4) by the first exhaust gas, the second exhaust gas and the third exhaust gas that are generated in step (1) and step (3) through low-temperature plasma
Body equipment is decomposed, is discharged after aqueous solution spray-absorption.
In the present embodiment, hydrogen peroxide is after being catalytically decomposed safely, and the mass content of hydrogen peroxide is in the first waste liquid
0.14%, hydrogen peroxide removal rate is 98.64%, COD 33g/L, and COD removal rate is 57.69%.First exhaust gas, first are given up
Before gas and third exhaust gas are handled in step (4), volatile organic matter (VOCs) is 585ppm, through low-temperature plasma in step (4)
VOCs content is less than 1ppm, and tail gas free from extraneous odour after body equipment and aqueous solution spray process.
Embodiment 2
Copper content is 3.10g/L in the copper waste etching solution to be processed of the present embodiment, and content of hydrogen peroxide is
18.20wt%, COD 109g/L.Specific processing method is as follows:
(1) copper waste etching solution is pumped into the catalytic decomposition device of sealing with the speed of 50mL/min, and etches copper
Catalyst decomposition reaction 30min of the waste liquid through being supported on solid packing, the first waste liquid and the first exhaust gas after being decomposed,
In, catalyst is copper oxide and manganese dioxide composite catalyst, and solid packing is that the mixing of silica gel, diatomite and wollastonite is filled out
Material.
(2) mixed-powder that potassium hydroxide, sodium hydroxide and calcium hydroxide are added into the first waste liquid adjusts pH to 9.5,
Obtain the second waste liquid.
(3) it will be transferred to after the filtering of the second waste liquid and be evaporated under reduced pressure to obtain distillate and concentrate in evaporator.Wherein evaporate
The volume ratio of liquid and the second waste liquid is 0.852: 1.0, COD 2.37g/L, BOD out5/ COD be 0.59, distillate through biochemistry at
Obtaining after reason can be with the scavenging solution of direct emission and the second exhaust gas.Concentrate obtains third exhaust gas through burning disposal.
(4) by the first exhaust gas, the second exhaust gas and the third exhaust gas that are generated in step (1) and step (3) through low-temperature plasma
Body equipment is decomposed, is discharged after lye spray-absorption.
In the present embodiment, hydrogen peroxide is after being catalytically decomposed safely, and the mass content of hydrogen peroxide is in the first waste liquid
0.79%, hydrogen peroxide removal rate is 95.66%, COD 39g/L, and COD removal rate is 64.22%.First exhaust gas, first are given up
Before gas and third exhaust gas are handled in step (4), VOCs 485ppm is sprayed through low temperature plasma equipment in step (4) and lye
VOCs content is less than 1ppm, and tail gas free from extraneous odour after leaching processing.
Embodiment 3
Copper content is 4.82g/L in the copper waste etching solution to be processed of the present embodiment, and content of hydrogen peroxide is
15.73wt%, COD 93g/L.Specific processing method is as follows:
(1) copper waste etching solution is pumped into the catalytic decomposition device of sealing with the speed of 100mL/min, and etches copper
Catalyst decomposition reaction 15min of the waste liquid through being supported on solid packing, the first waste liquid and the first exhaust gas after being decomposed,
In, catalyst Cr, Pt and Pb composite catalyst, solid packing is active carbon filler.
(2) calcium hydroxide slurry is added into the first waste liquid and adjusts pH to 8.0, obtain the second waste liquid.
(3) it will be transferred to after the filtering of the second waste liquid and be evaporated under reduced pressure to obtain distillate and concentrate in evaporator.Wherein evaporate
Liquid and the second waste liquid fever volume ratio are 0.835: 1.0, COD 2.24g/L, BOD out5/ COD is 0.63, and distillate is through biochemistry
Obtaining after processing can be with the scavenging solution of direct emission and the second exhaust gas.Concentrate obtains third exhaust gas through burning disposal.
(4) by the first exhaust gas, the second exhaust gas and the third exhaust gas that are generated in step (1) and step (3) through low-temperature plasma
Body equipment is decomposed, is discharged after acid solution spray-absorption.
In the present embodiment, hydrogen peroxide is after being catalytically decomposed safely, and the mass content of hydrogen peroxide is in the first waste liquid
0.36%, hydrogen peroxide removal rate is 97.71%, COD 45g/L, and COD removal rate is 51.61%.First exhaust gas, first are given up
Before gas and third exhaust gas are handled in step (4), VOCs 565ppm, through low temperature plasma equipment and acid solution in step (4)
VOCs content is less than 1ppm, and tail gas free from extraneous odour after spray process.
Embodiment 4
Copper content is 4.08g/L in the copper waste etching solution to be processed of the present embodiment, and content of hydrogen peroxide is
16.44wt%, COD 97g/L.Specific processing method is as follows:
(1) copper waste etching solution is pumped into the catalytic decomposition device of sealing with the speed of 75mL/min, and etches copper
Catalyst decomposition reaction 20min of the waste liquid through being supported on solid packing, the first waste liquid and the first exhaust gas after being decomposed,
In, catalyst Fe, Cu, Mn and iron oxide composite catalyst, solid packing are porous bentonite, porous vermiculite, porous kaolinite
The mixed fillers of soil and sepiolite.
(2) mixed solution that potassium hydroxide and sodium hydroxide are added into the first waste liquid adjusts pH to 10.0, obtains second
Waste liquid.
(3) it will be transferred to after the filtering of the second waste liquid and be evaporated under reduced pressure to obtain distillate and concentrate in evaporator.Wherein evaporate
The volume ratio of liquid and the second waste liquid is 0.847: 1.0, COD 2.35g/L, BOD out5/ COD be 0.60, distillate through biochemistry at
Obtaining after reason can be with the scavenging solution of direct emission and the second exhaust gas.Concentrate obtains third exhaust gas through burning disposal.
(4) by the first exhaust gas, the second exhaust gas and the third exhaust gas that are generated in step (1) and step (3) through low-temperature plasma
Body is decomposed, is discharged after aqueous solution spray-absorption.
In the present embodiment, hydrogen peroxide is after being catalytically decomposed safely, and the mass content of hydrogen peroxide is in the first waste liquid
1.20%, hydrogen peroxide removal rate is 92.70%, COD 41g/L, and COD removal rate is 57.73%.First exhaust gas, first are given up
Before gas and third exhaust gas are handled in step (4), VOCs 467ppm, through the decomposition of low temperature plasma equipment and water in step (4)
VOCs content is less than 1ppm, and tail gas free from extraneous odour after solution spraying processing.
Embodiment 5
Copper content is 4.53g/L in the copper waste etching solution to be processed of the present embodiment, and content of hydrogen peroxide is
12.56wt%, COD 85g/L.Specific processing method is as follows:
(1) copper waste etching solution is pumped into the catalytic decomposition device of sealing with the speed of 125mL/min, and etches copper
Catalyst decomposition reaction 12min of the waste liquid through being supported on solid packing, the first waste liquid and the first exhaust gas after being decomposed,
In, catalyst is silver oxide, chromium oxide and lead oxide composite catalyst, and solid packing is sepiolite filler.
(2) potassium hydroxide powder is added into the first waste liquid and adjusts pH to 8.5, obtain the second waste liquid.
(3) it will be transferred to after the filtering of the second waste liquid and be evaporated under reduced pressure to obtain distillate and concentrate in evaporator.Wherein evaporate
The volume ratio of liquid and the second waste liquid is 0.813: 1, COD 2.46g/L, BOD out5/ COD is 0.62, and distillate is through biochemical treatment
Obtaining afterwards can be with the scavenging solution of direct emission and the second exhaust gas.Concentrate obtains third exhaust gas through burning disposal.
(4) by the first exhaust gas, the second exhaust gas and the third exhaust gas that are generated in step (1) and step (3) through low-temperature plasma
Body is decomposed, is discharged after aqueous solution spray-absorption.
In the present embodiment, hydrogen peroxide is after being catalytically decomposed safely, and the mass content of hydrogen peroxide is in the first waste liquid
0.28%, hydrogen peroxide removal rate is 97.77%, COD 46g/L, and COD removal rate is 45.88%.First exhaust gas, first are given up
Before gas and third exhaust gas are handled in step (4), VOCs 632ppm, through the decomposition of low temperature plasma equipment and water in step (4)
VOCs content is less than 1ppm, and tail gas free from extraneous odour after solution spraying processing.
Comparative example 1
Copper content is 5.01g/L in the copper waste etching solution to be processed of this comparative example, and content of hydrogen peroxide is
10.32wt%, COD 78g/L.Specific processing method is as follows:
(1) copper waste etching solution is pumped into the catalytic decomposition device of sealing with the speed of 50mL/min, and etches copper
Waste liquid flows through the mixed filler layer of porous bentonite, porous vermiculite, porous kaolin and sepiolite, reacts 30min, is decomposed
The first waste liquid and the first exhaust gas afterwards.
In this comparative example, copper waste etching solution is passed through equipped with porous bentonite, porous vermiculite, porous kaolin and sepiolite
When the catalytic decomposition device of the sealing of mixed filler layer, the hydrogen peroxide in copper waste etching solution is not decomposed, but after placement 4h,
Uncontrollable violent decomposition occurs, generates tank boil-overs phenomenon, copper waste etching solution almost all sprays, and causes subsequent step that can not carry out.
Therefore, it is decomposed merely, is existed by the safety and stability that packing layer peroxynitrite decomposition hydrogen cannot achieve hydrogen peroxide in copper waste etching solution
Security risk.And catalyst is supported in solid packing and makes peroxide in copper waste etching solution in 1~embodiment of above-described embodiment 5
Change hydrogen and safety decomposition occurs.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of processing method of copper waste etching solution, which comprises the following steps:
Copper waste etching solution is decomposed under the action of load has the solid packing of catalyst, obtains the first waste liquid and the first exhaust gas,
The catalyst is selected from least one of transition metal simple substance and transition metal oxide, and the solid packing is porous material
Material；
The pH to 8~10 for adjusting first waste liquid, obtains the second waste liquid；
Second waste liquid is distilled, distillate and concentrate are obtained；
By the distillate through biochemical treatment, it is purified liquid and the second exhaust gas；
By the concentrate burning disposal, third exhaust gas is obtained；And
First exhaust gas, second exhaust gas and the third exhaust gas are handled with waste gas treatment equipment.
2. the processing method of copper waste etching solution according to claim 1, which is characterized in that the transition metal simple substance is selected from
At least one of Ag, Cu, Cr, Fe, Mn, Pb and Pt；And/or the transition metal oxide be selected from silver oxide, copper oxide,
At least one of chromium oxide, iron oxide, manganese dioxide and lead oxide.
3. the processing method of copper waste etching solution according to claim 1, which is characterized in that the solid packing is selected from oxidation
At least one of aluminium, silica gel, active carbon, float stone, diatomite, vermiculite, kaolin, bentonite, wollastonite and sepiolite.
4. the processing method of copper waste etching solution according to claim 1, which is characterized in that the copper waste etching solution is described
The reaction time decomposed under the action of catalyst is 10min~30min.
5. the processing method of copper waste etching solution according to claim 1, which is characterized in that load has the institute of the catalyst
It states solid packing to be arranged in the catalytic decomposition device of a sealing, the copper waste etching solution flows through the speed of the catalytic decomposition device
Degree is 50mL/min~150mL/min.
6. the processing method of copper waste etching solution according to claim 1, which is characterized in that adjust first waste liquor PH
Reagent is selected from least one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
7. the processing method of copper waste etching solution according to claim 1, which is characterized in that adjust the pH of first waste liquid
Value is to 8~10, further includes by described the before the step of distilling second waste liquid after the step of obtaining the second waste liquid
The step of two waste liquids are filtered separation.
8. the processing method of copper waste etching solution according to claim 1, which is characterized in that the distillation is vacuum distillation.
9. the processing method of copper waste etching solution according to claim 1, which is characterized in that the distillate and described second
The volume ratio of waste liquid is 0.8~0.9: 1.0.
10. the processing method of copper waste etching solution according to claim 1, which is characterized in that by first exhaust gas, described
The step of second exhaust gas and the third exhaust gas are handled through waste gas treatment equipment includes: that first exhaust gas, described second are given up
Gas and the third exhaust gas are decomposed through plasma apparatus, then by after decomposition first exhaust gas, second exhaust gas and
The third exhaust gas is handled through spray-absorption.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110304780A (en) * | 2019-07-24 | 2019-10-08 | 东江环保股份有限公司 | The processing method of TFT-LCD array substrate copper conductor etching waste water |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004143001A (en) * | 2002-10-25 | 2004-05-20 | The Inctec Inc | Method for recovering cerium |
| CN101391800A (en) * | 2007-09-20 | 2009-03-25 | 深圳市东江环保股份有限公司 | Method for producing basic copper chloride, cupric sulfate pentahydrate from copper-containing etching waste liquid |
| CN102718368A (en) * | 2012-07-10 | 2012-10-10 | 山东轻工业学院 | Method for treating high-concentration phenol-contained wastewater into easily-biochemically-treated wastewater |
| CN205974105U (en) * | 2016-08-12 | 2017-02-22 | 深圳市洁驰科技有限公司 | Lose liquid waste liquid treatment device a little |
-
2018
- 2018-11-29 CN CN201811462696.4A patent/CN109368936B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004143001A (en) * | 2002-10-25 | 2004-05-20 | The Inctec Inc | Method for recovering cerium |
| CN101391800A (en) * | 2007-09-20 | 2009-03-25 | 深圳市东江环保股份有限公司 | Method for producing basic copper chloride, cupric sulfate pentahydrate from copper-containing etching waste liquid |
| CN102718368A (en) * | 2012-07-10 | 2012-10-10 | 山东轻工业学院 | Method for treating high-concentration phenol-contained wastewater into easily-biochemically-treated wastewater |
| CN205974105U (en) * | 2016-08-12 | 2017-02-22 | 深圳市洁驰科技有限公司 | Lose liquid waste liquid treatment device a little |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110304780A (en) * | 2019-07-24 | 2019-10-08 | 东江环保股份有限公司 | The processing method of TFT-LCD array substrate copper conductor etching waste water |
| CN110304780B (en) * | 2019-07-24 | 2022-02-18 | 东江环保股份有限公司 | Treatment method of TFT-LCD array substrate copper conductor etching wastewater |
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