CN109761430B - Treatment method of alkaline etching waste liquid - Google Patents
Treatment method of alkaline etching waste liquid Download PDFInfo
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- CN109761430B CN109761430B CN201910178302.0A CN201910178302A CN109761430B CN 109761430 B CN109761430 B CN 109761430B CN 201910178302 A CN201910178302 A CN 201910178302A CN 109761430 B CN109761430 B CN 109761430B
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- waste liquid
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- etching waste
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- 239000007788 liquid Substances 0.000 title claims abstract description 51
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 238000005530 etching Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000000292 calcium oxide Substances 0.000 claims abstract description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005739 Bordeaux mixture Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000011550 stock solution Substances 0.000 claims abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 6
- 239000005750 Copper hydroxide Substances 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000002912 waste gas Substances 0.000 claims 1
- 239000013505 freshwater Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000010949 copper Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- -1 chlorine ions Chemical class 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 3
- 244000021273 Peumus boldus Species 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004763 spore germination Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 description 1
Classifications
-
- 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
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for treating alkaline etching waste liquid, which comprises the following steps of (1) adding excessive calcium oxide into the alkaline etching waste liquid, introducing the calcium oxide into an ammonia still, and carrying out solid-liquid separation to obtain a blue-white precipitate mixture; (2) absorbing ammonia gas by an absorption tower to prepare 20-40% ammonia water solution; (3) adding sulfuric acid into the blue-white precipitate mixture until the blue precipitate is dissolved, and carrying out solid-liquid separation to obtain a Bordeaux mixture stock solution; the invention introduces calcium oxide as an alkali source to produce Bordeaux mixture without introducing new pollutants, thereby avoiding the waste of fresh water resources caused by the massive salinization of fresh water and having high recovery value.
Description
Technical Field
The invention relates to the technical field of etching solution waste liquid treatment, in particular to a treatment method of alkaline etching waste liquid.
Background
The etching waste liquid is an important pollutant generated in the printed circuit board industry, the etching waste liquid contains a large amount of copper, if the etching waste liquid is not properly treated, the environment is polluted, and meanwhile, the resource is seriously wasted. When the circuit board is etched, the alkaline etching solution has the advantages of low consumption, low price, high copper dissolution amount, small side corrosion, high etching speed and the like, does not damage ink components on a copper-clad substrate, and is widely applied to PCB enterprises at present.
[ Cu (NH) in alkaline etching solution3)4]Cl2Can react with copper plating on the surface layer of the circuit board to generate a cuprous complex, and Cu (NH) plays a role in etching3)4 +Cu (NH) formed3)2 +Although it has no etching ability, in the case of an excessive amount of ammonia water and chlorine ions, the ammonia water and chlorine ions are oxidized quickly by air, and the copper ions are regenerated to gradually increase the concentration of copper ions in the etching solution, so that the etching rate of the etching solution is also decreased until the etching effect is finally lost and the etching solution becomes an etching waste solution, and therefore, the main component in the alkaline etching waste solution is complex Cu (NH)3)2Cl2Ammonia, chloride, etc., copper content of about 100-160g/L, total ammonia (NH)3、NH4 +) The content is about 150-g/L, if the waste water is directly discharged without proper disposal, not only is valuable resources wasted, but also huge damage is caused to the environment.
In the prior art, one of the commonly used methods for treating alkaline etching solution is to add sufficient sodium hydroxide solution into alkaline etching waste solution and heat the solution to generate copper oxide and ammonia gas so as to extract copper ions and ammonium ions in the waste solution, the process technology is mature and widely adopted due to large treatment capacity, multiple waste solution treatment plants are once built into a production line with treatment capacity of tens of thousands of tons, however, the technology needs to consume high-cost sodium hydroxide to produce low-value sodium chloride, and although the discharge of sodium chloride is not prohibited in the state, the patent CN103602988A proposes to largely salinize limited fresh water, the content of ammonia nitrogen in the treated waste water does not easily reach the standard, in order to effectively utilize chloride ions and ammonium chloride, the patent CN103602988A aims at the problem of recovering ammonium chloride, in addition of an alkali source, concentrated hydrochloric acid is used for absorbing ammonia water into ammonium chloride solution to realize the regeneration and reuse of the etching solution, however, this is equivalent to the introduction of new acid contaminants, and requires the consumption of hydrochloric acid fuel and equipment, the operation is complicated, the economic applicability is poor, and the alkali source is NaOH or Ca (OH)2If the NaOH solution is selected, high-concentration NaCl solution is discharged, limited and precious fresh water is largely salinized, the NaOH is largely used and expensive, the cost consumption is high when the NaOH solution is converted into NaCl, the NaOH solution has poor effect compared with NaOH solid, the reaction efficiency is high, the reaction efficiency is low, heating energy is wasted, and if Ca (OH) is used2Solutions, Ca (OH) per se2Are slightly water-soluble basic compounds, have low solute actually participating in the reaction, and inevitably have excessive Ca (OH) after the reaction2Precipitation phenomena, mixed with the precipitation of the copper compound, and in this patent, there is also no mention of a step of further treating the precipitation mixture, and therefore this technique has drawbacks.
Disclosure of Invention
In order to solve the problems, the invention provides a method for treating alkaline etching waste liquid, which does not introduce impurity ions into the waste liquid, realizes the recycling of raw materials, avoids the salinization of a large amount of fresh water, obtains the stock solution of the bactericide boldo liquid and has high recycling value.
The technical scheme for solving the problem is to provide a method for treating alkaline etching waste liquid, which is characterized by comprising the following steps of:
a method for treating alkaline etching waste liquid is characterized by comprising the following steps:
(1) adding excessive calcium oxide into the alkaline etching waste liquid, introducing into an ammonia still, and carrying out solid-liquid separation to obtain a blue-white precipitate mixture through the reaction of the formula (A);
formula (A):
(2) absorbing ammonia gas by an absorption tower to prepare 20-40% ammonia water solution;
(3) adding sulfuric acid into the blue-white precipitate mixture until the blue precipitate is dissolved, and carrying out solid-liquid separation to obtain a Bordeaux mixture stock solution;
preferably, the waste treatment capacity of the absorption tower is 1200-1500m3/h。
Preferably, the sulfuric acid is added in a molar amount equal to the molar amount of copper hydroxide.
Preferably, the boldo stock solution comprises copper sulfate and calcium hydroxide.
Preferably, the method further comprises the step (4) of evaporating and concentrating the calcium chloride solution to recover the calcium source.
The invention utilizes the reaction heat release of CaO and the alkaline etching waste liquid, reduces the heating condition required by the reaction of the alkaline etching waste liquid and the alkali, and reduces the generation of CaO and Cu (OH) caused by the inaccurate estimation of the input amount of the reaction raw material CaO or insufficient reaction of the raw material2The mixed white precipitate resulted in impure recovered copper source, so copper hydroxide was dissolved and the amount of sulfuric acid added was judged by the phenomenon, and boldo solution was an inorganic copper bactericide. Its effective componentsHas the chemical composition of CuSO4·xCu(OH)2·yCa(OH)2·zH2O, bordeaux is a protective biocide. The effective component is basic copper sulfate, which can effectively prevent spore germination, prevent germ infection, promote leaf color to be dark green, grow robustly and improve the disease resistance of trees. The preparation has the characteristics of wide bactericidal spectrum, long lasting period, no generation of resistance of germs, low toxicity to people and livestock and the like, is a bactericide with the longest application history, can be temporarily sealed in a container without being immediately mixed after the preparation of two liquid medicines is finished, and can be used when being mixed when spraying medicine, so that the copper hydroxide is dissolved for solid-liquid separation and sealing.
Compared with the prior art, the method introduces the calcium oxide as an alkali source to produce the Bordeaux mixture without introducing new pollutants, and avoids the waste of fresh water resources caused by the salinization of a large amount of fresh water.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
The water quality of certain alkaline etching waste liquid is as follows: the nitrogen-ammonia concentration is 40000 mg/L, the copper ion concentration is 50000mg/L, pH, the value is 8.3, the total volume is 100L, and the specific process is as follows:
1) adding excessive CaO solid into the raw material waste material until the pH value is 12.0, converting ammonium ions in the waste water into ammonia molecules including ammonia gas and ammonia molecules dissolved in the waste liquid, introducing the waste liquid into an ammonia still for full precipitation, evaporating the ammonia gas, and generating Cu (OH) by the existence of excessive hydroxide ions2Precipitation, conversion of excess CaO to white precipitate Ca (OH)2And Cu (OH)2Blending to obtain blue-white precipitate, wherein the residual waste liquid contains calcium chloride;
2) the overflowed ammonia gas is absorbed by an absorption tower and converted into 30% ammonia water solution, the ammonia gas absorption tower mainly utilizes the related principle of hydrodynamics, gas and absorption liquid are mixed in a pipeline, when the absorption liquid and the gas are mixed and then pass through the pipeline, the gas phase and the liquid phase are contacted with the pipe wall, the liquid on the contact surface is continuously cooled, and the gas and the liquid collide violently to ensure that the gas and the liquid are fully mixedAfter combination, the ammonia water falls into a circulating water tank under the action of gravity of liquid, the concentration of the ammonia water is continuously increased after repeated absorption, and the waste treatment capacity of the ammonia gas absorption tower is 1200-1500m3The diameter of the tower body is 1200nm, and the capacity of the mother liquor tank is 8m3The total height is 10000nm, the recovery rate is 98 percent, and the equipment power is 78 kw.
3) Adding sulfuric acid to dissolve copper hydroxide to obtain copper sulfate, observing that the blue-white precipitate gradually changes into white precipitate, and performing solid-liquid separation to obtain copper sulfate solution and calcium hydroxide precipitate;
4) pre-concentrating the calcium chloride solution by using a multi-effect evaporator until the concentration reaches 40%, then performing final concentration, directly heating the evaporator until the concentration reaches 65%, and crystallizing by using a flaker.
After treatment, the obtained calcium chloride solid can be used as a road ice melting agent and a drying agent to obtain a stock solution of Bordeaux mixture, copper sulfate and calcium hydroxide are mixed when the Bordeaux mixture is used, and the mixture is immediately used, and an ammonia water solution is obtained and used as an ammonia source to prepare other chemical reagents.
Example 2
The water quality of certain alkaline etching waste liquid is as follows: the nitrogen-ammonia concentration is 50000mg/L, the copper ion concentration is 60000mg/L, pH, the value is 8.0, the total volume is 200L, and the specific process is as follows:
1) adding excessive CaO solid into the raw material waste material until the pH value is 12.0, converting ammonium ions in the waste water into ammonia molecules including ammonia gas and ammonia molecules dissolved in the waste liquid, introducing the waste liquid into an ammonia still for full precipitation, evaporating the ammonia gas, and generating Cu (OH) by the existence of excessive hydroxide ions2Precipitation, conversion of excess CaO to white precipitate Ca (OH)2And Cu (OH)2Blending to obtain blue-white precipitate, wherein the residual waste liquid contains calcium chloride;
2) the overflowed ammonia gas is absorbed by an absorption tower and converted into 30% ammonia water solution, the ammonia gas absorption tower mainly utilizes the related principle of hydrodynamics, gas and absorption liquid are mixed in a pipeline, when the absorption liquid and the gas are mixed and then pass through the pipeline, gas-liquid phases are contacted with the pipeline wall, liquid on the contact surface is continuously cooled, the gas and the liquid are violently collided to enable the gas and the liquid to fall into a circulating water tank under the action of gravity of the liquid after being fully mixed, and the gas and the liquid are repeatedly absorbedThe concentration of the collected ammonia water is continuously increased, and the waste treatment capacity of the ammonia absorption tower is 1200-1500m3The diameter of the tower body is 1200nm, and the capacity of the mother liquor tank is 8m3The total height is 10000nm, the recovery rate is 98 percent, and the equipment power is 78 kw.
3) Adding sulfuric acid to dissolve copper hydroxide to obtain copper sulfate, observing that the blue-white precipitate gradually changes into white precipitate, and performing solid-liquid separation to obtain copper sulfate solution and calcium hydroxide precipitate;
4) pre-concentrating the calcium chloride solution by using a multi-effect evaporator until the concentration reaches 40%, then performing final concentration, directly heating the evaporator until the concentration reaches 65%, and crystallizing by using a flaker.
After treatment, the obtained calcium chloride solid can be used as a road ice melting agent and a drying agent to obtain a stock solution of Bordeaux mixture, copper sulfate and calcium hydroxide are mixed when the Bordeaux mixture is used, and the mixture is immediately used, and an ammonia water solution is obtained and used as an ammonia source to prepare other chemical reagents.
The above mentioned matters are not related, and all the matters are applicable to the prior art. The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (5)
1. A method for treating alkaline etching waste liquid is characterized by comprising the following steps:
(1) adding excessive calcium oxide into the alkaline etching waste liquid, introducing into an ammonia still, and carrying out solid-liquid separation to obtain a blue-white precipitate mixture through the reaction of the formula (A);
a compound of the formula (A),
(2) absorbing ammonia gas by an absorption tower to prepare 20-40% ammonia water solution;
(3) and adding sulfuric acid into the blue-white precipitate mixture until the blue precipitate is dissolved, and performing solid-liquid separation to obtain a Bordeaux mixture stock solution.
2. The method as claimed in claim 1, wherein the waste gas treatment amount of the absorption tower is 1200-1500m3/h。
3. The method according to claim 1, wherein said sulfuric acid is added in a molar amount equivalent to that of copper hydroxide.
4. The method as claimed in claim 1, wherein the Bordeaux mixture stock solution includes copper sulfate and calcium hydroxide.
5. The method for treating an alkaline etching waste liquid according to claim 1, further comprising the step (4) of recovering a calcium source by evaporating and concentrating a calcium chloride solution.
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| CN109761430B true CN109761430B (en) | 2021-12-03 |
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| CN100584760C (en) * | 2007-06-26 | 2010-01-27 | 深圳市万山红环保实业有限公司 | Method and device for preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor |
| CN101391800B (en) * | 2007-09-20 | 2011-06-15 | 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 |
| CN103602988B (en) * | 2013-10-30 | 2016-06-01 | 中国科学院过程工程研究所 | The recycling treatment of a kind of PCB etching waste liquor and recycle method |
| CN107973444B (en) * | 2017-12-05 | 2020-12-01 | 吴江市威士达铜业科技有限公司 | Treatment method of waste water generated in preparation of copper hydroxide powder from etching waste liquid |
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Non-Patent Citations (1)
| Title |
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| 印刷电路板蚀刻废母液的处理;吴昊 等;《沈阳大学学报》;20030630;第15卷(第2期);87-89 * |
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