CN114772628A - Method for recovering waste etching liquid - Google Patents
Method for recovering waste etching liquid Download PDFInfo
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- CN114772628A CN114772628A CN202210431688.3A CN202210431688A CN114772628A CN 114772628 A CN114772628 A CN 114772628A CN 202210431688 A CN202210431688 A CN 202210431688A CN 114772628 A CN114772628 A CN 114772628A
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- 238000005530 etching Methods 0.000 title claims abstract description 91
- 239000007788 liquid Substances 0.000 title claims abstract description 78
- 239000002699 waste material Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000010949 copper Substances 0.000 claims abstract description 58
- 229910052802 copper Inorganic materials 0.000 claims abstract description 58
- 239000003513 alkali Substances 0.000 claims abstract description 45
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 230000002378 acidificating effect Effects 0.000 claims abstract description 26
- 238000011084 recovery Methods 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 230000009615 deamination Effects 0.000 claims abstract description 19
- 238000006481 deamination reaction Methods 0.000 claims abstract description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005751 Copper oxide Substances 0.000 claims abstract description 13
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 12
- 239000007790 solid phase Substances 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 3
- 238000001704 evaporation Methods 0.000 claims description 22
- 230000008020 evaporation Effects 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical group [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000002360 preparation method 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/36—Aluminium phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to a method for recovering waste etching solution, which comprises the following steps: mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and performing solid-liquid separation to obtain a solid phase and a cuprammonium solution; and sequentially carrying out alkali treatment and deamination on the obtained cuprammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide. The effective recovery of the etching waste liquid generated in the copper etching process is realized by adopting a specific recovery flow. The method has the advantages that the valuable resources of the waste liquid are recycled, the environmental protection is facilitated, the sustainable utilization of the resources is realized, no new waste is generated in the process, and the closed loop of the whole recycling process is realized.
Description
Technical Field
The invention relates to the field of resource reutilization, and particularly relates to a recovery method of waste etching liquid.
Background
At present, the PCB is usually processed by etching technology during the manufacturing process, so as to achieve the purpose of further use.
For example, CN110191589A discloses a double-sided etching method applied to a flexible circuit board, which comprises synchronously etching two sides of a flexible circuit board sample plate, i.e. a thin copper surface facing upwards and a thick copper surface facing downwards, and etching each flexible circuit board sample plate by adjusting a transmission speed, a thin copper spraying pressure and a thick copper spraying pressure until the etching conditions are met. The circuit board standard board is etched by adopting a mode of synchronously etching a thin copper surface and a thick copper surface, the transmission speed, the thin copper spraying pressure and the thick copper spraying pressure corresponding to the etching requirements are used as final etching conditions by simulating the etching environment of the flexible circuit board, and after the final etching conditions are acted on the flexible circuit board to verify the etching effect, the flexible circuit board can be etched in batches by directly applying the final etching conditions, so that the etching efficiency is effectively improved.
CN110087397A discloses a method for etching thick copper plate of PCB by stages, comprising: step 1: selecting 2 copper plates, and cutting the 2 copper plates to the required size; step 2: drilling positioning holes, target holes and riveting holes at four corners of a copper plate, and then manufacturing single-sided mirror image circuit patterns on the front side and the back side; and step 3: copper and tin plating, and then film stripping and etching treatment; and 4, step 4: carrying out browning treatment on the plate surface, riveting two sets of copper plates by using a semi-cured resin sheet, and carrying out hot pressing; and 5: drilling a target hole and a via hole, then performing copper deposition and plate plating, plating a layer of copper in the via hole, communicating the upper layer with the lower layer, and then manufacturing a secondary circuit; and 6: and carrying out secondary copper tin plating, and then carrying out film stripping and etching treatment to form a complete circuit pattern. The problem of the incomplete copper deckle edge of circuit that appears after the etching is solved, and then with incomplete copper deckle edge control miniaturization, widened the scope of thick copper board preparation line width interval.
However, during the etching process, a large amount of etching waste liquid is formed, and the waste liquid contains a large amount of metallic copper element and other harmful elements, which can cause significant damage to the environment if directly discharged.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a method for recovering waste etching solution, which solves the problem that the prior copper-containing waste etching solution cannot be effectively recovered.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for recovering waste etching solution, which comprises the following steps:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and performing solid-liquid separation to obtain a solid phase and a cuprammonium solution;
and sequentially carrying out alkali treatment and deamination on the obtained cuprammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide.
The effective recovery of the etching waste liquid generated in the copper etching process is realized by adopting a specific recovery flow. The method has the advantages that the valuable resources of the waste liquid are recycled, the environmental protection is facilitated, the sustainable utilization of the resources is realized, no new waste is generated in the process, and the closed loop of the whole recycling treatment process is realized.
In the actual process of treating the waste etching solution, the schemes such as online utilization, etchant regeneration and the like are preferably selected, and the waste etching solution is acidic etching solution containing aluminum, ammonia nitrogen, phosphoric acid and the like, and waste liquid with impurities enriched to the extent that the waste etching solution cannot be used for the second time.
In the present invention, the ammonia gas collected in the deamination can be returned to the mixing process for reuse.
In a preferred embodiment of the present invention, the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid, and the aqueous ammonia in the mixing treatment is 1 (0.5-0.8) to (1.2-1.5), and the ratio may be, for example, 1:0.5:1.2, 1:0.5:1.3, 1:0.5:1.4, 1:0.5:1.5, 1:0.6:1.2, 1:0.7:1.2, 1:0.8:1.2, 1:0.6:1.3, 1:0.6:1.4, 1:0.6:1.5, 1:0.7:1.3, 1:0.7:1.4, 1:0.7:1.5, 1:0.8:1.3, 1:0.8:1.4, or 1:0.8:1.5, but not limited thereto, and the other values are not specifically recited in the same ranges.
In the present invention, the mass concentration of the aqueous ammonia in the mixing treatment may be 10 to 40%, for example, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.
In a preferred embodiment of the present invention, the mixing time is 30 to 45min, and may be, for example, 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min, 40min, 41min, 42min, 43min, 44min, or 45min, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In a preferred embodiment of the present invention, the mass ratio of the cuprammonium solution to the alkaline reagent in the alkaline treatment is 1:1.2 to 1.5, and examples thereof include 1:1.2, 1:1.21, 1:1.22, 1:1.23, 1:1.24, 1:1.25, 1:1.26, 1:1.27, 1:1.28, 1:1.29, 1:1.3, 1:1.31, 1:1.32, 1:1.33, 1:1.34, 1:1.35, 1:1.36, 1:1.37, 1:1.38, 1:1.39, 1:1.4, 1:1.41, 1:1.42, 1:1.43, 1:1.44, 1:1.45, 1:1.46, 1:1.47, 1:1.48, 1:1.49 and 1:1.5, and other values are not specifically included in the same range.
As a preferred technical scheme, the alkali reagent comprises 1 or at least 2 of sodium hydroxide solution, potassium hydroxide solution or ammonia water. The ammonia may be ammonia from a deamination process.
In the present invention, the mass concentration of the alkali agent is 20 to 40%, and may be, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40%, but is not limited to the values listed, and other values not listed in the range are also applicable.
In a preferred embodiment of the present invention, the alkali treatment time is 45 to 80min, for example, 45min, 46min, 48min, 50min, 52min, 54min, 56min, 58min, 60min, 62min, 64min, 66min, 68min, 70min, 72min, 74min, 76min, 78min, or 80min, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
As a preferable technical scheme of the invention, the deamination is to carry out flash evaporation treatment on the solution after alkali treatment.
In a preferred embodiment of the present invention, the temperature of the flash evaporation treatment is 90 to 120 ℃, and may be, for example, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃ or 120 ℃, but is not limited to the listed values, and other values not listed in the range are also applicable.
In a preferred embodiment of the present invention, the pressure of the flash evaporation treatment is 0.1 to 0.2MPa, and may be, for example, 0.1MPa, 0.11MPa, 0.12MPa, 0.13MPa, 0.14MPa, 0.15MPa, 0.16MPa, 0.17MPa, 0.18MPa, 0.19MPa or 0.2MPa, but is not limited to the above-mentioned values, and other values not listed in the range are also applicable.
As a preferable embodiment of the present invention, the recovery method comprises:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and performing solid-liquid separation to obtain a solid phase and a cuprammonium solution; the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and the ammonia water in the mixed treatment is 1 (0.5-0.8) to 1.2-1.5; the mixing treatment time is 30-45 min;
sequentially carrying out alkali treatment and deamination on the obtained cuprammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide; the mass ratio of the copper ammonium solution to the alkali reagent in the alkali treatment is 1 (1.2-1.5); the alkali reagent comprises 1 or a combination of at least 2 of sodium hydroxide solution, potassium hydroxide solution or ammonia water; the alkali treatment time is 45-80 min; the deamination is to carry out flash evaporation treatment on the solution after the alkali treatment; the temperature of the flash evaporation treatment is 90-120 ℃; the pressure of the flash evaporation treatment is 0.1-0.2 MPa.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the ammonia nitrogen contained in the waste etching solution is prevented from entering the downstream to pollute the environment, and the cyclic utilization is realized.
(2) The waste etching solution can obtain aluminum phosphate \ copper oxide and sodium chloride with high added values, which are difficult to realize in the conventional process, and the purity of the obtained aluminum phosphate is more than or equal to 98%, the purity of the obtained copper oxide is more than or equal to 98%, and the purity of the obtained sodium chloride is more than or equal to 98%.
(3) The method adopts a two-step treatment method, the first step is ammonia neutralization and aluminum separation, and the second step is copper separation and recovery, so that the quality of each product is ensured.
Drawings
FIG. 1 is a flow chart of the recovery method in example 1 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The composition of the acidic copper-containing etching waste liquid used in the examples was aluminum chloride, ammonium chloride, copper chloride, phosphoric acid, aluminum 2000ppm, copper 80000ppm, total phosphorus 2000ppm, ammonium radical 8000ppm, and the composition of the alkaline etching waste liquid was ammonia water, ammonium chloride, copper chloride, ammonia nitrogen 120000ppm, copper 90000 ppm.
This example provides a method for recovering a spent etching solution, as shown in fig. 1, the method includes:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and performing solid-liquid separation to obtain a solid phase and a cuprammonium solution; the mass ratio of the acidic copper-containing etching waste liquid to the alkaline etching waste liquid to the ammonia water in the mixed treatment is 1:0.7: 1.3; the mixing treatment time is 35 min;
sequentially carrying out alkali treatment and deamination on the obtained cuprammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide; the mass ratio of the copper ammonium solution to the alkali reagent in the alkali treatment is 1: 1.4; the alkali reagent is sodium hydroxide solution (the mass concentration is 40%); the alkali treatment time is 55 min; the deamination is to carry out flash evaporation treatment on the solution after alkali treatment; the temperature of the flash evaporation treatment is 100 ℃; the pressure of the flash evaporation treatment is 0.14 MPa.
The recovery index is detailed in Table 1.
Example 2
The composition of the acidic copper-containing etching waste liquid adopted in the embodiment is aluminum chloride, ammonium chloride, copper chloride, phosphoric acid, 1000ppm of aluminum, 100000ppm of copper, 5000ppm of total phosphorus and 2400ppm of ammonium radical, and the composition of the alkaline etching waste liquid is ammonia water, ammonium chloride, copper chloride, 100000ppm of ammonia nitrogen and 86500ppm of copper.
The embodiment provides a method for recovering waste etching liquid, which comprises the following steps:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and performing solid-liquid separation to obtain a solid phase and a cuprammonium solution; the mass ratio of the acidic copper-containing etching waste liquid to the alkaline etching waste liquid to the ammonia water in the mixing treatment is 1:0.5: 1.5; the mixing treatment time is 30 min;
sequentially carrying out alkali treatment and deamination on the obtained cuprammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide; the mass ratio of the copper ammonium solution to the alkali reagent in the alkali treatment is 1: 1.5; the alkali reagent is a potassium hydroxide solution (the mass concentration is 35%); the alkali treatment time is 45 min; the deamination is to carry out flash evaporation treatment on the solution after alkali treatment; the temperature of the flash evaporation treatment is 90 ℃; the pressure of the flash evaporation treatment is 0.1 MPa.
The recovery indices are detailed in Table 1.
Example 3
The acidic copper-containing etching waste liquid adopted in the embodiment comprises aluminum chloride, ammonium chloride, copper chloride, phosphoric acid, aluminum 3394ppm, copper 102392pm, total phosphorus 3432ppm and ammonium radical 3429ppm, and the alkaline etching waste liquid comprises ammonia water, ammonium chloride, copper chloride, ammonia nitrogen 95085ppm and copper 8764 ppm.
The embodiment provides a method for recovering waste etching solution, which comprises the following steps:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and performing solid-liquid separation to obtain a solid phase and a copper-ammonium solution; the mass ratio of the acidic copper-containing etching waste liquid to the alkaline etching waste liquid to the ammonia water in the mixing treatment is 1:0.8: 1.2; the mixing treatment time is 45 min;
sequentially carrying out alkali treatment and deamination on the obtained cuprammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide; the mass ratio of the copper ammonium solution to the alkali reagent in the alkali treatment is 1: 1.2; the alkali reagent is ammonia water (the mass concentration is 30%); the alkali treatment time is 80 min; the deamination is to carry out flash evaporation treatment on the solution after the alkali treatment; the temperature of the flash evaporation treatment is 120 ℃; the pressure of the flash evaporation treatment is 0.2 MPa.
The recovery indices are detailed in Table 1.
Example 4
The acidic copper-containing etching waste liquid adopted in the embodiment comprises aluminum chloride, ammonium chloride, copper chloride, phosphoric acid, aluminum 3326ppm, copper 97243ppm, total phosphorus 4657ppm and ammonium radical 7259ppm, and the alkaline etching waste liquid comprises ammonia water, ammonium chloride, copper chloride, ammonia nitrogen 80000ppm and copper 82362 ppm.
The embodiment provides a method for recovering waste etching solution, which comprises the following steps:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and performing solid-liquid separation to obtain a solid phase and a cuprammonium solution; the mass ratio of the acidic copper-containing etching waste liquid to the alkaline etching waste liquid to the ammonia water in the mixed treatment is 1:0.6: 1.4; the mixing treatment time is 40 min;
sequentially carrying out alkali treatment and deamination on the obtained cuprammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide; the mass ratio of the copper ammonium solution to the alkali reagent in the alkali treatment is 1: 1.3; the alkali reagent is a sodium hydroxide solution (with the mass concentration of 20%); the time of the alkali treatment is 65 min; the deamination is to carry out flash evaporation treatment on the solution after the alkali treatment; the temperature of the flash evaporation treatment is 110 ℃; the pressure of the flash evaporation treatment is 0.17 MPa.
The recovery index is detailed in Table 1.
Comparative example 1
The only difference from example 1 is that ammonia was not additionally added in the mixing treatment. The recovery indices are detailed in Table 1.
Comparative example 2
The difference from example 1 is only that the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and the ammonia water is 1:1.2: 1.3. The recovery index is detailed in Table 1.
Comparative example 3
The difference from example 1 is only that the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and the ammonia water in the mixing treatment is 1:0.2: 1.3. The recovery indices are detailed in Table 1.
Comparative example 4
The difference from example 1 is only that the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and the ammonia water in the mixing treatment is 1:0.7:1. The recovery index is detailed in Table 1.
Comparative example 5
The difference from example 1 is only that the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and the ammonia water in the mixing treatment is 1:0.7: 2. The recovery index is detailed in Table 1.
TABLE 1
According to the results of the above examples and comparative examples, different material ratios can significantly affect the separation degree of aluminum and copper, thereby affecting the purity of aluminum phosphate, and the material can also affect the degree of converting copper hydroxide into copper oxide, thereby affecting the quality of copper oxide, and also affecting the purity of sodium chloride.
It is to be understood that the present invention has been described in detail with reference to the above embodiments, but the present invention is not limited to the above detailed structural features, and it is not intended that the present invention be limited to the above detailed structural features. It should be understood by those skilled in the art that any modifications, equivalent substitutions of selected elements of the present invention, additions of auxiliary elements, selection of specific forms, etc., are intended to fall within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
Claims (10)
1. A method for recovering a spent etching solution, comprising:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and performing solid-liquid separation to obtain a solid phase and a copper-ammonium solution;
and sequentially carrying out alkali treatment and deamination on the obtained cuprammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide.
2. The recycling method according to claim 1, wherein the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and the ammonia water in the mixing treatment is 1 (0.5-0.8) to (1.2-1.5).
3. A recovery process according to claim 1 or 2, characterised in that the mixing treatment takes 30-45 min.
4. The recovery method according to any one of claims 1 to 3, wherein the mass ratio of the cuprammonium solution to the alkali agent in the alkali treatment is 1 (1.2-1.5).
5. A recovery process as claimed in any one of claims 1 to 4, characterized in that the alkaline reagent comprises 1 or a combination of at least 2 of sodium hydroxide solution, potassium hydroxide solution or ammonia water.
6. A recovery process as claimed in any one of claims 1 to 5, characterized in that the alkaline treatment is carried out for a period of 45 to 80 min.
7. The recovery process of any one of claims 1 to 6, wherein the deamination is a flash evaporation of the alkaline treated solution.
8. The recovery process of claim 7, wherein the temperature of the flash treatment is from 90 ℃ to 120 ℃.
9. The recovery process of claim 7, wherein the pressure of the flash treatment is from 0.1 to 0.2 MPa.
10. A recovery process as claimed in any one of claims 1 to 9, wherein the recovery process comprises:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and performing solid-liquid separation to obtain a solid phase and a copper-ammonium solution; the mass ratio of the acidic copper-containing etching waste liquid to the alkaline etching waste liquid to the ammonia water in the mixing treatment is 1 (0.5-0.8) to 1.2-1.5; the mixing treatment time is 30-45 min;
sequentially carrying out alkali treatment and deamination on the obtained cuprammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide; the mass ratio of the copper ammonium solution to the alkali reagent in the alkali treatment is 1 (1.2-1.5); the alkali reagent comprises 1 or a combination of at least 2 of sodium hydroxide solution, potassium hydroxide solution or ammonia water; the alkali treatment time is 45-80 min; the deamination is to carry out flash evaporation treatment on the solution after alkali treatment; the temperature of the flash evaporation treatment is 90-120 ℃; the pressure of the flash evaporation treatment is 0.1-0.2 MPa.
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