CN114772628B - Recovery method of waste etching liquid - Google Patents
Recovery method of waste etching liquid Download PDFInfo
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- CN114772628B CN114772628B CN202210431688.3A CN202210431688A CN114772628B CN 114772628 B CN114772628 B CN 114772628B CN 202210431688 A CN202210431688 A CN 202210431688A CN 114772628 B CN114772628 B CN 114772628B
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- 238000005530 etching Methods 0.000 title claims abstract description 92
- 239000007788 liquid Substances 0.000 title claims abstract description 88
- 239000002699 waste material Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000011084 recovery Methods 0.000 title abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000010949 copper Substances 0.000 claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 claims abstract description 59
- 239000003513 alkali Substances 0.000 claims abstract description 48
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 230000002378 acidificating effect Effects 0.000 claims abstract description 26
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 230000009615 deamination Effects 0.000 claims abstract description 19
- 238000006481 deamination reaction Methods 0.000 claims abstract description 19
- 238000000926 separation method 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- 239000000203 mixture Substances 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 3
- 238000005553 drilling Methods 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 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
- 239000012535 impurity Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 230000008685 targeting Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- ing And Chemical Polishing (AREA)
Abstract
The invention relates to a recovery method of 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 carrying out solid-liquid separation to obtain a solid phase and a copper ammonium solution; and sequentially carrying out alkali treatment and deamination on the obtained copper ammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide. By adopting a specific recovery flow, the etching waste liquid generated in the copper etching process is effectively recovered. The valuable resource of the waste liquid is reused, the environment is protected, the sustainable utilization of the resource is realized, meanwhile, no new waste is generated in the process, and the closed loop of the whole recovery treatment process is realized.
Description
Technical Field
The invention relates to the field of secondary utilization of resources, in particular to a method for recycling waste etching liquid.
Background
At present, the PCB is usually processed by etching technology in the manufacturing process so as to achieve the purpose of further use.
As disclosed in CN110191589a, a double-sided etching method applied to a flexible circuit board is disclosed, in which the thin copper surface and the thick copper surface of a flexible circuit board template are etched synchronously, and each flexible circuit board template is etched by adjusting the transmission speed, the thin copper spray pressure and the thick copper spray pressure until the etching conditions are satisfied. The circuit board standard board is etched by adopting a mode of synchronously etching the thin copper surface and the thick copper surface, and the flexible circuit board is etched in batches by simulating the etching environment of the flexible circuit board so as to meet the transmission speed, the thin copper spraying pressure and the thick copper spraying pressure corresponding to the etching requirement as final etching conditions, and after the final etching conditions are acted on the flexible circuit board to carry out etching effect verification, the flexible circuit board can be etched in batches by directly applying the final etching conditions, and the etching efficiency is effectively improved.
CN110087397a discloses a method for etching thick copper plate of PCB in sections, comprising: step 1: 2 copper plates are selected, and the 2 copper plates are cut into the required size; step 2: drilling positioning holes, target holes and riveting holes at four corners of the copper plate, and then manufacturing single-sided mirror image circuit patterns on the front side and the back side; step 3: plating copper and tin, and then carrying out film stripping etching treatment; step 4: the board surface is browned, and then two sets of copper plates are riveted by semi-cured resin sheets and hot-pressed; step 5: performing targeting hole drilling, via hole drilling, 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; step 6: and (5) carrying out secondary copper and 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 having solved the etching, and then control the incomplete copper deckle edge and thin, widened the scope of thick copper preparation linewidth interval.
However, during etching, a large amount of etching waste liquid is formed, and the waste liquid contains a large amount of metallic copper elements and other harmful elements, so that the environment is obviously damaged if the waste liquid is directly discharged.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a recovery method of waste etching liquid, which solves the problem that the prior copper-containing waste etching liquid cannot be effectively recovered.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a recovery method of 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 carrying out solid-liquid separation to obtain a solid phase and a copper ammonium solution;
and sequentially carrying out alkali treatment and deamination on the obtained copper ammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide.
By adopting a specific recovery flow, the etching waste liquid generated in the copper etching process is effectively recovered. The valuable resource of the waste liquid is reused, the environment is protected, the sustainable utilization of the resource is realized, meanwhile, no new waste is generated in the process, and the closed loop of the whole recovery treatment process is realized.
In the actual waste etching solution treatment process, the schemes of on-line utilization, etchant regeneration and the like are selected, and the waste etching solution in the invention is acidic etching solution containing aluminum, ammonia nitrogen, phosphoric acid and the like, and waste liquid with impurities enriched to be incapable of being used secondarily.
In the present invention, the ammonia gas collected in deamination can be returned to the mixing process for reuse.
As a preferred technical scheme of the invention, 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) (1.2-1.5), 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, etc., but the invention is not limited to the listed values, and other non-listed values are equally applicable in the range.
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% or 40%, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
In a preferred embodiment of the present invention, the mixing time is 30-45min, for example, 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, 39min, 40min, 41min, 42min, 43min, 44min or 45min, etc., but not limited to the values listed, and other values not listed in the range are equally applicable.
As a preferred technical scheme of the invention, the mass ratio of the copper ammonium solution to the alkali reagent in the alkali treatment is 1 (1.2-1.5), for example, 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 or 1:1.5, etc., but the invention is not limited to the listed values and other values are not applicable.
As a preferred embodiment of the present invention, the alkali agent includes 1 or a combination of at least 2 of sodium hydroxide solution, potassium hydroxide solution or aqueous ammonia. The aqueous ammonia may be aqueous ammonia from a deamination process.
In the present invention, the mass concentration of the alkali reagent is 20 to 40%, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%, etc., but the present invention is not limited to the values recited, and other values not recited in the range are equally applicable.
In a preferred embodiment of the present invention, the alkali treatment time is 45-80min, for example, 45min, 46min, 48min, 50min, 52min, 54min, 56min, 58min, 60min, 62min, 64min, 66min, 68min, 70min, 72min, 74min, 76min, 78min or 80min, etc., but not limited to the listed values, and other values not listed in the range are equally applicable.
As a preferable technical scheme of the invention, the deamination is to flash-process the solution after alkali treatment.
As a preferable embodiment of the present invention, the flash evaporation treatment may be carried out at a temperature of 90 to 120℃such as 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℃or the like, but are not limited to, the recited values, and other non-recited values within this range are equally applicable.
In a preferred embodiment of the present invention, the pressure of the flash evaporation treatment is 0.1 to 0.2MPa, and 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 may be used, but the present invention is not limited to the values listed, and other values not listed in the above range are equally applicable.
As a preferred technical scheme of the present invention, the recovery method includes:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and carrying out solid-liquid separation to obtain a solid phase and a copper ammonium solution; 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) (1.2-1.5); the mixing treatment time is 30-45min;
sequentially carrying out alkali treatment and deamination on the obtained copper ammonium 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 alkaline 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 45-80min; the deamination is to flash-process the solution after alkali treatment; the temperature of the flash evaporation treatment is 90-120 ℃; the pressure of the flash evaporation treatment is 0.1-0.2MPa.
Compared with the prior art, the invention has at least 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 recycling is realized.
(2) The waste etching solution obtains aluminum phosphate/copper oxide and sodium chloride with high added value, 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 copper oxide is more than or equal to 98% and the sodium chloride is more than or equal to 98%.
(3) The method adopts a two-step treatment method, wherein the first step is to neutralize and separate aluminum, and the second step is to separate and recycle copper, 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 will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The composition of the acidic copper-containing etching waste liquid adopted in the examples is aluminum chloride, ammonium chloride, copper chloride, phosphoric acid, 2000ppm of aluminum, 80000ppm of copper, 2000ppm of total phosphorus, 8000ppm of ammonium root, and the composition of the alkaline etching waste liquid is ammonia water, ammonium chloride, copper chloride, 120000ppm of ammonia nitrogen and 90000ppm of copper.
The embodiment provides a recovery method of waste etching solution, as shown in fig. 1, the recovery method includes:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and carrying out 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 1:0.7:1.3; the time of the mixing treatment is 35min;
sequentially carrying out alkali treatment and deamination on the obtained copper ammonium 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 55min; the deamination is to flash-process the solution after alkali treatment; the temperature of the flash evaporation treatment is 100 ℃; the pressure of the flash evaporation treatment is 0.14MPa.
The recovery index is shown in Table 1.
Example 2
The composition of the acidic copper-containing etching waste liquid adopted in the example is aluminum chloride, ammonium chloride, copper chloride, phosphoric acid, 1000ppm of aluminum, 100000ppm of copper, 5000ppm of total phosphorus, 2400ppm of ammonium root, 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 recovery method of 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 carrying out 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 1:0.5:1.5; the mixing treatment time is 30min;
sequentially carrying out alkali treatment and deamination on the obtained copper ammonium 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 potassium hydroxide solution (the mass concentration is 35%); the alkali treatment time is 45min; the deamination is to flash-process the solution after alkali treatment; the temperature of the flash evaporation treatment is 90 ℃; the pressure of the flash evaporation treatment is 0.1MPa.
The recovery index is shown in Table 1.
Example 3
The composition of the acidic copper-containing etching waste liquid used in the examples was ammonia water, ammonium chloride, copper chloride, phosphoric acid, aluminum 3394ppm, copper 102392pm, total phosphorus 3432ppm, ammonium radical 3429ppm, alkaline etching waste liquid containing ammonia water, ammonium chloride, copper chloride, ammonia nitrogen 95085ppm, copper 8764ppm.
The embodiment provides a recovery method of 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 carrying out 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 time of the mixing treatment is 45min;
sequentially carrying out alkali treatment and deamination on the obtained copper ammonium 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 80min; the deamination is to flash-process the solution after alkali treatment; the temperature of the flash evaporation treatment is 120 ℃; the pressure of the flash evaporation treatment is 0.2MPa.
The recovery index is shown in Table 1.
Example 4
The composition of the acidic copper-containing etching waste liquid used in the examples was ammonia water, ammonium chloride, copper chloride, phosphoric acid, aluminum 3326ppm, copper 97243ppm, total phosphorus 4657ppm, ammonium root 7259ppm, alkaline etching waste liquid, ammonia nitrogen 80000ppm, copper 82362ppm.
The embodiment provides a recovery method of 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 carrying out 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 1:0.6:1.4; the time of the mixing treatment is 40min;
sequentially carrying out alkali treatment and deamination on the obtained copper ammonium 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 sodium hydroxide solution (the mass concentration is 20%); the alkali treatment time is 65min; the deamination is to flash-process the solution after alkali treatment; the temperature of the flash evaporation treatment is 110 ℃; the pressure of the flash evaporation treatment is 0.17MPa.
The recovery index is shown in Table 1.
Comparative example 1
The difference from example 1 is only that no ammonia was additionally added in the mixing treatment. The recovery index is shown in Table 1.
Comparative example 2
The difference from example 1 was only that the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and the aqueous ammonia was 1:1.2:1.3. The recovery index is shown in Table 1.
Comparative example 3
The only difference from example 1 is that 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 1:0.2:1.3. The recovery index is shown in Table 1.
Comparative example 4
The only difference from example 1 is that the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and the aqueous ammonia in the mixing treatment was 1:0.7:1. The recovery index is shown in Table 1.
Comparative example 5
The only difference from example 1 is that the mass ratio of the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and the aqueous ammonia in the mixing treatment was 1:0.7:2. The recovery index is shown in Table 1.
TABLE 1
As can be seen from the results of the above examples and comparative examples, different material ratios significantly affect the degree of separation of aluminum and copper, and thus the purity of aluminum phosphate, and at the same time, the material also affects the degree of conversion of copper hydroxide into copper oxide, and thus the quality of copper oxide, and also affects the purity of sodium chloride.
It is stated that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e., it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (5)
1. A method for recovering a waste etching solution, the method comprising:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and carrying out solid-liquid separation to obtain a solid phase and a copper ammonium solution;
sequentially carrying out alkali treatment and deamination on the obtained copper ammonium solution, and then carrying out solid-liquid separation to obtain a sodium chloride solution and copper oxide;
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) (1.2-1.5);
the mass ratio of the copper ammonium solution to the alkali reagent in the alkali treatment is 1 (1.2-1.5); the deamination is to flash-process the solution after alkali treatment; the temperature of the flash evaporation treatment is 90-120 ℃; the pressure of the flash evaporation treatment is 0.1-0.2MPa.
2. The method for recovering a waste etching solution according to claim 1, wherein the time for the mixing treatment is 30 to 45 minutes.
3. The method for recovering waste etching liquid according to claim 1, wherein the alkali agent comprises 1 or a combination of at least 2 of sodium hydroxide solution, potassium hydroxide solution or aqueous ammonia.
4. The method for recovering waste etching liquid according to claim 1, wherein the alkali treatment time is 45 to 80 minutes.
5. The method for recovering a waste etching solution according to any one of claims 1 to 4, wherein the recovering method comprises:
mixing the acidic copper-containing etching waste liquid, the alkaline etching waste liquid and ammonia water, and carrying out solid-liquid separation to obtain a solid phase and a copper ammonium solution; 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) (1.2-1.5); the mixing treatment time is 30-45min;
sequentially carrying out alkali treatment and deamination on the obtained copper ammonium 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 alkaline 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 45-80min; the deamination is to flash-process the solution after alkali treatment;
the temperature of the flash evaporation treatment is 90-120 ℃; the pressure of the flash evaporation treatment is 0.1-0.2MPa.
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