CN110894114A - Copper separation system of high acidity copper-containing waste liquid of strong oxidation - Google Patents
Copper separation system of high acidity copper-containing waste liquid of strong oxidation Download PDFInfo
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- CN110894114A CN110894114A CN201911343890.5A CN201911343890A CN110894114A CN 110894114 A CN110894114 A CN 110894114A CN 201911343890 A CN201911343890 A CN 201911343890A CN 110894114 A CN110894114 A CN 110894114A
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- 239000007788 liquid Substances 0.000 title claims abstract description 112
- 239000010949 copper Substances 0.000 title claims abstract description 96
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 95
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 238000000926 separation method Methods 0.000 title claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 title claims description 4
- 230000003647 oxidation Effects 0.000 title claims description 3
- 239000012528 membrane Substances 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000002912 waste gas Substances 0.000 claims abstract description 39
- 238000011001 backwashing Methods 0.000 claims abstract description 32
- 239000012466 permeate Substances 0.000 claims abstract description 26
- 230000008021 deposition Effects 0.000 claims abstract description 25
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims abstract description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 62
- 239000000919 ceramic Substances 0.000 claims description 59
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 58
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 58
- 238000001556 precipitation Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 20
- 235000006408 oxalic acid Nutrition 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 9
- 239000012716 precipitator Substances 0.000 claims description 7
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 abstract description 26
- 239000002244 precipitate Substances 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 25
- 239000002253 acid Substances 0.000 description 19
- 239000011135 tin Substances 0.000 description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 13
- 229910052718 tin Inorganic materials 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000005530 etching Methods 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 238000003916 acid precipitation Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000009295 crossflow filtration Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/40—Acidic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/005—Processes using a programmable logic controller [PLC]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a copper separation system for strongly-oxidized high-acidity copper-containing waste liquid, which comprises a PLC control system, a copper deposition reaction system, a membrane concentration system, a centrifugal system, a waste gas recovery system and a backwashing system, wherein the copper deposition reaction system, the membrane concentration system, the centrifugal system, the waste gas recovery system and the backwashing system are connected with the PLC control system; the copper deposition reaction system comprises a precipitant feeding port and a waste liquid feeding port, and a reaction liquid discharging port of the copper deposition reaction system is connected with a reaction liquid feeding port of the membrane concentration system; a concentrated solution discharge port of the membrane concentration system is connected with a concentrated solution feed port of the centrifugal system, and a permeate discharge port of the membrane concentration system is connected with a feed port of the backwashing system; the centrifugal system also comprises a centrifugal liquid discharge port which is connected with the feed inlet of the backwashing system; a backwash liquid discharge port of the backwashing system is connected with a permeate liquid discharge port of the membrane concentration system; the copper deposition reaction system and the centrifugal system are both provided with a waste discharge port connected with the waste gas recovery system. The technical scheme of the invention realizes the high-efficiency separation of the copper oxalate precipitate.
Description
Technical Field
The invention relates to the field of wastewater treatment equipment, in particular to a copper separation system for strongly-oxidized high-acidity copper-containing waste liquid.
Background
In the PCB or electroplating industry, the stripping and hanging rack stripping solution often uses high-concentration nitric acid as an acid. With the continuous use of the deplating solution in the deplating process, the chemical reaction balance shows that the reaction is inhibited when the copper content in the deplating solution reaches a certain concentration, the deplating efficiency is reduced, and thus the copper-containing deplating nitric acid is generated. In the PCB tin stripping process, when the tin content of the tin stripping solution reaches a certain concentration (usually 100g/L higher), the tin stripping capability is also reduced, thereby generating tin stripping waste liquid. The tin stripping waste liquid not only has high acid content, but also contains a large amount of metal elements such as tin, copper, iron and the like. These two types of waste liquid belong to copper-containing waste liquid with high acidity and have strong oxidizing property. In addition, in the PCB etching process, the largest amount of the used acid etching solution is the acid etching solution, the main components of the acid etching solution are copper chloride, organic additives, hydrochloric acid, sodium chloride and the like, and the content of the hydrochloric acid in the scrapped acid etching solution is up to 2mol/L, which belongs to high-acidity copper-containing waste liquid. If the high-acidity copper-containing waste liquid is not effectively treated, the method causes great harm to the environment and resource waste.
The existing method for on-line resource copper extraction of strongly oxidized high-acidity copper-containing waste liquid is multiple. The main adopted technologies include an online electrolysis method, reduced pressure distillation, an oxalic acid precipitation method and the like. The electrolysis method or the reduced pressure distillation process is complex, the requirement on equipment is high, and the requirement on operators is also high. The oxalic acid precipitation method has simple process, is widely applied to the rare earth and nonferrous metal industries, and has mature process flow, simple operation and control, easy production and wide sources of oxalic acid raw materials. In recent years, the oxalic acid precipitation method is applied to the hazardous waste treatment industry, particularly the printed circuit board and electroplating industry, and the hazardous waste treatment mainly relates to copper-removing waste nitric acid, tin-removing waste liquid and acid etching waste liquid in a rack stripping process.
Although the principle and the flow of the copper oxalate precipitation method are simple, the operation process of the process is easy to control. However, because the copper oxalate precipitation particles are powdery, fine and easy to block filter cloth and are extremely difficult to filter, the oxalic acid precipitation method cannot be popularized and applied in the recycling of the copper-containing waste liquid with high acidity, and a feasible industrial technology is not provided so far to thoroughly solve the problem of high-efficiency filtration of the copper oxalate precipitation.
Disclosure of Invention
The invention mainly aims to provide a copper separation system for strongly-oxidized high-acidity copper-containing waste liquid, aiming at realizing the high-efficiency separation of copper oxalate precipitate in a strongly-oxidized high-acidity solution system.
In order to achieve the purpose, the copper separation system for the strong-oxidation high-acidity copper-containing waste liquid comprises a PLC control system, and further comprises a copper deposition reaction system, a membrane concentration system, a centrifugal system, a waste gas recovery system and a backwashing system which are connected with the PLC control system; the copper deposition reaction system comprises a precipitator feed inlet for adding oxalic acid or oxalate and a waste liquid feed inlet for adding copper-containing waste liquid, and a reaction liquid discharge port of the copper deposition reaction system is connected with a reaction liquid feed inlet of the membrane concentration system; the membrane concentration system is provided with at least one tubular silicon carbide ceramic membrane which is sequentially communicated in a plurality of stages, and comprises a concentrated solution discharge port and a permeate discharge port, wherein the concentrated solution discharge port is connected with a concentrated solution feed port of the centrifugal system, and the permeate discharge port is connected with a feed port of the backwashing system; the centrifugal system also comprises a centrifugal liquid discharge port, and the centrifugal liquid discharge port is connected with the feed port of the backwashing system; a backwash liquid discharge port of the backwashing system is connected with a permeate liquid discharge port of the membrane concentration system; the copper deposition reaction system and the centrifugal system are both provided with waste gas discharge ports, and the waste gas discharge ports are connected with a waste gas receiving port of the waste gas recovery system.
Preferably, the copper deposition reaction system is arranged as a reaction kettle, a precipitator feed inlet of the reaction kettle is connected with an oxalic acid dosing tank, a waste liquid feed inlet of the reaction kettle is connected with a waste liquid feed pump, and the waste liquid feed pump is communicated with external waste liquid.
Preferably, a radar level gauge is further arranged in the reaction kettle.
Preferably, the membrane concentration system is provided with tubular silicon carbide ceramic membranes with four stages communicated in sequence, and the tubular silicon carbide ceramic membranes comprise a first-stage tubular silicon carbide ceramic membrane, a second-stage tubular silicon carbide ceramic membrane, a third-stage tubular silicon carbide ceramic membrane and a fourth-stage tubular silicon carbide ceramic membrane, wherein the first-stage tubular silicon carbide ceramic membrane, the second-stage tubular silicon carbide ceramic membrane, the third-stage tubular silicon carbide ceramic membrane and the fourth-stage tubular silicon carbide ceramic membrane are respectively provided with a permeate liquid discharge port connected with a feed port of the backwashing system; the reaction liquid feed inlet of the first-stage tubular silicon carbide ceramic membrane is connected with the reaction liquid discharge outlet of the copper deposition reaction system through a reaction liquid feed pump, and the concentrated liquid discharge outlet of the fourth-stage tubular silicon carbide ceramic membrane is connected with the concentrated liquid feed inlet of the centrifugal system.
Preferably, the first-stage tubular silicon carbide ceramic membrane, the second-stage tubular silicon carbide ceramic membrane, the third-stage tubular silicon carbide ceramic membrane and the fourth-stage tubular silicon carbide ceramic membrane are respectively provided with a backwash liquid discharge port, and the backwash liquid discharge port is connected with a backwash liquid feed port of the copper deposition reaction system.
Preferably, the backwashing system is arranged as a storage tank, and a backwashing liquid discharge port of the storage tank is connected with a permeate discharge port of the membrane concentration system through a backwashing pump.
Preferably, the backwashing system further comprises an air compressor, and an air outlet of the air compressor is connected with a permeate discharge hole of the membrane concentration system.
Preferably, the centrifugal system is provided as a centrifuge, and an exhaust gas outlet of the centrifuge is connected with an exhaust gas receiving port of the exhaust gas recovery system through a gas collecting hood.
Preferably, the waste gas recovery system is provided as a waste gas absorption tank, and the waste gas absorption tank is internally provided with alkaline absorption liquid.
Compared with the prior art, the invention has the beneficial effects that:
1. aiming at the characteristic that copper oxalate precipitates are superfine and difficult to filter, the mixed solution of the reaction precipitates is concentrated by adopting a membrane separation cross flow filtration operation mode. The cross-flow filtration operation mode has pollution resistance, can maintain high-flux filtration, and effectively avoids the problem that the copper oxalate is easy to block the filter cloth and is difficult to filter;
2. the tubular ceramic membrane multistage cross flow filtration is adopted to concentrate the copper oxalate precipitation mixed liquor, and then a centrifuge is used for centrifugally separating the concentrated copper oxalate precipitation mixed liquor, so that the filtration time of the copper oxalate is greatly shortened through concentration and centrifugal dehydration, and the efficiency is improved.
3. The silicon carbide ceramic membrane has the characteristics of strong acid resistance, wear resistance and long service life, is particularly suitable for a high-concentration strong-oxidizing strong acid system, and can improve the efficiency and reduce the operation and maintenance cost compared with the conventional direct filter pressing or centrifugal separation and hollow fiber membrane submerged type filtration modes;
4. the method not only can be used for the high-efficiency separation of the copper oxalate precipitate in the high-acidity copper-containing waste liquid, but also can be used for the high-efficiency separation of the copper oxalate precipitate in other copper-containing waste liquids by using the copper oxalate as a precipitator.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic diagram of the copper separation system of the present invention;
the implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
Referring to fig. 1, the copper separation system for a strongly oxidized high-acidity copper-containing waste liquid provided in this embodiment includes a PLC control system (not shown in the figure), and further includes a copper deposition reaction system, a membrane concentration system, a centrifugal system, a waste gas recovery system, and a backwashing system, which are connected to the PLC control system;
the copper deposition reaction system comprises a precipitator feed inlet for adding oxalic acid or oxalate and a waste liquid feed inlet for adding copper-containing waste liquid, and a reaction liquid discharge port of the copper deposition reaction system is connected with a reaction liquid feed inlet of the membrane concentration system;
the membrane concentration system is provided with at least one tubular silicon carbide ceramic membrane which is sequentially communicated in a plurality of stages, and comprises a concentrated solution discharge port and a permeate discharge port, wherein the concentrated solution discharge port is connected with a concentrated solution feed port of the centrifugal system, and the permeate discharge port is connected with a feed port of the backwashing system;
the centrifugal system also comprises a centrifugal liquid discharge port, and the centrifugal liquid discharge port is connected with the feed port of the backwashing system;
a backwash liquid discharge port of the backwashing system is connected with a permeate liquid discharge port of the membrane concentration system;
the copper deposition reaction system and the centrifugal system are both provided with waste gas discharge ports, and the waste gas discharge ports are connected with a waste gas receiving port of the waste gas recovery system.
Further, the copper deposition reaction system is arranged as a reaction kettle 11, a precipitator feed inlet of the reaction kettle 11 is connected with an oxalic acid dosing tank 12, a waste liquid feed inlet of the reaction kettle 11 is connected with a waste liquid feed pump 13, and the waste liquid feed pump 13 is communicated with external waste liquid.
Further, a radar level gauge 14 is further arranged in the reaction kettle 11 and used for monitoring the addition amount of the reaction liquid in the reaction kettle 11.
Further, in this embodiment, the number of the membrane concentration systems is set to one, and the membrane concentration systems are set to four stages of tubular silicon carbide ceramic membranes which are sequentially communicated, including a first-stage tubular silicon carbide ceramic membrane 21, a second-stage tubular silicon carbide ceramic membrane 22, a third-stage tubular silicon carbide ceramic membrane 23, and a fourth-stage tubular silicon carbide ceramic membrane 24, where the first-stage tubular silicon carbide ceramic membrane 21, the second-stage tubular silicon carbide ceramic membrane 22, the third-stage tubular silicon carbide ceramic membrane 23, and the fourth-stage tubular silicon carbide ceramic membrane 24 are all provided with a permeate liquid discharge port connected with the feed port of the backwashing system; the reaction liquid feed inlet of the first-stage tubular silicon carbide ceramic membrane 21 is connected with the reaction liquid discharge outlet of the copper deposition reaction system through a reaction liquid feed pump 25, and the concentrated liquid discharge outlet of the fourth-stage tubular silicon carbide ceramic membrane 24 is connected with the concentrated liquid feed inlet of the centrifugal system.
Further, a backwash liquid discharge port is respectively added to the first-stage tubular silicon carbide ceramic membrane 21, the second-stage tubular silicon carbide ceramic membrane 22, the third-stage tubular silicon carbide ceramic membrane 23 and the fourth-stage tubular silicon carbide ceramic membrane 24, and the backwash liquid discharge port is connected with a backwash liquid feed port of the copper deposition reaction system.
Further, the backwashing system is provided as a storage tank 51, and a backwash liquid discharge port of the storage tank 51 is connected with a permeate discharge port of the membrane concentration system through a backwashing pump 52.
Further, the backwashing system further comprises an air compressor 53, and an air outlet of the air compressor 53 is connected with a permeate discharge port of the membrane concentration system.
Further, the centrifugal system is provided as a centrifuge 31, and an exhaust gas outlet of the centrifuge 31 is connected with an exhaust gas receiving port of the exhaust gas recovery system through a gas collecting hood 32.
Further, the waste gas recovery system is provided as a waste gas absorption tank 41, and the waste gas absorption tank 41 is filled with alkaline absorption liquid.
It should be noted that, in this embodiment, each system is controlled to operate by the PLC control system, which is the prior art and is not described herein again. Specifically, when the high-acidity copper-containing waste liquid is treated, the copper-containing acidic waste liquid is conveyed into a reaction kettle 11 through a waste liquid feed pump 13, the reaction kettle 11 is started to stir, oxalic acid or an oxalate solution is added into the reaction kettle 11 from an oxalic acid dosing tank 12 to perform a copper ion precipitation reaction, and a copper oxalate precipitation mixed solution is obtained.
After the reaction is completed, a reaction liquid discharge port of the reaction kettle 11 is opened, a reaction liquid feed pump 25 is started, the copper oxalate precipitation mixed liquid enters a membrane concentration system, and is subjected to cross-flow concentration and separation by a first-stage tubular silicon carbide ceramic membrane 21 to obtain a concentrated liquid and a permeate liquid of the first-stage copper oxalate precipitation mixed liquid, the concentrated liquid of the first-stage copper oxalate precipitation mixed liquid is subjected to cross-flow concentration and separation by a second-stage tubular silicon carbide ceramic membrane 22, and is subjected to four-stage cross-flow concentration and separation in sequence to obtain a concentrated liquid of a thick high-concentration copper oxalate precipitation mixed liquid, and the concentrated liquid of the thick high-concentration copper oxalate precipitation mixed liquid is conveyed into a centrifuge 31 to be subjected to high-speed centrifugal separation to obtain solid copper. Permeate generated by the cross-flow concentration and separation of each stage of tubular silicon carbide ceramic membrane can be used as regenerated acid and is conveyed into the storage tank 51 through the permeate discharge port.
It should be noted that the waste acid gas generated by the copper precipitation reaction in the reaction kettle 11 can be delivered into the waste gas absorption tank 41 through the waste gas outlet of the reaction kettle 11 via the gas pipe under negative pressure; waste acid gas generated by the centrifuge 31 can be collected by the upper gas collecting hood 32 connected with the centrifuge and is conveyed into the waste gas absorption tank 41 through a gas pipe under negative pressure; the waste gas absorption tank 41 is internally provided with alkaline absorption liquid, and the waste gas absorption tank 41 is externally connected with a vacuum pump 42, so that waste acid gas can be absorbed, and air pollution is prevented.
Further, the system can be flushed periodically to prevent blockage. Specifically, a pipeline valve is switched, the air compressor 53 is opened, and gas generated by the air compressor 53 enters through a permeate discharge port of the membrane concentration system, so that gas for the membrane concentration system is back-flushed; the regenerated acid in the storage tank 51 can enter the membrane concentration system through a permeate discharge port of the membrane concentration system by starting the backwashing pump 52, so that the membrane concentration system is backwashed with the regenerated acid.
In this embodiment, the number of the membrane concentration system is set to one, and the membrane concentration system is set to the structure that four tubular silicon carbide ceramic membranes are connected in series, it should be noted that, according to actual production requirements and cost requirements, the membrane concentration system can also be set to a single tubular silicon carbide ceramic membrane or a plurality of tubular silicon carbide ceramic membrane parallel structure, furthermore, the membrane concentration system can also be set to a plurality of membrane concentration systems which are connected in series or in parallel to form, thereby greatly improving the efficiency of copper oxalate precipitation, making the whole system have stronger adaptability, and meeting different production requirements.
Further, the following is further illustrated by specific examples:
example one
Get a certain PCB enterprise 1m3Copper-containing deplating waste nitric acid is conveyed to a reaction kettle 11 through a waste liquid feeding pump 13, the reaction kettle 11 is started to stir, oxalic acid solution is added into the reaction kettle 11 from an oxalic acid dosing tank 12 to precipitate copper ions, and copper oxalate precipitation mixed liquor is obtained. After the reaction is carried out for 2 hours, a reaction liquid discharge port of the reaction kettle 11 is opened, a reaction liquid feeding pump 25 is started, the copper oxalate precipitation mixed liquid enters a membrane concentration system, and is subjected to cross-flow concentration and separation by a first-stage tubular silicon carbide ceramic membrane 21 to obtain a concentrated liquid and a permeate liquid of the first-stage copper oxalate precipitation mixed liquid, the concentrated liquid of the first-stage copper oxalate precipitation mixed liquid is subjected to cross-flow concentration and separation by a second-stage tubular silicon carbide ceramic membrane 22, and is sequentially subjected to four-stage cross-flow concentration and separation to obtain a concentrated liquid of a thick high-concentration copper oxalate precipitation mixed liquid, and the concentrated liquid of the thick high-concentration copper oxalate precipitation mixed liquid enters a centrifuge 31 for high-speed centrifugal separation to obtain solid. The regenerated acid generated in each step is introduced into the storage tank 51. The copper separation system was recorded to take 0.5 hours.The test process has no waste gas emission and is environment-friendly.
Similarly, take the above PCB enterprise 1m3Pumping the copper-containing deplating waste nitric acid into a reaction vessel, stirring and adding the same amount of oxalic acid solution for reaction for 2 hours, and then separating by using a box filter press, wherein the time is required to be 4 hours. The filter press has waste gas emission and pollutes the environment in the test process.
The results show that the efficiency of the copper separation system is obviously improved, and the copper separation system is environment-friendly; the test results completely meet the requirements of the existing stripping solution, so that the aim of recycling the acid liquor can be fulfilled while the copper is recovered.
Example two
Take 1m3The PCB acid etching waste liquid containing 100g/L, HCl 2mol/L Cu produced by a certain PCB enterprise is compared by taking oxalic acid as a copper precipitation agent, and the operation is carried out in the same way. The copper separation system is used for 0.7 hour, has no waste gas emission in the test process, and is environment-friendly. The chamber type filter press is used for 4.5 hours, and the filter press has waste gas emission and pollutes the environment in the test process. The result shows that the efficiency of the copper separation system is obviously improved, and the copper separation system is environment-friendly; the regenerated acidic etching solution containing 3g/L of copper ions is obtained in a test, the regenerated acidic etching solution is used for preparing an acidic etching solution sub-solution, the test result completely meets the requirements of the existing etching solution, and the purpose of recycling acid liquor can be achieved while copper is recovered.
EXAMPLE III
Take 1m3Nitric acid 15% and Cu content produced by a certain PCB enterprise2+11.3g·L-1、Fe3+23.5g·L-1、Sn2+/Sn4+110g·L-1The nitric acid type tin stripping waste liquid is tested by taking oxalic acid as a copper precipitation agent, and the related reactions are as follows:
Cu2++H2C2O4→CuC2O4↓+2H+
2Fe3++3H2C2O4→Fe2(C2O4)3↓+6H+
Sn(OH)6 2-+2H+→Sn(OH)4↓+2H2O
adding oxalic acid solution according to the amount of 90 percent of the amount of the reaction formula, stirring the mixture for reaction for 2 hours, and carrying out a comparative test. The copper separation system is used for 0.5 hour, has no waste gas emission in the test process, and is environment-friendly. The chamber filter press is used for 5 hours, and the filter press has waste gas emission and pollutes the environment in the test process. The result shows that the efficiency of the copper separation system is obviously improved, and the copper separation system is environment-friendly; the test obtains the regenerated nitric acid with the copper and tin contents of 1.3g/L and 1.4g/L respectively, the regenerated nitric acid is used for preparing the nitric acid type tin stripping solution, and the tin stripping test shows that the regenerated tin stripping solution can be used, the regeneration cost is low, the process is simple, the resource recycling maximization is realized, the clean production of the tin stripping process is realized, and the application prospect is good.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (9)
1. A copper separation system for strongly oxidized high-acidity copper-containing waste liquid is characterized by comprising a PLC control system, a copper deposition reaction system, a membrane concentration system, a centrifugal system, a waste gas recovery system and a backwashing system, wherein the copper deposition reaction system, the membrane concentration system, the centrifugal system, the waste gas recovery system and the backwashing system are connected with the PLC control system;
the copper deposition reaction system comprises a precipitator feed inlet for adding oxalic acid or oxalate and a waste liquid feed inlet for adding copper-containing waste liquid, and a reaction liquid discharge port of the copper deposition reaction system is connected with a reaction liquid feed inlet of the membrane concentration system;
the membrane concentration system is provided with at least one tubular silicon carbide ceramic membrane which is sequentially communicated in a plurality of stages, and comprises a concentrated solution discharge port and a permeate discharge port, wherein the concentrated solution discharge port is connected with a concentrated solution feed port of the centrifugal system, and the permeate discharge port is connected with a feed port of the backwashing system;
the centrifugal system also comprises a centrifugal liquid discharge port, and the centrifugal liquid discharge port is connected with the feed port of the backwashing system;
a backwash liquid discharge port of the backwashing system is connected with a permeate liquid discharge port of the membrane concentration system;
the copper deposition reaction system and the centrifugal system are both provided with waste gas discharge ports, and the waste gas discharge ports are connected with a waste gas receiving port of the waste gas recovery system.
2. The system for separating copper from a strongly-oxidized and highly-acidic waste copper-containing liquid according to claim 1, wherein the copper precipitation reaction system is configured as a reaction kettle, a precipitator feed port of the reaction kettle is connected with an oxalic acid dosing tank, a waste liquid feed port of the reaction kettle is connected with a waste liquid feed pump, and the waste liquid feed pump is communicated with external waste liquid.
3. The system for separating copper from a strongly oxidized high-acidity waste copper-containing liquid according to claim 2, wherein a radar level gauge is further disposed in the reaction kettle.
4. The copper separation system for the strongly-oxidized high-acidity waste liquid containing copper according to claim 1, wherein the membrane concentration system is provided with four stages of sequentially-communicated tubular silicon carbide ceramic membranes, and comprises a first-stage tubular silicon carbide ceramic membrane, a second-stage tubular silicon carbide ceramic membrane, a third-stage tubular silicon carbide ceramic membrane and a fourth-stage tubular silicon carbide ceramic membrane, and the first-stage tubular silicon carbide ceramic membrane, the second-stage tubular silicon carbide ceramic membrane, the third-stage tubular silicon carbide ceramic membrane and the fourth-stage tubular silicon carbide ceramic membrane are all provided with a permeate liquid outlet connected with the feed inlet of the backwashing system; the reaction liquid feed inlet of the first-stage tubular silicon carbide ceramic membrane is connected with the reaction liquid discharge outlet of the copper deposition reaction system through a reaction liquid feed pump, and the concentrated liquid discharge outlet of the fourth-stage tubular silicon carbide ceramic membrane is connected with the concentrated liquid feed inlet of the centrifugal system.
5. The system for separating copper from a strongly-oxidized high-acidity waste copper-containing liquid according to claim 4, wherein a backwash liquid outlet is respectively formed in each of the first-stage tubular silicon carbide ceramic membrane, the second-stage tubular silicon carbide ceramic membrane, the third-stage tubular silicon carbide ceramic membrane and the fourth-stage tubular silicon carbide ceramic membrane, and the backwash liquid outlet is connected with a backwash liquid inlet of the copper precipitation reaction system.
6. The system for separating copper from a strongly oxidized high-acidity waste copper-containing liquid according to claim 1, wherein the backwashing system is configured as a storage tank, and a backwash liquid discharge port of the storage tank is connected with a permeate discharge port of the membrane concentration system through a backwashing pump.
7. The system for separating copper from a strongly oxidized high-acidity waste liquid containing copper according to claim 6, wherein the backwashing system further comprises an air compressor, and an air outlet of the air compressor is connected with a permeate discharge port of the membrane concentration system.
8. The copper separation system of high acidity copper-containing waste liquid according to claim 1, wherein the centrifugal system is configured as a centrifuge, and an exhaust gas discharge port of the centrifuge is connected to an exhaust gas receiving port of the exhaust gas recovery system through a gas collecting hood.
9. A system for separating copper from a spent copper-bearing liquor having high acidity and high oxidation level according to claim 1, wherein the waste gas recovery system is configured as a waste gas absorption tank, and alkaline absorption liquid is contained in the waste gas absorption tank.
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| US20130001275A1 (en) * | 2011-06-30 | 2013-01-03 | Thales | Process for Manufacturing a Device Comprising Brazes Produced from Metal Oxalate |
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| US20130001275A1 (en) * | 2011-06-30 | 2013-01-03 | Thales | Process for Manufacturing a Device Comprising Brazes Produced from Metal Oxalate |
| CN206070003U (en) * | 2016-06-17 | 2017-04-05 | 红板（江西）有限公司 | A kind of regeneration complete set of equipments of circuit board plant electro-coppering wire holder nitric acid deplating liquid |
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