CN114349240A - Resource utilization method of copper in etching waste liquid - Google Patents
Resource utilization method of copper in etching waste liquid Download PDFInfo
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- CN114349240A CN114349240A CN202111373468.1A CN202111373468A CN114349240A CN 114349240 A CN114349240 A CN 114349240A CN 202111373468 A CN202111373468 A CN 202111373468A CN 114349240 A CN114349240 A CN 114349240A
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- 239000002699 waste material Substances 0.000 title claims abstract description 52
- 238000005530 etching Methods 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 178
- 239000012528 membrane Substances 0.000 claims abstract description 104
- 238000001728 nano-filtration Methods 0.000 claims abstract description 86
- 239000000919 ceramic Substances 0.000 claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 69
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 69
- 238000000909 electrodialysis Methods 0.000 claims description 49
- 238000001704 evaporation Methods 0.000 claims description 30
- 230000008020 evaporation Effects 0.000 claims description 30
- 238000005086 pumping Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000013505 freshwater Substances 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000011033 desalting Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 14
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 239000011550 stock solution Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Abstract
The invention is suitable for the technical field of resource recovery, and provides a resource utilization method of copper in etching waste liquid, the etching waste liquid enters a ceramic membrane system water inlet tank, the etching waste liquid is pumped into a ceramic membrane system through a feed pump and a circulating pump, impurities such as large particles and suspended matters in the waste liquid are removed through filtering by a ceramic membrane, the obtained water produced by the ceramic membrane system enters a ceramic membrane system water production tank, the etching waste liquid is pretreated by adopting the ceramic membrane technology, and as the etching liquid has strong acidity and complex components, compared with other technologies, the ceramic membrane has excellent performances such as acid resistance, alkali resistance, organic solvent resistance, high temperature resistance and the like, the stable operation of the system can be ensured, meanwhile, the aperture of the ceramic membrane is nano-scale, the filtering precision is high, the impurities in the waste liquid can be removed, the turbidity of the water produced by the ceramic membrane system is less than 1NTU, and the water inlet requirement of a rear-stage nanofiltration system is met, can ensure the stable operation of the nanofiltration system.
Description
Technical Field
The invention belongs to the technical field of resource recovery, and particularly relates to a resource utilization method of copper in etching waste liquid.
Background
The etching solution of the circuit board contains a certain amount of copper sulfate, and if the copper sulfate is directly discharged, the environment can be seriously polluted. The traditional method is to extract part of copper by electrodeposition technology and then discharge. Thus not only wasting a large amount of copper, but also causing serious pollution to the environment.
Chinese patent application No. CN201210304391.7 discloses an acidic etching solution recycling system, which comprises an etching production line water device (1), a transfer mother liquor tank (2), a mother liquor tank (3), an acidic etching solution recycling device group (7), a recycling sub-liquor tank (8), a liquor preparation tank (9), a filter (10) and a sub-liquor tank (11) which are connected in sequence, wherein a high-pressure pump is further connected between the two adjacent components. The acid etching solution recycling system designed by the invention has the advantages of high efficiency, low cost and small occupied area, but can generate chlorine.
In view of the current situation, the invention develops a new method for resource utilization of copper in etching waste liquid. Through the verification of a small test and a pilot test, the purity of the finally obtained copper sulfate product is more than or equal to 95 percent and can be sold as industrial salt; meanwhile, all water resources can be reused in production; not only the copper sulfate is recovered, but also no new waste water is discharged. The environmental pollution caused by the waste water is reduced while the economic benefit is created.
The invention realizes the recovery of copper sulfate, the recycling of water resources and no discharge of waste water, and is a green and environment-friendly technology.
Disclosure of Invention
The invention provides a resource utilization method of copper in etching waste liquid, and aims to solve the problems in the background technology.
The invention is realized in this way, a resource utilization method of copper in etching waste liquid, comprising the following steps:
s1, feeding the waste etching solution into a water inlet tank of a ceramic membrane system, pumping the waste etching solution into the ceramic membrane system through a feed pump and a circulating pump, filtering by a ceramic membrane to remove impurities such as large particles, suspended matters and the like in the waste etching solution, feeding the obtained water produced by the ceramic membrane system into a water production tank of the ceramic membrane system,
s2, pumping the water produced in the water production tank of the ceramic membrane system stored in the S1 into a nanofiltration system through a nanofiltration system feed pump and a high-pressure pump, filtering the water by a nanofiltration membrane, concentrating the water produced in the ceramic membrane system in the S1 to increase the concentration of copper sulfate in the concentrated water of the nanofiltration system to 20-30g/L, and then conveying the nanofiltration concentrated water into the concentrated water tank of the nanofiltration system,
s3, pumping the concentrated water generated by the nanofiltration system in S2 into an electrodialysis system through a feed pump, providing an electric field through a direct current power supply, enabling the concentration of copper sulfate in the concentrated water of the electrodialysis system to reach 150-200g/L through an electrodialysis membrane, conveying the concentrated water into an inlet water tank of an evaporation system, returning the fresh water of the electrodialysis system to the ceramic membrane system water generating tank in S1, continuously concentrating the fresh water through the nanofiltration system, and then feeding the concentrated water into the inlet water tank of the electrodialysis system,
and S4, pumping the concentrated water of the electrodialysis system into an evaporation system through a feeding pump and a circulating pump in S3, introducing steam, concentrating the wastewater, and passing through a salt crystallization system and a drying system to finally obtain a copper sulfate product.
Preferably, the method further comprises S5, which has: and discharging the produced water of the nanofiltration system of S2 into a reuse water tank, and pumping the produced water to a use point of the production water through a reuse water pump so as to realize the recycling of water resources.
Preferably, in S1, the waste etching solution discharged into the water inlet tank of the ceramic membrane system contains suspended matters, the content of copper sulfate in the waste etching solution is 0.3-0.5g/L, and the turbidity of the waste etching solution is 10-30 NTU.
Preferably, in S1, the ceramic membrane system comprises: the device comprises components such as a water inlet tank, a water production tank, a feeding pump, a circulating pump, a ceramic membrane and the like, wherein the ceramic membrane is an inorganic membrane with the membrane aperture of 5 nm-5 mu m, the operating pressure of 0-1.0MPa and the operating temperature of 15-60 ℃.
Preferably, in S2, the nanofiltration system comprises: the nanofiltration system comprises components such as a water inlet tank, a water production tank, a feeding pump, a high-pressure pump, a nanofiltration membrane and the like, wherein the interception molecular weight of the nanofiltration membrane is 150-300Da, the operation pressure is 0.5-4.0MPa, the operation temperature is 15-40 ℃, concentrated water and produced water of the nanofiltration system are obtained through the nanofiltration system respectively, the concentration of copper sulfate in the concentrated water in the nanofiltration system is 20-30g/L, and the concentration of copper sulfate in the produced water in the nanofiltration system is less than 20 mg/L.
Preferably, in S3, the electrodialysis system comprises: the device comprises components such as a desalting liquid tank, a concentrated liquid tank, an electrode liquid tank, a feeding pump, a circulating pump, a direct current power supply, an electrodialysis membrane and the like, wherein the electrodialysis membrane is an ion exchange membrane with the molecular weight cutoff of 150-.
Preferably, in S4, the evaporation system includes: the copper sulfate crystallization system comprises a water inlet tank, a feeding pump, a circulating pump, a steam system, a crystallization system, a drying system and other components, wherein the evaporation system is one of a single-effect evaporation system, a multi-effect evaporation system, an MVR (mechanical vapor recompression) system or other types of evaporation systems, a copper sulfate product is finally obtained through the evaporation system, and the purity is more than or equal to 95%.
Compared with the prior art, the invention has the beneficial effects that: the invention discloses a resource utilization method of copper in etching waste liquid, which comprises the following steps:
after the treatment of the system, more than 98 percent of copper sulfate in the etching waste liquid can be recovered, the cyclic utilization of water resources can be realized, no new waste water is generated, and the environmental pollution is greatly reduced while certain economic benefit is created. Compared with other technologies, the invention has the following advantages:
in S1, a ceramic membrane technology is adopted to pretreat the etching waste liquid, and because the etching liquid is strong in acidity and complex in components, compared with other technologies, the ceramic membrane has excellent performances of acid resistance, alkali resistance, organic solvent resistance, high temperature resistance and the like, and can ensure the stable operation of the system, meanwhile, the ceramic membrane has a nanoscale pore diameter and high filtering precision, can remove suspended matter impurities in the waste liquid, and the turbidity of the produced water of the ceramic membrane system is less than 1NTU, so that the water inlet requirement of a rear-stage nanofiltration system is met, and the stable operation of the nanofiltration system can be ensured;
in S2, the nanofiltration technology is adopted to concentrate copper sulfate, because the nanofiltration membrane is negatively charged, the rejection rate of divalent anions is high (more than 98%), the nanofiltration technology is adopted to realize the recovery of more than 98% of copper sulfate in the etching solution, in addition, compared with other concentration technologies (such as reverse osmosis), the nanofiltration membrane has a loose structure and lower filtration pressure, the energy consumption is lower, the concentration of copper sulfate in nanofiltration produced water is less than 20mg/L, the water quality is better, and the copper sulfate can be directly reused for production;
in S3, the copper sulfate is further concentrated by electrodialysis technology, and the salt content in the concentrated water can be controlled between 150-200 g/L. Compared with other salt concentration technologies (such as high-pressure reverse osmosis or DTRO and the like), the salt concentration can be concentrated to 100g/L at most. Thus, the investment scale of the evaporation system can be reduced by 30-50%, the steam consumption is reduced, and the steam operation cost is saved by 30-40%.
Compared with the prior art, the invention realizes the recycling of all resources, does not discharge waste water, waste gas and waste residue, and is a green and environment-friendly technology.
Drawings
FIG. 1 is a flow chart of the method steps of the present invention;
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and embodiments, it being understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.
Referring to fig. 1, the present invention provides a technical solution,
a resource utilization method of copper in etching waste liquid comprises the following steps:
s1, feeding the waste etching solution into a water inlet tank of a ceramic membrane system, pumping the waste etching solution into the ceramic membrane system through a feeding pump and a circulating pump, filtering by a ceramic membrane to remove impurities such as large particles and suspended matters in the waste etching solution, and feeding the obtained water produced by the ceramic membrane system into a water production tank of the ceramic membrane system;
s2, pumping the water produced in the water production tank of the ceramic membrane system stored in the S1 into a nanofiltration system through a nanofiltration system feed pump and a high-pressure pump, filtering the water by a nanofiltration membrane, concentrating the water produced in the ceramic membrane system in the S1 to increase the concentration of copper sulfate in the concentrated water of the nanofiltration system to 20-30g/L, and then conveying the nanofiltration concentrated water into the concentrated water tank of the nanofiltration system;
s3, pumping the concentrated water generated by the nanofiltration system in S2 into an electrodialysis system through a feed pump, providing an electric field by using a direct-current power supply, enabling the concentration of copper sulfate in the concentrated water of the electrodialysis system to reach 150-200g/L through an electrodialysis membrane, conveying the concentrated water into an inlet water tank of an evaporation system, returning the fresh water of the electrodialysis system to the ceramic membrane system water generating tank in S1, continuously concentrating the fresh water by the nanofiltration system, and then feeding the concentrated water into the inlet water tank of the electrodialysis system;
and S4, pumping the concentrated water of the electrodialysis system into an evaporation system through a feeding pump and a circulating pump in S3, introducing steam, concentrating the wastewater, and passing through a salt crystallization system and a drying system to finally obtain a copper sulfate product.
Further included is S5 having: and discharging the produced water of the nanofiltration system of S2 into a reuse water tank, and pumping the produced water to a use point of the production water through a reuse water pump so as to realize the recycling of water resources.
In S1, the waste etching solution discharged into the water inlet tank of the ceramic membrane system contains suspended matters, the content of copper sulfate in the waste etching solution is 0.3-0.5g/L, and the turbidity of the waste etching solution is 10-30NTU, and the ceramic membrane system comprises: the device comprises components such as a water inlet tank, a water production tank, a feeding pump, a circulating pump, a ceramic membrane and the like, wherein the ceramic membrane is an inorganic membrane with the membrane aperture of 5 nm-5 mu m, the operating pressure of 0-1.0MPa and the operating temperature of 15-60 ℃.
In S2, the nanofiltration system comprises: the nanofiltration system comprises components such as a water inlet tank, a water production tank, a feeding pump, a high-pressure pump, a nanofiltration membrane and the like, wherein the interception molecular weight of the nanofiltration membrane is 150-300Da, the operation pressure is 0.5-4.0MPa, the operation temperature is 15-40 ℃, concentrated water and produced water of the nanofiltration system are obtained through the nanofiltration system respectively, the concentration of copper sulfate in the concentrated water in the nanofiltration system is 20-30g/L, and the concentration of copper sulfate in the produced water in the nanofiltration system is less than 20 mg/L.
In S3, the electrodialysis system includes: the device comprises components such as a desalting liquid tank, a concentrated liquid tank, an electrode liquid tank, a feeding pump, a circulating pump, a direct current power supply, an electrodialysis membrane and the like, wherein the electrodialysis membrane is an ion exchange membrane with the molecular weight cutoff of 150-.
At S4, the evaporation system includes: the copper sulfate crystallization system comprises a water inlet tank, a feeding pump, a circulating pump, a steam system, a crystallization system, a drying system and other components, wherein the evaporation system is one of a single-effect evaporation system, a multi-effect evaporation system, an MVR (mechanical vapor recompression) system or other types of evaporation systems, a copper sulfate product is finally obtained through the evaporation system, and the purity is more than or equal to 95%.
Various examples are proposed for the above materials as follows:
the first embodiment is as follows: the method comprises the following specific steps:
1) the etching waste liquid is treated by a ceramic membrane system, so that impurities such as large particles, suspended matters and the like in the waste liquid are removed, the water inlet requirement of a subsequent nanofiltration system is met, the aperture of a ceramic membrane is 50nm, the operating pressure is 0.1-0.3MPa, and the operating temperature is 20-40 ℃; specific data are shown in the following table.
| Item | Copper sulfate (g/L) | Turbidity (NTU) |
| Etching waste liquid | 0.3 | 20 |
| Ceramic membrane produced water | 0.3 | 0.5 |
As can be seen from the table, the ceramic membrane system has a good effect of removing impurities such as large particles, suspended matters and the like, the final turbidity of the produced water of the system is less than 1NTU, the water inlet requirement of a subsequent nanofiltration system is met, the stable operation of the system can be ensured, and meanwhile, the ceramic membrane does not intercept copper sulfate and cannot cause loss of products.
2) And (2) treating the water produced by the ceramic membrane system in the step 1) by using a nanofiltration system, concentrating copper sulfate in the waste liquid to ensure that the concentration of the copper sulfate meets the requirements of the next process, and simultaneously ensuring that the water quality of the water produced by the nanofiltration system meets the requirements of reuse water. The molecular weight cut-off of the nanofiltration membrane is 150-300Da, the operating pressure of the nanofiltration membrane is 7-4.0MPa, and the operating temperature is 20-35 ℃; specific data are shown in the following table.
| Item | Stock solution | Produce water | Concentrated water |
| Copper sulfate | 0.30g/L | 10mg/L | 23g/L |
As can be seen from the table, the concentration of copper sulfate in the concentrated water of the nanofiltration system reaches 23g/L, the water inlet requirement of the subsequent electrodialysis system is met, and meanwhile, the content of copper sulfate in the produced water of the nanofiltration system is only 10mg/L, so that the use standard of reuse water is met.
3) Treating the concentrated water of the nanofiltration system in the step 2) by adopting an electrodialysis system, and concentrating the copper sulfate in the waste liquid to ensure that the concentration of the copper sulfate meets the requirements of the next process, wherein the molecular weight cut-off of an electrodialysis membrane is 150-; specific data are shown in the following table.
| Item | Stock solution | Produce water | Concentrated water |
| Copper sulfate | 23g/L | 5g/L | 160g/L |
As can be seen from the table, the concentrated water of the electrodialysis system reaches 160g/L, and the expected concentration of salt is improved by 60 percent; the investment and the operation cost of a subsequent evaporation system are greatly reduced;
4) treating the concentrated water of the electrodialysis system in the step 3) by an evaporation system to finally obtain a copper sulfate product, wherein the purity of the product is 96.5% after analysis.
Example two: the method comprises the following specific steps:
1) the etching waste liquid is treated by a ceramic membrane system, so that impurities such as large particles, suspended matters and the like in the waste liquid are removed, the water inlet requirement of a subsequent nanofiltration system is met, the aperture of a ceramic membrane is 100nm, the operating pressure is 0.1-0.3MPa, and the operating temperature is 20-40 ℃; specific data are shown in the following table.
| Item | Copper sulfate (g/L) | Turbidity (NTU) |
| Etching waste liquid | 0.5 | 25 |
| Ceramic membrane produced water | 0.5 | 0.5 |
As can be seen from the table, the ceramic membrane system has good effect of removing impurities such as large particles, suspended matters and the like, the final turbidity of the produced water of the system is less than 1NTU, the water inlet requirement of a subsequent nanofiltration system is met, and the stable operation of the system can be ensured; meanwhile, the ceramic membrane does not trap copper sulfate, and does not cause loss to products.
2) And (2) treating the water produced by the ceramic membrane system in the step 1) by using a nanofiltration system, concentrating copper sulfate in the waste liquid to ensure that the concentration of the copper sulfate meets the requirements of the next process, and simultaneously ensuring that the water quality of the water produced by the nanofiltration system meets the requirements of reuse water, wherein the intercepted molecular weight of the nanofiltration membrane is 150-300Da, the operating pressure of the nanofiltration membrane is 7-4.0MPa, the operating temperature is 20-35 ℃, and the specific data are shown in the following table.
| Item | Stock solution | Produce water | Concentrated water |
| Copper sulfate | 0.50g/L | 15mg/L | 25g/L |
As can be seen from the table, the concentration of copper sulfate in the concentrated water of the nanofiltration system reaches 25g/L, and the water inlet requirement of a subsequent electrodialysis system is met; meanwhile, the content of copper sulfate in the water produced by the nanofiltration system is only 15mg/L, so that the reuse water use standard is met.
3) Treating the concentrated water of the nanofiltration system in the step 2) by adopting an electrodialysis system, and concentrating the copper sulfate in the waste liquid to ensure that the concentration of the copper sulfate meets the requirements of the next process, wherein the cut-off molecular weight of an electrodialysis membrane is 150-300Da, the operating pressure is 0.05-0.1MPa, the operating temperature is 20-35 ℃, and the specific data are shown in the following table.
| Item | Stock solution | Produce water | Concentrated water |
| Copper sulfate | 25g/L | 5g/L | 180g/L |
As can be seen from the table, the concentrated water of the electrodialysis system reaches 180g/L, which reaches the expectation; the salt concentration is improved by 80 percent; the investment and the operation cost of a subsequent evaporation system are greatly reduced;
4) treating the concentrated water of the electrodialysis system in the step 3) by an evaporation system to finally obtain a copper sulfate product, wherein the purity of the product is 97.3% after analysis.
Example three: the method comprises the following specific steps:
1) the etching waste liquid is treated by a ceramic membrane system, impurities such as large particles, suspended matters and the like in the waste liquid are removed, the water inlet requirement of a subsequent nanofiltration system is met, the aperture of a ceramic membrane is 20nm, the operating pressure is 0.1-0.3MPa, the operating temperature is 20-40 ℃, and the specific data are shown in the following table.
| Item | Copper sulfate (g/L) | Turbidity (NTU) |
| Etching waste liquid | 0.45 | 15 |
| Ceramic membrane produced water | 0.45 | 0.5 |
As can be seen from the table, the ceramic membrane system has a good effect of removing impurities such as large particles, suspended matters and the like, the final turbidity of the produced water of the system is less than 1NTU, the water inlet requirement of a subsequent nanofiltration system is met, the stable operation of the system can be ensured, and meanwhile, the ceramic membrane does not intercept copper sulfate and cannot cause loss of products.
2) And (2) treating the water produced by the ceramic membrane system in the step 1) by using a nanofiltration system, concentrating copper sulfate in the waste liquid to ensure that the concentration of the copper sulfate meets the requirements of the next process, and simultaneously ensuring that the water quality of the water produced by the nanofiltration system meets the requirements of reuse water. The molecular weight cut-off of the nanofiltration membrane is 150-300Da, the operating pressure of the nanofiltration membrane is 7-4.0MPa, the operating temperature is 20-35 ℃, and the specific data are shown in the following table.
| Item | Stock solution | Produce water | Concentrated water |
| Copper sulfate | 0.45g/L | 13mg/L | 25g/L |
As can be seen from the table, the concentration of copper sulfate in the concentrated water of the nanofiltration system reaches 25g/L, the water inlet requirement of the subsequent electrodialysis system is met, and meanwhile, the content of copper sulfate in the produced water of the nanofiltration system is only 13mg/L, so that the use standard of reuse water is met.
3) Treating the concentrated water of the nanofiltration system in the step 2) by adopting an electrodialysis system, and concentrating the copper sulfate in the waste liquid to ensure that the concentration of the copper sulfate meets the requirements of the next process, wherein the cut-off molecular weight of an electrodialysis membrane is 150-300Da, the operating pressure is 0.05-0.1MPa, the operating temperature is 20-35 ℃, and the specific data are shown in the following table.
| Item | Stock solution | Produce water | Concentrated water |
| Copper sulfate | 25g/L | 5g/L | 170g/L |
As can be seen from the table, the concentrated water of the electrodialysis system reaches 170g/L, the expectation is reached, the salt concentration is improved by 70 percent, the investment and the operation cost of the subsequent evaporation system are greatly reduced,
4) treating the concentrated water of the electrodialysis system in the step 3) by an evaporation system to finally obtain a copper sulfate product, wherein the purity of the product is 95.5% after analysis.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A resource utilization method of copper in etching waste liquid is characterized by comprising the following steps:
s1, feeding the waste etching solution into a water inlet tank of a ceramic membrane system, pumping the waste etching solution into the ceramic membrane system through a feeding pump and a circulating pump, filtering by a ceramic membrane to remove large particles and suspended impurities in the waste etching solution, and feeding the obtained water produced by the ceramic membrane system into a water production tank of the ceramic membrane system;
s2, pumping the water produced in the water production tank of the ceramic membrane system stored in the S1 into a nanofiltration system through a nanofiltration system feed pump and a high-pressure pump, filtering the water by a nanofiltration membrane, concentrating the water produced in the ceramic membrane system in the S1 to increase the concentration of copper sulfate in the concentrated water of the nanofiltration system to 20-30g/L, and then conveying the nanofiltration concentrated water into the concentrated water tank of the nanofiltration system;
s3, pumping the concentrated water generated by the nanofiltration system in S2 into an electrodialysis system through a feed pump, providing an electric field by using a direct-current power supply, enabling the concentration of copper sulfate in the concentrated water of the electrodialysis system to reach 150-200g/L through an electrodialysis membrane, conveying the concentrated water into an inlet water tank of an evaporation system, returning the fresh water of the electrodialysis system to the ceramic membrane system water generating tank in S1, continuously concentrating the fresh water by the nanofiltration system, and then feeding the concentrated water into the inlet water tank of the electrodialysis system;
and S4, pumping the concentrated water of the electrodialysis system into an evaporation system through a feeding pump and a circulating pump in S3, introducing steam, concentrating the wastewater, and passing through a salt crystallization system and a drying system to finally obtain a copper sulfate product.
2. A method as claimed in claim 1, further comprising S5, comprising:
and discharging the produced water of the nanofiltration system of S2 into a reuse water tank, and pumping the produced water to a use point of the production water through a reuse water pump so as to realize the recycling of water resources.
3. The method according to claim 1, wherein the etching waste liquid discharged into the water inlet tank of the ceramic membrane system contains suspended matters in S1, the content of copper sulfate in the etching waste liquid is 0.3-0.5g/L, and the turbidity of the etching waste liquid is 10-30 NTU.
4. A method as claimed in claim 1, wherein in S1, the ceramic membrane system comprises:
the ceramic membrane module comprises a water inlet tank, a water production tank, a feeding pump, a circulating pump and a ceramic membrane module;
wherein the ceramic membrane is an inorganic membrane with the membrane aperture of 5 nm-5 mu m, the operating pressure of 0-1.0MPa and the operating temperature of 15-60 ℃.
5. The method of claim 1, wherein in S2, the nanofiltration system comprises:
the device comprises a water inlet tank, a water production tank, a feeding pump, a high-pressure pump and a nanofiltration membrane component;
wherein the interception molecular weight of the nanofiltration membrane is 150-300Da, the operation pressure is 0.5-4.0MPa, the operation temperature is 15-40 ℃, and concentrated water and produced water of the nanofiltration system are respectively obtained through the nanofiltration system;
moreover, the concentration of copper sulfate in the concentrated water in the nanofiltration system is between 20 and 30 g/L;
and the concentration of copper sulfate in the produced water in the nanofiltration system is less than 20 mg/L.
6. The method according to claim 1, wherein in S3, the electrodialysis system comprises:
components such as a desalting liquid tank, a concentrated liquid tank, an electrode liquid tank, a feeding pump, a circulating pump, a direct current power supply, an electrodialysis membrane and the like;
wherein the electrodialysis membrane is an ion exchange membrane with the molecular weight cutoff of 150-300Da, the operating pressure of 0.05-0.1MPa and the operating temperature of 15-40 ℃;
respectively obtaining concentrated water and fresh water generated by the electrodialysis system through the electrodialysis system, wherein the concentrated water of the electrodialysis system enters the evaporation system water inlet tank in S4, and the fresh water of the electrodialysis system returns to the ceramic membrane system water generating tank in S1;
the concentration of copper sulfate in the concentrated water in the electrodialysis system is between 150 and 200 g/L;
and the concentration of copper sulfate in the fresh water in the electrodialysis system is 5 g/L.
7. A method as claimed in claim 1, wherein in S4, the evaporation system comprises:
the system comprises a water inlet tank, a feeding pump, a circulating pump, a steam system, a crystallization system, a drying system and the like;
wherein the evaporation system is one of single-effect, multi-effect, MVR system or other types of evaporation systems, and the copper sulfate product is finally obtained through the evaporation system, and the purity is more than or equal to 95%.
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