CN116639769B - Method and system for recycling polished waste acid - Google Patents
Method and system for recycling polished waste acid Download PDFInfo
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- CN116639769B CN116639769B CN202310927369.6A CN202310927369A CN116639769B CN 116639769 B CN116639769 B CN 116639769B CN 202310927369 A CN202310927369 A CN 202310927369A CN 116639769 B CN116639769 B CN 116639769B
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- 239000002253 acid Substances 0.000 title claims abstract description 216
- 239000002699 waste material Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004064 recycling Methods 0.000 title claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 103
- 239000012528 membrane Substances 0.000 claims abstract description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 230000005484 gravity Effects 0.000 claims abstract description 52
- 238000001728 nano-filtration Methods 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 38
- 239000008237 rinsing water Substances 0.000 claims abstract description 30
- 238000005498 polishing Methods 0.000 claims abstract description 29
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 239000002351 wastewater Substances 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- -1 aluminum ion Chemical class 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000003795 desorption Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003957 anion exchange resin Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000010790 dilution Methods 0.000 abstract description 5
- 239000012895 dilution Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000011001 backwashing Methods 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000010865 sewage Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
Classifications
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/28—Evaporating with vapour compression
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method and a device for recycling polishing waste acid. The processing method comprises the following steps: (1) separating and concentrating the rinse water by a nanofiltration membrane; (2) separating and concentrating by a purified acid reverse osmosis membrane; (3) diluting the tank liquor; (4) resin adsorption; (5) evaporating and concentrating the purified acid. According to the invention, the acid recovery treatment is carried out on the polishing bath liquid and the rinsing water respectively by using a resin method and a membrane method, a large amount of clear water contained in the rinsing water is recovered, the recovered clear water can be used in production processes of bath liquid dilution, resin backwashing, workshop rinsing and the like, and finally the discharged waste water is greatly reduced; meanwhile, the wastewater obtained after the tank liquor is concentrated by using the nanofiltration membrane is diluted, and then resin recovery treatment is carried out, so that the additional dilution by using clear water is avoided; the MVR evaporator is used for concentrating the acid until the specific gravity is 1.20-1.40, and then the single-effect evaporator is used for obtaining the finished product recycle acid with the specific gravity of 1.72-1.78, so that the energy consumption is reduced.
Description
Technical Field
The invention relates to the technical field of wastewater resource recovery, in particular to a method and a system for recovering polishing waste acid.
Background
The chemical polishing is a method for eliminating grinding marks and etching leveling by selectively dissolving tiny pits and bulges on the metal surface by using polishing bath liquid, and the polishing bath liquid is generally composed of phosphoric acid, sulfuric acid or nitric acid and the like in different proportions. In the continuous use process of the polishing bath liquid, as the metal parts are continuously dissolved, hydrogen ions are consumed, and the concentration of metal ions such as aluminum, iron and the like is continuously increased, the polishing effect of the polishing bath liquid is gradually deteriorated, and therefore, a part of old polishing bath liquid needs to be discharged after a period of use, and new acid is supplemented in proportion, so that the polishing bath liquid meets the technological requirements. Meanwhile, the metal part after chemical polishing is finished needs to be rinsed for a plurality of times, so that the polishing solution remained on the surface is prevented from continuously corroding the metal surface and affecting the polishing effect, and a large amount of rinsing water containing the polishing solution and the metal can be generated in the process. Therefore, the polishing waste acid generated in the chemical polishing process comprises two parts of waste bath liquid and rinsing water, wherein the discharged waste bath liquid is mixed concentrated acid waste liquid with high concentration of metal ions such as aluminum, iron and the like and acid radical ions, and the specific gravity of the mixed concentrated acid waste liquid is generally up to 1.7; the specific gravity of the discharged rinsing water relative to the waste tank liquor is low and is only 1.05, but the acidity is high, the discharged rinsing water contains a large amount of aluminum ions and other impurities, and the discharged rinsing water is huge in quantity and can be discharged after environmental protection treatment.
Traditional treatment methods for polishing waste acid (waste tank liquor and rinse water) comprise the steps of firstly, delivering the waste acid to a qualified hazardous waste treatment unit for treatment, and then, the cost is high; secondly, the wastewater enters a sewage station for treatment, but a large amount of alkali is consumed, a large amount of sludge is generated, the cost of the medicament is high, and the cost waste of acid liquor is caused.
At present, although some recycling methods for polishing waste acid also appear, the recycling methods all face the problems of low recovery rate or higher equipment investment and operation cost, for example, patent CN107761101A mixes aged chemical polishing tank liquid and rinsing water containing the chemical polishing tank liquid to form mixed liquid, high-concentration aluminum waste liquid and acid liquid after aluminum removal purification are obtained after nanofiltration membrane treatment, and the acid liquid reaches the recycling standard after evaporation and concentration, but the high-concentration aluminum waste liquid is not reasonably treated, and the high-concentration aluminum ions and the residual acid liquid are also a difficult problem for treatment. The patent CN203794723U dilutes the aluminum anodic oxidation/electroplating waste liquid, so that the concentration of aluminum ions is reduced to 3-7g/L, the diluted waste liquid is subjected to rough filtration and then is separated into metal ions by using cation exchange resin, the obtained acid liquid can be recovered after evaporation and concentration, the regenerated cation exchange resin is washed by dilute hydrochloric acid after a period of operation, the generated waste acid liquid is sent into a dilute acid liquid recovery unit, but the patent does not mention a subsequent treatment method of the partial acid liquid, the concentration of aluminum ions in the treatable waste liquid is lower, the concentration of aluminum ions in general waste acid can reach 40g/L, the water consumption of dilution water is extremely high at the moment, the volume of the recovered acid liquid is expanded, and the energy consumption of subsequent concentration is also greatly increased. Therefore, it is the key of the invention to develop a treatment method and a system which can effectively recycle valuable components in the waste liquid and reduce the comprehensive cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a system for recycling polishing waste acid, which are characterized in that rinse water and waste tank liquor are respectively treated by a membrane method and a resin method to obtain purified acid, a large amount of dilute acid in the rinse water is fully recycled, a pre-concentration evaporator with an MVR pump and a single-effect evaporator are used for concentrating the purified acid, and the treated acid liquor can be directly recycled in the production process.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for recycling polishing waste acid comprises the following steps:
(1) Separating and concentrating the rinse water by a nanofiltration membrane: sending rinsing water into a nanofiltration membrane by using a high-pressure pump for separation and concentration, intercepting metal ions at the upstream of the nanofiltration membrane to obtain concentrated water, sending the concentrated water into a waste tank liquor storage tank, obtaining purified acid at the downstream of the nanofiltration membrane, and storing the purified acid in a purified acid storage tank a;
(2) Separating and concentrating by a purified acid reverse osmosis membrane: delivering the purified acid in the purified acid storage tank a into a reverse osmosis membrane by using a high-pressure pump for separation and concentration, intercepting acid liquor at the upstream of the reverse osmosis membrane to obtain concentrated purified acid, storing the concentrated purified acid into a purified acid storage tank b, obtaining clear water at the downstream of the reverse osmosis membrane, and storing the clear water into a clear water storage tank;
(3) And (3) diluting waste bath solution: mixing and diluting the waste tank liquor in the waste tank liquor storage tank with nanofiltration membrane to obtain concentrated water until the specific gravity reaches 1.25-1.35;
(4) Resin adsorption: pumping diluted waste tank liquor into a shallow resin bed from bottom to top by using a booster pump, enabling effluent to enter a metal salt wastewater storage tank, introducing backwash water into the shallow resin bed from top to bottom after resin adsorption is saturated, desorbing purified acid, and storing the purified acid into a purified acid storage tank c;
(5) Purifying acid and evaporating and concentrating: and (3) introducing the purified acid in the purified acid storage tank b into an MVR evaporator for pre-evaporation concentration, mixing the purified acid with the purified acid in the purified acid storage tank c after the specific gravity reaches 1.20-1.40, introducing the mixture into a single-effect evaporator, and evaporating concentration until the specific gravity reaches 1.72-1.78, thus obtaining the finished product recycled acid.
The rinsing water is treated by the nanofiltration membrane and the reverse osmosis membrane through the step (1) and the step (2) so as to simultaneously recover and purify the acid and clean water, and the recovered clean water can be used for resin backwash water or workshop rinsing and other processes, so that the resin backwash water is effectively recovered and reused;
the concentrated water obtained by treating the waste tank liquor with rinsing water through a nanofiltration membrane is diluted to a specific gravity reaching 1.25-1.35 through the step (3) and the step (4), and then the high-concentration purified acid is recovered by a resin method, so that the dilution of clear water is avoided, the waste water finally entering a sewage station is greatly reduced, and the sewage discharge pressure of enterprises is reduced;
the MVR evaporator is used for evaporating and concentrating the low-concentration purified acid to the specific gravity of 1.20-1.40 in the step (5), the purified acid and the steam are evaporated and concentrated in a countercurrent way, the steam consumption is low, the waste heat utilization rate is high, and the energy conservation and the environment friendliness are realized; the acid gas pollution is reduced, the operation is simple and safe, and the total benefit is high; the purified acid with the specific gravity of about 1.2 is evaporated and concentrated by using a single-effect evaporator, the boiling point of the acid liquid is reduced under the negative pressure condition, the energy consumption is reduced, the risk of waste acid gas leakage is avoided, the specific gravity of the obtained finished product recycled acid can reach 1.72-1.78, and the specific gravity requirement of a user on the recycled acid is met.
Further, the purified acid in the purified acid storage tank a in the step (1), the purified acid storage tank b in the step (2) and the purified acid in the purified acid storage tank c in the step (4) each contain phosphoric acid and sulfuric acid, and the metal ion in the step (1) is trivalent aluminum ion.
Furthermore, the nanofiltration membrane and the reverse osmosis membrane are acid-resistant separation membranes, so that the nanofiltration membrane and the reverse osmosis membrane can be used for treating waste acid without being damaged.
Furthermore, the high-pressure pump is an acid-resistant high-pressure pump so as to meet the process requirement of pumping acid-containing rinsing water and ensure the stability of the recovery work of the polished waste acid.
Furthermore, the shallow resin bed is formed by filling strong-alkaline anion exchange resin in a short bed compact mode and is used for adsorbing free acid.
The invention also provides a recovery system of the polished waste acid, which comprises a rinsing water storage tank, a high-pressure pump a, a nanofiltration membrane, a purified acid storage tank a, a high-pressure pump b, a reverse osmosis membrane, a clear water storage tank, a purified acid storage tank b, an MVR evaporator, a single-effect evaporator, a waste tank liquid storage tank, a booster pump, a shallow resin bed, a metal salt waste water storage tank, a backwash water storage tank and a purified acid storage tank c; the water outlet of the rinsing water storage tank is connected with the liquid inlet at the upstream of the nanofiltration membrane through a pipeline by a high-pressure pump a; the upstream of the nanofiltration membrane is provided with a liquid inlet and a liquid outlet, the downstream of the nanofiltration membrane is provided with a liquid outlet, the liquid outlet at the upstream of the nanofiltration membrane is connected with a waste tank liquid storage tank through a pipeline, and the liquid outlet at the downstream of the nanofiltration membrane is connected with a purified acid storage tank a through a pipeline; the outlet of the purified acid storage tank a is connected with the liquid inlet at the upstream of the reverse osmosis membrane through a high-pressure pump b through a pipeline, the upstream of the reverse osmosis membrane is provided with a liquid inlet and a liquid outlet, the downstream of the reverse osmosis membrane is provided with a liquid outlet, the liquid outlet at the upstream of the reverse osmosis membrane is connected with the purified acid storage tank b through a pipeline, and the liquid outlet at the downstream of the reverse osmosis membrane is connected to the clean water storage tank through a pipeline; the shallow resin bed is provided with a backwash water inlet, a desorption liquid outlet, a tank liquid inlet and a filtrate outlet, and the liquid outlet of the waste tank liquid storage tank is connected with the tank liquid inlet of the shallow resin bed through a pipeline by a booster pump; the backwash water inlet is connected with the backwash water storage tank through a pipeline, the filtrate outlet is connected with the metal salt wastewater storage tank through a pipeline, and the desorption liquid outlet is connected with the purified acid storage tank c through a pipeline; the outlet of the purified acid storage tank b is connected with an MVR evaporator through a pipeline, and the acid outlet of the MVR evaporator is connected with a single-effect evaporator through a pipeline; the outlet of the purified acid storage tank c is connected with a single-effect evaporator through a pipeline.
Compared with the prior art, the invention has the beneficial effects that:
1. the specific gravity of the waste tank liquor is generally higher than 1.7, acid recovery cannot be directly carried out, resin treatment can be carried out only by acid liquor with the specific gravity of 1.25-1.35, the specific gravity of rinsing water is lower than about 1.03-1.04, acid recovery treatment is carried out after the specific gravity of the tank liquor is reduced by using the rinsing water by adopting a traditional method, and a large amount of rinsing water still needs to be treated because the rinsing water quantity is a plurality of times of that of the tank liquor, so that the cost is high and resources are wasted. The invention provides a method for treating rinse water and bath liquid by using a membrane method and a resin method respectively, which fully gives full play to the respective advantages, and compared with the membrane method treatment, the anion resin method can treat high-concentration waste acid with the specific gravity of about 1.3 with high efficiency and low cost, and output high-concentration recycled acid with the specific gravity of about 1.17, thereby saving evaporation energy consumption. The low-concentration rinsing water can be efficiently and fully recovered through nanofiltration membrane separation and reverse osmosis membrane concentration treatment, purified acid and clean water are produced, and the clean water can be used for resin backwash water or workshop rinsing and the like. The concentrated water obtained by the rinsing water is diluted to a certain specific gravity range by the nanofiltration membrane, and then the purified acid is recovered by a resin method, so that a large amount of clear water is recovered and utilized while the effective acid is recovered and utilized in the whole process, valuable components in waste acid are fully utilized, the waste water finally entering a sewage station is greatly reduced, and the sewage discharge pressure and cost of enterprises are reduced.
2. The purified acid obtained by recovery treatment in the prior art is generally low in concentration, cannot be directly recycled and needs concentration treatment. The traditional method adopts normal pressure evaporation concentration, and the normal pressure evaporation concentration is carried out by blowing the dilute acid circularly sprayed from the top through hot air, but a large amount of waste acid gas is generated, and the more the hot air is used, the more the entrained waste acid gas is, so that the environment is seriously affected; and the concentration (the highest specific gravity of 1.68) of the product obtained by evaporating and concentrating the hot air-purged waste acid under the normal pressure condition can not meet the specific gravity requirement (the specific gravity of more than 1.75) of a user on the recycled acid, if the concentration or the specific gravity is further increased, the consumption of the hot air can only be increased, so that the energy consumption is increased and the waste acid gas loss is increased. According to the invention, the MVR evaporator is used for evaporating and concentrating low-concentration purified acid (with the specific gravity of 1.05-1.10) to the specific gravity of 1.20-1.40, so that the consumption of steam is small, the utilization rate of waste heat is high, and the energy conservation and the environmental protection are realized; and the acid gas pollution is reduced, the operation is simple and safe, and the total benefit is high. The purified acid with the specific gravity of about 1.2 is evaporated and concentrated by using a single-effect evaporator, the boiling point of the acid liquid is reduced under the negative pressure condition, the energy consumption is reduced, the risk of waste acid gas leakage is avoided, the specific gravity of the obtained finished product recycled acid can reach 1.72-1.78, and the specific gravity requirement of a user on the recycled acid is met.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
Reference numerals illustrate: 1-a rinsing water storage tank; 2-high pressure pump a; 3-nanofiltration membrane; 4-purified acid storage tank a; 5-a high-pressure pump b; 6-reverse osmosis membrane; 7-a clean water storage tank; 8-a purified acid tank b;9-MVR evaporator; 10-a single-effect evaporator; 11-a waste tank liquor storage tank; 12-a booster pump; 13-shallow resin bed; 14-a metal salt wastewater storage tank; 15-a backwash water storage tank; 16-purified acid storage tank c.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments, but the examples are not intended to limit the present invention in any way.
Example 1:
as shown in fig. 1, the recovery system of polished waste acid provided by the invention comprises a rinsing water storage tank 1, a high-pressure pump a2, a nanofiltration membrane 3, a purified acid storage tank a4, a high-pressure pump b5, a reverse osmosis membrane 6, a clear water storage tank 7, a purified acid storage tank b8, an MVR evaporator 9, a single-effect evaporator 10, a waste tank liquid storage tank 11, a booster pump 12, a shallow resin bed 13, a metal salt waste water storage tank 14, a backwash water storage tank 15 and a purified acid storage tank c16.
The water outlet of the rinsing water storage tank 1 is connected with the liquid inlet at the upstream of the nanofiltration membrane 3 through a pipeline by a high-pressure pump a 2; the upstream of the nanofiltration membrane 3 is provided with a liquid inlet and a liquid outlet, the downstream of the nanofiltration membrane 3 is provided with a liquid outlet, the liquid outlet at the upstream of the nanofiltration membrane 3 is connected with a waste tank liquid storage tank 11 through a pipeline, and the liquid outlet at the downstream of the nanofiltration membrane 3 is connected with a purified acid storage tank a4 through a pipeline; the outlet of the purified acid storage tank a4 is connected with the liquid inlet at the upstream of the reverse osmosis membrane 6 through a high-pressure pump b5 by pipelines, the upstream of the reverse osmosis membrane 6 is provided with a liquid inlet and a liquid outlet, the downstream of the reverse osmosis membrane 6 is provided with a liquid outlet, the liquid outlet at the upstream of the reverse osmosis membrane is connected with the purified acid storage tank b8 by pipelines, and the liquid outlet at the downstream of the reverse osmosis membrane 6 is connected to the clean water storage tank 7 by pipelines; the shallow resin bed 13 is provided with a backwash water inlet, a desorption liquid outlet, a tank liquid inlet and a filtrate outlet, and the liquid outlet of the waste tank liquid storage tank 11 is connected with the tank liquid inlet of the shallow resin bed 13 through a pipeline by a booster pump 12; the backwash water inlet is connected with a backwash water storage tank 15 through a pipeline, the filtrate outlet is connected with a metal salt wastewater storage tank 14 through a pipeline, and the desorption liquid outlet is connected with a purified acid storage tank c16 through a pipeline; the outlet of the purified acid storage tank b8 is connected with the MVR evaporator 9 through a pipeline, and the acid outlet of the MVR evaporator 9 is connected with the single-effect evaporator 10 through a pipeline; the outlet of the purified acid tank c16 is connected to the single effect evaporator 10 via a line.
In this embodiment, the nanofiltration membrane 3 and the reverse osmosis membrane 6 are acid-resistant separation membranes.
In this embodiment, the high-pressure pump a2 and the high-pressure pump b5 are both acid-resistant high-pressure pumps, ensuring that the operation thereof is not damaged by acid.
In this embodiment, the shallow resin bed 13 is packed with a short bed of strongly basic anion exchange resin.
The recovery process method of the polishing waste acid in the embodiment comprises the following steps: the rinsing water in the rinsing water storage tank 1 is sent into the nanofiltration membrane 3 by the high-pressure pump a2 for separation and concentration, the permeate liquid obtained at the downstream outlet of the rinsing water storage tank is purified acid (specific weight of 1.02-1.06) without metal ions, the purified acid is sent into the purified acid storage tank a4, and the concentrated water left at the upstream of the nanofiltration membrane is sent into the waste tank liquid storage tank 11 for mixing and dilution with the waste tank liquid; starting a high-pressure pump b5, sending the specific gravity (1.02-1.06) of the purified acid in a purified acid storage tank a4 into a reverse osmosis membrane 6 for separation and concentration, then storing permeate liquid obtained from the downstream of the reverse osmosis membrane 6 into a clear water storage tank 7, wherein the permeate liquid can be used for resin backwash water and workshop rinse water, and the concentrated water left at the upstream is the purified acid with the specific gravity raised to 1.08-1.12, and sending the purified acid into a purified acid storage tank b8; the purified acid (specific gravity of 1.08-1.12) in the purified acid storage tank b8 is introduced into an MVR evaporator 9 to be evaporated and concentrated to specific gravity of 1.20-1.40; the specific gravity of the waste tank liquor is generally more than 1.7, resin treatment can be carried out only by acid liquor with the specific gravity of between 1.25 and 1.35, so that concentrated water obtained after nanofiltration membrane treatment rinse water is introduced into a waste tank liquor storage tank 11 to dilute the waste tank liquor, after the specific gravity adjustment of the waste tank liquor is finished, an acid-resistant booster pump 12 is started, the waste tank liquor is introduced into a shallow resin bed 13 from bottom to top, free acid in the waste tank liquor is adsorbed by resin, metal salt quickly passes through and flows into a metal salt waste water storage tank 14, and the metal salt waste water can be further purified to prepare various salt products, and can be neutralized by lime and then discharged.
When the acid adsorption of the shallow resin bed 13 is saturated, namely, when the free acid is detected to flow out from the top through the shallow resin bed 13, the acid-resistant booster pump 12 is closed, clean water in the backwash water storage tank 15 is input from the top of the shallow resin bed 13, purified acid on the desorbed resin is stored in the purified acid storage tank c16, backwash is stopped when the concentration of the discharged purified acid is lower than about 30% of the concentration of the original tank liquid, purified acid with the specific gravity of 1.16-1.25 is obtained and is sent into the purified acid storage tank c16, and then the acid-resistant booster pump 12 is restarted, mixed tank liquid is input, and the cyclic operation is performed.
The purified acid in the purified acid storage tank c16 and the purified acid concentrated by the MVR evaporator 9 are both led into a single-effect evaporator for evaporation concentration again until the specific gravity is 1.72-1.78, and are discharged to be finished product recycled acid, and the finished product recycled acid can be reused in the production process.
Specifically, the method and system described in example 1 were used to treat phosphorus-containing polishing waste acid (rinse water and waste bath solution), the rinse water throughput was 50m 3 And/d, main components of the waste acid: 17.9g/L of phosphoric acid, 7.8g/L of sulfuric acid, 1.1g/L of aluminum ions and 1.02 specific gravity.
The method is adopted to treat polished waste acid, rinsing water with the specific gravity of 1.02 is sent into the nanofiltration membrane 3 for separation and concentration, metal ions are trapped on the liquid inlet side of the nanofiltration membrane 3 to obtain concentrated water, and purified acid with the specific gravity of 1.02 is obtained on the liquid outlet side of the nanofiltration membrane 3.
TABLE 1 concentration of each component of the phosphorus-containing polishing waste acid after nanofiltration membrane treatment
Nanofiltration membrane 3 downstream purification of acid 45m 3 ，H 3 PO 4 10.6g/L，H 2 SO 4 5.6g/L，Al 3+ 0.05g/L, and continuously using an acid-proof reverse osmosis membrane 6, and operating at 5MPaConcentrating under pressure to obtain purified acid with specific gravity of 1.06 of 20m 3 ，H 3 PO 4 23.8g/L，H 2 SO 4 12.6g/L，Al 3+ 0.1g/L; simultaneously producing clear water 25m 3 ，PH2.1。
The waste tank liquid with the specific gravity of 1.7 is treated with the nanofiltration membrane 3 to obtain concentrated water, and the concentrated water is mixed and diluted to reach the specific gravity of 1.35;
TABLE 2 concentration of the components of the phosphorus-containing polishing waste acid after mixing
The mixed feed liquid is treated with a negative resin.
TABLE 3 concentration of the components of the resin-treated phosphorus-containing Mixed feed solution
And (3) the purified acid with the specific gravity of 1.06 obtained after the reverse osmosis membrane 6 is treated is required to be firstly introduced into an MVR evaporator for evaporation concentration because the water content is too high, and the purified acid with the specific gravity of 1.14 produced after the treatment of the anion resin is mixed with the purified acid with the specific gravity of 1.20 and introduced into a single-effect evaporator for evaporation concentration until the specific gravity is 1.72, so that the finished product of recycled acid is obtained.
The strong basic anion exchange resin can only separate the free acid and the salt, and the residual free acid and the salt in the waste tank liquor are separated. In the production process of recycling acid by adopting the strong-alkaline anion exchange resin, in order to further reduce the concentration of aluminum ions in the recycled acid in actual operation, a part of the produced recycled acid is often required to be refluxed into the feed acid liquor for further treatment, and as a result, the content of the aluminum ions in the recycled acid is low, the quality is good, the amount of discharged aluminum salt is increased, the concentration is reduced, and the production efficiency is reduced. So the acid recovery is flexibly adjusted according to the needs in the actual operation. This patent is for explaining the convenience to 2 feed volume, 2 discharge volume according to 1 basically: 1:1:1 ratio is introduced simply.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (7)
1. The method for recycling the polishing waste acid is characterized by comprising the following steps of:
(1) Separating and concentrating the rinse water by a nanofiltration membrane: sending rinsing water into a nanofiltration membrane by using a high-pressure pump for separation and concentration, wherein metal ions are trapped at the upstream of the nanofiltration membrane to obtain concentrated water, the concentrated water is sent into a waste tank liquor storage tank, purified acid is obtained at the downstream of the nanofiltration membrane, and then the purified acid is stored into a purified acid storage tank a, and the specific gravity of the rinsing water is 1.03-1.10;
(2) Separating and concentrating by a purified acid reverse osmosis membrane: delivering the purified acid in the purified acid storage tank a into a reverse osmosis membrane by using a high-pressure pump for separation and concentration, intercepting acid liquor at the upstream of the reverse osmosis membrane to obtain concentrated purified acid, storing the concentrated purified acid into a purified acid storage tank b, obtaining clear water at the downstream of the reverse osmosis membrane, and storing the clear water into a clear water storage tank;
(3) And (3) diluting waste bath solution: mixing and diluting the waste tank liquor in the waste tank liquor storage tank with nanofiltration membrane to obtain concentrated water until the specific gravity reaches 1.25-1.35, wherein the specific gravity of the waste tank liquor is more than 1.7;
(4) Resin adsorption: pumping diluted waste tank liquor into a shallow resin bed from bottom to top by using a booster pump, enabling effluent to enter a metal salt wastewater storage tank, introducing backwash water into the shallow resin bed from top to bottom after resin adsorption is saturated, desorbing purified acid, and storing the purified acid into a purified acid storage tank c;
(5) Purifying acid and evaporating and concentrating: and (3) introducing the purified acid in the purified acid storage tank b into an MVR evaporator for evaporation concentration, mixing the purified acid with the purified acid in the purified acid storage tank c after the specific gravity reaches 1.20-1.40, introducing the mixture into a single-effect evaporator, and evaporating concentration until the specific gravity reaches 1.72-1.78, thus obtaining the finished product recycled acid.
2. The method for recovering polishing waste acid according to claim 1, wherein the purified acid in the purified acid tank a in step (1), the purified acid in the purified acid tank b in step (2) and the purified acid in the purified acid tank c in step (4) each contain phosphoric acid and sulfuric acid, and the metal ion in step (1) is trivalent aluminum ion.
3. The method for recovering waste polishing acid according to claim 1, wherein the shallow resin bed is packed with strong basic anion exchange resin in a compact manner.
4. A system employing a method for recovering polished waste acid according to any one of claims 1 to 3, comprising a rinse water tank, a high pressure pump a, a nanofiltration membrane, a purified acid tank a, a high pressure pump b, a reverse osmosis membrane, a clean water tank, a purified acid tank b, an MVR evaporator, a single effect evaporator, a waste tank liquid tank, a booster pump, a shallow resin bed, a metal salt waste water tank, a backwash water tank, a purified acid tank c; the water outlet of the rinsing water storage tank is connected with the liquid inlet at the upstream of the nanofiltration membrane through a pipeline by a high-pressure pump a; the upstream of the nanofiltration membrane is provided with a liquid inlet and a liquid outlet, the downstream of the nanofiltration membrane is provided with a liquid outlet, the liquid outlet at the upstream of the nanofiltration membrane is connected with a waste tank liquid storage tank through a pipeline, and the liquid outlet at the downstream of the nanofiltration membrane is connected with a purified acid storage tank a through a pipeline; the outlet of the purified acid storage tank a is connected with the liquid inlet at the upstream of the reverse osmosis membrane through a high-pressure pump b through a pipeline, the upstream of the reverse osmosis membrane is provided with a liquid inlet and a liquid outlet, the downstream of the reverse osmosis membrane is provided with a liquid outlet, the liquid outlet at the upstream of the reverse osmosis membrane is connected with the purified acid storage tank b through a pipeline, and the liquid outlet at the downstream of the reverse osmosis membrane is connected to the clean water storage tank through a pipeline; the shallow resin bed is provided with a backwash water inlet, a desorption liquid outlet, a tank liquid inlet and a filtrate outlet, and the liquid outlet of the waste tank liquid storage tank is connected with the tank liquid inlet of the shallow resin bed through a pipeline by a booster pump; the backwash water inlet is connected with the backwash water storage tank through a pipeline, the filtrate outlet is connected with the metal salt wastewater storage tank through a pipeline, and the desorption liquid outlet is connected with the purified acid storage tank c through a pipeline; the outlet of the purified acid storage tank b is connected with an MVR evaporator through a pipeline, and the acid outlet of the MVR evaporator is connected with a single-effect evaporator through a pipeline; the outlet of the purified acid storage tank c is connected with a single-effect evaporator through a pipeline.
5. The system of claim 4, wherein the high pressure pumps are each acid-resistant high pressure pumps.
6. The system of claim 4, wherein the nanofiltration membrane and the reverse osmosis membrane are both acid-resistant separation membranes.
7. The system of claim 4, wherein the booster pump is an acid-resistant booster pump.
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