CN116655191A - Zero-emission recovery method and recovery system for aluminum foil waste acid - Google Patents
Zero-emission recovery method and recovery system for aluminum foil waste acid Download PDFInfo
- Publication number
- CN116655191A CN116655191A CN202310919727.9A CN202310919727A CN116655191A CN 116655191 A CN116655191 A CN 116655191A CN 202310919727 A CN202310919727 A CN 202310919727A CN 116655191 A CN116655191 A CN 116655191A
- Authority
- CN
- China
- Prior art keywords
- acid
- storage tank
- concentration
- pipeline
- aluminum foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 275
- 239000002699 waste material Substances 0.000 title claims abstract description 97
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 82
- 238000011084 recovery Methods 0.000 title claims abstract description 58
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000011888 foil Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000012528 membrane Substances 0.000 claims abstract description 97
- 239000011347 resin Substances 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 238000001728 nano-filtration Methods 0.000 claims abstract description 54
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 44
- 239000012266 salt solution Substances 0.000 claims abstract description 37
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 238000003860 storage Methods 0.000 claims description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- -1 aluminum ions Chemical class 0.000 claims description 25
- 238000011144 upstream manufacturing Methods 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012466 permeate Substances 0.000 claims description 10
- 239000012629 purifying agent Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 239000003957 anion exchange resin Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 239000012224 working solution 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/44—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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a zero emission recovery method and a recovery system of aluminum foil waste acid, wherein the method comprises the following steps: (1) pretreatment; (2) free acid recovery; (3) nanofiltration membrane circulating concentration of aluminum salt solution; (4) reverse osmosis membrane circulating concentration acid liquor; (5) recycling the purified acid. According to the zero-emission recovery method and the recovery system for the aluminum foil waste acid, provided by the invention, the free acid is recovered by using the resin, and simultaneously, the aluminum salt waste water generated by the nanofiltration membrane and the reverse osmosis membrane is treated and recycled, so that the emission of the waste water is reduced, and the zero-emission recovery treatment of the aluminum foil waste acid is realized.
Description
Technical Field
The invention relates to a treatment method of aluminum foil waste acid, in particular to a zero emission recovery method and a recovery system of aluminum foil waste acid.
Background
The aluminum foil waste acid mainly refers to waste water generated in the corrosion and acid washing processes of the electronic aluminum foil. In order to remove the oxide film on the surface of the aluminum foil, increase the surface area of the aluminum foil and remove trace metal impurities such as copper, iron and the like in the aluminum foil, the surface treatment is carried out by acid, and a large amount of waste acid solution is generated every year. The acids widely used at present are mainly sulfuric acid, hydrochloric acid, nitric acid and their mixed acids. The polished aluminum foil is contacted with the free acid after entering the corrosion groove, and chemical reaction is carried out, and the surface part of the polished aluminum foil is dissolved to form corrosion pits. At the same time, free H+ in the etching tank is gradually consumed, the concentration is reduced, and the concentration of Al3+ ions is gradually increased. Along with the reduction of H+ concentration and the increase of Al3+ concentration in the bath solution, the corrosion effect is weaker and weaker, and the production process is unstable. The general solution is to add fresh free acid into the etching bath solution, and replace part of the etching bath working solution without interruption in an overflow manner so as to maintain the stability and purity of the bath solution. The part of the displaced working fluid of the corrosion tank is so-called aluminum foil waste acid, which still contains high concentration of unreacted free acids such as sulfuric acid, nitric acid, hydrochloric acid and the like, and also contains a large amount of Al3+ ions. The replaced aluminum foil waste acid not only causes the increase of the amount of free acid required by the corrosion and acid washing working section, but also greatly increases the cost of purchasing the chemicals for enterprises; meanwhile, the discharged waste acid has great corrosiveness and pollution risk, and enterprises have to pay extra harmless treatment cost to treat the waste liquid, so that the cost is further increased.
At present, enterprises singly use nanofiltration membranes to treat aluminum foil waste acid, and the defect is that concentrated water is generated after the nanofiltration membranes separate concentrated acid liquor, and about 60% of acid is separated, and about 40% of the remaining acid liquor can not be separated by the nanofiltration membranes due to the fact that the acid liquor contains very high concentration of aluminum ions, so that the enterprises select to add aluminum oxide to react with the remaining acid liquor, and finally aluminum sulfate solution is formed, and the aluminum sulfate solution can be sold as aluminum sulfate water purifying agent. But this also results in the enterprise having to replenish this 40% acid, which is costly each year. Although aluminum sulfate water purifier is commercially available, the amount is too large and the business is not a water purifier manufacturer and still takes time to process it additionally.
The acid retardation resin process can well recover effective free acid in waste acid, does not need to additionally add chemical reagents, recovers acid liquor, greatly reduces enterprise cost, and can be applied to waste acid recovery in a plurality of industries. The acid retarding resin process utilizes strong base anion resin to adsorb free acid, metal ions in the solution flow out in the form of salt solution, and then back washing water is introduced to desorb acid liquor in the resin. The resin process has the characteristics of simple equipment and low running cost, and is very attractive in economy. Patent CN106745887a proposes that the industrial waste acid is treated by using a resin chromatographic column, metal salt impurities are separated and removed, low-salt purified waste acid is recovered, the acid recovery rate is 60-90% by one resin separation and recovery, the metal salt removal rate is 60-90%, and the acid recovery rate is 60-80% and the metal salt removal rate is 88-99% by two resin separation and recovery. However, the resin process also has its inherent problems in that it necessarily produces a large amount of waste brine while recovering the acid. In the treatment of aluminum foil waste acid, these waste salt solutions are produced which contain not only a large amount of aluminum salt but also a certain amount of unrecovered free acid (about 10-20% of the original waste acid) due to the recovery rate limitation. The discharge of these waste brine solutions has become a new problem for enterprises.
Patent CN101759250A discloses that inorganic ceramic membrane filters are used for removing solid suspended matters in pickling waste liquid; the ceramic membrane permeate is subjected to diffusion dialysis to realize separation of acid and salt; heating the dialysate of the diffusion dialyzer, then entering a nanofiltration membrane, and cooling, crystallizing and centrifugally separating the concentrated solution of the nanofiltration device to obtain ferric salt; the permeate of the nanofiltration device passes through a reverse osmosis membrane device, the concentrated solution of the reverse osmosis device returns to the pickling section, the effluent of the reverse osmosis device enters a diffusion dialysis section for recycling, and the metal salt and the residual acid solution in the dialysate of the diffusion dialyzer are recovered through the nanofiltration membrane and the reverse osmosis membrane, so that the zero emission of the pickling waste liquid is realized. However, the diffusion dialyzer has small daily throughput, is not suitable for enterprises with large waste acid amount, and has narrow application range.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a zero-emission recovery method and a recovery system for aluminum foil waste acid, which are used for treating and recycling aluminum salt waste water generated by using a nanofiltration membrane and a reverse osmosis membrane while recovering free acid by using resin, so that the emission of the waste water is reduced, and the zero-emission recovery treatment of the aluminum foil waste acid is realized.
In order to achieve the above purpose, the present invention provides the following technical solutions: a zero emission recovery method of aluminum foil waste acid comprises the following steps:
step one, pretreatment: sending the original aluminum foil waste acid into a precision filter to remove greasy dirt and suspended impurities;
step two, free acid recovery: sending the aluminum foil waste acid obtained in the first step into a shallow resin bed from bottom to top, so that free acid in the aluminum foil waste acid is adsorbed by resin, filtering out an aluminum salt solution at the same time, introducing the resin into the shallow resin bed from top to bottom by using backwash water after the resin is adsorbed and saturated, and desorbing the free acid blocked by the resin to form a purified acid recovery liquid;
step three, nanofiltration membrane circulating concentration aluminum salt solution: the aluminum salt solution formed in the second step is sent into a nanofiltration membrane for separation and concentration, low-concentration acid liquor is obtained at the downstream of the nanofiltration membrane, aluminum ions are trapped at the upstream of the nanofiltration membrane, the concentration of the aluminum ions in the aluminum salt solution reaches 40-50g/L, the concentration of the nanofiltration membrane can be finished, and the discharge is the concentrated aluminum salt solution used as a raw material of the water purifying agent;
step four, reverse osmosis membrane circulating concentration acid liquor: sending the low-concentration acid liquor formed in the third step into a reverse osmosis membrane for separation and concentration, obtaining clear water at the downstream of the reverse osmosis membrane, reusing the clear water by other technical processes in production, intercepting the acid at the upstream of the reverse osmosis membrane, ending circulation when the mass concentration of the acid reaches 5-8%, and leading the effluent into the purified acid recovery liquor in the second step;
step five, recycling the purified acid: according to the production requirements of enterprises, the purified acid is added with acid for concentration or evaporated for concentration to increase the acid concentration and then is reused as a finished product recycling acid.
Further, the free acid in the aluminum foil waste acid after the first step comprises one or more of sulfuric acid, hydrochloric acid and nitric acid.
Further, the shallow resin bed in the second step is filled with strong alkaline anion exchange resin, so that most of free acid in the aluminum foil waste acid can be recovered.
Furthermore, the nanofiltration membrane and the reverse osmosis membrane in the second step and the third step are acid-resistant separation membranes.
In the fourth step, the clean water is used as the backwash water in the second step, and the remaining clean water can be used for workshop rinsing, acid preparation and other procedures.
The invention also provides a recovery system for implementing the zero emission recovery method of aluminum foil waste acid, which comprises an original waste acid storage tank, a precise filter, a waste acid storage tank, a shallow resin bed, an aluminum salt solution storage tank, a backwash water storage tank, a purified acid storage tank, a nanofiltration membrane, a dilute acid storage tank, a reverse osmosis membrane and a clear water storage tank; the bottom outlet of the original waste acid storage tank is connected with the liquid inlet of the precise filter through a pipeline, the liquid outlet of the precise filter is connected to the waste acid storage tank, the top of the shallow resin bed is provided with a backwash water inlet and a filtrate outlet, and the bottom of the shallow resin bed is provided with a waste acid liquid inlet and an eluent outlet; the liquid outlet of the waste acid storage tank is connected with the waste acid liquid inlet of the shallow resin bed through a pipeline, the eluent outlet is connected with the purified acid storage tank through a pipeline, the filtrate outlet is connected with the aluminum salt solution storage tank through a pipeline, the liquid outlet of the aluminum salt solution storage tank is connected with the upstream liquid inlet of the nanofiltration membrane through a pipeline, the permeate outlet of the downstream of the nanofiltration membrane is connected with the dilute acid storage tank through a pipeline, the concentrated water of the upstream of the nanofiltration membrane is discharged and used as a raw material of the water purifying agent, the liquid outlet at the bottom of the dilute acid storage tank is connected with the upstream liquid inlet of the reverse osmosis membrane through a pipeline, the permeate outlet of the downstream of the reverse osmosis membrane is connected with the clean water storage tank through a pipeline, and the acid liquid trapped at the upstream of the reverse osmosis membrane is connected with the purified acid storage tank through another outlet through a pipeline.
Further, the water outlet of the clean water storage tank is connected with the inlet of the backwash water storage tank through a pipeline.
Further, the recovery system further comprises an acid-resistant booster pump a, an acid-resistant booster pump b, an acid-resistant booster pump c and an acid-resistant booster pump d, wherein the acid-resistant booster pump a is arranged on a pipeline between an original waste acid storage tank and a precise filter, the acid-resistant booster pump b is arranged on a pipeline between a waste acid storage tank liquid outlet and a waste acid liquid inlet of the shallow resin bed, the acid-resistant booster pump is arranged on a pipeline between a liquid outlet of the aluminum salt solution storage tank and a liquid inlet of the nanofiltration membrane, and the acid-resistant high-pressure pump is arranged on a pipeline between a liquid outlet of the dilute acid storage tank and a liquid inlet of the reverse osmosis membrane.
Compared with the prior art, the invention has the beneficial effects that:
the method solves the problem of concentrated water generated after the acid liquor is recovered by the nanofiltration membrane, and the anion resin method can efficiently recover about 95% of free acid in the aluminum foil waste acid with low cost. However, after the free acid in the aluminum foil waste acid is recovered by adopting a resin method, a large amount of aluminum salt waste water flows out to enter a sewage station for treatment, so that the sewage treatment capacity of manufacturers is greatly increased, the dosage of backwash water is large, and tap water needs to be always replenished. The invention uses nanofiltration membrane to remove aluminum ions in aluminum salt wastewater after resin treatment, recovers residual low concentration free acid, then uses reverse osmosis membrane to treat the low concentration acid solution to obtain clear water, which can be reused as backwash water required by resin method, the rest clear water can be used for workshop rinsing, acid compounding and the like, dilute acid is concentrated into recoverable acid, which reduces the consumption of tap water, greatly reduces the wastewater discharge in the recovery treatment process, and finally the discharged strong brine contains high concentration aluminum ions, can be used as raw material for producing aluminum water purifying agent, and can be sold to related factories, thus having certain economic benefit. Therefore, the zero-emission recovery method of aluminum foil waste acid can solve the problems of acid-containing concentrated water generated by a nanofiltration membrane method and the problems of large dosage of backwash water and excessive discharged aluminum salt wastewater in the traditional resin recovery method, and realizes zero emission of wastewater on the basis of recovering effective acid.
Drawings
Fig. 1 is a schematic flow chart of a zero emission recovery method of aluminum foil waste acid in an embodiment of the invention.
Fig. 2 is a schematic diagram of a zero emission recovery system of aluminum foil waste acid according to an embodiment of the present invention.
Reference numerals illustrate: 1-waste acid; 2-an original waste acid storage tank; 3-acid-resistant booster pump a; 4-a precision filter; 5-a waste acid storage tank; 6-acid-resistant booster pump b; 7-shallow resin bed; 8-an aluminum salt solution storage tank; 9-backwash water storage tank; 10-a purified acid storage tank; 11-acid-resistant booster pump c; 12-nanofiltration membrane; 13-a dilute acid storage tank; 14-acid-resistant booster pump d; 15-a reverse osmosis membrane; 16-clean water storage tank.
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.
As shown in fig. 1, the method for recycling aluminum foil waste acid in a zero emission manner provided by the embodiment comprises the following steps:
step one, pretreatment: sending the original aluminum foil waste acid into a precision filter to remove greasy dirt and suspended impurities;
step two, free acid recovery: sending the aluminum foil waste acid obtained in the first step into a shallow resin bed from bottom to top, so that free acid in the aluminum foil waste acid is adsorbed by resin, filtering out an aluminum salt solution at the same time, introducing the resin into the shallow resin bed from top to bottom by using backwash water after the resin is adsorbed and saturated, and desorbing the free acid blocked by the resin to form a purified acid recovery liquid;
step three, nanofiltration membrane circulating concentration aluminum salt solution: the aluminum salt solution formed in the second step is sent into a nanofiltration membrane for separation and concentration, low-concentration acid liquor is obtained at the downstream of the nanofiltration membrane, aluminum ions are trapped at the upstream of the nanofiltration membrane, the concentration of the aluminum ions in the aluminum salt solution reaches 40-50g/L, the concentration of the nanofiltration membrane can be finished, and the discharge is the concentrated aluminum salt solution used as a raw material of the water purifying agent;
step four, reverse osmosis membrane circulating concentration acid liquor: sending the low-concentration acid liquor formed in the third step into a reverse osmosis membrane for separation and concentration, obtaining clear water at the downstream of the reverse osmosis membrane, reusing the clear water by other technical processes in production, intercepting the acid at the upstream of the reverse osmosis membrane, ending circulation when the mass concentration of the acid reaches 5-8%, and leading the effluent into the purified acid recovery liquor in the second step;
step five, recycling the purified acid: according to the production requirements of enterprises, the purified acid is added with acid for concentration or evaporated for concentration to increase the acid concentration and then is reused as a finished product recycling acid.
The free acid in the spent acid of the aluminum foil after the first step generally comprises one or more of sulfuric acid, hydrochloric acid and nitric acid.
And in the second step, the shallow resin bed is filled with strong alkaline anion exchange resin, about 95% of free acid in the aluminum foil waste acid can be recovered, and the strong alkaline anion exchange resin can be selected from Tulsimer A853E, DIAION SA20ALLP, MA-13J and other marks.
The nanofiltration membrane and the reverse osmosis membrane in the second and the third steps are acid-resistant separation membranes, and commercial brands such as Ke's (KOCH), dow (DOW), heidenergy (HYDRANATICS), toray (TORAY) and the like can be used.
The recovery system for zero emission of aluminum foil waste acid in the present embodiment includes an original waste acid storage tank 2, an acid-resistant booster pump a3, a precision filter 4, a waste acid storage tank 5, an acid-resistant booster pump b6, a shallow resin bed 7, an aluminum salt solution storage tank 8, a backwash water storage tank 9, a purified acid storage tank 10, an acid-resistant booster pump c11, a nanofiltration membrane 12, a dilute acid storage tank 13, an acid-resistant booster pump d14, a reverse osmosis membrane 15, and a clean water storage tank 16; the bottom outlet of the original waste acid storage tank 2 is connected with the liquid inlet of the precise filter 4 through an acid-resistant booster pump a3 and a pipeline, the liquid outlet of the precise filter 4 is connected to the waste acid storage tank 5, the shallow resin bed 7 is a short-bed compact filling resin tank which contains strong-alkaline anion exchange resin, the top of the shallow resin bed is provided with a backwash water inlet and a filtrate outlet, and the bottom of the shallow resin bed is provided with a waste acid liquid inlet and an eluent outlet; the liquid outlet of the waste acid storage tank 5 is connected with the waste acid liquid inlet of the shallow resin bed 7 through an acid-resistant booster pump b6 through a pipeline, the eluent outlet of the shallow resin bed 7 is connected with the purified acid storage tank 10 through a pipeline, the filtrate outlet is connected with the aluminum salt solution storage tank 8 through a pipeline, the liquid outlet of the aluminum salt solution storage tank 8 is connected with the upstream liquid inlet of the nanofiltration membrane 12 through an acid-resistant booster pump c11, the permeate outlet of the downstream of the nanofiltration membrane is connected with the dilute acid storage tank 13 through a pipeline, the concentrated water on the upstream liquid inlet side of the nanofiltration membrane is discharged and used as a raw material of the water purifying agent, the liquid outlet at the bottom of the dilute acid storage tank 13 is connected with the liquid inlet of the upstream of the reverse osmosis membrane 15 through an acid-resistant booster pump d14 through a pipeline, the permeate outlet of the downstream of the reverse osmosis membrane is connected with the clean water storage tank 16 through a pipeline, and the acid liquid trapped on the liquid inlet side of the upstream of the reverse osmosis membrane 15 is connected with the purified acid storage tank 10 through another outlet through a pipeline.
The technological process of the device is as follows: the aluminum foil waste acid 1 discharged in the production process is stored in an original waste acid storage tank 2, when the amount reaches the process operation requirement, an acid-resistant booster pump a3 is started to lead the original aluminum foil waste acid into a precision filter 4, pollutants such as greasy dirt and suspended impurities are filtered, and then the aluminum foil waste acid is stored in a waste acid storage tank 5 for subsequent recovery treatment. The acid-resistant booster pump b6 is started to pump the waste acid in the waste acid storage tank 5 into the shallow resin bed 7 from bottom to top, free acid in the waste acid is adsorbed by the resin, and the residual aluminum salt solution flows into the aluminum salt solution storage tank 8. After the resin in the shallow resin bed 7 is adsorbed and saturated, namely when the pH of the aluminum salt solution is suddenly reduced, the acid-resistant booster pump b6 is closed, the pumping of waste acid is stopped, the backwash water in the backwash water storage tank 9 is introduced into the shallow resin bed 7 from top to bottom, the free acid adsorbed in the resin is desorbed, and the purified acid is introduced into the purified acid storage tank 10. The aluminum salt solution in the aluminum salt solution storage tank 8 is introduced into the nanofiltration membrane 12 through the acid-resistant booster pump c11, low-concentration acid liquor for removing aluminum ions is obtained at the liquid outlet side of the downstream of the nanofiltration membrane, the low-concentration acid liquor is stored into the dilute acid storage tank 13 for subsequent treatment, and the concentration of the aluminum ions in the aluminum salt concentrated water left on the upstream of the nanofiltration membrane 12 reaches 40-50g/L, so that the nanofiltration membrane can be finished to be concentrated, and the concentrated aluminum water purifying agent raw material is formed, so that the economic benefit is certain. The dilute acid in the dilute acid storage tank 13 is sent into the reverse osmosis membrane 15 through the acid-resistant booster pump d14 for separation and concentration, the permeate liquid formed on the liquid outlet side of the downstream side of the reverse osmosis membrane is almost free of acid liquor and aluminum salt, the permeate liquid is sent into the clean water storage tank 16, and when the concentration of the dilute acid in the concentrated water left on the upstream side of the reverse osmosis membrane 15 reaches 5-8%, the reverse osmosis membrane concentration can be finished, and the concentrated water is sent into the purified acid storage tank 10. According to the production requirements of enterprises, the purified acid can be reused as a finished product recycling acid after the acid concentration is increased by methods such as evaporation concentration. Through the process flow, the acid liquor is effectively recycled, meanwhile, the waste water is almost recycled completely, only part of the aluminum salt concentrated water is discharged, and the waste water can be used as raw materials for manufacturing the water purifying agent, so that the problem that a large amount of waste water generated by a resin process enters a sewage station is solved, the consumption of external tap water is reduced, and zero discharge recycling treatment of aluminum foil waste acid is completed.
The zero emission recovery method of the embodiment is adopted to treat aluminum foil waste acid, and the treatment capacity of the waste acid is 100m 3 and/D, main components of the waste acid: 372g/L sulfuric acid (calculated as aluminum ion concentration, sulfate concentration 96g/L and free sulfuric acid 276 g/L), aluminum ion 18.0g/L. The waste acid impurity is filtered by a precise filter and then is subjected to acid recovery treatment, resin MA-13J imported by Korean Sanyang company is filled in a shallow resin bed, and 105M3 purified acid is obtained after the waste acid is subjected to resin treatment, wherein sulfuric acid is 258.2g/L (sulfate 9.1g/L and free sulfuric acid is 249.1 g/L), aluminum ions are 1.7g/L, sulfuric acid recovery rate is 72.9%, free sulfuric acid recovery rate is 94.8%, and aluminum ion removal rate is 90.1%. 100m of aluminum salt solution was discharged 3 Wherein the sulfuric acid concentration is 100.8g/L (86.4 g/L for sulfate radical and 14.4g/L for free sulfuric acid), and the aluminum ion concentration is 16.2g/L. Removing aluminum from the aluminum salt solution by using a nanofiltration membrane to recover residual sulfuric acid, wherein the working pressure of the nanofiltration membrane is 5MPa, and the dilute acid is produced by 63m 3 26.2g/L of sulfuric acid (containing 4.6g/L of sulfuric acid radical and 21.6g/L of free sulfuric acid), 0.87g/L of aluminum ions, 94.5% of free sulfuric acid recovery rate and 96.6% of aluminum ions removal rate. Discharge liquid aluminum sulfate 37m 3 Wherein the aluminum ion content is 42.3g/L, sulfuric acid content is 227.7g/L (sulfate radical 225.6g/L and free sulfuric acid content is 2.1 g/L). Concentrating the obtained dilute acid with reverse osmosis membrane with working pressure of 5MPa to obtain purified acid 23m 3 Sulfuric acid 70.3g/L, aluminum ion concentration near zero, clear water 40m 3 ，PH1.6。
The system is 100m to 3 372g/L of/D sulfuric acid and 18g/L of aluminum ion concentration, and obtaining 2 recovered acids in a 10-purified acid storage tank through anion resin recovery, nanofiltration separation and reverse osmosis concentration, wherein the total amount of the recovered acids is 128m 3 And (D), the concentration of sulfuric acid is 224.4g/L, the concentration of aluminum ions is 1.4g/L, the sulfuric acid recovery rate is 77.2%, and the aluminum ion removal rate is 90.0%.
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 (8)
1. The zero emission recovery method of the aluminum foil waste acid is characterized by comprising the following steps of:
step one, pretreatment: sending the original aluminum foil waste acid into a precision filter to remove greasy dirt and suspended impurities;
step two, free acid recovery: sending the aluminum foil waste acid obtained in the first step into a shallow resin bed from bottom to top, so that free acid in the aluminum foil waste acid is adsorbed by resin, filtering out an aluminum salt solution at the same time, introducing the resin into the shallow resin bed from top to bottom by using backwash water after the resin is adsorbed and saturated, and desorbing the free acid blocked by the resin to form a purified acid recovery liquid;
step three, nanofiltration membrane circulating concentration aluminum salt solution: the aluminum salt solution formed in the second step is sent into a nanofiltration membrane for separation and concentration, low-concentration acid liquor is obtained at the downstream of the nanofiltration membrane, aluminum ions are trapped at the upstream of the nanofiltration membrane, water is added into the feed liquid when the output flow of the nanofiltration membrane is smaller at about 5MPa of operating pressure, the acid liquor is further separated, the concentration of the aluminum ions in the aluminum salt solution reaches 40-50g/L, the concentration of the nanofiltration membrane can be finished, and the discharged product is the concentrated aluminum salt solution used as a raw material of the water purifying agent;
step four, reverse osmosis membrane circulating concentration acid liquor: sending the low-concentration acid liquor formed in the third step into a reverse osmosis membrane for separation and concentration, obtaining clear water at the downstream of the reverse osmosis membrane, reusing the clear water by other technical processes in production, intercepting the acid at the upstream of the reverse osmosis membrane, ending circulation when the mass concentration of the acid reaches 5-8%, and leading the effluent into the purified acid recovery liquor in the second step;
step five, recycling the purified acid: according to the production requirements of enterprises, the purified acid is added with acid for concentration or evaporated for concentration to increase the acid concentration and then is reused as a finished product recycling acid.
2. The method for zero emission recovery of aluminum foil waste acid according to claim 1, wherein the free acid in the aluminum foil waste acid after the first step comprises one or more of sulfuric acid, hydrochloric acid and nitric acid.
3. The zero release recovery method of aluminum foil waste acid according to claim 1, wherein the shallow resin bed in the second step is filled with a strong base anion exchange resin.
4. The method for zero emission recovery of aluminum foil waste acid according to claim 1, wherein the nanofiltration membrane and the reverse osmosis membrane in the second step and the third step are acid-resistant separation membranes.
5. The method for zero emission recovery of spent acid from aluminum foil according to claim 1, wherein in step four, the clean water is used as backwash water in step two.
6. A recovery system for implementing the zero emission recovery method of aluminum foil waste acid according to any one of claims 1 to 5, characterized by comprising an original waste acid storage tank (2), a precision filter (4), a waste acid storage tank (5), a shallow resin bed (7), an aluminum salt solution storage tank (8), a backwash water storage tank (9), a purified acid storage tank (10), a nanofiltration membrane (12), a dilute acid storage tank (13), a reverse osmosis membrane (15) and a clear water storage tank (16); the bottom outlet of the original waste acid storage tank (2) is connected with the liquid inlet of the precise filter (4) through a pipeline, the liquid outlet of the precise filter (4) is connected to the waste acid storage tank (5), the top of the shallow resin bed (7) is provided with a backwash water inlet and a filtrate outlet, and the bottom of the shallow resin bed is provided with a waste acid liquid inlet and an eluent outlet; the liquid outlet of the waste acid storage tank (5) is connected with the waste acid liquid inlet of the shallow resin bed (7) through a pipeline, the eluent outlet is connected with the purified acid storage tank (10) through a pipeline, the filtrate outlet is connected with the aluminum salt solution storage tank (8) through a pipeline, the liquid outlet of the aluminum salt solution storage tank (8) is connected with the upstream liquid inlet of the nanofiltration membrane (12) through a pipeline, the permeate outlet at the downstream of the nanofiltration membrane is connected with the dilute acid storage tank (13) through a pipeline, the concentrated water at the upstream of the nanofiltration membrane is discharged and used as a water purifying agent raw material, the liquid outlet at the bottom of the dilute acid storage tank (13) is connected with the upstream liquid inlet of the reverse osmosis membrane (15) through a pipeline, the permeate outlet at the downstream of the reverse osmosis membrane is connected with the clean water storage tank (16) through a pipeline, and the acid liquid trapped at the upstream of the reverse osmosis membrane is connected with the purified acid storage tank (10) through another outlet through a pipeline.
7. The recovery system of claim 6, wherein: still include acid-proof booster pump a (3), acid-proof booster pump b (6), acid-proof high pressure pump c (11), acid-proof booster pump d (14), acid-proof booster pump a (3) set up on the pipeline between original spent acid storage tank and the precision filter, acid-proof booster pump b (6) set up on the pipeline between spent acid storage tank liquid outlet with the spent acid feed liquor mouth of shallow resin bed (7), acid-proof high pressure pump c (11) set up on the pipeline between the liquid outlet of aluminium salt solution storage tank (8) and the upstream feed liquor mouth of nanofiltration membrane (12), acid-proof high pressure pump d (14) set up on the pipeline between the liquid outlet of dilute acid storage tank and the upstream feed liquor mouth of reverse osmosis membrane.
8. The recovery system of claim 6, wherein: the water outlet of the clean water storage tank (16) is connected with the inlet of the backwash water storage tank through a pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310919727.9A CN116655191A (en) | 2023-07-26 | 2023-07-26 | Zero-emission recovery method and recovery system for aluminum foil waste acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310919727.9A CN116655191A (en) | 2023-07-26 | 2023-07-26 | Zero-emission recovery method and recovery system for aluminum foil waste acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116655191A true CN116655191A (en) | 2023-08-29 |
Family
ID=87722721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310919727.9A Pending CN116655191A (en) | 2023-07-26 | 2023-07-26 | Zero-emission recovery method and recovery system for aluminum foil waste acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116655191A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966400A (en) * | 2010-08-24 | 2011-02-09 | 上海西恩化工设备有限公司 | Method for separating inorganic acid and inorganic acid salt in waste acid |
| CN106966414A (en) * | 2016-12-22 | 2017-07-21 | 新疆智诚同欣环保科技有限公司 | A kind of waste phosphoric acid processing method for producing electrode foil |
| CN107311345A (en) * | 2017-07-28 | 2017-11-03 | 科海思（北京）科技有限公司 | A kind of waste acidity recovery method and apparatus |
| CN207210139U (en) * | 2017-08-22 | 2018-04-10 | 北京欧美环境工程有限公司 | A kind of coking wastewater processing system |
| CN111186931A (en) * | 2019-03-26 | 2020-05-22 | 麦王环境技术股份有限公司 | Stainless steel pickling wastewater recycling equipment and process |
| CN112960735A (en) * | 2021-02-04 | 2021-06-15 | 苏州碧芯湶环境科技有限公司 | Method for adsorbing strong acid by non-ion exchange of strongly basic anion exchange resin |
-
2023
- 2023-07-26 CN CN202310919727.9A patent/CN116655191A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966400A (en) * | 2010-08-24 | 2011-02-09 | 上海西恩化工设备有限公司 | Method for separating inorganic acid and inorganic acid salt in waste acid |
| CN106966414A (en) * | 2016-12-22 | 2017-07-21 | 新疆智诚同欣环保科技有限公司 | A kind of waste phosphoric acid processing method for producing electrode foil |
| CN107311345A (en) * | 2017-07-28 | 2017-11-03 | 科海思（北京）科技有限公司 | A kind of waste acidity recovery method and apparatus |
| CN207210139U (en) * | 2017-08-22 | 2018-04-10 | 北京欧美环境工程有限公司 | A kind of coking wastewater processing system |
| CN111186931A (en) * | 2019-03-26 | 2020-05-22 | 麦王环境技术股份有限公司 | Stainless steel pickling wastewater recycling equipment and process |
| CN112960735A (en) * | 2021-02-04 | 2021-06-15 | 苏州碧芯湶环境科技有限公司 | Method for adsorbing strong acid by non-ion exchange of strongly basic anion exchange resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3671644B2 (en) | Photoresist developing waste liquid recycling method and apparatus | |
| JP5189255B2 (en) | Iodine recovery from polarizing film manufacturing wastewater | |
| JP3543915B2 (en) | Recycling treatment method for photoresist developing waste liquid | |
| CN108975556B (en) | Method for purifying and recovering aged phosphoric acid polishing solution | |
| CN205603387U (en) | Strong brine zero release divides membrane concentrator of matter crystallization | |
| CN114180768A (en) | Multi-stage nanofiltration salt separation system for separating sodium sulfate and sodium chloride in coking wastewater and method for treating wastewater by using same | |
| US6080315A (en) | Process for the partial desalination of water | |
| CN112400039A (en) | Acid liquid regeneration device and regeneration method | |
| CN108793568A (en) | A kind of stainless steel cleaning containing acid wastewater zero discharge waste water unit equipment | |
| RU2471767C1 (en) | Simple method and system for efficient recycling of mother solution from apparatus for producing purified terephthalic acid | |
| CN116655191A (en) | Zero-emission recovery method and recovery system for aluminum foil waste acid | |
| RU2738105C1 (en) | Method of closed water circulation of galvanic production | |
| CN116639769B (en) | Method and system for recycling polished waste acid | |
| WO2011074495A1 (en) | Method for reusing waste liquid from which tetraalkylammonium ions have been removed | |
| CN104229942B (en) | Method and device for decarbonizing and desalting liquid | |
| JPS586297A (en) | Treatment of raw water of high content of silica | |
| CN205838758U (en) | The many qualities of electroplating waste-water reutilizing produce water device | |
| CN113754122B (en) | Process for removing sodium by returning electroplating heavy metal ions to tank | |
| CN216584296U (en) | System for getting rid of fluorinion in ferric phosphate waste water | |
| CN116621402B (en) | Near-zero emission recovery method and system for phosphorus-containing polishing waste acid | |
| JP2003215810A (en) | Method for recovering developer from photoresist developer waste liquid | |
| CN218620523U (en) | Recovery processing system of copper-containing waste water of electron trade | |
| JPH09887A (en) | Method for regenerating acid waste liquid | |
| CN216191596U (en) | Concentrated water emission reduction treatment system for boiler desalination water system | |
| CN219449506U (en) | System for efficiently removing metal ions in ferric phosphate wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |