CN117430149A - Recycling method of electrode foil formation bath liquid waste liquid - Google Patents
Recycling method of electrode foil formation bath liquid waste liquid Download PDFInfo
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- CN117430149A CN117430149A CN202210813683.7A CN202210813683A CN117430149A CN 117430149 A CN117430149 A CN 117430149A CN 202210813683 A CN202210813683 A CN 202210813683A CN 117430149 A CN117430149 A CN 117430149A
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- 239000007788 liquid Substances 0.000 title claims abstract description 74
- 238000004064 recycling Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000011888 foil Substances 0.000 title claims abstract description 29
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 23
- 239000010808 liquid waste Substances 0.000 title claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000243 solution Substances 0.000 claims abstract description 50
- 239000013078 crystal Substances 0.000 claims abstract description 48
- 239000000706 filtrate Substances 0.000 claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 43
- 238000001914 filtration Methods 0.000 claims abstract description 38
- 238000001704 evaporation Methods 0.000 claims abstract description 36
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 34
- -1 aluminum ions Chemical class 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 30
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 26
- 230000008020 evaporation Effects 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000010413 mother solution Substances 0.000 claims abstract description 8
- 238000011010 flushing procedure Methods 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims description 79
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 48
- 239000001741 Ammonium adipate Substances 0.000 claims description 48
- 235000019293 ammonium adipate Nutrition 0.000 claims description 48
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 31
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 27
- 239000001393 triammonium citrate Substances 0.000 claims description 27
- 235000011046 triammonium citrate Nutrition 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 16
- 239000010865 sewage Substances 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910018626 Al(OH) Inorganic materials 0.000 claims description 9
- 238000011272 standard treatment Methods 0.000 claims description 9
- 230000033228 biological regulation Effects 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010979 pH adjustment Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000002910 solid waste Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 4
- 238000012946 outsourcing Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- 238000011084 recovery Methods 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000012535 impurity Chemical group 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- RATMLZHGSYTFBL-UHFFFAOYSA-N azanium;6-hydroxy-6-oxohexanoate Chemical compound N.OC(=O)CCCCC(O)=O RATMLZHGSYTFBL-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses a recycling method of electrode foil formation bath liquid waste liquid, which comprises the following steps: filtering the waste liquid to remove solid suspended matters in the waste liquid to obtain filtrate and filter residues; adding ammonia water into the filtrate, stirring, and adjusting the pH value to 7-8; filtering the solution with the pH value adjusted to obtain aluminum hydroxide solids and filtrate without aluminum ions; carrying out primary membrane concentration on the filtrate without aluminum ions to obtain primary concentrated solution and water; performing secondary evaporation concentration on the primary concentrated solution, cooling for crystallization, flushing crystals by using water in the step four, separating and filtering the mixed solution containing the crystals to obtain crystals and mother solution, and returning the mother solution to the step four for recycling; the crystals are sent into the heated fresh pure water, stirred and dissolved and returned to use. By adopting the method, all substances in the waste liquid are recycled, so that the classified recycling of useful substances is fundamentally solved, the emission is little or even no, and the production cost and the environmental protection cost of enterprises are greatly reduced.
Description
Technical Field
The invention relates to a recycling method of electrode foil formation bath liquid waste liquid, in particular to a recycling method of electrode foil formation into ammonium adipate waste liquid (or citric acid waste liquid), belonging to the field of energy conservation and environmental protection.
Background
The production process of the aluminum foil for the aluminum electrolytic capacitor comprises two steps of corrosion and formation. Wherein, the aluminum foil is formed by taking the corroded aluminum foil as a raw material. Hydrochloric acid is adopted in the production process of the corroded aluminum foil, so that chlorine residues are generated on the surface of the corroded aluminum foil product and brought into formation production, and the admission index of the chlorine is the strictest in the formation process, and is usually required to be within 0.1 PPm. The concentration of the bath solution ammonium adipate used in the formation production is 30-70g/l, or the concentration of the tri-ammonium citrate (6-8%) gradually increases along with chloride, aluminum ions and other impurities substituted by the corrosion foil to cause aging of the bath solution, and the produced formation foil performance does not reach the standard, so the bath solution ammonium adipate must be replaced periodically. The changed waste tank liquor is the ammonium adipate waste liquor (or ammonium citrate waste liquor), and the waste liquor contains a large amount of adipate and ammonium salt, so that the content of chloride is 20-40PPM, and serious environmental pollution can be caused if the waste tank liquor is not well treated. At present, enterprises commonly adopt biochemical treatment or partial recovery and biochemical treatment methods, and the method has the defects of low treatment efficiency, high treatment cost and environment protection and is difficult to reach standards, and simultaneously causes great waste of resources.
Patent 201210226436.3 discloses a system for treating ammonium adipate washing wastewater and a recovery method thereof. The method is used for recovering the washing wastewater generated when the ammonium adipate bath solution which is used in the production and is contained on the surface of the aluminum foil is required to be washed by pure water before the next working procedure is carried out. The ammonium adipate content in the wastewater is low (generally 100-300 ppm), but the cleaning water amount is large, and the method has value in recovering water and cannot treat high-concentration waste tank liquor. The method can recover the water and simultaneously produce concentrated water (namely, the concentrated water contains ammonium adipate) and other impurities such as chloride ions, which are not effectively removed, and the concentrated water can not be returned to be used in actual production, but is continuously discharged into a sewage station for centralized treatment to reach the discharge standard.
201911060696.6 discloses a zero treatment method for recycling aluminum foil to adipic acid. The method adopts a method of preparing weak acid from strong acid, and uses hydrochloric acid to replace adipic acid in ammonium adipate so as to obtain adipic acid crystals. The method is characterized in that the method is carried out in a way that electrolysis (membrane electrolysis or bipolar membrane electrolysis) is carried out to electrolyze ammonium chloride salt to generate hydrochloric acid (system acidification before returning) and ammonia water (ammonium adipate is synthesized by adipic acid), so that the method has no problem on the surface and is not practically and completely operable.
Firstly, the chemical process has extremely strict requirements on the chlorine content in the returned ammonium adipate bath solution, which is usually less than 0.1PPM, and the most main reason for the requirement of periodic replacement of the bath solution is that the chlorine content carried along with the aluminum foil exceeds the standard (generally 5-40PPM, the first stage bath solution is the highest and sequentially decreases later). The technology directly adopts hydrochloric acid to carry out acid precipitation and then synthesizes ammonia water for returning use, wherein the content of chlorine radicals attached to adipic acid exceeds thousands of times. The adipic acid recovered by this method cannot be used directly at all in any one link.
Secondly, the step of obtaining ammonia water by electrolyzing the ammonium chloride solution ignores the dissolved aluminum ions in the bath solution, aluminum hydroxide colloid generated along with the rise of the pH value of the solution is attached to the surface of an electrode to cause the electrode to be uncharged, meanwhile, the conductivity of the ammonium chloride in water is weak, hydroxide ions are difficult to ionize to generate ammonia water, and the step is difficult to implement.
Finally, in actual production, the adipic acid recovered by the method can be used for formation production through repeated washing with a large amount of high-purity water and synthesizing with high-purity ammonia water after repeated crystallization. However, if the method is operated, a large amount of washing wastewater containing ammonium chloride is generated in the process, the wastewater is difficult to recycle because of low ammonium chloride, the wastewater needs to enter a sewage treatment system, an ammonium chloride solution generated after acid precipitation also enters the sewage treatment system and needs to be treated again, ammonia ions reach the standard through treatment, but salt containing the ammonium chloride cannot be precipitated through precipitation and filtration, and the salt cannot be completely dissolved in water, so that the salt content in the water is increased, namely, the water resource is polluted again.
Therefore, the method has the major defects that the recycling and zero discharge of the ammonium adipate waste liquid are not realized, and new impurities are introduced, so that the product cannot be used, the sewage treatment cost is increased, and new pollution is generated.
In the prior art, as in patent CN103508596A and 200710125602.X, a clear wastewater treatment system of ammonium adipate is disclosed, only adipic acid in ammonium adipate cleaning wastewater is subjected to acidification, filtration and recovery, and a large amount of wastewater is discharged and a new pollution source is introduced.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a recycling method of electrode foil formation bath liquid waste liquid. By adopting the method, all substances in the waste liquid are recycled, so that the classified recycling of useful substances is fundamentally solved, the emission is little or even no, and the production cost and the environmental protection cost of enterprises are greatly reduced.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the method for recycling the electrode foil formation bath liquid waste liquid is characterized by comprising the following steps of:
step one, filtering the waste liquid to remove solid suspended matters in the waste liquid to obtain filtrate and filter residues;
adding ammonia water into the filtrate, stirring, and adjusting the pH value to 7-8;
step three, filtering the solution with the pH value adjusted to obtain aluminum hydroxide solids and filtrate without aluminum ions;
step four, carrying out primary membrane concentration on the filtrate without aluminum ions to obtain primary concentrated solution and water;
step five, carrying out secondary evaporation concentration on the primary concentrated solution, cooling and crystallizing, flushing the crystals by utilizing water in the step four, separating and filtering the mixed solution containing the crystals to obtain crystals and mother solution, and returning the mother solution to the step four for recycling;
and step six, delivering the crystals into the heated fresh pure water, stirring and dissolving the crystals, and returning the crystals to use.
The recycling system related to the recycling method comprises the following steps: the device comprises a first pump for pumping waste liquid, a first filter, a pH adjusting tank, a second pump, a second filter, a first storage tank, a membrane concentration device, evaporation equipment, a third filter and a second storage tank, wherein the first filter, the pH adjusting tank, the second pump, the second filter, the third storage tank, the fourth storage tank, the third membrane concentration device, the evaporation equipment, the third storage tank and the fourth storage tank are sequentially connected, the ammonia water adding device is arranged at the pH adjusting tank, the second filter is connected with a dryer, the third membrane concentration device is connected with the third storage tank, the third storage tank is connected with the third filter, the evaporation equipment is connected with the third storage tank, the third filter is connected with the fourth storage tank, the fourth storage tank is connected with the membrane concentration device through the third pump, and the second storage tank is connected with a pure water storage tank.
The waste liquid is ammonium adipate waste liquid or triammonium citrate waste liquid.
In the first step, the filter residues are collected in a concentrated mode and then are treated according to the fixed waste regulation at fixed time.
In the second step, the following reaction occurs during the adjustment of the pH value:
AlCl 3 + 3 NH 3 .H 2 O ==3 NH 4 Cl + Al(OH) 3 ↓。
in the third step, the aluminum hydroxide solid is dried to prepare an aluminum hydroxide product for sale.
Recycling the recovered pure water obtained in the step four in a system, and recycling the rest of recovered pure water returned to a waste production enterprise; in the fifth step, a trace amount of ammonium chloride solution in the solution is discharged into a sewage station for standard treatment and discharge; and (d) returning the product recovered in the step (six) to the waste production enterprises for recycling.
When the waste liquid is ammonium adipate waste liquid, the recycling method comprises the following steps:
step one, ammonium adipate waste liquid from waste producing enterprises is sent into a filter I through a pump I to be filtered, solid suspended matters in the ammonium adipate waste liquid are removed, ammonium adipate filtrate and filter residues are obtained, the filtrate is sent into a pH adjusting tank, and the filter residues are collected in a concentrated mode and are treated according to the regulation of solid waste at fixed time;
step two, ammonia water is added into the pH adjusting tank through an ammonia water adding device, and the pH value is adjusted to 7-8 by stirring; the following reactions will occur in the pH adjustment tank:
AlCl 3 + 3 NH 3 .H 2 O ==3 NH 4 Cl + Al(OH) 3 ↓；
step three, delivering the solution in the pH adjusting tank into a filter II through a pump II for filtering to obtain aluminum hydroxide solids and filtrate without aluminum ions, drying the aluminum hydroxide solids through a dryer to prepare aluminum hydroxide products for sale, and delivering the filtrate without aluminum ions into a storage tank I;
step four, delivering the filtrate which does not contain aluminum ions in the first storage tank into a membrane concentration device for primary concentration to obtain ammonium adipate concentrated solution and water, delivering the water into the third storage tank, returning the ammonium adipate concentrated solution to a waste production enterprise for recycling, and delivering the ammonium adipate concentrated solution into evaporation equipment;
step five, evaporating the second-stage concentration by an evaporation device, cooling and crystallizing, and sending the mixed solution containing the crystals into a filter III for separation and filtration to obtain ammonium adipate crystals;
step six, sending the filtered mother liquor into a storage tank IV, returning the mother liquor to the membrane concentration device for circulation through a pump III, and discharging the mother liquor in the storage tank IV into a sewage station periodically for standard treatment and discharge;
step seven, adding the recovered pure water in the storage tank III into the filter III through the pump IV to rinse crystals, and enabling the cleaning water generated after cleaning to enter a membrane concentration device;
and step eight, delivering the crystals in the filter III into a storage tank II, adding heated pure water into the pure water storage tank, stirring and dissolving, and returning to use.
When the waste liquid is the citric acid tri-ammonium waste liquid, the recycling method comprises the following steps:
step one, delivering the waste liquid of the tri-ammonium citrate from the waste producing enterprises into a filter I through a pump I for filtering, removing solid suspended matters in the waste liquid to obtain tri-ammonium citrate filtrate and filter residues, delivering the filtrate into a pH adjusting tank, and treating the filter residues according to the regulation of solid waste after centralized collection;
step two, ammonia water is added into the pH adjusting tank through an ammonia water adding device, and the pH value is adjusted to 7-8 by stirring; the following reactions will occur in the pH adjustment tank:
AlCl 3 + 3 NH 3 .H 2 O ==3 NH 4 Cl + Al(OH) 3 ↓；
step three, delivering the solution in the pH adjusting tank into a filter II through a pump II for filtering to obtain aluminum hydroxide solids and filtrate without aluminum ions, drying the aluminum hydroxide solids through a dryer to prepare aluminum hydroxide products for sale, and delivering the filtrate without aluminum ions into a storage tank I;
step four, delivering the filtrate which does not contain aluminum ions in the first storage tank into a membrane concentration device for primary concentration to obtain a concentrated solution of the tri-ammonium citrate and water, delivering the water into the third storage tank, returning the concentrated solution of the tri-ammonium citrate to a waste production enterprise for recycling, and delivering the concentrated solution of the tri-ammonium citrate into evaporation equipment;
step five, evaporating the second-stage concentration by an evaporation device, cooling and crystallizing, and sending the mixed solution containing the crystals into a filter III for separation and filtration to obtain the tri-ammonium citrate crystals;
step six, sending the filtered mother liquor into a storage tank IV, returning the mother liquor to the membrane concentration device for circulation through a pump III, and discharging the mother liquor in the storage tank IV into a sewage station periodically for standard treatment and discharge;
step seven, adding the recovered pure water in the storage tank III into the filter III through the pump IV to rinse crystals, and enabling the cleaning water generated after cleaning to enter a membrane concentration device;
and step eight, delivering the crystals in the filter III into a storage tank II, adding heated pure water into the pure water storage tank, stirring and dissolving, and returning to use.
The invention has the advantages that:
1. the invention adds excessive ammonia water before the secondary filtration after the primary filtration, controls the PH value between 7.0 and 8.0, and generates aluminum hydroxide and ammonium chloride by the reaction of aluminum chloride and ammonia water; the aluminum ions can be effectively removed through the secondary filtration, and the aluminum hydroxide solid obtained through the filtration can be used as a product for recycling.
2. The water obtained after the reverse osmosis membrane concentration is pure water, can be recycled in the system as cleaning water and also can be returned to the waste production enterprises for recycling, the concentration of the concentrated solution after the reverse osmosis concentration is further improved, and the next evaporation cost is saved.
3. The concentrated solution is cooled and crystallized after evaporation, impurities on the surface are quickly washed by pure water, and the purity of the recovered crystals is further improved.
4. The invention can recycle the useful substances in the ammonium adipate waste liquid/the triammonium citrate waste liquid greatly, no new pollutant is produced in the whole process, the residual recoverable substances (ammonium adipate and triammonium citrate) in the mother liquor are recycled for many times, the treated quantity of the recovered substances discharged into a sewage station is smaller in proportion to the total receiving quantity, and the recovery process flow and investment are shortened.
In summary, according to the invention, aluminum, ammonium adipate/triammonium citrate and water in the ammonium adipate waste liquid/triammonium citrate waste liquid can be separated and recycled respectively. The adipic acid ammonium/citric acid triammonium and pure water are returned to the chemical forming process system for recycling, and aluminum is converted into high-purity aluminum hydroxide to be sold as a product. Most of substances in the waste liquid are recycled, so that the sorting recycling of useful substances is fundamentally solved, the emission is reduced as much as possible, and the production cost and the environmental protection cost of enterprises are greatly reduced. Most importantly, the resources are saved, and the economic benefit and the social benefit are remarkable.
Drawings
FIG. 1 is a schematic diagram of a recycling system and method route according to the present invention;
marked in the figure as: 101. filter one, 102, pH adjusting tank 103, ammonia adding device, 104, filter two, 105, dryer, 106, tank one, 107, membrane concentrating device, 108, tank three, 109, evaporating device, 110, filter three, 111, tank four, 112, tank two, 113, pure water tank, P1, pump one, P2, pump two, P3, pump three.
Detailed Description
The invention will be further described with reference to the drawings and embodiments, but the embodiments of the invention are not limited thereto.
The following description is merely representative of the invention and should not be taken as limiting the invention in any way, and any simple modifications and equivalent variations of the embodiments according to the technical spirit of the invention fall within the scope of the invention.
A recycling method of electrode foil formation tank liquor waste liquid comprises the following steps:
step one, filtering the waste liquid to remove solid suspended matters in the waste liquid to obtain filtrate and filter residues;
adding ammonia water into the filtrate, stirring, and adjusting the pH value to 7-8;
step three, filtering the solution with the pH value adjusted to obtain aluminum hydroxide solids and filtrate without aluminum ions;
step four, carrying out primary membrane concentration on the filtrate without aluminum ions to obtain primary concentrated solution and water;
step five, carrying out secondary evaporation concentration on the primary concentrated solution, cooling and crystallizing, flushing the crystals by utilizing water in the step four, separating and filtering the mixed solution containing the crystals to obtain crystals and mother solution, and returning the mother solution to the step four for recycling;
and step six, delivering the crystals into the heated fresh pure water, stirring and dissolving the crystals, and returning the crystals to use.
The recycling system related to the recycling method comprises the following steps: the device comprises a first pump P1 for pumping waste liquid, a first filter 101, a pH adjusting tank 102, a second pump P2, a second filter 104, a first storage tank 106, a membrane concentration device 107, an evaporation device 109, a third filter 110 and a second storage tank 112, wherein the pH adjusting tank 102 is provided with an ammonia water adding device 103, the second filter 104 is connected with a dryer 105, the membrane concentration device 107 is connected with a third storage tank 108, the third storage tank 108 is connected with a third filter 110, the evaporation device 109 is connected with a third storage tank 108, the third filter 110 is connected with a fourth storage tank 111, the fourth storage tank 111 is connected with the membrane concentration device 107 through a third pump P3, and the second storage tank 112 is connected with a pure water storage tank 113.
In the recovery system, the first filter 101 is a cartridge filter, a bag filter, an ultrafiltration or other membrane filter, and the second filter 104 is a filter press filter, a centrifuge filter or a vacuum pumping filter; the membrane concentration device 107 is a membrane concentration device such as a nanofiltration membrane or a reverse osmosis membrane, the pump one P1 is a self-priming pump/centrifugal pump, and the pump two P2 and the pump three P3 are pipeline pumps/centrifugal pumps.
The waste liquid is ammonium adipate waste liquid or triammonium citrate waste liquid.
In the first step, the filter residues are collected in a concentrated mode and then are treated according to the fixed waste regulation at fixed time.
In the second step, the following reaction occurs during the adjustment of the pH value:
AlCl 3 + 3 NH 3 .H 2 O ==3 NH 4 Cl + Al(OH) 3 ↓。
in the third step, the aluminum hydroxide solid is dried to prepare an aluminum hydroxide product for sale.
Recycling the recovered pure water obtained in the step four in a system, and recycling the rest of recovered pure water returned to a waste production enterprise; in the fifth step, a trace amount of ammonium chloride solution in the solution is discharged into a sewage station for standard treatment and discharge; and (d) returning the product recovered in the step (six) to the waste production enterprises for recycling.
This example illustrates a specific application of the present invention. The data of ammonium adipate wastewater generated by a company in the electrode foil corrosion process are as follows: the amount of wastewater produced per day was 20m 3 Ammonium adipate content 5.0%, chloride content 24ppm, aluminum ion content 200ppm.
The embodiments are as follows:
step one, ammonium adipate waste liquid is sent to a first filter 101 through a pump P1 to be filtered, solid suspended matters in the ammonium adipate waste liquid are removed, filtrate and filter residues are obtained, a PP cotton filter element filter or a bag filter is adopted as a precision filter, the filtering precision is 5us, the filtrate is sent to a pH adjusting tank 102, the quantity of the filter residues is small, and the filter residues are treated in a concentrated mode according to the solid waste;
step two, ammonia water is metered into the pH adjusting tank 102 through the ammonia water adding device 103, and the pH value is adjusted to 7.8 by stirring, and the following reaction occurs in the pH adjusting tank 102:
AlCl 3 + 3 NH 3 .H 2 O ==3 NH 4 Cl + Al(OH) 3 ↓；
step three, delivering the solution in the pH adjusting tank 102 to a filter II 104 through a pipeline pump II P2 for filtering to obtain aluminum hydroxide solids and filtrate without aluminum ions, drying the aluminum hydroxide solids by a dryer 105 to prepare an aluminum hydroxide product, delivering the filtrate without aluminum ions to a storage tank I106, and delivering the filter II 104 to a vacuum filter with the filtering precision of 5us;
step four, delivering the filtrate which does not contain aluminum ions in the first storage tank 106 into a reverse osmosis membrane of a membrane concentration device 107 for concentration, wherein the pressure is 3.0Mpa, so as to obtain ammonium adipate concentrate and pure water, delivering the pure water into the third storage tank 108 for recycling, and delivering the ammonium adipate concentrate (ammonium adipate concentration is 10.2%) into an evaporation device 109;
step five, evaporating and concentrating the evaporation equipment 109 to be cooled and crystallized by utilizing the heat source of a client company under negative pressure, and sending the mixed solution containing crystals into a filter III 110 for separation and filtration to obtain ammonium adipate crystals;
step six, the filtered mother liquor is sent into a storage tank IV 111 and returned to the membrane concentration device 107 for circulation for 2 times through a pump III P3; discharging the rest mother liquor in the storage tank IV 111 into a sewage station for standard treatment and discharge;
step seven, recovering pure water (recycling) in a storage tank III 108 through a pump IV P4, adding the recovered pure water into a filter III 110 to quickly wash crystals, and enabling washing water generated after washing to enter a membrane concentration device 107;
and step eight, delivering the crystals in the filter III 110 into a storage tank II 112, adding pure water (fresh pure water) at 50-60 ℃ through a pure water storage tank 113, stirring and dissolving, and returning to use.
By adopting the method for recycling the ammonium adipate waste liquid, the recovery rate of ammonium adipate, aluminum ions, chlorine, ammonium and water in the waste liquid exceeds 90%. The ammonium adipate liquid is recovered for 19m, the concentration is 5 percent, and the recovery rate is 90 percent; recovering 11KG of aluminum hydroxide, recovering more than 95%, recovering 19T of water, recovering more than 95%, and discharging 150 KG of residual liquid containing ammonium adipate and ammonium chloride into a sewage station. The comprehensive recovery rate of substances in the waste liquid is 90%, negative pressure evaporation is adopted in the evaporation process, and a rich heat source of a waste production enterprise is used, so that the energy consumption is not increased additionally, and the benefit is remarkable.
Example 2
This example illustrates a specific application of the present invention. The data of the citric acid tri-ammonium wastewater generated by a company in the electrode foil corrosion process are as follows: the amount of wastewater produced per day was 20m 3 The content of the tri-ammonium citrate is 8 percent, the content of the chlorine radical is 40ppm, and the content of the aluminum ion is 800ppm.
The embodiments are as follows:
step one, delivering the triammonium citrate waste liquid into a filter one 101 through a pump one P1 for filtering, and removing solid suspended matters in the waste liquid to obtain filtrate and filter residues. The precision filter adopts a PP cotton filter element filter with the filtering precision of 5us, the filtrate is sent into the pH adjusting tank 102, the quantity of filter residues is small, and the filter residues are treated in a centralized way according to solid wastes;
step two, ammonia water is metered into the pH adjusting tank 102 through the ammonia water adding device 103, and stirred, the pH value is adjusted to 7.8, and the following reaction occurs in the pH adjusting tank 102:
AlCl 3 + 3 NH 3 .H 2 O ==3 NH 4 Cl + Al(OH) 3 ↓
step three, delivering the solution in the pH adjusting tank 102 to a filter II 104 through a pipeline pump II P2 for filtering to obtain aluminum hydroxide solids and filtrate without aluminum ions, drying the aluminum hydroxide solids by a dryer 105 to prepare an aluminum hydroxide product, delivering the filtrate without aluminum ions to a storage tank I106, and delivering the filter II 104 to a vacuum filter with the filtering precision of 5us;
step four, delivering the filtrate which does not contain aluminum ions in the first storage tank 106 into a reverse osmosis membrane of a membrane concentration device 107 for concentration once to obtain a tri-ammonium citrate concentrate and pure water, delivering the pure water into the third storage tank 108, returning the pure water to a waste production enterprise for recycling, and delivering the tri-ammonium citrate concentrate into an evaporation device 109;
step five, evaporating and concentrating for the second time through an evaporating device 109, cooling and crystallizing, and sending the mixed solution containing the crystals into a filter III 110 for separation and filtration to obtain the tri-ammonium citrate crystals;
step six, the filtered mother liquor is sent into a storage tank IV 111 and returned to the membrane concentration device 107 for circulation for 2 times through a pump III P3; discharging the rest mother liquor in the storage tank IV 111 into a sewage station for standard treatment and discharge;
step seven, recovering pure water (recycling) in a storage tank III 108 through a pump IV P4, adding the recovered pure water into a filter III 110 to quickly wash crystals, and enabling washing water generated after washing to enter a membrane concentration device 107;
and step eight, delivering the crystals in the filter III 110 into a storage tank II 112, adding pure water (fresh pure water) at 50-60 ℃ through a pure water storage tank 113, stirring and dissolving, and returning to use.
By adopting the method for recycling the waste liquid of the tri-ammonium citrate, the recycling of the tri-ammonium citrate is performed for 18m, the concentration is 7.5%, and the recycling rate is 85%; recovering 36.46KG of aluminum hydroxide, and the recovery rate is more than 95%; the recovery rate of ammonium chloride is >90% and the recovery rate of water is >95%. 150 kg of residual liquid containing the tri-ammonium citrate and the ammonium chloride is discharged into a sewage station. The comprehensive recovery rate of substances in the waste liquid is 85%, negative pressure evaporation is adopted in the evaporation process, and a rich heat source of a waste production enterprise is used, so that the energy consumption is not increased additionally, and the benefit is remarkable.
Claims (9)
1. The method for recycling the electrode foil formation bath liquid waste liquid is characterized by comprising the following steps of:
step one, filtering the waste liquid to remove solid suspended matters in the waste liquid to obtain filtrate and filter residues;
adding ammonia water into the filtrate, stirring, and adjusting the pH value to 7-8;
step three, filtering the solution with the pH value adjusted to obtain aluminum hydroxide solids and filtrate without aluminum ions;
step four, carrying out primary membrane concentration on the filtrate without aluminum ions to obtain primary concentrated solution and water;
step five, carrying out secondary evaporation concentration on the primary concentrated solution, cooling and crystallizing, flushing the crystals by utilizing water in the step four, separating and filtering the mixed solution containing the crystals to obtain crystals and mother solution, and returning the mother solution to the step four for recycling;
and step six, delivering the crystals into the heated fresh pure water, stirring and dissolving the crystals, and returning the crystals to use.
2. The recycling method of the electrode foil formation bath liquid waste liquid according to claim 1, characterized by comprising the following steps: the recycling system related to the recycling method comprises the following steps: a pump one (P1) for pumping waste liquid, filter one (101), pH adjustment tank (102), pump two (P2), filter two (104), storage tank one (106), membrane enrichment facility (107), evaporation plant (109), filter three (110) and storage tank two (112) are connected gradually with pump one (P1), pH adjustment tank (102) department is provided with aqueous ammonia throw-in device (103), filter two (104) are connected with drying-machine (105), membrane enrichment facility (107) are connected with storage tank three (108), storage tank three (108) are connected to filter three (110), evaporation plant (109) are connected to storage tank three (108), filter three (110) are connected to storage tank four (111), storage tank four (111) are connected to membrane enrichment facility (107) through pump three (P3), storage tank two (112) are connected with pure water storage tank (113).
3. The recycling method of the electrode foil formation bath liquid waste liquid according to claim 2, characterized by comprising the following steps: the waste liquid is ammonium adipate waste liquid or triammonium citrate waste liquid.
4. The method for recycling the waste liquid of the electrode foil formation bath solution according to claim 3, characterized by comprising the steps of: in the first step, the filter residues are collected in a concentrated mode and then are treated according to the fixed waste regulation at fixed time.
5. The method for recycling the waste liquid of the electrode foil formation bath solution according to claim 4, which is characterized in that: in the second step, the following reaction occurs during the adjustment of the pH value:
AlCl 3 + 3 NH 3 .H 2 O ==3 NH 4 Cl + Al(OH) 3 ↓。
6. the method for recycling the waste liquid of the electrode foil formation bath solution according to claim 5, wherein the method comprises the steps of: in the third step, the aluminum hydroxide solid is dried to prepare an aluminum hydroxide product for sale.
7. The method for recycling the waste liquid of the electrode foil formation bath solution according to claim 6, characterized by comprising the steps of: recycling the recovered pure water obtained in the step four in a system, and recycling the rest of recovered pure water returned to a waste production enterprise; in the fifth step, a trace amount of ammonium chloride solution in the solution is discharged into a sewage station for standard treatment and discharge; and (d) returning the product recovered in the step (six) to the waste production enterprises for recycling.
8. The method for recycling the waste liquid of the electrode foil formation bath solution according to claim 7, characterized by comprising the steps of: when the waste liquid is ammonium adipate waste liquid, the recycling method comprises the following steps:
step one, ammonium adipate waste liquid from a waste production enterprise is sent to a filter I (101) through a pump I (P1) for filtering, solid suspended matters in the ammonium adipate waste liquid are removed, ammonium adipate filtrate and filter residues are obtained, the filtrate is sent to a pH adjusting tank (102), and the filter residues are collected in a concentrated mode and then are treated according to the fixed waste regulation at fixed time;
step two, ammonia water is added into the pH adjusting tank (102) through an ammonia water adding device (103), and the pH value is adjusted to 7-8 by stirring; the following reactions will occur in the pH adjustment tank (102):
AlCl 3 + 3 NH 3 .H 2 O ==3 NH 4 Cl + Al(OH) 3 ↓；
step three, delivering the solution in the pH adjusting tank (102) into a filter II (104) through a pump II (P2) for filtering to obtain aluminum hydroxide solids and filtrate without aluminum ions, drying the aluminum hydroxide solids through a dryer (105) to prepare aluminum hydroxide product outsourcing, and delivering the filtrate without aluminum ions into a storage tank I (106);
step four, delivering the filtrate which does not contain aluminum ions in the first storage tank (106) into a membrane concentration device (107) for primary concentration to obtain ammonium adipate concentrate and water, delivering the water into the third storage tank (108) for recycling, and delivering the ammonium adipate concentrate into an evaporation device (109);
step five, evaporating the second-stage concentration by an evaporating device (109), cooling and crystallizing, and sending the mixed solution containing the crystals into a filter III (110) for separation and filtration to obtain ammonium adipate crystals;
step six, sending the filtered mother liquor into a storage tank IV (111) to return to a membrane concentration device (107) for circulation through a pump III (P3), and discharging the mother liquor in the storage tank IV (111) into a sewage station periodically for standard treatment and discharge;
step seven, adding the recovered pure water in the storage tank III (108) into the filter III (110) through a pump IV (P4) to flush crystals, and enabling the cleaning water generated after cleaning to enter a membrane concentration device (107);
and step eight, delivering the crystals in the filter III (110) into a storage tank II (112), adding heated pure water into the pure water storage tank (113), stirring and dissolving, and returning to use.
9. The recycling method of the electrode foil formation bath liquid waste liquid according to claim 8, characterized by comprising the following steps: when the waste liquid is the citric acid tri-ammonium waste liquid, the recycling method comprises the following steps:
step one, delivering the waste liquid of the tri-ammonium citrate from the waste producing enterprises into a first filter (101) through a first pump (P1) for filtering, removing solid suspended matters in the waste liquid to obtain tri-ammonium citrate filtrate and filter residues, delivering the filtrate into a pH adjusting tank (102), and treating the filter residues according to the regulation of the solid waste after centralized collection;
step two, ammonia water is added into the pH adjusting tank (102) through an ammonia water adding device (103), and the pH value is adjusted to 7-8 by stirring; the following reactions will occur in the pH adjustment tank (102):
AlCl 3 + 3 NH 3 .H 2 O ==3 NH 4 Cl + Al(OH) 3 ↓；
step three, delivering the solution in the pH adjusting tank (102) into a filter II (104) through a pump II (P2) for filtering to obtain aluminum hydroxide solids and filtrate without aluminum ions, drying the aluminum hydroxide solids through a dryer (105) to prepare aluminum hydroxide product outsourcing, and delivering the filtrate without aluminum ions into a storage tank I (106);
step four, delivering the filtrate which does not contain aluminum ions in the first storage tank (106) into a membrane concentration device (107) for primary concentration to obtain a concentrated solution of the tri-ammonium citrate and water, delivering the water into the third storage tank (108) for recycling, and delivering the concentrated solution of the tri-ammonium citrate into evaporation equipment (109);
step five, evaporating the second-stage concentration by an evaporating device (109), cooling and crystallizing, and sending the mixed solution containing the crystals into a filter III (110) for separation and filtration to obtain the tri-ammonium citrate crystals;
step six, sending the filtered mother liquor into a storage tank IV (111) to return to a membrane concentration device (107) for circulation through a pump III (P3), and discharging the mother liquor in the storage tank IV (111) into a sewage station periodically for standard treatment and discharge;
step seven, adding the recovered pure water in the storage tank III (108) into the filter III (110) through a pump IV (P4) to flush crystals, and enabling the cleaning water generated after cleaning to enter a membrane concentration device (107);
and step eight, delivering the crystals in the filter III (110) into a storage tank II (112), adding heated pure water into the pure water storage tank (113), stirring and dissolving, and returning to use.
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