CN112919427A - Method and device for recycling waste acid in lead storage battery production process - Google Patents
Method and device for recycling waste acid in lead storage battery production process Download PDFInfo
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- CN112919427A CN112919427A CN202110312385.5A CN202110312385A CN112919427A CN 112919427 A CN112919427 A CN 112919427A CN 202110312385 A CN202110312385 A CN 202110312385A CN 112919427 A CN112919427 A CN 112919427A
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- 239000002253 acid Substances 0.000 title claims abstract description 89
- 239000002699 waste material Substances 0.000 title claims abstract description 78
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000003860 storage Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000001914 filtration Methods 0.000 claims abstract description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000006004 Quartz sand Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 26
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002522 Wood fibre Polymers 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000002025 wood fiber Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 23
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 23
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 19
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 19
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000006479 redox reaction Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 12
- -1 iron ions Chemical class 0.000 claims description 8
- 238000005070 sampling Methods 0.000 claims description 6
- 238000009298 carbon filtering Methods 0.000 claims description 4
- 238000011045 prefiltration Methods 0.000 claims description 3
- 239000013618 particulate matter Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 59
- 239000007788 liquid Substances 0.000 description 20
- 238000011001 backwashing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000011550 stock solution Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000009287 sand filtration Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052681 coesite Inorganic materials 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
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011268 retreatment Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
- C01B17/904—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
Abstract
The invention discloses a method for recycling waste acid in the production process of lead storage batteries, which comprises the following steps: (1) adding a mixing agent into the waste acid, wherein the components of the mixing agent are potassium sulfate, potassium permanganate and acrylamide monomers, the potassium sulfate and the potassium permanganate in the mixing agent are subjected to oxidation-reduction reaction to induce the acrylamide monomers to undergo polymerization reaction, and cotton-shaped precipitates are generated to adsorb metal ion impurities in the waste acid; (2) and (3) filtering the waste acid reacted in the step (1) to remove flocculent precipitates, and recycling the acid liquor without metal ion impurities. Still disclose a recycle device, include along the waste acid flow path thick filtration treatment tank, reaction tank, first active carbon filter jar, quartz sand filter jar, second active carbon filter jar, wood fiber filter jar, ion exchange resin adsorption tank and the buffer tank that sets gradually.
Description
Technical Field
The invention relates to the technical field of waste acid recovery, in particular to a method and a device for recycling waste acid in the production process of lead storage batteries.
Background
In the lead-acid storage battery industry, the treatment mode of waste acid is mostly that liquid alkali is added into the waste acid for acid-base neutralization, other preparations are added to extract heavy metal lead in acid, and the heavy metal lead is discharged outside a factory after the sulfate ions, lead ions and PH values in the heavy metal lead meet the discharge requirements. In fact, the treated wastewater contains a large amount of industrial salt, and the environment can be polluted again when the wastewater is discharged too much. In order to treat the waste acid and recycle the waste acid, the method mainly solves the problem of how to remove metal ions and other organic matters which are harmful to the battery in the waste acid, and cannot cause secondary pollution of other substances to the acid liquor in the process of removing the impurities.
The patent specification with the publication number of CN207024771U discloses a recovery and reuse system of waste liquid of a lead-acid storage battery, which consists of a waste liquid pool, an acid-resistant pump, an acid pump outlet valve, a flushing valve, a backwashing device outlet, a layer-collecting filter inlet, a layer-collecting filter, a layer-collecting filtering membrane, a differential pressure gauge, a layer-collecting filter outlet, a dilute sulfuric acid valve, a backwashing pump outlet valve, a backwashing pump, a filtering net, a dilute acid liquid flow passage and a dilute sulfuric acid pool; the method is characterized in that an inlet of an acid-resistant pump is inserted into a waste liquid pool, an outlet of the acid-resistant pump is communicated and fixedly connected with an inlet of an outlet valve of the acid pump, an outlet of the outlet valve of the acid pump is communicated and fixedly connected with an inlet of a layered filter, and the layered filter membrane is arranged in the layered filter to divide the layered filter into an inlet section and an outlet section; the outlet of the layered filter is communicated and consolidated with the inlet of the dilute sulfuric acid valve, and the outlet of the dilute sulfuric acid valve is communicated with the dilute sulfuric acid pool; the inlet of the back washing pump is communicated with the dilute sulfuric acid pool, the outlet of the back washing pump is communicated and fixedly connected with the inlet of the outlet valve of the back washing pump, the outlet of the outlet valve of the back washing pump is communicated with the outlet of the layered filter, the outlet of the back washing device is communicated and fixedly connected with the inlet of the flushing valve, the outlet of the flushing valve is communicated with the dilute sulfuric acid flow passage, and the filter screen is laid above the dilute sulfuric acid flow passage.
The patent specification with the publication number CN100569664 discloses a method for recovering sulfuric acid from high-concentration waste acid in a storage battery plant, which comprises the following steps: a. firstly, performing diffusion dialysis on formed sulfuric acid waste liquid in the production of storage batteries, and performing diffusion dialysis when the volume ratio of the sulfuric acid waste liquid to tap water is 1: 1-1: 3; b. b, performing bipolar membrane electrodialysis on the primary residual liquid treated in the step a, performing electrodialysis for 90-200 min under the condition of 8-15V to obtain recovered sulfuric acid in a concentration chamber, and discharging secondary residual liquid in a dilution chamber after the sulfuric acid is recovered; c. mixing the sulfuric acid recovered in the steps a and b, and then concentrating the sulfuric acid by a distillation method or mixing the sulfuric acid with commercially available chemical pure concentrated sulfuric acid to prepare sulfuric acid solution for the formation process of the lead plate; in the step b, the bipolar membrane electrodialysis is in a form of two compartments, and bipolar membranes and negative membranes are alternately arranged.
Although the two schemes can recycle the sulfuric acid in the waste acid in the storage battery, the purity of the recycled sulfuric acid is not high, and the recycled sulfuric acid cannot be directly used for the production of the storage battery.
Disclosure of Invention
The invention aims to provide a method for recycling waste acid in the production process of lead storage batteries, which can directly use the recycled sulfuric acid for the production of the storage batteries.
The invention also aims to provide a device for recycling waste acid in the production process of lead storage batteries, which can ensure higher purity of the recycled sulfuric acid.
A method for recycling waste acid in the production process of lead storage batteries comprises the following steps:
(1) adding a mixing agent into the waste acid, wherein the components of the mixing agent are potassium sulfate, potassium permanganate and acrylamide monomers, the potassium sulfate and the potassium permanganate in the mixing agent are subjected to oxidation-reduction reaction to induce the acrylamide monomers to undergo polymerization reaction, and cotton-shaped precipitates are generated to adsorb metal ion impurities in the waste acid;
(2) and (3) filtering the waste acid reacted in the step (1) to remove flocculent precipitates, and recycling the acid liquor without metal ion impurities.
In the scheme, the acrylamide monomer induces the polymerization reaction of the acrylamide monomer through the redox reaction of potassium persulfate and potassium permanganate to generate the flocculent precipitate of the polyacrylamide, and the metal ions with positive charges can be adsorbed and removed because the polyacrylamide is negatively charged.
Meanwhile, because the chloride ions in the waste acid belong to valence-variable ions, the chloride ions can be discharged automatically, the performance of the battery and the service life of the battery are influenced, and the content of the chloride ions is important for the performance of the lead-acid battery; the chloride ions have weak reducibility, potassium permanganate as an oxidant is greatly influenced by pH, has the strongest oxidizing capability in an acid solution, and can react with the chloride ions to generate chlorine, so that the chloride ions in the waste acid can be removed.
Preferably, before the mixing agent is added into the waste acid in the step (1), the waste acid is pre-filtered to remove particulate impurities insoluble in the waste acid, such as lead slag, solid suspended matters and the like, so as to ensure that relatively pure dilute sulfuric acid is obtained.
Preferably, the metal ion impurities are iron ions. The iron ions are main metal ions, the occupied ratio is high, the detection method is simple, and the phenomenon is obvious (potassium permanganate titration detection), so the detection method is used as a main detection item.
Preferably, in the step (1), the content of the iron ions in the waste acid is measured, and then the mixing agent with the corresponding amount is added into the waste acid according to the amount of the iron ions.
Preferably, in the step (2), when the flocculent precipitate is filtered off, activated carbon adsorption filtration, quartz sand filtration, activated carbon adsorption filtration, wood fiber filtration and ion exchange resin adsorption filtration are sequentially used. Through the filtration of the above procedures, pure dilute sulfuric acid with the quality meeting the standard requirements can be finally purified.
A recycle device of spent acid in lead accumulator production process includes:
the pre-filtering net is used for pre-filtering the waste acid to remove particulate matter impurities insoluble in the waste acid;
the reaction tank is used for receiving the waste acid after pre-filtration, adding a mixing agent into the waste acid, wherein the mixing agent comprises potassium sulfate, potassium permanganate and acrylamide monomers, the potassium sulfate and the potassium permanganate in the mixing agent are subjected to redox reaction to induce the acrylamide monomers to undergo polymerization reaction, and cotton-shaped precipitates are generated to adsorb metal ion impurities in the waste acid;
the first activated carbon filter tank takes activated carbon as a filter medium and is used for filtering waste acid after reaction in the reaction tank;
the quartz sand filter tank takes quartz sand as a filter medium and is used for filtering the filtrate of the first activated carbon filter tank;
the second active carbon filter tank takes active carbon as a filter medium and is used for filtering the filtrate in the quartz sand filter tank;
the wood fiber filtering tank takes wood fiber as a filtering medium and is used for filtering the filtrate of the second activated carbon filtering tank;
the ion exchange resin adsorption tank takes ion exchange resin as a filter medium and is used for filtering the filtrate in the wood fiber filter tank.
The electrolyte containing the cotton-shaped precipitates can better remove the precipitates and other unadsorbed metal ions in the electrolyte after multiple filtering processes; in the selection of the filtering material, the filtering material which can resist acid and alkali is selected to ensure that the waste acid can not be polluted again. Quartz sand, active carbon, wood fiber, ion exchange resin and the like are adopted as filtering materials in the scheme.
Quartz sand, main component SiO2The content reaches 99%, and the quartz sand is acid and alkali resistant, and 1% of impurities in the quartz sand are removed by cleaning with a chemical cleaning agent when the quartz sand is used, so that the purity of the quartz sand is higher. The quartz sand mainly plays a role in filtration.
The activated carbon has good stability, does not react with acid and alkali, and mainly plays a role in adsorption.
Wood fiber, which mainly plays a role in filtration.
The ion exchange resin is mainly separated from metal in the recovered liquidExchanging, adsorbing and purifying the seeds; the purification principle is as follows: strongly acidic cationic resin, R-SO3H, wherein R represents a resin matrix and can be a sulfonic acid group and the like; h + is dissociated in the solution, wherein the H + exchanges with metal ions and other cations in the solution. Negatively charged groups, -SO contained in the bulk after dissociation of the resin3 -Can adsorb and combine other cations in the solution.
After various filter materials are used for many times, the filtering and adsorbing capacity of the filter materials is gradually reduced, when a certain value is reached, relevant chemical cleaning agents are added, and the filter materials are subjected to forward and reverse washing actions to remove harmful substances in the filter materials, so that the filter materials are regenerated.
Preferably, a first conveying pipe is arranged between the outlet of the reaction tank and the inlet of the first active carbon filter tank,
a second delivery pipe is arranged between the outlet of the first active carbon filter tank and the inlet of the quartz sand filter tank,
a third delivery pipe is arranged between the outlet of the quartz sand filter tank and the inlet of the second active carbon filter tank,
a fourth conveying pipe is arranged between the outlet of the second active carbon filtering tank and the inlet of the wood fiber filtering tank,
and a fifth conveying pipe is arranged between the outlet of the wood fiber filtering tank and the inlet of the ion exchange resin adsorption tank.
Further preferably, each delivery pipe is provided with a valve.
Further preferably, each of the transport pipes is provided with a sampling port.
The invention has the beneficial effects that:
(1) the quality of the sulfuric acid treated by the waste acid recycling device is tested, the copper content is less than or equal to 1.0ppm, the iron content is less than or equal to 5.0ppm, the chlorine content is less than or equal to 0.5ppm, and the quality can meet the standard recycling requirement.
(2) More than 90% of waste acid in the formation workshop is effectively recycled, the emission of pollutants is reduced, the environment is improved, and the cost is saved.
(3) The battery produced by the recovered acid treated by the device and the method of the invention is qualified in the tests of voltage, internal resistance, open-close voltage and the like, and has no difference with the battery produced by normal sulfuric acid.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 is an enlarged view of portion A of FIG. 1;
FIG. 3 is a front cross-sectional view of a first activated carbon filter canister;
FIG. 4 is a front cross-sectional view of a quartz sand filter canister;
FIG. 5 is a front cross-sectional view of a second activated carbon filter canister;
FIG. 6 is a front cross-sectional view of a wood fiber filter canister;
fig. 7 is a front sectional view of the ion exchange resin adsorption tank.
Detailed Description
As shown in fig. 1 to 7, a waste acid recycling device in the production process of lead storage batteries comprises a coarse filtration treatment tank 100, a reaction tank 200, a first activated carbon filtration tank 300, a quartz sand filtration tank 400, a second activated carbon filtration tank 500, a wood fiber filtration tank 600, an ion exchange resin adsorption tank 700 and a buffer tank 800, which are sequentially arranged along a waste acid flow path.
A pre-filtering net is arranged in the coarse filtering treatment tank 100 and is used for pre-filtering the waste acid to remove particulate impurities, such as lead slag, solid suspended matters and the like, which are insoluble in the waste acid.
The waste acid after pre-filtration flows into a reaction tank 200, and a mixing agent is added into the reaction tank 200 to adsorb metal ion impurities in the waste acid; specifically, a mixing agent containing potassium sulfate, potassium permanganate and acrylamide monomers is added into the waste acid in the reaction tank 200, the potassium sulfate and the potassium permanganate in the mixing agent undergo an oxidation-reduction reaction to induce the acrylamide monomers to undergo a polymerization reaction, and cotton-like precipitates are generated to adsorb metal ion impurities in the waste acid. The reaction tank 200 is provided with metering pumps 1 ', 2' and 3 'for respectively adding potassium sulfate, potassium permanganate and acrylamide monomers, and the working time of the metering pumps 1', 2 'and 3' is accurately controlled by an electric cabinet.
The first activated carbon filter tank 300 uses activated carbon as a filter medium for filtering waste acid after reaction in the reaction tank 200; the quartz sand filter tank 400 uses quartz sand as a filter medium and is used for filtering the filtrate of the first activated carbon filter tank 300; the second activated carbon filter tank 500 uses activated carbon as a filter medium for re-filtering the filtrate in the quartz sand filter tank 400; the wood fiber filter tank 600 uses wood fibers as a filter medium and is used for filtering the filtrate of the second activated carbon filter tank 500; the ion exchange resin adsorption tank 700 uses ion exchange resin as a filtering medium for filtering the filtrate of the wood fiber filtering tank 600.
The inlet of the coarse filtration treatment tank 100 is connected with the outlet of the waste acid tank 900 through a pipeline, the pipeline is provided with a valve 1 and a pump 1# 1, the outlet of the coarse filtration treatment tank 100 is connected with the inlet of the reaction tank 200 through a pipeline, the pipeline is provided with a valve 1-1, the outlet of the exchange resin adsorption tank 700 is connected with the inlet of the buffer tank 800 through a pipeline, the pipeline is provided with a valve 8, the buffer tank 800 is provided with an acid outlet pipe and a return pipe, the acid outlet pipe is provided with a valve 9 for enabling qualified products to flow into a finished product barrel (or tank) for use, the return pipe is provided with a valve 1-2 and a pump 3# 3, and the other end of the return pipe leads into the coarse filtration treatment tank 100. The pump No. 1 and the pump No. 3 are controlled by an electric cabinet.
In addition, a first delivery pipe 201 is provided between the outlet of the reaction tank 200 and the inlet of the first activated carbon filter canister 300, a second delivery pipe 301 is provided between the outlet of the first activated carbon filter canister 300 and the inlet of the quartz sand filter canister 400, a third delivery pipe 401 is provided between the outlet of the quartz sand filter canister 400 and the inlet of the second activated carbon filter canister 500, a fourth delivery pipe 501 is provided between the outlet of the second activated carbon filter canister 500 and the inlet of the wood fiber filter canister 600, and a fifth delivery pipe 601 is provided between the outlet of the wood fiber filter canister 600 and the inlet of the ion exchange resin adsorption canister 700.
Be provided with No. 2 pumps 2# on the first conveyer pipe 201 and be located valve 2 and the valve 3 of No. 2 pump 2# both sides, be provided with valve 4 on the second conveyer pipe 301, be provided with valve 5 on the third conveyer pipe 401, be provided with valve 6 on the fourth conveyer pipe 501, be provided with valve 7 on the fifth conveyer pipe 601. And the No. 2 pump 2# is controlled by the electric cabinet.
The pipeline where the valves 1-8 are located is a total liquid inlet route, namely, the waste liquid can be filtered and purified by opening the valves 1-8.
The outlets of the first activated carbon filter tank 300, the quartz sand filter tank 400, the second activated carbon filter tank 500, the wood fiber filter tank 600 and the ion exchange resin adsorption tank 700 are all provided with sampling pipes, and each sampling pipe is provided with valves 10, 11, 12, 13 and 14.
The recycling device also comprises a backwashing and waste liquid recycling route, namely a pipeline where the valves 15-29 are located, and specifically comprises the following steps:
opening valves 15, 26, 27 and 29, closing valves 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 and 28, and cleaning the first activated carbon filter tank 300;
15. 24, 25 and 29 are opened, 16, 17, 18, 19, 20, 21, 22, 23, 26, 27 and 28 are closed, and the quartz sand filter tank 400 is cleaned;
15. 22, 23 and 29 are opened, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27 and 28 are closed, and the second activated carbon filter tank 500 is cleaned;
15. 20, 21 and 29 are opened, 16, 17, 18, 19, 22, 23, 24, 25, 26, 27 and 28 are closed, and the wood fiber filter tank 600 is cleaned;
15. 18, 19 and 29 are opened, and 16, 17, 20, 21, 22, 23, 24, 25, 26, 27 and 28 are closed, and the ion exchange resin adsorption tank 700 is cleaned.
A method for recycling waste acid in the production process of lead storage batteries is characterized in that a mixing agent is added into waste liquid, specifically, the amount of each component in the mixing agent is determined according to the amount of iron ions in the waste liquid, and the using amount of each component in the mixing agent is as follows:
1. the dosage and pumping time of the waste liquid with iron content (Fe < 7PPM)
| Treating fluid (amount) | Potassium sulfate | | Acrylamide | |
| 1 ton of | 1.25L/4min74s | 2L/7min44s | 2L/ |
|
| 2 ton of | 2.5L/9min44s | 4L/14min88s | 4L/14min17s |
2. The dosage and time of the waste liquid containing iron (Fe is more than or equal to 7 and less than 10PPM)
| Treating fluid (amount) | Potassium sulfate | | Acrylamide | |
| 1 ton of | 2.5L/9min44s | 4L/14min88s | 4L/ |
|
| 2 ton of | 5L/19min14s | 8L/29min58s | 8L/28min34s |
3. The dosage and time of the waste liquid containing iron (Fe is more than or equal to 10 and less than 13PPM)
| Treating fluid (amount) | Potassium sulfate | | Acrylamide | |
| 1 ton of | 5L/19min14s | 8L/29min58s | 8L/ |
|
| 2 ton of | 7.5L/28min54s | 12L/44min43s | 12L/42min51s |
4. The iron content of the waste liquid (Fe is more than or equal to 13 and less than 15 PPM) is not suitable for the treatment of the process equipment.
Taking the recycling of 1000kg of electrolyte waste liquid as an example, the specific operation steps are as follows:
example 1
(1) Taking a sample of 50ml of the stock solution, and detecting to obtain a sample with the iron content of 5.6 ppm;
(2) setting the specific time for correspondingly adding reagents (potassium sulfate, potassium permanganate and acrylamide monomers) on the electric cabinet:
potassium sulfate: 1.25L/4min74 s; potassium permanganate: 2L/7min44 s; acrylamide monomer: 2L/7min9 s;
(3) opening valves 1 and 1-1, enabling stock solution to enter a coarse filtration treatment tank 100 through a pump 1# of a No. 1, then entering a reaction tank 200, opening a power switch of a pump 1# of an electric cabinet 1, starting operation of the pump 1# of the No. 1, and enabling the stock solution to flow into the coarse filtration treatment tank 100 in an increased manner;
(4) after the stock solution enters the reaction tank 200 for 5 minutes, turning on a switch (automatic mode) of a metering pump 1 ' of the electric cabinet, starting to add potassium sulfate into the reaction tank 200, turning on a switch of a metering pump 2 ' of the electric cabinet after 1 minute, adding potassium permanganate, turning on a switch of a metering pump 3 ' of the electric cabinet after 1 minute, and adding an acrylamide monomer; until the automatic reagent addition is complete, the metering pumps 1 ', 2 ' and 3 ' control switches are restored to a stop (off).
(5) When the stock solution enters the reaction tank 200 to the highest position (visible position) of the water level glass, stopping the No. 1 pump 1 #; taking 50ml of the sample in the reaction tank 200, sending the sample for detection, and if the sample is abnormal, readjusting the dosage of the added sample until the abnormality is removed;
(6) opening valves 2-8, simultaneously opening the multipurpose control valves at the upper parts of the first activated carbon filter tank 300, the quartz sand filter tank 400, the second activated carbon filter tank 500, the wood fiber filter tank 600 and the ion exchange resin adsorption tank 700, and sequentially filtering the stock solution;
(7) and opening the valve 14, carrying out sampling detection through a sampling port at the position, opening a valve 9 switch after the qualified product is qualified, enabling the qualified product to flow into a finished product barrel (or tank) for use, and opening the valve 1-2 if the qualified product is not qualified, and returning the liquid in the buffer tank 800 to the coarse filtration treatment tank 100 for retreatment.
Example 2
(1) Taking a sample of 50ml of the stock solution, and detecting to obtain a sample with iron content of 8 ppm;
(2) setting the specific time for correspondingly adding reagents (potassium sulfate, potassium permanganate and acrylamide monomers) on the electric cabinet:
potassium sulfate: 2.5L/9min44 s; potassium permanganate: 4L/14min88 s; acrylamide monomer: 4L/14min17 s;
the following steps are the same as those in embodiment 1 and are not described herein again.
Example 3
(1) Taking a sample of 50ml of the stock solution, and detecting to obtain a sample with the iron content of 12 ppm;
(2) setting the specific time for correspondingly adding reagents (potassium sulfate, potassium permanganate and acrylamide monomers) on the electric cabinet:
potassium sulfate: 14s at 5L/19 min; potassium permanganate: 8L/29min58 s; acrylamide monomer: 8L/28min34 s;
the following steps are the same as those in embodiment 1 and are not described herein again.
Comparative example 1
1. The electrolyte formula of the conventional storage battery is as follows: 66kg of pure water (the conductivity is less than 0.3 mu S/cm), 34kg of sulfuric acid (analytically pure) and 15g/L of anhydrous sodium sulfate.
2. Preparation method
Slowly injecting sulfuric acid into water, stirring, cooling to below 45 deg.C, adding anhydrous sodium sulfate, and stirring.
Application example 1
The storage battery electrolytes prepared in the comparative example 1, the example 2 and the example 3 are respectively adopted to be assembled into a storage battery with the model number of 6-DZF-20 according to a conventional process, and the produced storage battery is detected according to a standard GB/T22199.1-2017.
TABLE 1
As can be seen from the above table, the indexes of the batteries assembled by using the electrolytes of examples 1, 2 and 3, such as low temperature, charge retention capacity, and life, do not change significantly from the performance of the battery of comparative example 1, and the batteries produced by using the recovered acid according to the technical scheme of the present invention have all passed the tests of voltage, internal resistance, open/close voltage, etc., and are not different from the batteries produced by using normal sulfuric acid.
Claims (9)
1. A method for recycling waste acid in the production process of lead storage batteries is characterized by comprising the following steps:
(1) adding a mixing agent into the waste acid, wherein the components of the mixing agent are potassium sulfate, potassium permanganate and acrylamide monomers, the potassium sulfate and the potassium permanganate in the mixing agent are subjected to oxidation-reduction reaction to induce the acrylamide monomers to undergo polymerization reaction, and cotton-shaped precipitates are generated to adsorb metal ion impurities in the waste acid;
(2) and (3) filtering the waste acid reacted in the step (1) to remove flocculent precipitates, and recycling the acid liquor without metal ion impurities.
2. The recycling method according to claim 1, wherein the waste acid is pre-filtered to remove particulate impurities insoluble in the waste acid before the mixing agent is added to the waste acid in the step (1).
3. The recycling method according to claim 1, wherein the metal ion impurities are iron ions.
4. The recycling method according to claim 1, wherein the content of iron ions in the waste acid is determined in step (1), and then the mixing agent is added into the waste acid according to the amount of the iron ions.
5. The recycling method according to claim 1, wherein the step (2) of filtering to remove the flocculent precipitate comprises sequentially performing adsorption filtration with activated carbon, quartz sand, activated carbon, wood fiber and ion exchange resin.
6. The utility model provides a recycle device of spent acid in lead accumulator production process which characterized in that includes:
the pre-filtering net is used for pre-filtering the waste acid to remove particulate matter impurities insoluble in the waste acid;
the reaction tank is used for receiving the waste acid after pre-filtration, adding a mixing agent into the waste acid, wherein the mixing agent comprises potassium sulfate, potassium permanganate and acrylamide monomers, the potassium sulfate and the potassium permanganate in the mixing agent are subjected to redox reaction to induce the acrylamide monomers to undergo polymerization reaction, and cotton-shaped precipitates are generated to adsorb metal ion impurities in the waste acid;
the first activated carbon filter tank takes activated carbon as a filter medium and is used for filtering waste acid after reaction in the reaction tank;
the quartz sand filter tank takes quartz sand as a filter medium and is used for filtering the filtrate of the first activated carbon filter tank;
the second active carbon filter tank takes active carbon as a filter medium and is used for filtering the filtrate in the quartz sand filter tank;
the wood fiber filtering tank takes wood fiber as a filtering medium and is used for filtering the filtrate of the second activated carbon filtering tank;
the ion exchange resin adsorption tank takes ion exchange resin as a filter medium and is used for filtering the filtrate in the wood fiber filter tank.
7. The recycling apparatus according to claim 6,
a first conveying pipe is arranged between the outlet of the reaction tank and the inlet of the first active carbon filter tank,
a second delivery pipe is arranged between the outlet of the first active carbon filter tank and the inlet of the quartz sand filter tank,
a third delivery pipe is arranged between the outlet of the quartz sand filter tank and the inlet of the second active carbon filter tank,
a fourth conveying pipe is arranged between the outlet of the second active carbon filtering tank and the inlet of the wood fiber filtering tank,
and a fifth conveying pipe is arranged between the outlet of the wood fiber filtering tank and the inlet of the ion exchange resin adsorption tank.
8. A recycling apparatus according to claim 7, wherein each of the ducts is provided with a valve.
9. The recycling apparatus according to claim 7, wherein each of the transport pipes is provided with a sampling port.
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| CN211384144U (en) * | 2019-08-09 | 2020-09-01 | 天能集团贵州能源科技有限公司 | Waste acid recovery processing device in storage battery production process |
| CN111799525A (en) * | 2020-07-17 | 2020-10-20 | 天能集团（濮阳）再生资源有限公司 | Waste lead-acid storage battery residual acid recovery device and recovery method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN211384144U (en) * | 2019-08-09 | 2020-09-01 | 天能集团贵州能源科技有限公司 | Waste acid recovery processing device in storage battery production process |
| CN111799525A (en) * | 2020-07-17 | 2020-10-20 | 天能集团（濮阳）再生资源有限公司 | Waste lead-acid storage battery residual acid recovery device and recovery method |
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