CN1760116A - Method and equipment for recovering waste vitriol produced in fabricating pole plates of lead-acid accumulator - Google Patents
Method and equipment for recovering waste vitriol produced in fabricating pole plates of lead-acid accumulator Download PDFInfo
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- CN1760116A CN1760116A CN 200410060943 CN200410060943A CN1760116A CN 1760116 A CN1760116 A CN 1760116A CN 200410060943 CN200410060943 CN 200410060943 CN 200410060943 A CN200410060943 A CN 200410060943A CN 1760116 A CN1760116 A CN 1760116A
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Abstract
A process for recovering the used sulfuric acid generated in preparing plate electrodes of lead-acid accumulator includes such steps as filtering by microfilter (or ultrafilter) membrane, and filtering by nanofilter membrane to make the content of Fe ions 0-5 ppm. Its apparatus is composed of a main body with inlet and outlet, microfilter or ultrafilter unit and its washing unit, and nanofilter unit and its washing unit.
Description
One, technical field
The present invention relates to sulfur waste acid recovery method and apparatus in the battery plate production, especially a kind of membrane separation technique, battery plate production technology and battery plate manufacturing enterprise pollution environment protection treating technology are coupled together carried out the Technology of comprehensive management of environmental protection.
Two, background technology
At present, mostly in chemical synthesis technology and the sour technology of pouring, use dilute sulphuric acid in the battery plate production both at home and abroad, what a large amount of sulfur waste acid of production generation were taked mostly is the outward transport treatment process, waste financial resources and manpower, the sulfuric acid utilization ratio is very low, and the cost that is used to transport outward is very high, lacks economic, effective treatment process for the sulfuric acid reuse.The intermediate raw material that also therefore causes the pole plate production technique produces a large amount of environmental pollutions when consuming a large amount of acquisition cost of enterprise, taking a large amount of environmental protection resources.
Polar plate of lead acid storage battery production need be used a large amount of tap water and pure water, and used water becomes the waste water of sulfur acid and heavy metal lead.Environmental administration of battery plate manufacturing enterprise administers waste water, a large amount of sheet alkali that use are as neutralizing agent in waste water treatment, (fund, place, personnel) are very high for the environment protection treating cost, and sodium sulfate concentration accumulative total raises and reaches 15000～25000mg/l crystallization and separate out in the departures water of waste water processing station, if reuse departures water is in dashing ground, greening, recirculated water, white crystals then after moisture evaporation, occurs, influence the attractive in appearance of place.If efflux then influence environment.Along with production-scale continuous expansion, battery plate manufacturing enterprise existing equipment can not satisfy the requirement of environment protection and water of productive use and a large amount of environmental issue of needs enlarging or the like is perplexing enterprise.
Three, summary of the invention
The present invention is directed to the problems referred to above provides a kind of and is not influencing under the pole plate quality product prerequisite, improving the sulfuric acid comprehensive utilization ratio, when reducing the vitriolic acquisition cost, reduce sulfur waste acid treatment cost, reduce the waste water treatment cost, reduce departures aqueous sodium persulfate concentration, increase substantially lead acid cell and produce sulfur waste acid recovery method and apparatus in a kind of battery plate production of environmental protection of enterprise benefit, social benefit, economic benefit.
Technical scheme provided by the invention is: useless vitriolic recovery method in a kind of polar plate of lead acid storage battery production technique, the sulfur waste acid that chemical synthesis technology in the polar plate of lead acid storage battery production process is produced is with microfiltration membrane or ultrafiltration membrance filter, obtain the one-level filtrate, the one-level filtrate is pumped into nanofiltration membrane, obtain the secondary filtrate of iron ion content between 0-5ppm.
In aforesaid method, with the sulfur waste acid by microfiltration membrane or ultra-filtration membrane not with microfiltration membrane or ultrafiltration membrance filter; The one-level filtrate by nanofiltration membrane is not pumped into nanofiltration membrane filters.
In aforesaid method, the pressure that the one-level filtrate is pumped into nanofiltration membrane is 5-40kg/cm
2The scope of application of the pH value of nanofiltration membrane is 0-7.
The present invention is for the enterprise of drenching sour technology is arranged in the battery plate production, polar plate of lead acid storage battery can be drenched sulfur waste acid that sour technology produces with microfiltration membrane or ultra-filtration membrane micro-filtration, obtain drenching the useless vitriolic one-level filtrate of acid, to drench the useless vitriolic one-level filtrate of acid and pump into nanofiltration membrane, obtain the secondary filtrate of iron ion content between 0-5ppm.
According to aforesaid method of the present invention, with the pouring acid sulfur waste acid by microfiltration membrane or ultra-filtration membrane not with microfiltration membrane or ultrafiltration membrance filter; Filter not pumping into nanofiltration membrane by the sour sulfur waste acid of the pouring of nanofiltration membrane one-level filtrate.
The present invention also provides the sulfur waste acid-recovery plant of realizing aforesaid method, comprise body, body is provided with opening for feed and discharge port, and body is provided with micro-filtration or ultra filtration unit, nano-filtration unit from opening for feed to discharge port order, is provided with micro-filtration or ultra-filtration membrane cleaning unit and nanofiltration membrane cleaning unit.
One-level pump and storage tank that above-mentioned micro-filtration or ultra filtration unit pump into microfiltration membrane or hyperfiltration membrane assembly by microfiltration membrane or hyperfiltration membrane assembly, with sulfur waste acid are formed, the two stage pump that nano-filtration unit pumps into nanofiltration membrane component by nanofiltration membrane component, with the filtrate of micro-filtration or ultra filtration unit is formed, the import of one-level pump is the opening for feed of body, and outlet connects the inlet of microfiltration membrane or hyperfiltration membrane assembly; The filtrate outlet of microfiltration membrane or hyperfiltration membrane assembly connects the import of two stage pump through storage tank, exports the discharge port into body.
The outlet of above-mentioned microfiltration membrane or ultra-filtration membrane cleaning unit connects micro-filtration or ultra filtration unit import; The filter unit inlet is admitted in the outlet of nanofiltration membrane cleaning unit.
The invention has the advantages that:
Can solve the acid-treated environmental protection difficult problem of most of sulfur wastes of long-term puzzlement polar plate of lead acid storage battery manufacturing enterprise comprehensively.Do not influencing under the pole plate quality product prerequisite, improve the sulfuric acid comprehensive utilization ratio, when reducing the vitriolic acquisition cost, reduce sulfur waste acid treatment cost, reduce the waste water treatment cost, reduce departures aqueous sodium persulfate concentration, increase substantially environmental benefit, social benefit and the economic benefit of polar plate of lead acid storage battery manufacturing enterprise.
1. main benefit: environmental protection, social benefit
A. environmental benefit: spent acid, waste water reclaiming, alleviated pollution when reducing production costs significantly, the sulfuric acid reclamation rate is greater than 70%, when improving the environmental protection of enterprise level, reduce material input, fund input and human input that enterprise is used for environmental protection significantly, on the environmental benefit of polar plate of lead acid storage battery manufacturing enterprise, has epoch making significance;
B. improve the on-site aqueous condition: because of minimizing that acid waste liquid the causes use of sheet alkali that neutralizes is in a large number drenched in reuse, thereby effected a radical cure the sodium sulfate of wastewater treatment middle and high concentration, departures waste water such as reuse water quality are better.Being back to the water quality of dashing ground, greening, recirculated water improves.If qualified discharge, sodium sulfate concentration is more preceding also greatly to be reduced, and is of value to environment.
C. water saving to the full extent: the present invention has reclaimed the water in most of solution when handling the spent acid reuse, directly applies to preparation and changes into dilution heat of sulfuric acid, and the repeating utilization factor of water is very high, has reduced the demand of pure water.
D. enterprise to obtain water-saving policy preferential.Various places water savings is done, and all there are a lot of relevant preferential policies in the north especially to the water saving aspect of industrial enterprise, by the water saving of enterprise, for enterprise strives for that more policy is preferential, also contributes for social water saving simultaneously.Reduced the processing load of waste water processing station, carried out basic substance for enterprise increases production capacity.When enterprise increases production capacity, the increase-volume of the waste water disposal facility that do not need to worry again.
2. auxiliary benefit: economic benefit
A. reduce the sulfuric acid amount of purchase;
B. reduce sheet alkali amount of purchase;
C. reduce former technology and change into spent acid outward transport processing cost;
D. water saving: only change into spent acid and reclaim the water saving water rate of bringing with the sour spent acid recovery of pouring;
E. this year, international plumbous valency promoted significantly, for the difficult problem that lead acid cell brings cost to rise, used this production technique to reduce production costs, and can alleviate the unfavorable factor that the plumbous valency of part rises and brings because of cost reduces.Use this environment-friendly production process can reduce the enhancing of the competitive power of bringing the selling market because of cost.
F. the lead acid cell chemical synthesis technology with drench sour technological transformation after, the growth that enterprise can bring enterprise's annual returns because of the enhancing of the saving of above-mentioned a, b, c, d, the production of e item and sales competitiveness.
Four, description of drawings
Accompanying drawing is the structural representation of sulfur waste acid reclamation set of the present invention.
Five, embodiment:
Sulfur waste acid recovery method embodiment is in the battery plate production of the present invention:
1. drench sour spent acid solution through the multifeed clarifier post precipitation, handle the spent acid solution that drenches sour technology (have part battery plate manufacturing enterprise not have and drench sour process section) generation in the pole plate production with little (surpassing) filter membrane, spent acid solution enters little (surpassing) filter membrane circular treatment unit through the pump pressurization, concentrated solution enters the sewage works of factory and handles or the outward transport processing, filtrate pumps in the header tank and stores, and is used to dispose the chemical synthesis technology dilute sulphuric acid.Sulfuric acid unnecessary in the sour technology and the water in the solution are drenched in the main reuse of this processing unit, remove solid substance and the suspended substances such as lead powder, plumbous oxide and lead sulfate that drench in the acid waste liquid; And main component is the iron ion, lead ion etc. of sulfuric acid, water, lower concentration in the filtrate, and iron ion content is less than 5ppm, and constituent concentration meets the requirement that configuration changes into sulphuric acid soln fully.
2. in chemical synthesis technology, changing into acid solution raises because of iron concentration increases gradually in time, after iron concentration is higher than 5ppm, can produce negative influence to the pole plate quality in the technique for making polar plate, this acid solution loses utility value and goes out of use in original production technique at this moment.
The spent acid solution that the present invention produces with little (surpassing) filter membrane processing chemical synthesis technology, spent acid solution enters little (surpassing) filter membrane cycling element through the pump pressurization and handles, and it is basic identical that sour spent acid solution is drenched in method and processing.Difference is that concentrated solution does not enter waste water processing station but outward transport is handled.Little (surpassing) filter membrane processing unit mainly is as the unitary pretreatment unit of secondary nanofiltration membrane treatment, removes the materials such as lead powder, plumbous oxide and lead sulfate that change in the waste liquid and produces solid substance and suspended substance; And main component is sulfuric acid, water, iron ion, lead ion etc. in the filtrate, and constituent concentration meets the requirement of secondary nanofiltration organic membrane processing unit to treating material fully.Little (surpassing) filter filtrate is at 5-40kg/cm
2Pressure under pump into next stage nanofiltration membrane treatment unit, spent acid solution is done the iron ion circulation to be concentrated, this processing unit has higher interception capacity to non-monovalent metallic ions such as iron ions, play the effect that reduces iron concentration in the filtrate, iron concentration is between 0-5ppm in the secondary filtrate.Filtrate can be back to again and change into complex acid.Concentrated solution is worth because of the iron ion that contains high density loses reuse, does outward transport and handles.Through behind this processing step, the spent acid amount of outward transport has reduced more than 70%.Filtrate enter change into acid preparing system reconfigure the back reuse.
Referring to accompanying drawing, the present invention realizes the sulfur waste acid-recovery plant of aforesaid method, comprise body 1, body 1 is provided with opening for feed 2 and discharge port 3,3 orders are provided with micro-filtration or ultra filtration unit 4, nano-filtration unit 5 to body 1 from opening for feed 2 to discharge port, are provided with micro-filtration or ultra-filtration membrane cleaning unit 6 and nanofiltration membrane cleaning unit 7.Micro-filtration or ultra filtration unit 4 are made up of storage tank 8, one-level pump 9 and microfiltration membrane or hyperfiltration membrane assembly 10.Nano-filtration unit 5 is made up of circulation tank 13, two stage pump 11 and nanofiltration membrane component 12, and the filtrate of micro-filtration or ultra filtration unit 4 is pumped into nano-filtration unit 5.Sulfur waste acid is pumped into microfiltration membrane or hyperfiltration membrane assembly 10 through one-level pump 9, and the filtrate that obtains enters circulation tank 13.The import of storage tank 8 is the opening for feed 2 of body 1, exports the import 15 of 14 one-level pumps 9, and the import 17 of microfiltration membrane or hyperfiltration membrane assembly 10 is the outlet 16 of one-level pump 9, and filter unit inlet 19 is admitted in the outlet 18 of microfiltration membrane or hyperfiltration membrane assembly 10.With the filtrate of micro-filtration or ultra filtration unit 4 through circulation tank 13 after two stage pump 11 pumps into nanofiltration membrane component 12, the filtrate that obtains enters finished product jar 27.The import 19 of circulation tank 13 is the outlet 18 of microfiltration membrane or hyperfiltration membrane assembly 10, outlet 20 connects the import 21 of two stage pump 11, the import 23 of nanofiltration membrane component 12 is the outlet 22 of two stage pump 11, the outlet 24 finished product jar imports 25 of nanofiltration membrane component 12, and the outlet 26 of finished product jar connects discharge port 3.
Micro-filtration of the present invention or ultra-filtration membrane cleaning unit and nanofiltration membrane cleaning unit and purging method all adopt prior art.
Use the acid-treated environmental protection difficult problem of most of sulfur wastes that the present invention can solve long-term puzzlement polar plate of lead acid storage battery manufacturing enterprise comprehensively.Improve the sulfuric acid comprehensive utilization ratio, when reducing the vitriolic acquisition cost, reduce sulfur waste acid treatment cost, reduce the waste water treatment cost, reduce departures aqueous sodium persulfate concentration, increase substantially environmental benefit, social benefit and the economic benefit of polar plate of lead acid storage battery manufacturing enterprise.Can not introduce other secondary pollution when particularly carrying out sulfur waste acid Treatment for Reuse, can not influence the quality product of pole plate because of reuse.
Claims (8)
1. useless vitriolic recovery method in the polar plate of lead acid storage battery production technique, it is characterized in that: the sulfur waste acid that chemical synthesis technology in the polar plate of lead acid storage battery production process is produced is with microfiltration membrane or ultrafiltration membrance filter, obtain the one-level filtrate, the one-level filtrate is pumped into nanofiltration membrane, obtain the secondary filtrate of iron ion content between 0-5ppm.
2. method according to claim 1 is characterized in that: will be not sulfur waste acid by microfiltration membrane or ultra-filtration membrane with microfiltration membrane or ultrafiltration membrance filter; The one-level filtrate by nanofiltration membrane is not pumped into nanofiltration membrane filters.
3. method according to claim 1 is characterized in that: the pressure that the one-level filtrate is pumped into nanofiltration membrane is 5-40kg/cm2; The scope of application of the pH value of nanofiltration membrane is 0-7.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that: polar plate of lead acid storage battery is drenched sulfur waste acid that sour technology produces with microfiltration membrane or ultra-filtration membrane micro-filtration, obtain drenching the useless vitriolic one-level filtrate of acid, to drench the useless vitriolic one-level filtrate of acid and pump into nanofiltration membrane, obtain the secondary filtrate of iron ion content between 0-5ppm.
5. method according to claim 4 is characterized in that: will be not pouring acid sulfur waste acid by microfiltration membrane or ultra-filtration membrane with microfiltration membrane or ultrafiltration membrance filter; Filter not pumping into nanofiltration membrane by the sour sulfur waste acid of the pouring of nanofiltration membrane one-level filtrate.
6. useless vitriolic recovery system in the polar plate of lead acid storage battery production technique, comprise body, body is provided with opening for feed and discharge port, it is characterized in that: body is provided with micro-filtration or ultra filtration unit, nano-filtration unit from opening for feed to discharge port order, is provided with micro-filtration or ultra-filtration membrane cleaning unit and nanofiltration membrane cleaning unit.
7. recovery system according to claim 6, it is characterized in that: one-level pump and storage tank that micro-filtration or ultra filtration unit pump into microfiltration membrane or hyperfiltration membrane assembly by microfiltration membrane or hyperfiltration membrane assembly, with sulfur waste acid are formed, the two stage pump that nano-filtration unit pumps into nanofiltration membrane component by nanofiltration membrane component, with the filtrate of micro-filtration or ultra filtration unit is formed, the import of one-level pump is the opening for feed of body, and outlet connects the inlet of microfiltration membrane or hyperfiltration membrane assembly; The filtrate outlet of microfiltration membrane or hyperfiltration membrane assembly connects the import of two stage pump through storage tank, exports the discharge port into body.
8. according to claim 6 or 7 described recovery systems, it is characterized in that: the outlet of micro-filtration or ultra-filtration membrane cleaning unit connects micro-filtration or ultra filtration unit import; The filter unit inlet is admitted in the outlet of nanofiltration membrane cleaning unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410060943XA CN100469689C (en) | 2004-10-11 | 2004-10-11 | Method and equipment for recovering waste vitriol produced in fabricating pole plates of lead-acid accumulator |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200410060943XA CN100469689C (en) | 2004-10-11 | 2004-10-11 | Method and equipment for recovering waste vitriol produced in fabricating pole plates of lead-acid accumulator |
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| CN1760116A true CN1760116A (en) | 2006-04-19 |
| CN100469689C CN100469689C (en) | 2009-03-18 |
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| CNB200410060943XA Expired - Fee Related CN100469689C (en) | 2004-10-11 | 2004-10-11 | Method and equipment for recovering waste vitriol produced in fabricating pole plates of lead-acid accumulator |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101540395B (en) * | 2009-04-07 | 2011-08-31 | 赵恒祥 | Processing method of waste acid dripping sludge |
| CN103172036A (en) * | 2013-03-27 | 2013-06-26 | 刘立文 | Method for decoloring sulfuric acid by using nanomaterial filter screen |
| CN103643232A (en) * | 2013-12-10 | 2014-03-19 | 天能电池(芜湖)有限公司 | Smearing acid-leaching waste acid recycling device |
| CN104183886A (en) * | 2013-10-12 | 2014-12-03 | 天能电池(芜湖)有限公司 | System for recycling waste acid obtained after formation of lead acid storage battery used in winter |
| CN104183884A (en) * | 2013-07-31 | 2014-12-03 | 天能电池(芜湖)有限公司 | Lead acid storage battery waste acid recycling technology |
| TWI504558B (en) * | 2013-02-05 | 2015-10-21 | High efficiency recovery of nitric acid separation equipment and its method | |
| CN110548338A (en) * | 2019-09-16 | 2019-12-10 | 界首市南都华宇电源有限公司 | Acid liquor collecting device for polar plate production and operation method thereof |
| CN110844890A (en) * | 2019-11-18 | 2020-02-28 | 济源豫光有色冶金设计研究院有限公司 | Resource recycling method of waste sulfuric acid of storage battery |
-
2004
- 2004-10-11 CN CNB200410060943XA patent/CN100469689C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101540395B (en) * | 2009-04-07 | 2011-08-31 | 赵恒祥 | Processing method of waste acid dripping sludge |
| TWI504558B (en) * | 2013-02-05 | 2015-10-21 | High efficiency recovery of nitric acid separation equipment and its method | |
| CN103172036A (en) * | 2013-03-27 | 2013-06-26 | 刘立文 | Method for decoloring sulfuric acid by using nanomaterial filter screen |
| CN104183884A (en) * | 2013-07-31 | 2014-12-03 | 天能电池(芜湖)有限公司 | Lead acid storage battery waste acid recycling technology |
| CN104183886A (en) * | 2013-10-12 | 2014-12-03 | 天能电池(芜湖)有限公司 | System for recycling waste acid obtained after formation of lead acid storage battery used in winter |
| CN104183886B (en) * | 2013-10-12 | 2016-09-07 | 天能电池(芜湖)有限公司 | Spent acid recycling system after being melted into lead-acid accumulator a kind of winter |
| CN103643232A (en) * | 2013-12-10 | 2014-03-19 | 天能电池(芜湖)有限公司 | Smearing acid-leaching waste acid recycling device |
| CN103643232B (en) * | 2013-12-10 | 2016-04-06 | 天能电池(芜湖)有限公司 | A kind of smear drenches the rear waste acid recycling device of acid |
| CN110548338A (en) * | 2019-09-16 | 2019-12-10 | 界首市南都华宇电源有限公司 | Acid liquor collecting device for polar plate production and operation method thereof |
| CN110844890A (en) * | 2019-11-18 | 2020-02-28 | 济源豫光有色冶金设计研究院有限公司 | Resource recycling method of waste sulfuric acid of storage battery |
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| CN100469689C (en) | 2009-03-18 |
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