CN106337112A - Wet low-liquid-solid-ratio desulfurization process for waste lead-acid storage battery lead plaster - Google Patents
Wet low-liquid-solid-ratio desulfurization process for waste lead-acid storage battery lead plaster Download PDFInfo
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- CN106337112A CN106337112A CN201610725307.7A CN201610725307A CN106337112A CN 106337112 A CN106337112 A CN 106337112A CN 201610725307 A CN201610725307 A CN 201610725307A CN 106337112 A CN106337112 A CN 106337112A
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- lead
- ore pulp
- desulfurization
- solid
- lead plaster
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Secondary Cells (AREA)
Abstract
A wet low-liquid-solid-ratio desulfurization process for waste lead-acid storage battery lead plaster comprises the steps that (1) the waste lead plaster generated during waste lead-acid battery assembling is collected, and according to the different sulfur contents of the waste lead plaster, the waste lead plaster is added with water in a reaction still to be prepared into ore pulp with the mass fraction ranging from 35% to 65%, wherein strong convection can be formed in the reaction still; (2) Na2CO3 is added into the ore pulp in the step (1), wherein the adding quantity of the Na2CO3 is 1.3-1.4 times the theoretical quantity, constant stirring is carried out for 25 min to 35 min after sodium carbonate is added, and no heating is needed in the process; (3) the ore pulp is placed in equipment with the functions of strong impacting, extruding and friction to react, a PbCO3 layer applied to the surface of PbSO4 is opened in the desulfurization process, and the PbSO4 is in full contact with the Na2CO3 in a solution; and (4) after reacting is carried out for 20 min to 30 min, a reactant is subjected to solid-liquid separation, and desulfurization mother liquor, desulfurized lead plaster and desulfurized lead plaster washing water are obtained. According to the wet low-liquid-solid-ratio desulfurization process, high-temperature roasting is not needed, and energy consumption is low; no secondary pollutants such as lead dust and SO2 are generated; desulfurization is achieved at a time; the desulfurization rate is higher than or equal to 99%; and green and efficient recycling is achieved.
Description
Technical field
The present invention relates to reviver technical field is and in particular to a kind of wet method, low liquid-solid ratio waste lead acid battery lead cream take off
Sulfur technique.
Background technology
Although various battery new techniques are evolving now, have the lead-acid battery of 150 years development history still with
By means of its excellent cost performance, stable chemical property, ripe production technology and its higher recycling of waste product etc.
Advantage occupies first place in secondary cell market.The sustainable growth of annual production had both represented the importance to the mankind for the lead-acid battery,
Mean have substantial amounts of lead to be consumed on lead-acid accumulator product every year.
Lead-acid accumulator, as the main consumer products in the whole world, also becomes topmost lead regenerated resources simultaneously.China
The primary raw material of reviver has more than 80% to be derived from waste and old lead acid accumulator.Lead as a kind of highly toxic heavy metal, from environmental protection
From the point of view of, the recycling to lead in waste and old lead acid accumulator is significant.
The recovery process of lead-acid battery scrap lead cream at this stage is broadly divided into: pyrometallurgical smelting technique and wet recycling process.
Pyrometallurgical smelting technique can produce the secondary pollutions such as lead dust and sulfur dioxide in heating process, and high energy consumption, utilization rate are low.Wet
Method recovery process useless diachylon desulphurization method the most frequently used at present is with na2co3Or nahco3For desulfurizing agent, stirring reaction makes it take off
Sulfur, by pbso4It is converted into pbco3, then Hydrocerussitum (Ceruse) is obtained to its roasting or electrolysis.Chinese patent literature cn103880630a and
Cn103771459a etc. is all using the method, but the method, when adding desulfurizing agent excessive (ph 10), can produce impurity napb2
(co3)2oh；When desulfurizing agent is not enough, have part pbso again4Cannot desulfurization.Chinese patent literature cn103523820a is using containing
Amino material and the method for carbonaceous material desulfurization, make the desulfurization degree of scrap lead cream reach 99%；Chinese patent literature
Cn103374657a adopts the sulfur method of the compound desulfuration solution that the molar ratio of sodium carbonate and sodium bicarbonate is 1:2, makes to give up
The desulfurization degree of lead plaster has reached more than 98.5%.Above sulfur removal technology obtains target product after needing roasting or electrolysis, and flow process is longer,
There is the shortcomings of, high energy consumption high to production equipment requirements, long flow path.
Content of the invention
The technical problem to be solved is to provide a kind of method simple, and the good wet method of desulfurized effect, low liquid are solid
Ratio lead plaster sulfur removal technology.
The technical problem to be solved employs the following technical solutions to realize:
A kind of wet method, low liquid-solid ratio waste lead acid battery lead cream sulfur removal technology, comprise the following steps that:
(1) collect the scrap lead cream that waste lead acid battery disassembles middle generation, according to the difference of scrap lead cream sulfur content, can formed
In the reactor of strong convection, scrap lead cream is added water and be configured to the ore pulp of mass fraction 55%-75%；
(2) to addition na interior in the ore pulp of step (1)2co3, wherein na2co3Addition be according to waste diachylon sulfur-bearing
1.3-1.4 times of the theoretical amount that amount calculates, adds continuous stirring 25-35 minute after sodium carbonate, and process does not need to heat；
(3) ore pulp is put in the equipment that can produce strong impaction, extruding, rubbing action and reacted, utilize simultaneously
High-concentration ore slurry material particles form frictional force, will apply in pbso in sweetening process4The pbco on surface3Layer open, makes pbso4?
With na in solution2co3Being fully contacted, thus improving desulfuration efficiency, reaching the purpose forcing desulfurization；
(4), after reaction 20-30 minute, solid-liquid separation is carried out to reactant, obtains desulphurization mother solution and desulfurization lead plaster, wherein de-
Unnecessary na in sulfur mother solution2co3Removed using the lead sulfate in waste diachylon lead plaster, remove unnecessary na2co3Desulphurization mother solution straight
Connect desalination, desulfurization lead plaster wash water uses as configuring new doctor solution, can be, in return to step (1), to be used for preparing ore pulp.
The invention has the beneficial effects as follows: compared with other more advanced regeneration lead plaster recovery process domestic and international, the present invention sets
Standby and Factory Building expense is low, and capital expenditure saves, doctor solution cycle-index is few, and process water amount is little, and water process expense is low, once takes off
Sulfur rate >=99%, reaches green high-efficient and reclaims.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention realizes are easy to understand, tie below
Close specific embodiment, the present invention is expanded on further.
Embodiment 1
A kind of wet method, low liquid-solid ratio waste lead acid battery lead cream sulfur removal technology, comprise the following steps that:
(1) collect the scrap lead cream that waste lead acid battery disassembles middle generation, according to the difference of scrap lead cream sulfur content, can formed
In the reactor of strong convection, scrap lead cream is added water and be configured to the ore pulp of mass fraction 55%；
(2) to addition na interior in the ore pulp of step (1)2co3, wherein na2co3Addition be theoretical amount 1.3-1.4
Times, after adding sodium carbonate, after 25 minutes, process does not need to heat continuous stirring；
(3) ore pulp is put into one to be reacted with strong impaction, extruding, the equipment of rubbing action, utilize height simultaneously
Concentration ore pulp material particles form frictional force, will apply in pbso in sweetening process4The pbco on surface3Layer open, makes pbso4Molten
With na in liquid2co3Being fully contacted, thus improving desulfuration efficiency, reaching the purpose forcing desulfurization；
(4), after reacting 20 minutes, solid-liquid separation is carried out to reactant, obtains desulphurization mother solution and desulfurization lead plaster, wherein desulfurization
Unnecessary na in mother solution2co3Removed using lead plaster, remove unnecessary na2co3The direct desalination of desulphurization mother solution, desulfurization lead plaster wash water make
Use for configuring new doctor solution, can be, in return to step (1), to be used for preparing ore pulp.
Embodiment 2
A kind of wet method, low liquid-solid ratio waste lead acid battery lead cream sulfur removal technology, comprise the following steps that:
(1) collect the scrap lead cream that waste lead acid battery disassembles middle generation, according to the difference of scrap lead cream sulfur content, can formed
In the reactor of strong convection, scrap lead cream is added water and be configured to the ore pulp of mass fraction 65%；
(2) to addition na interior in the ore pulp of step (1)2co3, wherein na2co3Addition be theoretical amount 1.3-1.4
Times, after adding sodium carbonate, after 30 minutes, process does not need to heat continuous stirring；
(3) ore pulp is put into one to be reacted with strong impaction, extruding, the equipment of rubbing action, utilize height simultaneously
Concentration ore pulp material particles form frictional force, will apply in pbso in sweetening process4The pbco on surface3Layer open, makes pbso4Molten
With na in liquid2co3Being fully contacted, thus improving desulfuration efficiency, reaching the purpose forcing desulfurization；
(4), after reacting 25 minutes, solid-liquid separation is carried out to reactant, obtains desulphurization mother solution and desulfurization lead plaster, wherein desulfurization
Unnecessary na in mother solution2co3Removed using lead plaster, remove unnecessary na2co3The direct desalination of desulphurization mother solution, desulfurization lead plaster wash water make
Use for configuring new doctor solution, can be, in return to step (1), to be used for preparing ore pulp.
Embodiment 3
A kind of wet method, low liquid-solid ratio waste lead acid battery lead cream sulfur removal technology, comprise the following steps that:
(1) collect the scrap lead cream that waste lead acid battery disassembles middle generation, according to the difference of scrap lead cream sulfur content, can formed
In the reactor of strong convection, scrap lead cream is added water and be configured to the ore pulp of mass fraction 75%；
(2) to addition na interior in the ore pulp of step (1)2co3, wherein na2co3Addition be theoretical amount 1.3-1.4
Times, after adding sodium carbonate, after 35 minutes, process does not need to heat continuous stirring；
(3) ore pulp is put into one to be reacted with strong impaction, extruding, the equipment of rubbing action, utilize height simultaneously
Concentration ore pulp material particles form frictional force, will apply in pbso in sweetening process4The pbco on surface3Layer open, makes pbso4Molten
With na in liquid2co3Being fully contacted, thus improving desulfuration efficiency, reaching the purpose forcing desulfurization；
(4), after reacting 30 minutes, solid-liquid separation is carried out to reactant, obtains desulphurization mother solution and desulfurization lead plaster, wherein desulfurization
Unnecessary na in mother solution2co3Removed using lead plaster, remove unnecessary na2co3The direct desalination of desulphurization mother solution, desulfurization lead plaster wash water make
Use for configuring new doctor solution, can be, in return to step (1), to be used for preparing ore pulp.
It should be understood by those skilled in the art that, the present invention is not restricted to the described embodiments, above-described embodiment and explanation
Merely illustrating the principles of the invention described in book, without departing from the spirit and scope of the present invention, the present invention also has
Various changes and modifications, these changes and improvements both fall within scope of the claimed invention.Claimed scope
By appending claims and its equivalent thereof.
Claims (5)
1. a kind of wet method, low liquid-solid ratio waste lead acid battery lead cream sulfur removal technology are it is characterised in that comprise the following steps that:
(1) collect the scrap lead cream that waste lead acid battery disassembles middle generation, according to the difference of scrap lead cream sulfur content, right by force being formed
In the reactor of stream, scrap lead cream is added water and be configured to the ore pulp of mass fraction 55%-75%；
(2) to addition na interior in the ore pulp of step (1)2co3, wherein na2co3Addition be 1.3-1.4 times of theoretical amount, plus
Continuous stirring 25-35 minute after complete sodium carbonate, process does not need to heat；
(3) ore pulp is put into one to be reacted with strong impaction, extruding, the equipment of rubbing action, utilize high concentration simultaneously
Ore pulp material particles form frictional force, will apply in pbso in sweetening process4The pbco on surface3Layer open, makes pbso4In the solution
With na2co3It is fully contacted；
(4), after reaction 20-30 minute, solid-liquid separation is carried out to reactant, obtains the desulphurization mother solution containing sodium carbonate and desulfurization lead
Cream.
2. a kind of wet method according to claim 1, low liquid-solid ratio waste lead acid battery lead cream sulfur removal technology, its feature exists
In unnecessary na in above-mentioned desulphurization mother solution2co3Removed using lead plaster, remove unnecessary na2co3The direct desalination of desulphurization mother solution.
3. a kind of wet method according to claim 2, low liquid-solid ratio waste lead acid battery lead cream sulfur removal technology, its feature exists
Use as configuring new doctor solution in, the desulphurization mother solution after above-mentioned desalination and desulfurization lead plaster wash water, in return to step (1), be used for
Prepare ore pulp.
4. a kind of wet method according to claim 1, low liquid-solid ratio waste lead acid battery lead cream sulfur removal technology, its feature exists
In the connection mixing time in above-mentioned steps (2) is 30 clocks.
5. a kind of wet method according to claim 1, low liquid-solid ratio waste lead acid battery lead cream sulfur removal technology, its feature exists
In in above-mentioned steps (4), the response time is 25 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610725307.7A CN106337112A (en) | 2016-08-25 | 2016-08-25 | Wet low-liquid-solid-ratio desulfurization process for waste lead-acid storage battery lead plaster |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610725307.7A CN106337112A (en) | 2016-08-25 | 2016-08-25 | Wet low-liquid-solid-ratio desulfurization process for waste lead-acid storage battery lead plaster |
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| CN106337112A true CN106337112A (en) | 2017-01-18 |
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| CN201610725307.7A Pending CN106337112A (en) | 2016-08-25 | 2016-08-25 | Wet low-liquid-solid-ratio desulfurization process for waste lead-acid storage battery lead plaster |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106834734A (en) * | 2017-03-18 | 2017-06-13 | 江西理工大学 | A kind of agitating ball mill high-efficiency desulfurization method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3612491A1 (en) * | 1986-04-14 | 1987-10-15 | Preussag Ag Metall | Process for recovering lead from oxidic or oxidic/sulphatic secondary precursor materials |
| US4769116A (en) * | 1986-01-09 | 1988-09-06 | Engitec Impianti S.P.A. | Hydrometallurgical process for an overall recovery of the components of exhausted lead-acid batteries |
| CN101244831A (en) * | 2008-03-18 | 2008-08-20 | 华中科技大学 | Method and device for recycling anhydrous sodium sulfate from desulfurization lead plaster filter liquor |
| CN102351217A (en) * | 2011-06-21 | 2012-02-15 | 南京大学 | Method of removing lead in by-product sodium sulfate of recovery and processing of waste lead storage batteries |
| CN104192869A (en) * | 2014-08-25 | 2014-12-10 | 湖南江冶机电科技股份有限公司 | Purification method and device of desulfurization lead plaster filtrate |
| CN104263944A (en) * | 2014-09-29 | 2015-01-07 | 湖南江冶机电科技股份有限公司 | Lead paste desulfurization method based on grinding mechanism |
| CN105420489A (en) * | 2015-11-28 | 2016-03-23 | 湘潭大学 | Diachylon desulphurization method based on throttling self-collision |
-
2016
- 2016-08-25 CN CN201610725307.7A patent/CN106337112A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4769116A (en) * | 1986-01-09 | 1988-09-06 | Engitec Impianti S.P.A. | Hydrometallurgical process for an overall recovery of the components of exhausted lead-acid batteries |
| DE3612491A1 (en) * | 1986-04-14 | 1987-10-15 | Preussag Ag Metall | Process for recovering lead from oxidic or oxidic/sulphatic secondary precursor materials |
| CN101244831A (en) * | 2008-03-18 | 2008-08-20 | 华中科技大学 | Method and device for recycling anhydrous sodium sulfate from desulfurization lead plaster filter liquor |
| CN102351217A (en) * | 2011-06-21 | 2012-02-15 | 南京大学 | Method of removing lead in by-product sodium sulfate of recovery and processing of waste lead storage batteries |
| CN104192869A (en) * | 2014-08-25 | 2014-12-10 | 湖南江冶机电科技股份有限公司 | Purification method and device of desulfurization lead plaster filtrate |
| CN104263944A (en) * | 2014-09-29 | 2015-01-07 | 湖南江冶机电科技股份有限公司 | Lead paste desulfurization method based on grinding mechanism |
| CN105420489A (en) * | 2015-11-28 | 2016-03-23 | 湘潭大学 | Diachylon desulphurization method based on throttling self-collision |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106834734A (en) * | 2017-03-18 | 2017-06-13 | 江西理工大学 | A kind of agitating ball mill high-efficiency desulfurization method |
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Application publication date: 20170118 |