CN104975168A - Method for rapidly desulfurizing lead-sulfate-containing substances - Google Patents
Method for rapidly desulfurizing lead-sulfate-containing substances Download PDFInfo
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- CN104975168A CN104975168A CN201410128966.3A CN201410128966A CN104975168A CN 104975168 A CN104975168 A CN 104975168A CN 201410128966 A CN201410128966 A CN 201410128966A CN 104975168 A CN104975168 A CN 104975168A
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- lead
- sulfur
- packed bed
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- sulfate
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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
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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
- 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
Abstract
The invention discloses a method for rapidly desulfurizing lead-sulfate-containing substances. The method comprises the following steps: setting the rotation speed of a rotor of a supergravity external-circulating rotary packed bed at 500rpm-2500rpm, simultaneously adding an alkali water solution and the lead-sulfate-containing substances into the supergravity external-circulating rotary packed bed, and reacting for less than or equal to 1 second to obtain turbid liquid, thereby finishing desulfurization; or setting the rotation speed of the rotor of the supergravity external-circulating rotary packed bed at 500rpm-2500rpm, adding the alkali water solution and the lead-sulfate-containing substances into the supergravity external-circulating rotary packed bed, and reacting for 1-4 minutes to obtain turbid liquid, thereby finishing desulfurization. According to the method, lead in lead plaster of waste lead-acid storage batteries can be efficiently recycled; meanwhile, the method has the characteristics of simple processing process and equipment, short reaction time, easiness in operation and the like; the particle sizes of the processed product reach micron level or are even smaller, and the secondary pollution is avoided; the method is applicable to industrial production.
Description
Technical field
The present invention relates to technical field of desulfurization.More specifically, the method for sulfur-bearing lead plumbate material desulfurization rapidly is related to.
Background technology
Since the nineties in last century, China is just the fastest-rising country of plumbous production and consumption always.In the consumption structure of lead, the consumption lead amount of lead-acid cell accounts for about 85% of total plumbous consumption, and China's lead-acid cell output accounts for 1/3 of world wide production.From the eighties in last century, China starts to occur private car, reaches 1,219 ten thousand to social recoverable amount in 2003, and private car breaks through ten million with nearly 20 years, and breaks through 2,000 ten thousand and only used for 3 years.2010, the recoverable amount of China's automobile reached 7,000 ten thousand.By in by the end of August, 2011, national vehicle guaranteeding organic quantity reaches 2.19 hundred million.Along with the continuous growth of automobile pollution, the learies of automobile also increases thereupon, according to statistics, within 2011, China's motor vehicle liquidation amount is more than 4,000,000, expect the year two thousand twenty, China's motor vehicle liquidation amount will reach 1,400 ten thousand, and the lead-acid cell scrapped every year reaches more than 1,500,000 tons.The continuous increase of waste lead acid battery society burden has become a huge renewable secondary lead resource.
Illegal smeltery adopt the native stove soil stove that falls behind and little reverberatory furnace roasting by lead grid and lead plaster mixing, the lead steam of discharging, lead dust and sulfurous gas exceed national standard several times even tens times, and the whole nation every year several ten thousand tons of lead be lost in fusion process, serious environment pollution.
Waste lead acid battery is generally made up of parts such as grid, lead plaster, shell, electrolytic solution, dividing plates, and because each manufacturer manufacturing process is different, the content of each component in store battery is also not quite similar.Through finding the research of some conventional waste lead acid batteries, its constituent mass mark is: grid 24%-30%, lead plaster 30%-40%, dividing plate 2%-3%, plastic casing 5%-7.5%, electrolytic solution 11%-30%.And the lead plaster pulp-like material that mainly active substance is formed after discharge and recharge on pole plate: PbSO
4(about 50%), PbO
2(about 28%), PbO(about 9%), Pb(about 4%) etc., also may containing a small amount of Sb (about 0.5%).Due to the oxide compound of the various valence states of the vitriol and lead that there is a large amount of lead in lead plaster, therefore, the recycling of lead plaster normally lead-acid accumulator recycle the difficult point needing research emphatically.
In the world majority state especially western developed country pay much attention to reclaim secondary lead from waste lead acid battery, according to correlative study data statistics, the industrial level of countries in the world secondary lead is inconsistent, amount of regeneration and the reuse technology level of industrially developed country are higher, the output of secondary lead accounts for 65% of plumbous ultimate production, the U.S. is up to 76.2%, and basically eliminate environmental pollution; Developing country is lower, and lower than 30%, China is 17.5%, and lead recovery is also low, is generally 80%-85%, and low only has about 50%.How improving the rate of recovery plumbous in waste lead acid battery, is a great problem perplexing people at present.
The wet method combined method of pyrogenic process, wet method and pyrogenic process is generally divided into the treatment technology of waste lead acid battery lead cream.There is the shortcomings such as technique is backward, the rate of recovery is low, secondary pollution is serious, energy consumption is large in pyrogenic process.Wet processing lead plaster reclaims the plumbous concern being always subject to secondary lead industry.Wet processing is roughly divided into direct electrowinning method, Indirect Electro area method and non-electrodeposition method.Direct electrowinning method is directly placed in by lead plaster the technology that electrolyzer carries out electrolytic recovery lead.The direct electrowinning method that present stage has developed is Solid phase electrolysis reduction method.Solid phase electrolysis reduction method is that the one utilization that Chemical Industry & Metallrygy Research Office of CAS of China proposes fills NaOH solution electrolyzer, using the various lead compounds in lead plaster as negative electrode, insoluble metal polar plate, as anode, passes to direct current in NaOH solution, the technology of Direct Electrolysis process lead plaster.Due to PbSO in lead plaster
4, PbO
2existence, most of electrodeposition process cannot adopt direct electrowinning process lead plaster, need first lead plaster to be carried out transforming, leach after just can carry out the process of electrodeposition.Indirect electrodeposition process lead plaster technique comprises as RSR technique, USBM technique, CX-EW technique, NaOH-KNaC
4h
4o
6technique etc.These techniques are all first by PbSO
4and PbO
2transform, and then leaching process is carried out to lead plaster, finally adopt electrodeposition method to obtain highly purified lead.Non-electrodeposition method, by Placid technological development, is the wet method combined technique of a kind of pyrogenic process, is to adopt lime precipitation step to replace electrolysis.
High gravity rotating packed bed is the new technology utilizing the many Elevated Gravity larger than earth gravity acceleration to strengthen mass transfer and micro mixing, obtains on earth by rotating the Elevated Gravity of generation simulation.It can increase substantially transformation efficiency and the selectivity of reaction, reduces the volume of reactor significantly, Simplified flowsheet, flow process, implementation procedure energy-efficient.Under Elevated Gravity, molecular diffusion between different sized molecules and interphase mass transfer process are all than in earth gravity after the match faster, flowing contact is produced in solution-air, liquid-liquid, the liquid-solid two-phase porous medium under the Elevated Gravity of large hundreds of times to thousand times than earth gravity field, huge shearing force makes liquid crushing become nano level film, silk and drip, produce phase interface that is huge and that upgrade fast, make to improve 1-3 the order of magnitude in the traditional tower of interphase mass transfer speed ratio, mass transfer process is greatly strengthened.It is as a kind of brand-new engineering, just day by day be subject to the attention of every field scientific worker, it can not only reinforcing mass transfer process, the object of alternate separation can be reached equally because of its powerful centrifugation, material can mix fast in rotating bed, the liquid phase of reaction can be cut into tiny drop by filler, augmenting response area, thus the efficiency of the reaction improved.
In prior art, the method of a Chinese Patent Application No. 200910089686(recovering lead from lead paste of waste lead-acid battery), low-temperature bake-potassium cloride technique is adopted to reclaim plumbous, processing method is simple, but lead reclaims with lead chloride form, and product application scope is little, added value is low, the method also needs through twice press filtration simultaneously, pressure filtration conditions requires strict, and equipment requirements is strict.
The method and apparatus of Footwall drift lead in Chinese Patent Application No. 201010601277(waste lead acid battery lead cream), processed continuously mode is adopted to carry out, treatment process and equipment simple, but treating processes adopts sinter process and uses nitric acid, while increase energy consumption, also there is higher requirement to the erosion resistance of equipment.
Chinese Patent Application No. 201310540070(lead plaster wet method forces sulfur removal technology), by lead plaster being diluted to the ore pulp that mass percent is 10-30%, stir with sodium carbonate at 50-80 DEG C in desulfurization stirred pot afterwards, rely on simultaneously and force devulcanizer (roll extrusion, grinding, hypergravity stir) by large PbSO
4crystalline particle is pulverized, and makes the wet desulphurization time shorten to 60 minutes by 90 minutes.The thinking of this application is on can Formed lead plumbate at sodium carbonate and lead sulfate, in order to the lead carbonate product layer being wrapped in lead sulfate particle exterior surface in sweetening process is pulverized, make lead sulfate fully be exposed in sodium carbonate solution, be therefore provided with pressure devulcanizer when desulfurization is stirred simultaneously.This application Problems existing has: 1) require high to the solid content of lead plaster in ore pulp, the scope of application is little.Because the alkalescence of sodium carbonate is relatively weak, make the speed of reaction of sodium carbonate and lead sulfate slow, when the solid content of lead plaster is more than 30%, the processing mode of this application can cause sodium carbonate can not contact with lead sulfate fully and react, thus makes the decreased effectiveness of reaction.2) require high to temperature of reaction, the scope of application is little.This may be the desulfurization stirred pot because this application uses, and to make in tank reaction can not under well-beaten prerequisite, and carry out of temperature on reaction has impact.3) desulfurization time is still longer, need 60 minutes, possible reason is when the ore pulp after desulfurization process being circulated to pressure devulcanizer process, can not guarantee up hill and dale the carbonic acid lead layer of lead sulfate Surface Creation to be sloughed completely once, fast, this makes sodium carbonate less with contacting of lead sulfate, causes the time of needs long; Also may be for this reason, in this application, the requirement of ore pulp solid content is set within 30%.4) reactor is complicated, needs use desulfur agitator simultaneously and force devulcanizer.
Therefore, need to provide a kind of easy, fast by the method for sulfur-bearing lead plumbate material desulfurization.
Summary of the invention
The technical problem to be solved in the present invention is to provide the method for sulfur-bearing lead plumbate material desulfurization rapidly; By hypergravity outer circulation rotating packed bed rotor speed is set to 500-2500rpm, afterwards the slurry of alkaline aqueous solution and sulfur-bearing lead plumbate material is added in hypergravity outer circulation rotating packed bed simultaneously, reaction times≤1s, obtain suspension liquid, complete desulfurization; Or hypergravity internal recycle rotating packed bed rotor speed is set to 500-2500rpm, adds in hypergravity internal recycle rotating packed bed by the slurry of alkaline aqueous solution and sulfur-bearing lead plumbate material, reaction 1-4min obtains suspension liquid, completes desulfurization; The method can not only reclaim the lead in waste lead acid battery lead cream efficiently, also there is treatment process and equipment is simple, the reaction times is short, the feature such as easy to operate simultaneously, it is even less that product grain size after process reaches micron order, non-secondary pollution, is applicable to suitability for industrialized production.
The present invention adopts following technical proposals:
The method of sulfur-bearing lead plumbate material desulfurization rapidly, comprising:
Hypergravity outer circulation rotating packed bed rotor speed is set to 500-2500rpm, afterwards the slurry of alkaline aqueous solution and sulfur-bearing lead plumbate material is added in hypergravity outer circulation rotating packed bed simultaneously, reaction times≤1s, obtain suspension liquid, complete desulfurization; Added by the slurry of alkaline aqueous solution and sulfur acid material both ensureing simultaneously and complete reaction within the shortest time, if overlong time, in product, by product can be more.
Or
Hypergravity internal recycle rotating packed bed rotor speed is set to 500-2500rpm, adds in hypergravity internal recycle rotating packed bed by the slurry of alkaline aqueous solution and sulfur-bearing lead plumbate material, reaction 1-4min obtains suspension liquid, completes desulfurization;
Frequency modulation speed change instrument is adopted to regulate the rotor speed of rotating packed bed.When rotating speed is lower than this scope, the strengthening effect of reaction is poor; When rotating speed is higher than this scope, equipment can not operate for a long time, affects continuous prodution.This rotating speed cooperatively interacts set with the concentration of alkaline aqueous solution, the solid content etc. of lead sulfate.
The concentration of described alkaline aqueous solution is 2wt%-10wt%;
When the concentration of alkaline aqueous solution is lower than this scope, because alkaline matter content is lower, treatment capacity is reduced, and efficiency is too low; And alkalescence can be made comparatively strong when the excessive concentration of alkaline aqueous solution, pH value is higher, and product lead carbonate or lead hydroxide can not stable existences.The concentration of alkaline aqueous solution cooperatively interacts with used reactor, rotating speed and reaction times etc. to set.When using the reaction of hypergravity outer circulation rotating packed bed, within the most short reaction time, make both react, and the concentration of 2wt%-10wt% alkaline aqueous solution can ensure that in product, by product is less, such as in sodium carbonate system, within the scope of this concentration of lye, the pH value of solution can ensure the stable existence of lead carbonate, if concentration of sodium carbonate exceedes this scope or the reaction times exceedes setting range, reaction can generate by product white lead carbonate, and then the carrying out of impact reaction; Meanwhile, the setting of two kinds of scopes in turn ensure that reaction can be carried out continuously fast, meets the demand of suitability for industrialized production.When using the reaction of hypergravity internal recycle rotating packed bed, concentration of lye avoids in conjunction with same the problem that a large amount of by products that are that cause generate because concentration of lye is too high or the reaction times is long with 1-4min's.
In the slurry of described sulfur-bearing lead plumbate material, the solid content of lead sulfate is 5wt%-80wt%;
Lead sulfate solid content is set as that 5wt%-80wt% is to match with concentration of lye, reaction time range.Within the scope of this, alkali lye can react with lead sulfate fully in the short period of time, takes into account the size of reaction product while ensureing higher reaction desulfuration rate.Because the relative molecular mass of lead sulfate is larger, be insoluble in water again, if solid content exceedes this concentration range, lead sulfate slurry will be caused can not to be injected rotating packed bed continuously by flow pump better react, and also can cause the generation making the problems such as reaction desulfuration rate reduction because solid content is too high simultaneously.If the reaction times is long, then reaction product can be caused to continue to react with alkali lye, generate more by product, reduce the desulfurization degree of reaction, if long reaction time simultaneously, the particle diameter of product also has growth to a certain degree.
In described alkaline aqueous solution and sulfur-bearing lead plumbate material, the mol ratio of lead sulfate is 1-1.2:1.
When mol ratio is lower than this scope, because alkaline matter is less, lead sulfate can not complete reaction, makes reaction effect poor; And when mol ratio is higher than this scope, the alkaline grow of basic solution, the product lead carbonate generated after desulfurization or lead hydroxide can not stable existences, can form plumbite and be dissolved in solution.By controlling the rate of injection of two kinds of reactants to control both mol ratios, impeller pump, peristaltic pump or volume pump band under meter can be adopted to regulate rate of injection.
Preferably, described sulfur-bearing lead plumbate material is the lead plaster of lead acid cell.
More preferably, in the slurry of described sulfur-bearing lead plumbate material, the solid content of lead sulfate is 10wt%-60wt%.
Most preferably, in described lead plaster slurry, the solid content of lead sulfate is 60wt%-80wt%.When this scope, lead sulfate can be processed to greatest extent the most energy-conservationly.
Preferably, described method temperature range applicatory is 10-80 DEG C.Consider that Chinese territory distributes, the temperature contrast in south and the north is obvious, mostly existing process lead plaster is more than 50 DEG C, and this just makes that conditional request is high and energy consumption is high, and adopts during method process lead plaster of the present invention and do not need to a great extent additionally to provide thermal source.
More preferably, temperature range is 20-35 DEG C.Substantially belong to ambient operation in the reaction of this scope or heat a little.
Preferably, described alkaline aqueous solution is one or more the aqueous solution in following material: sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, volatile salt, bicarbonate of ammonia.
After completing desulfurization, obtain for suspension liquid, by suspension liquid after filtration, washing, the operation such as dry, obtain powdered product.Use scanning electron microscope to test to powdered product, the particle diameter of product is between 0.5-2 μm.
Filtrate after filtration uses hydrochloric acid to carry out titration, to determine the transformation efficiency reacted.Used salt acid concentration is 0.01-1mol/L, and the transformation efficiency of reaction is more than 90%.Unnecessary filtrate can again utilize after recovery catalyst reclaims.
The calculation formula of desulfurization degree: illustrate as sweetening agent using sodium carbonate, because the stoichiometry of lead sulfate and sodium carbonate is 1:1, then the desulfurization degree of lead sulfate is similar to the rate of utilization of sodium carbonate, therefore:
C
initial, C
finalfor the volumetric molar concentration of sodium carbonate before and after reaction.
Beneficial effect of the present invention is as follows:
1, the reaction times is short and reaction conversion ratio is high: the present invention, by adopting suitable reactor and arranging suitable rotating speed, under the condition limiting alkaline aqueous solution concentration and lead sulfate solid content, can complete desulfurization in a short period of time.
2, the size controlling of final product of the present invention is good, and only at 0.5-2 μm, applied range, added value are high.
3, the present invention adopt alkaline aqueous solution and due to speed of response fast, almost corrosion-free to reactor, the long service life of reactor; And without the need to carrying out pre-treatment to reactant, without the need to carrying out complicated aftertreatment to product, require low to reaction conditions.
4, conversion unit is simple: only need to buy existing high gravity rotating packed bed, is applicable to suitability for industrialized production.
5, the invention solves existing lead sulfate treatment technology owing to being mixed and the restriction of mass transfer condition, cause reacting the problem that transformation time is long, reaction conversion ratio is low.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is a kind of process flow sheet of hypergravity outer circulation rotating packed bed of the present invention;
Fig. 2 is hypergravity outer circulation rotating packed-bed reactor schematic diagram of the present invention;
Fig. 3 is a kind of process flow sheet of hypergravity internal recycle rotating packed bed of the present invention;
Fig. 4 is hypergravity internal recycle rotating packed-bed reactor schematic diagram of the present invention;
Fig. 5 is the XRD figure that the embodiment of the present invention 1 reacts after product plumbous oxide;
Fig. 6 is the XRD figure that the embodiment of the present invention 5 reacts after product lead carbonate;
Fig. 7 is the scanning electron microscope (SEM) photograph that the embodiment of the present invention 6 reacts after product;
Fig. 8 is the electron microscope picture that the embodiment of the present invention 8 reacts after product.
Numerical markings in accompanying drawing:
101-hypergravity outer circulation rotating packed bed; 102,103,104,105-pump; 106-alkaline solution storage tank; 107-lead sulfate pulp storing tank; 108-reaction product storage tank; 109-filtration unit; 110-washings storage tank; 111-drying installation; 112-filtrate outlet; 113-electric motor; 114-rotor; 115-reaction solution exports; The import of 116-alkaline solution; The import of 117-lead sulfate slurry.
201-hypergravity internal recycle rotating packed bed; 202,203,204,205-pump; 206-lead sulfate pulp storing tank; 207-alkaline solution storage tank; 208-reaction product storage tank; 209-filtration unit; 210-washings storage tank; 211-drying installation; 212-filtrate outlet; 213-electric motor; 214-rotor; 215-import; 216-temperature control chuck; 217-reaction chamber; 218-liquid lifting unit; 219-outlet; 220-liquid distributor; 221-temperature control Jacket outlet; 222-baffle plate; The import of 223-temperature control chuck; 224-cock switch.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiment, the present invention is described further.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
High gravity rotating packed bed reactor used in the present invention is prior art, such as publication (ZL952155430.7); The present invention adopts the reacting flow chart of a kind of embodiment of hypergravity outer circulation rotating packed-bed reactor as shown in Figure 1, and hypergravity outer circulation rotating packed-bed reactor schematic diagram as shown in Figure 2.Embodiment is as follows:
Open hypergravity outer circulation rotating packed bed 101, regulate frequency conversion instrument to corresponding frequency to make the rotating speed of super-gravity device rotor reach preset value.Alkaline aqueous solution in alkaline solution storage tank 106 uses peristaltic pump 102 to squeeze into the aqueous alkaline solution fed mouth 116 of high gravity rotating packed bed; Lead sulfate slurry in lead sulfate pulp storing tank 107 squeezes into the lead sulfate slurry import 117 of high gravity rotating packed bed by peristaltic pump 103.Rotor 114 in super-gravity device is driven by motor 113 and carries out high speed rotating, produces Elevated Gravity; Afterwards, alkaline aqueous solution and lead sulfate slurry are sprayed rear flank and filler in super-gravity device rotor via the liquid distributor on feed-pipe collide and enter in filler, enter the cutting through filler of the alkaline solution of packing layer and lead sulfate slurry, produce a large amount of reaction table area upgraded fast, greatly strengthen the mass transfer process of molecule, Reaction time shorten; After reaction, namely precipitation suspension liquid flows out from the liquid-phase outlet 115 being positioned at super-gravity device bottom, flows into reaction product storage tank 108; Imported in filtration unit 109 through pump 104 by product and filter, the filtrate outlet 112 of filtrate bottom of device is after filtration discharged; After filtration completes, pass into washings 110 pairs of filter cakes by pump 105 and repeatedly wash; Filter cake after washing is obtained final reacting product by moisture eliminator 111 after drying treatment.
Hypergravity internal recycle rotating packed-bed reactor used in the present invention is prior art, the present invention adopts the reacting flow chart of a kind of embodiment of hypergravity internal recycle rotating packed-bed reactor as shown in Figure 3, and hypergravity internal recycle rotating packed-bed reactor schematic diagram as shown in Figure 4.Embodiment is as follows:
Open hypergravity internal recycle rotating packed-bed reactor 201; Rotor 214 in super-gravity device is driven by motor 213 and carries out high speed rotating, produces Elevated Gravity.Alkaline aqueous solution in alkaline solution storage tank 207 uses peristaltic pump 203 to squeeze into the alkaline solution opening for feed 215 of internal recycle rotating packed-bed reactor; Lead sulfate slurry in lead sulfate pulp storing tank 206 squeezes into the lead sulfate slurry import 215 of internal recycle rotating packed-bed reactor by peristaltic pump 202.Reaction raw materials liquid via the lifting of liquid lifting unit 218, carries out hybrid reaction fully in the inner chamber 217 of inner circulation reactor.Afterwards, the precipitation suspension liquid be obtained by reacting flows out from the outlet 219 be positioned at below reaction chamber, flows into reaction product storage tank 208; Imported in filtration unit 209 through pump 204 by product and filter, the filtrate outlet 212 of filtrate bottom of device is after filtration discharged; After filtration completes, pass into washings 210 pairs of filter cakes through pump 205 and repeatedly wash; By the filter cake after washing by moisture eliminator 211, after drying treatment, obtain final reacting product.Outside hypergravity internal recycle rotating packed bed shell, temperature control chuck 216 is set, comprises temperature control chuck import 223 and temperature control Jacket outlet 221.Liquid distributor 220 and baffle plate 222 is also provided with in reactor.
Embodiment 1
By mass concentration be 2% sodium hydroxide solution 500ml add in alkali lye storage tank; Be 40wt% by the lead sulfate slurry 500ml(lead sulfate solid content reacted with sodium hydroxide solution equimolar ratio) add in slurry storage tank.
Open hypergravity outer circulation rotating packed bed, adjusting rotary speed is to 1100rpm;
Open fresh feed pump, sodium hydroxide solution and lead sulfate slurry are delivered in rotating bed simultaneously and react, control sodium hydroxide solution and lead sulfate slurry feed flow are 1100ml/min, and the temperature controlling reaction system is 20 DEG C of reactions;
Deng sodium hydroxide solution with after lead sulfate slurry feed is complete, suspension liquid all flows out high gravity rotating packed bed, close hypergravity outer circulation rotating packed bed, the suspension liquid of gained is carried out suction filtration process, after filtration, washing, obtains final reacting product after drying.Use the hydrochloric acid of 0.1mol/L to carry out titration to filtrate after filtration, record lead sulfate desulfurization degree and reach 96.7%, products obtained therefrom particle diameter is 0.5-2 μm.
Fig. 5 is the XRD figure that the embodiment of the present invention 1 reacts after product plumbous oxide.
Embodiment 2
With embodiment 1, change is: sodium hydroxide mass concentration is 6%, excessive 5%, and use the HCI of 0.2mol/L, record lead sulfate desulfurization degree and reach 98.7%, products obtained therefrom particle diameter is 0.5-2 μm.
Embodiment 3
With embodiment 1, change is: functional quality concentration is the potassium hydroxide solution replacement sodium hydroxide of 4%; Record lead sulfate desulfurization degree and reach 96.3%, products obtained therefrom particle diameter is 0.5-2 μm.
Embodiment 4
With embodiment 1, change is: use the mass concentration of excessive 5% be 8% potassium hydroxide solution replace sodium hydroxide; Use the hydrochloric acid of 0.01mol/L to carry out titration to filtrate after filtration, record lead sulfate desulfurization degree and reach 99.4%, products obtained therefrom particle diameter is 0.5-1 μm.
Embodiment 5
By mass concentration be 8.04% sodium carbonate solution 500ml add in alkali lye storage tank; Be 50wt% by the lead sulfate slurry 500ml(lead sulfate solid content reacted with sodium carbonate solution equimolar ratio) add in slurry storage tank.
Open hypergravity outer circulation rotating packed bed, adjusting rotary speed is to 2000rpm;
Open fresh feed pump, sodium carbonate solution and lead sulfate slurry are delivered in rotating bed simultaneously and react, control sodium carbonate solution and lead sulfate slurry feed flow are 1500ml/min, and the temperature controlling reaction system is 20 DEG C of reactions 1 second;
Deng sodium carbonate solution with after lead sulfate slurry feed is complete, suspension liquid all flows out high gravity rotating packed bed, close hypergravity outer circulation rotating packed bed; The suspension liquid of gained is carried out suction filtration process, after filtration, washing, obtains final reacting product after drying.Use the hydrochloric acid of 0.09mol/L to carry out titration to filtrate after filtration, record lead sulfate desulfurization degree and reach 96.0%, products obtained therefrom particle diameter is 1-2 μm.
Fig. 6 is the XRD figure that the embodiment of the present invention 5 reacts after product lead carbonate.
Embodiment 6
With embodiment 1, change is: use the mass concentration of excessive 20% be 8% sodium carbonate solution replace sodium hydroxide; Use the hydrochloric acid of 0.08mol/L to carry out titration to filtrate after filtration, record lead sulfate desulfurization degree and reach 96.2%, products obtained therefrom particle diameter is 1-2 μm.
Fig. 7 is the scanning electron microscope (SEM) photograph that the embodiment of the present invention 6 reacts after product.
Embodiment 7
By mass concentration be 6% sodium hydrogen carbonate solution 500ml add in alkali lye storage tank; Be 60wt% by the lead sulfate slurry 500ml(lead sulfate solid content reacted with sodium hydrogen carbonate solution equimolar ratio) add in slurry storage tank.
Open hypergravity internal recycle rotating packed bed, adjusting rotary speed is to 2240rpm;
Open fresh feed pump, sodium hydrogen carbonate solution and lead sulfate slurry are delivered in rotating bed simultaneously and react, control sodium hydrogen carbonate solution and lead sulfate slurry feed flow are 1500ml/min, the temperature controlling reaction system is 20 DEG C, after sodium hydrogen carbonate solution and lead sulfate slurry feed, reaction 2min.
After gained suspension liquid all flows out, close hypergravity internal recycle rotating packed bed; The suspension liquid of gained is carried out suction filtration process, after filtration, washing, obtains final reacting product after drying.Use the hydrochloric acid of 0.10mol/L to carry out titration to filtrate after filtration, recording lead sulfate desulfurization degree is 96%, and products obtained therefrom particle diameter is 0.5-2 μm.
Embodiment 8
With embodiment 7, change is: functional quality concentration is the solution of potassium carbonate replacement sodium bicarbonate of 5%; Use the hydrochloric acid of 0.13mol/L to carry out titration to filtrate after filtration, recording lead sulfate desulfurization degree is 97.2%, and products obtained therefrom particle diameter is 0.5-1 μm.
Fig. 8 is the electron microscope picture that the embodiment of the present invention 8 reacts after product.
Embodiment 9
With embodiment 7, change is: functional quality concentration is the sal volatile replacement sodium bicarbonate of 8.04%; Use the hydrochloric acid of 0.15mol/L to carry out titration to filtrate after filtration, recording lead sulfate desulfurization degree is 96.1%, and products obtained therefrom particle diameter is 0.5-2 μm.
The changing conditions of material component before and after table 1 embodiment 1-9 reacts
Embodiment 10
The method of sulfur-bearing lead plumbate material desulfurization rapidly, comprising:
Hypergravity outer circulation rotating packed bed rotor speed is set to 2500rpm, afterwards the slurry of alkaline aqueous solution and sulfur-bearing lead plumbate material is added in hypergravity outer circulation rotating packed bed simultaneously, be obtained by reacting suspension liquid, complete desulfurization
The concentration of described alkaline aqueous solution is 10wt%;
In the slurry of described sulfur-bearing lead plumbate material, the solid content of lead sulfate is 80wt%;
In described alkaline aqueous solution and sulfur-bearing lead plumbate material, the mol ratio of lead sulfate is 1.2:1.
The temperature range of described method is 10 DEG C.
After completing desulfurization, obtain for suspension liquid, by suspension liquid after filtration, washing, dry, obtain powdered product.Result is similar to Example 1.
Embodiment 11
The method of sulfur-bearing lead plumbate material desulfurization rapidly, comprising:
Hypergravity outer circulation rotating packed bed rotor speed is set to 500rpm, afterwards the slurry of alkaline aqueous solution and sulfur-bearing lead plumbate material is added in hypergravity outer circulation rotating packed bed simultaneously, be obtained by reacting suspension liquid, complete desulfurization;
The concentration of described alkaline aqueous solution is 2wt%;
In the slurry of described sulfur-bearing lead plumbate material, the solid content of lead sulfate is 5wt%;
In described alkaline aqueous solution and sulfur-bearing lead plumbate material, the mol ratio of lead sulfate is 1:1.
Preferably, described method temperature is 80 DEG C.
After completing desulfurization, obtain for suspension liquid, by suspension liquid after filtration, washing, dry, obtain powdered product.Result is similar to Example 1.
Embodiment 12
With embodiment 10, difference is, rotor speed is 1500rpm, and the concentration of alkaline aqueous solution is 6wt%; In the slurry of sulfur-bearing lead plumbate material, the solid content of lead sulfate is 60wt%; In alkaline aqueous solution and sulfur-bearing lead plumbate material, the mol ratio of lead sulfate is 1.1:1; Described sulfur-bearing lead plumbate material is the lead plaster of lead acid cell; Temperature is 20 DEG C.Alkaline aqueous solution is ammoniacal liquor.After completing desulfurization, obtain for suspension liquid, by suspension liquid after filtration, washing, dry, obtain powdered product.Result is similar to Example 1.
Embodiment 13
The method of sulfur-bearing lead plumbate material desulfurization rapidly, comprising:
Be 500rpm by hypergravity internal recycle rotating packed bed rotor speed, by potassium bicarbonate solution (10wt%) and lead acid cell lead plaster slurry, (in slurry, the solid content of lead sulfate is 40wt%, both mol ratios are 1.2:1) add in hypergravity internal recycle rotating packed bed, reaction 1-4min obtains suspension liquid, completes desulfurization; Temperature is 35 DEG C.After completing desulfurization, obtain for suspension liquid, by suspension liquid after filtration, washing, the operation such as dry, obtain powdered product.Result is similar to Example 1.
Embodiment 14
Identical with embodiment 13, difference is: rotor speed is 2500rpm, and potassium bicarbonate solution bicarbonate of ammonia replaces.Result is similar to Example 1.
Embodiment 15
Identical with embodiment 13, difference is: potassium bicarbonate solution ammoniacal liquor (5wt%) and ammonium bicarbonate solution (4wt%) (blending ratio 1:2) replace.Result is similar to Example 1.
Embodiment 16
Identical with embodiment 13, difference is: potassium bicarbonate solution sodium hydroxide solution (3wt%), potassium bicarbonate solution (10wt%) and sal volatile (2wt%) (blending ratio 1:2:1) replacement.Result is similar to Example 1.
Embodiment 17
Using sodium carbonate (concentration is for 6wt%) as sweetening agent, with lead plaster slurry (lead sulfate solid content 20wt%, amount ratio are 1.1:1), rotating speed 1500rpm, outer circulation reacts 1 second, and internal recycle reacts 2 minutes.Test differing temps, on the impact of reaction result, the results are shown in Table 2.
Table 2 sodium carbonate as sweetening agent, the reaction result of differing temps
Embodiment 18
Using sodium hydroxide as sweetening agent, with lead plaster slurry (solid content 20wt%, amount ratio are 1.1:1), rotating speed 1500rpm, outer circulation reacts 1 second, and internal recycle reacts 2 minutes, temperature of reaction 25 DEG C.Test the impact of different concentration of lye on reaction result, the results are shown in Table 3.
Table 3 sodium hydroxide as sweetening agent, the reaction result of different concentration of lye
Embodiment 19
Using sodium carbonate (concentration is for 6wt%) as sweetening agent, with lead plaster slurry (solid content 20wt%, amount ratio is 1.1:1) at rotating speed 1500rpm, 1 second outer circulation reaction times, 2 minutes internal recycle reaction times, temperature of reaction 25 DEG C, the different solid contents of test lead plaster, on the impact of reaction result, the results are shown in Table 4.
Table 4 sodium carbonate as sweetening agent, the reaction result of different solid content
Embodiment 20
Using sodium hydroxide (concentration is for 6wt%) as sweetening agent, with lead plaster slurry (amount ratio is 1.1:1, solid content 20wt%) temperature of reaction 25 DEG C, 1 second outer circulation reaction times, 2 minutes internal recycle reaction times.Test different rotor rotating speed, on the impact of reaction result, the results are shown in Table 5.
Table 5 sodium hydroxide as sweetening agent, the reaction result of different rotor rotating speed
Embodiment 21
Using sodium carbonate (concentration is for 6wt%) as sweetening agent, with lead plaster slurry (amount ratio is 1.1:1, solid content 20wt%) temperature of reaction 25 DEG C, rotating speed 1500rpm.The test differential responses time, on the impact of reaction result, the results are shown in Table 6-1 and table 6-2.
Sodium carbonate as sweetening agent, the reaction result of differential responses time
Table 6-1
Table 6-2
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (8)
1. the method for sulfur-bearing lead plumbate material desulfurization rapidly, is characterized in that, comprising:
Hypergravity outer circulation rotating packed bed rotor speed is set to 500-2500rpm, afterwards the slurry of alkaline aqueous solution and sulfur-bearing lead plumbate material is added in hypergravity outer circulation rotating packed bed simultaneously, reaction times≤1s, obtain suspension liquid, complete desulfurization; Or
Hypergravity internal recycle rotating packed bed rotor speed is set to 500-2500rpm, adds in hypergravity internal recycle rotating packed bed by the slurry of alkaline aqueous solution and sulfur-bearing lead plumbate material, reaction 1-4min obtains suspension liquid, completes desulfurization;
The concentration of described alkaline aqueous solution is 2wt%-10wt%;
In the slurry of described sulfur-bearing lead plumbate material, the solid content of lead sulfate is 5wt%-80wt%;
In described alkaline aqueous solution and sulfur-bearing lead plumbate material, the mol ratio of lead sulfate is 1-1.2:1.
2. the method for sulfur-bearing lead plumbate material desulfurization rapidly according to claim 1, is characterized in that, preferably, described sulfur-bearing lead plumbate material is the lead plaster of lead acid cell.
3. the method for sulfur-bearing lead plumbate material desulfurization rapidly according to claim 1, is characterized in that, preferably, in the slurry of described sulfur-bearing lead plumbate material, the solid content of lead sulfate is 10wt%-60wt%.
4. the method for the sulfur-bearing lead plumbate material desulfurization rapidly according to claim 1 or 3, is characterized in that, preferably, in described lead plaster slurry, the solid content of lead sulfate is 60wt%-80wt%.
5. the method for sulfur-bearing lead plumbate material desulfurization rapidly according to claim 1, is characterized in that, the temperature range that described method is suitable for is 10-80 DEG C.
6. the method for sulfur-bearing lead plumbate material desulfurization rapidly according to claim 5, is characterized in that, preferably, temperature range is 20-35 DEG C.
7. the method for sulfur-bearing lead plumbate material desulfurization rapidly according to claim 1, it is characterized in that, preferably, described alkaline aqueous solution is one or more the aqueous solution in following material: sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, volatile salt, bicarbonate of ammonia.
8. the method for lead plaster desulfurization rapidly according to claim 1, is characterized in that, by suspension liquid after filtration, washing, dry, obtain powdered product.
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| CN105420489A (en) * | 2015-11-28 | 2016-03-23 | 湘潭大学 | Diachylon desulphurization method based on throttling self-collision |
| CN105655661A (en) * | 2016-01-06 | 2016-06-08 | 湘潭大学 | Lead plaster pre-desulphurization method based on limestone |
| CN106282540A (en) * | 2016-08-25 | 2017-01-04 | 安徽华铂再生资源科技有限公司 | Lead metal low energy consumption high-efficiency recovery process in lead plaster |
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| CN109694955A (en) * | 2019-02-20 | 2019-04-30 | 湘潭大学 | A kind of pre- sulfur method of lead plaster based on the double alkali of sodium calcium |
| CN113846223A (en) * | 2021-10-16 | 2021-12-28 | 安徽省华鑫铅业集团有限公司 | Method for desulfurizing, processing and recycling lead slime of waste battery |
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