CN101318692B - Method for preparing high quality lead dioxide with plumbum mud in waste lead acid accumulator - Google Patents
Method for preparing high quality lead dioxide with plumbum mud in waste lead acid accumulator Download PDFInfo
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- CN101318692B CN101318692B CN2007100350537A CN200710035053A CN101318692B CN 101318692 B CN101318692 B CN 101318692B CN 2007100350537 A CN2007100350537 A CN 2007100350537A CN 200710035053 A CN200710035053 A CN 200710035053A CN 101318692 B CN101318692 B CN 101318692B
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Abstract
The invention relates to a method for preparing high-quality lead dioxide through lead slime of waste lead acid storage batteries, comprising the following steps that: the lead slime in the waste lead acid storage batteries is taken out, washed repeatedly to neutrality, dried, and crushed into lead slime powder the granularity of which is over 200 meshes; the lead slime powder is mixed with a water solution which contains a dispersant and a desulfurizer according to a certain proportion, and then the mixture is fully stirred and desulfurized for 1 to 24 hours at a room temperature of 90 DEG C; separation is performed to remove a liquid part, and lead-bearing solid materials obtained are fully dried; the lead-bearing solid materials are mixed with a water solution which contains oxidant according to a certain proportion, and the mixture is fully stirred and oxidized for 1 to 2 hours at a room temperature of 90 DEG C; and separation is performed to remove a liquid part, and a solid part obtained is the lead dioxide after washing and drying. The method prepares the lead dioxide through the lead slime in the waste lead acid storage batteries, and has low cost and energy consumption, simple equipment, and high lead recovery rate and product quality of the lead dioxide.
Description
Technical field
The present invention relates to by the plumbous clay method that is equipped with the high quality plumbic oxide in the lead-acid accumulator.
Background technology
Lead occupies critical role in the national economic development, be one of non-ferrous metal that purposes is the widest, consumption is maximum.Lead is again worldwide short resource, and China is particularly outstanding.Plumbous still one of deleterious heavy metal, plumbous pollution has become global environmental problem.
Along with rapid development of social economy, plumbous demand is continuing increase, and problems such as lead resource waste that is brought after being discarded by leadwork production process and use and environmental pollution are also being aggravated.Lead acid cell is plumbous maximum user, and the plumbous consumption that is used to make lead acid cell in developed country accounts for more than 80% of total plumbous consumption, and China also surpasses 50%, and its ratio is also improving constantly.China has nearly 1,000,000 tons of lead-acid accumulators to produce every year at present, yet its recovery utilization rate is less than 90% still, and developed country best near 100%, waste lead accumulator has become secondary lead and has produced the main source of Lead contamination, scientifically carry out plumbous recycling utilization, the produced quantity of lead ore be can reduce on the one hand, effectively lead resource shortage and control Lead contamination alleviated, produce secondary lead on the other hand, its energy consumption only for producing 25～30% of primary lead energy consumption, can significantly reduce plumbous production cost.Developed country's secondary lead accounts for more than 80% of plumbous total amount at present, and China is still less than 30%.
Lead-acid accumulator is made up of plastic casing, sulfur waste acid, lead electrode plate, plumbous grid, lead joint the end of a thread, scrap lead mud, wherein the first five kind component all can be recycled by the simple physics process, the recycling of plumbous mud then difficulty is bigger, has become the key problem in technology and the difficult point of lead-acid accumulator efficient recovery comprehensive utilization.Plumbous mud accounts for 30～35% of lead-acid accumulator gross weight, and main component is lead sulfate and a small amount of lead powder, yellow lead oxide and plumbic oxide, and wherein lead content reaches 75%.The recycling of relevant plumbous mud mainly contains three kinds of technologies in the world at present, that is: pyrometallurgical smelting, wet processing and dried-wet method combined processing, and its finished product are metallic lead.Pyrometallurgical smelting is the method that present most countries adopts, and technical process is based on soda, iron filings method.The shortcoming that this method is outstanding be smelting temperature up to more than 1350 ℃, energy consumption is big, plumbous volatilization is serious, lead recovery low (70～90%), the wasting of resources is big, also has SO simultaneously
2Emission problem, therefore, economic benefit is lower, and brings environmental pollution.Improved pyrogenic attack technology is to adopt many smelting furnaces associating pyrogenic attack, and the plumbous rate of recovery has obtained bigger raising.Adopt secondary reflection stove/blast furnace combined process flow as U.S. RSR company, adopt sorting technology and oxygen enriched blast, lead recovery brings up to 90%, but SO
2And Lead contamination fails to be solved; Wet processing has only a few countries to adopt at present, is representative with Italian Ji Lata factory wherein, and this factory is the factory that adopts full wet processing scrap lead battery in the world first.The essence of wet processing technology is a kind of electrochemical method.Advantage is the lead recovery height, can effectively eliminate lead and SO near 95%
2Deng the pollution to environment, but current consumption is big; Do-wet combination treatment method is advanced in the world at present technology, by Blaw Bach factory of German LURGI is adopted.Its technological process is at first carrying out wet desulphurization to plumbous mud, and the solids after the desulfurization carries out pyrorefining in the temperature more than 1350 ℃ again.This method is in the whole bag of tricks, and lead recovery is the highest, has reached 95%, has also solved SO
2Emission pollution problem, but still exist energy consumption height and lead dust and lead steam pollution problem.At present, more domestic enterprises have also adopted above-mentioned each technology to carry out the recycling of plumbous mud, but the plumbous rate of recovery only has about 80%, are starkly lower than external advanced level.
Except that above-mentioned technology, there are some patents also to report by plumbous mud being prepared into other products and it being recycled.Chinese patent CN1105784 discloses a kind of reducing and conversion method of waste lead accumulator dregs, waste lead accumulator dregs is reduced into lead sulfate is recycled.Chinese patent CN1830804 discloses a kind of plumbous clay method that is equipped with lead sulfate tribasic in the waste lead accumulator of utilizing; Chinese patent CN1258753 disclose a kind of the scrap battery reclaiming is produced plumbous, the method for red lead and lead nitrate; Chinese patent 200610136891.9 discloses a kind of method that plumbous mud is prepared into high quality red lead by hydrometallurgy.
Chinese patent CN1805208A then discloses and a kind of plumbic oxide in the lead acid cell has been carried out cyclic utilization method and corresponding device thereof.Described according to this patent, at first when 80～100 ℃ of temperature to the positive plate oven dry of battery, take out positive plate when treating moisture content less than 10wt%, grid is separated with lead plaster, then lead plaster is ground into PbO at crusher
2Powder.By controlling the air output of positive pressure fan and negative-pressure air fan pressure and tuyere, make to form little negative pressure in the pulverizer, with PbO
2Also collect in the powder collection powder device; The PbO that collects
2Powder adds in the lead plaster with 4.5～5.0wt% of lead powder amount, thereby has realized recycling of lead dioxide from storage cells.But this method is to the equipment requirements height, and resulting plumbic oxide purity low (content only is about 50%, and all the other impurity are mainly lead sulfate), and poor activity particularly is not used for the plumbous mud in the lead-acid accumulator.
Plumbic oxide claims lead peroxide, anhydrous plumbic acid again, is chocolate brown powder, and crystalline structure belongs to rhombic system, water insoluble and ethanol, but be dissolved in hydrochloric acid.Plumbic oxide is a kind of strong oxidizer, contacts inflammable with organism; Be subjected to easily to resolve into tri-lead tetroxide and oxygen behind the light; Generate lead sesquioxide and oxygen when being heated to 290 ℃, continue to heat up and then resolve into tri-lead tetroxide and oxygen.Plumbic oxide is the good conductor of electricity still, and electroconductibility is not worse than mercury and titanium.Owing to have good corrosion resistance, electroconductibility is strong, the overpotential for oxygen evolution height, and catalytic is good, and therefore low cost and other advantages, as a kind of well behaved anode material, mainly is used as electrode.Both at home and abroad for PbO
2Demand bigger always.
Chinese patent CN1101685A has reported that electrolytic process prepares the method for highly purified plumbic oxide.The negative electrode of electrolyzer and anode all adopt pure lead, at rare H
2SO
4Electrolysis in the solution, the plumbic oxide purity (87～93%) of preparation is high, impure less, active high.This plumbic oxide can shorten the time of changing into as the anode additive of various lead acid cells, improves the initial capacity of battery, and without any side effect.But the raw material that is adopted in this invention is pure lead (purity〉99%), and it is expensive, and therefore, the production cost that electrolytic process is produced plumbic oxide is very high.
As can be seen from the above analysis, the present plumbic oxide preparation method who is reported in the patent, or adopt electrolytic process directly to prepare plumbic oxide, but because what use is pure leady raw materials, its cost is very high; Or by the contained plumbic oxide of the anode of lead-acid accumulator is reclaimed and recycle, but very low, the poor activity of gained plumbic oxide purity, and the equipment complexity, and the plumbous mud in the lead-acid accumulator is not used.
Summary of the invention
The purpose of this invention is to provide a kind ofly by the plumbous clay method that is equipped with the high quality plumbic oxide in the lead-acid accumulator, its preparation cost is low, lead recovery and quality product height, to cutting down the consumption of energy and reducing environmental pollution positive effect is arranged.
Technical solution of the present invention is that the described plumbous clay processing step that is equipped with the high quality plumbic oxide by lead-acid accumulator is:
(1) the plumbous mud in the lead-acid accumulator is taken out, to the oven dry of neutral back, grinding into granularity is the above plumbous mud powder of 200 orders through repetitive scrubbing;
(2) the certain density aqueous solution that contains dispersion agent and sweetening agent of preparation to wherein adding plumbous mud powder, makes that the mass ratio of plumbous mud and this solution is 1:1～10, and plumbous mud powder: sweetening agent: the mass ratio of dispersion agent is 1:0.15～0.5:0～0.1.Under ℃ temperature of room temperature～90, fully stir then, carry out desulphurization reaction 1～24h.Described sweetening agent is the basic metal of solubility or oxyhydroxide, carbonate or the acid carbonate of ammonium.Described dispersion agent is anionic, cationic, nonionic surface active agent or solubility organic acid salt;
(3) separate and to remove liquid portion, to neutral, oven dry then obtains the lead-contained solid material after the desulfurization with gained lead-contained solid material thorough washing;
(4) the certain density aqueous solution that contains oxygenant of preparation, lead-contained solid material after wherein adding desulfurization, make that the lead-contained solid material after the desulfurization and the mass ratio of this solution are 1:1～10, and the mass ratio of lead-contained solid material after the desulfurization and oxygenant is 1:0.1～1.Under ℃ temperature of room temperature～90, stir then, carry out oxidizing reaction 1～24h.The oxygenant that is adopted is solubility inorganic oxidizer, comprising: sodium peroxide, hydrogen peroxide, nitric acid, chloric acid and salt thereof, hypochlorous acid and salt thereof etc., or organic oxidizing agent comprise:, benzoyl hydroperoxide, trifluoro peroxyacetic acid, Peracetic Acid etc.
(5) liquid portion is removed in separation, and with the solid product thorough washing, oven dry promptly obtains the product plumbic oxide then.
Below the present invention made further specify.
Described sweetening agent is the basic metal of solubility or oxyhydroxide, carbonate or the acid carbonate of ammonium, preferably yellow soda ash or sodium hydroxide.
Described dispersion agent is anionic, cationic or nonionic surface active agent or solubility organic acid salt, and preferably molecular weight is at 12000～15000 polyvinyl alcohol;
Described plumbous mud powder: sweetening agent: the mass ratio of dispersion agent is 1:0.15～0.5:0～0.1, preferably 1:0.25～0.3:0～0.05;
Described plumbous mud powder is 1:1～10 with the mass ratio that contains the aqueous solution of dispersion agent and sweetening agent, preferred 1:2～3;
Described oxygenant is the inorganic strong oxidizer of solubility, comprise: sodium peroxide, hydrogen peroxide, nitric acid, chloric acid and salt thereof, hypochlorous acid and salt thereof etc., or organic oxidizing agent, comprising: benzoyl hydroperoxide, trifluoro peroxyacetic acid, Peracetic Acid etc., preferably hypochlorite;
The mass ratio of plumbous mud is 0.1～1:1, preferably 0.2～0.6:1 after described oxygenant and the desulfurization.
Plumbous mud is 1:1～10 with the mass ratio that contains the aqueous solution of oxygenant after the described desulfurization, preferred 1:2～6.
Described desulfurization temperature is room temperature～90 ℃, preferred 60～80 ℃; Desulfurization time is 1～24h, preferred 2～6h;
Described oxidizing temperature is room temperature～90 ℃, preferably 60～80 ℃; Oxidization time is 1～24h, preferred 2～12h;
Invention is compared with traditional method for preparing plumbic oxide by the plumbous clay method that is equipped with the high quality plumbic oxide of lead-acid accumulator, and its outstanding advantage is that technology of the present invention does not adopt metallic lead, is raw material and replace plumbous mud, has saved the metallic lead resource; Prepare the high quality plumbic oxide with electrolytic process and compare, facility investment is simple, and power consumption is few.With compare by accumulator anode plate system plumbic oxide in the existing patent, reduced facility investment, plumbic oxide and lead sulfate in the plumbous mud of raw material have all obtained utilization, technology is very simple, production cost is low.The rate of recovery of the lead in the plumbous mud is up to more than 94%, and prepared plumbic oxide particle is thin, and granularity is less than 30 microns; The purity height of plumbic oxide, content is up to more than 92.43%.
Description of drawings
Fig. 1: the x-ray diffraction of embodiment sample (XRD) spectrogram: 1) press embodiment 4, adopt the plumbic oxide of concentrated nitric acid oxidation preparation; 2) press embodiment 1, adopt the plumbic oxide of hypochlorite oxidation preparation; 3) press embodiment 2, adopt the plumbic oxide of hypochlorite oxidation preparation;
Below by specific embodiment the present invention is made and to further specify.
Embodiment 1
Plumbous mud takes out from store battery, to the oven dry of neutral back, is ground to 200～300 purpose powder through repetitive scrubbing, and is standby.250 gram sodium hydroxide and 20 grams, 12000～15000 polyvinyl alcohol dispersion agents are dissolved in the 2600 gram water, add the above-mentioned plumbous mud powder of 1000 grams then, stirring reaction is 2 hours under 80 ℃ of temperature, filtering separation, and filter cake uses the clear water repetitive scrubbing until neutrality.With plumbous mud drying after the gained desulfurization, add saturated chlorine bleach liquor (available chlorine〉10%), (plumbic oxide: the chlorine bleach liquor) be 1:4, stirring reaction took out after 2 hours solid-to-liquid ratio under 80 ℃ of temperature, and filtering separation is dry then.Gained pressed powder sample is identified through XRD, turns out to be plumbic oxide; Identify that through chemical analysis the content of the plumbic oxide that obtains is 92.43%.The rate of recovery of the lead in the whole process is 94%.Granularity is about 25 microns.
Embodiment 2
Plumbous mud is dried after neutral through repetitive scrubbing, is ground to 200～300 purpose powder.250 gram sodium hydroxide and 20 grams, 12000～15000 polyvinyl alcohol dispersion agents are dissolved in the 2600 gram water, add the above-mentioned plumbous mud powder of 1000 grams then, and stirring reaction is 2 hours under 80 ℃ of temperature, filtering separation, and filter cake uses the clear water repetitive scrubbing until neutrality.After the gained desulfurization lead hydroxide drying, add saturated chlorine bleach liquor, (plumbic oxide: the chlorine bleach liquor) be 1:4, stirring reaction took out after 24 hours solid-to-liquid ratio in 25 ℃, and filtering separation is dry then.Gained pressed powder sample is identified through XRD, turns out to be plumbic oxide.Sample identifies that through chemical analysis the content of the plumbic oxide that obtains reaches 88.18%, and the rate of recovery of the lead in the whole process reaches 93%, and granularity is about 20 microns.
Plumbous mud is dried after neutral through repetitive scrubbing, be ground to 200～300 purpose powder, 331 gram yellow soda ash and 20 grams, 12000～15000 polyvinyl alcohol dispersion agents are dissolved in the 2700 gram water, add the above-mentioned plumbous mud powder of 1000 grams then, stirring reaction is 6 hours under 60 ℃ of temperature, filtering separation, filter cake use the clear water repetitive scrubbing until neutrality.After the plumbous mud drying, add saturated chlorine bleach liquor after the gained desulfurization, (plumbic oxide: the chlorine bleach liquor) be 1:4, stirring reaction is 6 hours under 60 ℃ of temperature, and filtering separation is dry then for solid-to-liquid ratio.Gained pressed powder sample is identified through XRD, turns out to be plumbic oxide.Sample identifies that through chemical analysis the content of the plumbic oxide that obtains reaches 91.17%, and the rate of recovery of the lead in the whole process reaches 95%, and granularity is about 20 microns.
Embodiment 4
Desulfurized step and embodiment 1 are identical.The plumbous mud of gained adds concentrated nitric acid solution, solid-to-liquid ratio (plumbic oxide: concentrated nitric acid) be 1:2 after drying after the desulfurization, stirring reaction took out after 24 hours in 25 ℃, and filtering separation obtains high-quality plumbic oxide, gained pressed powder sample is identified through XRD, turns out to be plumbic oxide.Sample identifies that through chemical analysis the content of the plumbic oxide that obtains is up to 96.67%, and the rate of recovery of the lead in the whole process reaches 45%, and granularity is about 25 microns.
Embodiment 5
Desulfurized step and embodiment 1 are identical, and the plumbous mud of gained adds the saturated Losantin aqueous solution after drying after the desulfurization, and (plumbic oxide: calcium hypochlorite solution) be 1:4, stirring reaction took out after 2 hours solid-to-liquid ratio in 80 ℃, filtering separation.Sample identifies that through chemical analysis the content of the plumbic oxide that obtains reaches 88.45%, and the rate of recovery of the lead in the whole process reaches 88%, and granularity is about 20 microns.
Embodiment 6
Desulfurized step and embodiment 1 are identical, and the plumbous mud of gained adds chlorine bleach liquor's (available chlorine) 5% after drying after the desulfurization), solid-to-liquid ratio (plumbic oxide: the chlorine bleach liquor) be 1:6, stirring reaction took out after 2 hours under 80 ℃ of temperature, and filtering separation is dry then.Identify that through chemical analysis the content of the plumbic oxide that obtains is 91.12%.The rate of recovery of the lead in the whole process is 94%.Granularity is about 25 microns.
Embodiment 7
Plumbous mud takes out from store battery, to the oven dry of neutral back, is ground to 200～300 purpose powder through repetitive scrubbing, and is standby.250 gram sodium hydroxide are dissolved in the 2500 gram water, add the above-mentioned plumbous mud powder of 1000 grams then, stirring reaction is 2 hours under 80 ℃ of temperature, filtering separation, and filter cake uses the clear water repetitive scrubbing until neutrality.With plumbous mud drying after the gained desulfurization, add saturated chlorine bleach liquor, (plumbic oxide: the chlorine bleach liquor) be 1:4, stirring reaction took out after 2 hours solid-to-liquid ratio under 80 ℃ of temperature, and filtering separation is dry then.Identify that through chemical analysis the content of the plumbic oxide that obtains is 89.82%.The rate of recovery of the lead in the whole process is 91%.Granularity is about 30 microns.
Claims (8)
1. one kind is utilized the plumbous clay method that is equipped with the high quality plumbic oxide in the lead-acid accumulator, it is characterized in that its processing step is:
(1) the plumbous mud in the lead-acid accumulator is taken out, to the oven dry of neutral back, grinding into granularity is the above plumbous mud powder of 200 orders through repetitive scrubbing;
(2) the certain density aqueous solution that contains dispersion agent and sweetening agent of preparation, to wherein adding plumbous mud powder, make that the mass ratio of plumbous mud and this solution is 1: 1～10, and plumbous mud powder: sweetening agent: the mass ratio of dispersion agent is 1: 0.15～0.5: 0～0.1, under ℃ temperature of room temperature～90, fully stir then, carry out desulphurization reaction 1～24h, dispersion agent is that molecular weight is 12000～15000 polyvinyl alcohol;
(3) after desulphurization reaction finishes, separate and remove liquid portion, to neutral, drying obtains the lead-contained solid material after the desulfurization with gained lead-contained solid material thorough washing;
(4) the certain density aqueous solution that contains oxygenant of preparation, lead-contained solid material after wherein adding desulfurization, make that the lead-contained solid material after the desulfurization and the mass ratio of this solution are 1: 1～10, and the lead-contained solid material after the desulfurization and the mass ratio of oxygenant are 1: 0.1～1, under ℃ temperature of room temperature～90, stir then, carry out oxidizing reaction 1～24h;
(5) after oxidizing reaction finishes, separate and remove liquid portion, with gained solid product thorough washing, drying obtains the product plumbic oxide.
2. according to the described plumbous clay method of utilizing in the lead-acid accumulator that is equipped with the high quality plumbic oxide of claim 1, it is characterized in that described sweetening agent is the basic metal of solubility or oxyhydroxide, carbonate or the acid carbonate of ammonium.
3. according to the described plumbous clay method of utilizing in the lead-acid accumulator that is equipped with the high quality plumbic oxide of claim 2, it is characterized in that sweetening agent is sodium hydroxide or yellow soda ash.
4. according to the described plumbous clay method of utilizing in the lead-acid accumulator that is equipped with the high quality plumbic oxide of claim 1, it is characterized in that described oxygenant is sodium peroxide, hydrogen peroxide, nitric acid, chloric acid and salt thereof, hypochlorous acid and salt thereof.
5. according to the described plumbous clay method of utilizing in the lead-acid accumulator that is equipped with the high quality plumbic oxide of claim 1, it is characterized in that, in step 2) in, plumbous mud powder is 1: 2～3 with the mass ratio that contains the aqueous solution of dispersion agent and sweetening agent, and plumbous mud powder: sweetening agent: the mass ratio of dispersion agent is 1: 0.25～0.3: 0～0.05.
6. according to the described plumbous clay method of utilizing in the lead-acid accumulator that is equipped with the high quality plumbic oxide of claim 1, it is characterized in that, in step 2) in, the temperature of desulphurization reaction is 60～80 ℃, the time of desulphurization reaction is 2～6h;
7. according to the described plumbous clay method of utilizing in the lead-acid accumulator that is equipped with the high quality plumbic oxide of claim 1, it is characterized in that, in step 4), gained lead-contained solid material is 1: 2～6 with the mass ratio that contains the aqueous solution of oxygenant after the desulfurization, and the mass ratio of lead-contained solid material after the desulfurization and oxygenant is 1: 0.2～0.6.
8. according to the described plumbous clay method of utilizing in the lead-acid accumulator that is equipped with the high quality plumbic oxide of claim 1, it is characterized in that in step 4), the temperature of oxidizing reaction is 60～80 ℃, the time of oxidizing reaction is 2～12h.
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| CN102723538B (en) * | 2012-07-03 | 2015-02-18 | 山东瑞宇蓄电池有限公司 | Waste diachylon processing method, lead powder for lead-acid storage battery, waste diachylon processing device, pole plate and lead-acid storage battery |
| CN102925698B (en) * | 2012-10-30 | 2014-09-03 | 湖北楚凯冶金有限公司 | Method for desulfurizing waste lead-acid battery diachylon |
| CN103000968B (en) * | 2012-10-31 | 2015-10-07 | 高金菊 | A kind of waste lead acid battery lead cream desulfurization and transformation method |
| CN102897828B (en) * | 2012-11-08 | 2014-03-05 | 山东大学 | Controllable preparation method of PbO1.44 hollow spheroidal aggregate |
| CN103305695B (en) * | 2013-05-02 | 2014-09-24 | 华中科技大学 | Method for preparing nano-lead dioxide powder from waste lead paste by wet process |
| CN103633394A (en) * | 2013-12-13 | 2014-03-12 | 华南师范大学 | Waste diachylon desulphurization method |
| US9757702B2 (en) | 2014-06-20 | 2017-09-12 | Johnson Controls Technology Company | Systems and methods for purifying and recycling lead from spent lead-acid batteries |
| US9670565B2 (en) | 2014-06-20 | 2017-06-06 | Johnson Controls Technology Company | Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries |
| US10062933B2 (en) | 2015-12-14 | 2018-08-28 | Johnson Controls Technology Company | Hydrometallurgical electrowinning of lead from spent lead-acid batteries |
| CN112694118A (en) * | 2020-12-09 | 2021-04-23 | 超威电源集团有限公司 | Preparation method of red lead |
| 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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