CN103523820A - Lead oxide taking lead paste in waste battery as main raw material and preparation method thereof - Google Patents
Lead oxide taking lead paste in waste battery as main raw material and preparation method thereof Download PDFInfo
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- CN103523820A CN103523820A CN201310434181.4A CN201310434181A CN103523820A CN 103523820 A CN103523820 A CN 103523820A CN 201310434181 A CN201310434181 A CN 201310434181A CN 103523820 A CN103523820 A CN 103523820A
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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
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention relates to lead oxide taking lead paste in a waste battery as a main raw material and a preparation method thereof. The technical scheme comprises the steps of adding waste lead paste into a reaction tank, adding an amino-containing substance and stirring; adding a carbon-containing substance for desulfurization; performing solid-liquid separation to obtain desulfurized lead paste and filtrate; evaporating and crystallizing the filtrate to obtain a byproduct ammonium sulfate; cooling the evaporated liquid in the evaporation and crystallization processes to room temperature for recycling; drying the washed desulfurized lead paste at 60-120 DEG C for 1-24 hours to obtain dried lead paste; calcining the dried lead paste at a temperature higher than 400 DEG C and lower than or equal to 500 DEG C for 1-10 hours to obtain lead tetraoxide, namely red lead; or calcining the dried lead paste at a temperature higher than 500 DEG C and lower than or equal to 650 DEG C for 1-10 hours to obtain lead oxide, namely yellow lead; recycling the carbon dioxide generated by calcining. The lead oxide and preparation method thereof provided by the invention have the characteristics of simple process, low raw material consumption, high recovery rate and high product purity.
Description
Technical field
The invention belongs to plumbous oxide technical field.Be specifically related to a kind of lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof of take.
Background technology
The continuous increase with the market requirement that develops rapidly along with industry, lead acid cell moves the accumulation power supply with electrical source of power, sun power and the wind energy stand alone generating system of standby power supply, submarine and the power truck etc. in power station etc. as startup power supply, the telecommunications of automobile and boats and ships etc., in novel material application, show more and more brighter prospect, expect 2015, its output will reach 24,000 ten thousand kVAh.Along with the technical progress of advanced lead acid cell and superbattery etc., the application in the new-energy automobile fields such as plumbic acid hybrid power has more obvious cost advantage.But according to the reserve-production ratio of current lead ore resource, the plumbous reserves of 2003 and reserves basis static state guarantee that the time limit is respectively 21 years and 43 years, and lead resource is exhaustion day by day, and the recovery of secondary lead becomes the only way of realizing plumbing Sustainable development.
The recovery of secondary lead is mainly derived from polar plate of lead acid storage battery, cable armoring, pipeline, plumb and stereotype, and wherein lead-acid accumulator accounts for more than 85%.According to statistics, ended for the end of the year 2010, the annual automobile used and scrapped battery of 670,000 tons and the electric vehicle used and scrapped battery of 900,000 tons of approximately producing of China, if consider the industries such as communication, boats and ships, the amount of scrap battery can be more.But in current recovery process, inevitably can produce waste gas containing lead, waste liquid, waste residue, by skin, digestive tube and respiratory tract, enter in body affinely with multiple organ, cause the imbalance of anemia, nervous function and injury of the kidney, even can bring out cancer.Therefore, realizing efficient, the clean and free of contamination recovery of lead acid cell, not only solved resource problem, turn waste into wealth, solved again environmental problem, is a problem shouldering heavy responsibilities.
At present, the treatment process of lead acid cell, for first by lead storage battery cracking and sorting, is isolated waste electrolyte, grid, organism and lead plaster both at home and abroad.Wherein: waste electrolyte discharges or reuse after further processing; Grid mainly be take lead and alloy and can independently be recycled as main; Organism as acrylic plastering can be as byproduct regeneration; Lead plaster is mainly the Slurries material that on pole plate, active substance forms after discharging and recharging use, and main component is lead sulfate, plumbic oxide, plumbous oxide and lead etc.Owing to containing a large amount of leaded vitriol in lead plaster, and have the lead oxides of different valence state, therefore, the recycling of lead plaster becomes the research emphasis that waste lead acid battery is recycled, and it reclaims is mainly to be undertaken by pyrogenic process, wet method or dry wet integrated process.
In pyrogenic process removal process, can produce a large amount of sulfur dioxide gas and lead dust pollution, and smelting temperature is too high, energy consumption is many; During reclaiming, wet method or dry wet integrated process normally lead sulfate is converted into easy-to-handle lead carbonate, conventional sweetening agent is sodium carbonate, volatile salt or bicarbonate of ammonia, there is certain drawback in these sweetening agents: sodium carbonate is strong base-weak acid salt, higher being not easy of pH value regulates, cause the lead salt after Partial Conversion to dissolve, and sodium sulfate byproduct economic worth is not high; Volatile salt, the unstable easy decomposition of bicarbonate of ammonia, reduce desulfurization degree, increased cost of investment.In addition; applying above-mentioned desulfurization transforming agent is converted into lead sulfate in the process of lead carbonate; lead sulfate in lead plaster usually can be wrapped up and can not continue to react (PbSO4 that generally also has 5% left and right remains in the lead plaster after conversion) by newborn lead carbonate particle; cause lead plaster desulfurization incomplete, to subsequent disposal, do not bring sulphur emissions up to standard and reclaim plumbous Product Process trouble.
The recovery product of waste lead acid battery lead cream mainly contains lead, plumbous oxide, lead nitrate, lead chloride and lead sulfate tribasic etc." a kind of method of being prepared plumbous oxide by lead-acid accumulator " be patented technology (CN101514395A), has proposed a kind of method that obtains plumbous oxide with oxalic acid reduction, nitric acid dissolve, volatile salt conversion, nitric acid dissolve, ammonia precipitation process, lead hydroxide roasting; " a kind of method of being produced lead nitrate, plumbous oxide by waste lead accumulator lead plaster " be patented technology (CN101857919A), has proposed to obtain with volatile salt conversion, hydrogen peroxide reduction, nitrate leaching, sodium hydroxide precipitation, lead hydroxide roasting the method for plumbous oxide; " recoverying and utilizing method of lead plaster in a kind of waste lead storage battery " be patented technology (CN102306855A), has proposed a kind of method that obtains plumbous oxide with ammonium hydrogen carbonate, plumbic oxide Roasting Decomposition, lead carbonate Roasting Decomposition; " a kind of method for making of the lead compound nano-powder that is applied to lead acid cell recovery and manufactures " be patented technology (CN102689922A), proposed a kind of lead in lead plaster to be converted into solubility lead salt or lead hydroxide, then correspondingly add a kind of in alkali or acid and salt, make it to be converted into lead compound nano-powder; " a kind of method of being prepared the plumbous compound of nanometer by waste lead acid battery lead cream " (CN102820496A) proposed a kind ofly with calcining plumbic acetate crystal after acetate dissolution, hydrogen peroxide reduction, to obtain Nanometer sized lead oxide.
As can be seen from the above, though the method for preparing plumbous oxide with lead-acid accumulator perfect step by step, but still Shortcomings part: technical process is complicated, and raw materials consumption is many, the low and low problem of product purity of lead recovery.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, and object is to provide that a kind of technical process is simple, raw materials consumption is few, the rate of recovery is high and product purity is high take plumbous oxide that lead plaster is main raw material in refuse battery and preparation method thereof.
For achieving the above object, technical scheme of the present invention is: the preparation process of described method is:
Step 1, waste lead accumulator is broken, sorting, obtains scrap lead cream.
Step 2, described scrap lead cream is added in retort, then add containing amino material, the lead sulfate in scrap lead cream is 1 ︰ (2 ~ 10) with the amino amount of substance ratio containing in amino material; Then add water and adjust liquid-solid ratio to (1 ~ 10) ︰ 1 stirs 0.5 ~ 5h under normal temperature condition, finally adds carbonaceous material to carry out desulfurization, and desulfurization time is 0.5 ~ 10h, and solid-liquid separation obtains desulfurization lead plaster and filtrate.
Step 3, by described filtrate evaporative crystallization, obtain by product ammonium sulfate, then the evaporated liquor in evaporation and crystal process be cooled to room temperature, be transported to recycle in step 2; Water is by described desulfurization lead plaster washing to neutral, and the desulfurization lead plaster after washing is dry 1 ~ 24h under 60 ~ 120 ℃ of conditions, obtains dry lead plaster.
Step 4, by described dry lead plaster 400 ℃ of temperature > and≤calcine 1 ~ 10h under the condition of 500 ℃, obtain tri-lead tetroxide, obtain red lead; Or by described dry lead plaster 500 ℃ of temperature > and≤calcine 1 ~ 10h under the condition of 650 ℃, obtain plumbous oxide, obtain yellow lead.
Step 5, the carbonic acid gas that calcining in step 4 is produced are delivered to step 2, recycle.
Described is one or both in ammoniacal liquor, urea, quadrol, diethylamine and triethylamine containing amino material.
Described carbonaceous material is one or both in carbonic acid gas, volatile salt, bicarbonate of ammonia.
The main chemical compositions of described scrap lead cream is: PbSO
4content is 50 ~ 65wt%, PbO
2content is 25 ~ 35wt%, and PbO content is 4 ~ 10wt%, and Pb content is 1 ~ 6wt%.
Because the present invention adopts containing amino material, carry out complexing dissolving, with carbonaceous material, precipitate desulfurization, desulfurization degree is up to more than 99%; Its by product ammonium sulfate market value is higher, is widely used in nitrogenous fertilizer, manufactures the aspects such as refractory materials and exploitation rare earth; Roasting under cold condition, energy consumption is low, and roasting environmental requirement is low, is easy to control convenient operation, nonstaining property γ-ray emission; PbSO in prepared red lead
4content is more than 97.0wt%, and the PbO content in yellow lead is that more than 99wt% product purity is higher, reaches state-set standard.
Due to technique scheme, the present invention will be dried lead plaster and obtain tri-lead tetroxide, i.e. red lead through calcining.Red lead is the conventional raw material of a kind of industry, is widely used in and manufactures store battery, glass, pottery and enamel etc., also for making dyestuff and as irreplaceable raw material in oxygenant, the especially heavy-duty coating of some organic syntheses.
Owing to adopting technique scheme, the present invention obtains dry lead plaster rhombic system plumbous oxide through calcining, be yellow lead, yellow lead can be used as pigment white lead, manufactures the intermediate raw material of lead soap, metallurgical solubility promoter, paint drier, ceramic raw material, thiofide, sterilant, lead salt stabilizer for plastics, lead glass industrial raw material, lead salts industry, also can be used for the manufacture of Chinese medicine, the Storage Battery Industry in China and radiation-proof rubber goods, be widely used.
The present invention compared with prior art has following positively effect:
(1) technical process of the present invention is simple, cost is lower, conversion rate of products is high and purity is higher.
(2) utilization of the present invention is containing the method for amino material and carbonaceous material desulfurization, and desulfurization degree is high, has reached more than 99%, and by product is worth higher, can be used as nitrogenous fertilizer, manufactures refractory materials, exploits rare earth etc.
(3) the present invention utilizes low-temperature bake, has avoided the generation of waste gas, environmentally safe; Compare with pyrotic smelting, reduced reaction environment conditional request, reduced cost of investment.
(4) final product plumbous oxide of the present invention (red lead and yellow lead) is widely used, the huge market demand, and market value is higher, and economic benefits comparison is considerable.
Therefore, the present invention has the advantages that technical process is simple, raw materials consumption is few, the rate of recovery is high and product purity is high.
Embodiment
Below in conjunction with embodiment, the invention will be further described, not the restriction to its protection domain.
For avoiding repetition, first the main chemical compositions unification of the scrap lead cream described in this embodiment is described below, in embodiment, repeat no more: PbSO
4content is 50 ~ 65wt%; PbO
2content is 25 ~ 35wt%; PbO content is 4 ~ 10wt%; Pb content is 1 ~ 6wt%.
embodiment 1
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.The preparation process of described method is:
Step 1, waste lead accumulator is broken, sorting, obtains scrap lead cream.
Step 2, described scrap lead cream is added in retort, then add containing amino material, the lead sulfate in scrap lead cream is 1 ︰ (2 ~ 3) with the amino amount of substance ratio containing in amino material; Then add water and adjust liquid-solid ratio to (1 ~ 3) ︰ 1 stirs 0.5 ~ 1h under normal temperature condition, finally adds carbonaceous material to carry out desulfurization, and desulfurization time is 0.5 ~ 3h, and solid-liquid separation obtains desulfurization lead plaster and filtrate.
Step 3, by described filtrate evaporative crystallization, obtain by product ammonium sulfate, then the evaporated liquor in evaporation and crystal process be cooled to room temperature, be transported to recycle in step 2; Water is by described desulfurization lead plaster washing to neutral, and the desulfurization lead plaster after washing is dry 1 ~ 5h under 60 ~ 80 ℃ of conditions, obtains dry lead plaster.
Step 4, by described dry lead plaster 400 ℃ of temperature > and≤calcine 1 ~ 2h under the condition of 420 ℃, obtain tri-lead tetroxide, obtain red lead; Or by described dry lead plaster 500 ℃ of temperature > and≤calcine 1 ~ 2h under the condition of 540 ℃, obtain plumbous oxide, obtain yellow lead.
Step 5, the carbonic acid gas that calcining in step 4 is produced are delivered to step 2, recycle.
In the present embodiment: described is ammoniacal liquor containing amino material; Described carbonaceous material is carbonic acid gas.
The goods of the present embodiment are after testing: desulfurization degree is 99 ~ 99.3%; PbSO in red lead
4content is 97.0 ~ 97.3wt%; PbO content in yellow lead is 99 ~ 99.24wt%.
embodiment 2
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.The preparation process of described method is:
Step 1, waste lead accumulator is broken, sorting, obtains scrap lead cream.
Step 2, described scrap lead cream is added in retort, then add containing amino material, the lead sulfate in scrap lead cream is 1 ︰ (3 ~ 5) with the amino amount of substance ratio containing in amino material; Then add water and adjust liquid-solid ratio to (2 ~ 4) ︰ 1 stir 1 ~ 2h under normal temperature condition, finally add carbonaceous material to carry out desulfurization, and desulfurization time is 3 ~ 6h, and solid-liquid separation obtains desulfurization lead plaster and filtrate.
Step 3, by described filtrate evaporative crystallization, obtain by product ammonium sulfate, then the evaporated liquor in evaporation and crystal process be cooled to room temperature, be transported to recycle in step 2; Water is by described desulfurization lead plaster washing to neutral, and the desulfurization lead plaster after washing is dry 5 ~ 10h under 70 ~ 90 ℃ of conditions, obtains dry lead plaster.
Step 4, by described dry lead plaster 420 ℃ of temperature > and≤calcine 2 ~ 4h under the condition of 440 ℃, obtain tri-lead tetroxide, obtain red lead; Or by described dry lead plaster 530 ℃ of temperature > and≤calcine 2 ~ 4h under the condition of 570 ℃, obtain plumbous oxide, obtain yellow lead.
Step 5, the carbonic acid gas that calcining in step 4 is produced are delivered to step 2, recycle.
In the present embodiment: described is urea containing amino material; Described carbonaceous material is volatile salt.
The goods of the present embodiment are after testing: desulfurization degree is 99.1 ~ 99.5%; PbSO in red lead
4content is 97.1 ~ 97.4wt%; PbO content in yellow lead is 99.18 ~ 99.40wt%.
embodiment 3
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.The preparation process of described method is:
Step 1, waste lead accumulator is broken, sorting, obtains scrap lead cream.
Step 2, described scrap lead cream is added in retort, then add containing amino material, the lead sulfate in scrap lead cream is 1 ︰ (5 ~ 7) with the amino amount of substance ratio containing in amino material; Then add water and adjust liquid-solid ratio to (4 ~ 6) ︰ 1 stir 2 ~ 3h under normal temperature condition, finally add carbonaceous material to carry out desulfurization, and desulfurization time is 4 ~ 7h, and solid-liquid separation obtains desulfurization lead plaster and filtrate.
Step 3, by described filtrate evaporative crystallization, obtain by product ammonium sulfate, then the evaporated liquor in evaporation and crystal process be cooled to room temperature, be transported to recycle in step 2; Water is by described desulfurization lead plaster washing to neutral, and the desulfurization lead plaster after washing is dry 10 ~ 15h under 80 ~ 100 ℃ of conditions, obtains dry lead plaster.
Step 4, by described dry lead plaster 440 ℃ of temperature > and≤calcine 4 ~ 6h under the condition of 460 ℃, obtain tri-lead tetroxide, obtain red lead; Or by described dry lead plaster 560 ℃ of temperature > and≤calcine 4 ~ 6h under the condition of 600 ℃, obtain plumbous oxide, obtain yellow lead.
Step 5, the carbonic acid gas that calcining in step 4 is produced are delivered to step 2, recycle.
In the present embodiment: described is quadrol containing amino material; Described carbonaceous material is bicarbonate of ammonia.
The goods of the present embodiment are after testing: desulfurization degree is 99.3 ~ 99.6%; PbSO in red lead
4content is 97.2 ~ 97.6wt%; PbO content in yellow lead is 99.27 ~ 99.51wt%.
embodiment 4
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.The preparation process of described method is:
Step 1, waste lead accumulator is broken, sorting, obtains scrap lead cream.
Step 2, described scrap lead cream is added in retort, then add containing amino material, the lead sulfate in scrap lead cream is 1 ︰ (7 ~ 9) with the amino amount of substance ratio containing in amino material; Then add water and adjust liquid-solid ratio to (6 ~ 8) ︰ 1 stir 3 ~ 4h under normal temperature condition, finally add carbonaceous material to carry out desulfurization, and desulfurization time is 5 ~ 8h, and solid-liquid separation obtains desulfurization lead plaster and filtrate.
Step 3, by described filtrate evaporative crystallization, obtain by product ammonium sulfate, then the evaporated liquor in evaporation and crystal process be cooled to room temperature, be transported to recycle in step 2; Water is by described desulfurization lead plaster washing to neutral, and the desulfurization lead plaster after washing is dry 15 ~ 20h under 90 ~ 100 ℃ of conditions, obtains dry lead plaster.
Step 4, by described dry lead plaster 460 ℃ of temperature > and≤calcine 6 ~ 8h under the condition of 480 ℃, obtain tri-lead tetroxide, obtain red lead; Or by described dry lead plaster 590 ℃ of temperature > and≤calcine 6 ~ 8h under the condition of 630 ℃, obtain plumbous oxide, obtain yellow lead.
Step 5, the carbonic acid gas that calcining in step 4 is produced are delivered to step 2, recycle.
In the present embodiment: described is diethylamine containing amino material; Described carbonaceous material is carbonic acid gas and volatile salt.
The goods of the present embodiment are after testing: desulfurization degree is 99.4 ~ 99.8%; PbSO in red lead
4content is 97.5 ~ 98.0wt%; PbO content in yellow lead is 99.40 ~ 99.55wt%.
embodiment 5
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.The preparation process of described method is:
Step 1, waste lead accumulator is broken, sorting, obtains scrap lead cream.
Step 2, described scrap lead cream is added in retort, then add containing amino material, the lead sulfate in scrap lead cream is 1 ︰ (9 ~ 10) with the amino amount of substance ratio containing in amino material; Then add water and adjust liquid-solid ratio to (8 ~ 10) ︰ 1 stir 4 ~ 5h under normal temperature condition, finally add carbonaceous material to carry out desulfurization, and desulfurization time is 6 ~ 10h, and solid-liquid separation obtains desulfurization lead plaster and filtrate.
Step 3, by described filtrate evaporative crystallization, obtain by product ammonium sulfate, then the evaporated liquor in evaporation and crystal process be cooled to room temperature, be transported to recycle in step 2; Water is by described desulfurization lead plaster washing to neutral, and the desulfurization lead plaster after washing is dry 20 ~ 24h under 100 ~ 120 ℃ of conditions, obtains dry lead plaster.
Step 4, by described dry lead plaster 480 ℃ of temperature > and≤calcine 8 ~ 10h under the condition of 500 ℃, obtain tri-lead tetroxide, obtain red lead; Or by described dry lead plaster 620 ℃ of temperature > and≤calcine 8 ~ 10h under the condition of 650 ℃, obtain plumbous oxide, obtain yellow lead.
Step 5, the carbonic acid gas that calcining in step 4 is produced are delivered to step 2, recycle.
In the present embodiment: described is triethylamine containing amino material; Described carbonaceous material is carbonic acid gas and bicarbonate of ammonia.
The goods of the present embodiment are after testing: desulfurization degree is 99.7 ~ 99.9%; PbSO in red lead
4content is 97.7 ~ 98.2wt%; PbO content in yellow lead is 99.48 ~ 99.59wt%.
embodiment 6
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 1.
In the present embodiment: described is ammoniacal liquor and urea containing amino material; Described carbonaceous material is volatile salt and bicarbonate of ammonia.
The goods of the present embodiment are after testing: desulfurization degree is 99.1 ~ 99.4%; PbSO in red lead
4content is 97.1 ~ 97.3wt%; PbO content in yellow lead is 99.12 ~ 99.25wt%.
embodiment 7
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 2.
In the present embodiment: described is ammoniacal liquor and quadrol containing amino material; Described carbonaceous material is carbonic acid gas.
The goods of the present embodiment are after testing: desulfurization degree is 99.2 ~ 99.5%; PbSO in red lead
4content is 97.2 ~ 97.5wt%; PbO content in yellow lead is 99.20 ~ 99.42wt%.
embodiment 8
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 3.
In the present embodiment: described is ammoniacal liquor and diethylamine containing amino material; Described carbonaceous material is volatile salt.
The goods of the present embodiment are after testing: desulfurization degree is 99.4 ~ 99.7%; PbSO in red lead
4content is 97.4 ~ 97.7wt%; PbO content in yellow lead is 99.29 ~ 99.50wt%.
embodiment 9
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 4.
In the present embodiment: described is ammoniacal liquor and triethylamine containing amino material; Described carbonaceous material is bicarbonate of ammonia.
The goods of the present embodiment are after testing: desulfurization degree is 99.5 ~ 99.8%; PbSO in red lead
4content is 97.6 ~ 98.2wt%; PbO content in yellow lead is 99.43 ~ 99.57wt%.
embodiment 10
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 5.
In the present embodiment: described is urea and quadrol containing amino material; Described carbonaceous material is carbonic acid gas and volatile salt.
The goods of the present embodiment are after testing: desulfurization degree is 99.7 ~ 99.92%; PbSO in red lead
4content is 97.8 ~ 98.4wt%; PbO content in yellow lead is 99.50 ~ 99.61wt%.
embodiment 11
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 1.
In the present embodiment: described is urea and diethylamine containing amino material; Described carbonaceous material is carbonic acid gas and bicarbonate of ammonia.
The goods of the present embodiment are after testing: desulfurization degree is 99 ~ 99.4%; PbSO in red lead
4content is 97.0 ~ 97.4wt%; PbO content in yellow lead is 99.10 ~ 99.24wt%.
embodiment 12
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 2.
In the present embodiment: described is urea and triethylamine containing amino material; Described carbonaceous material is volatile salt and bicarbonate of ammonia.
The goods of the present embodiment are after testing: desulfurization degree is 99.3 ~ 99.6%; PbSO in red lead
4content is 97.2 ~ 97.7wt%; PbO content in yellow lead is 99.19 ~ 99.40wt%.
embodiment 13
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 3.
In the present embodiment: described is quadrol and diethylamine containing amino material; Described carbonaceous material is carbonic acid gas.
The goods of the present embodiment are after testing: desulfurization degree is 99.5 ~ 99.7%; PbSO in red lead
4content is 97.4 ~ 97.9wt%; PbO content in yellow lead is 99.32 ~ 99.51wt%.
embodiment 14
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 4.
In the present embodiment: described is quadrol and triethylamine containing amino material; Described carbonaceous material is volatile salt.
The goods of the present embodiment are after testing: desulfurization degree is 99.6 ~ 99.9%; PbSO in red lead
4content is 97.8 ~ 98.2wt%; PbO content in yellow lead is 99.45 ~ 99.58wt%.
embodiment 15
A kind ofly take lead plaster is main raw material in refuse battery plumbous oxide and preparation method thereof.In the present embodiment, except following technical parameter, all the other are with embodiment 5.
In the present embodiment: described is diethylamine and triethylamine containing amino material; Described carbonaceous material is bicarbonate of ammonia.
The goods of the present embodiment are after testing: desulfurization degree is 99.8 ~ 99.94%; PbSO in red lead
4content is 98.0 ~ 98.5wt%; PbO content in yellow lead is 99.50 ~ 99.59wt%.
Because this embodiment adopts containing amino material, carry out complexing dissolving, with carbonaceous material, precipitate desulfurization, desulfurization degree is up to more than 99%; Its by product ammonium sulfate market value is higher, is widely used in nitrogenous fertilizer, manufactures the aspects such as refractory materials and exploitation rare earth; Roasting under cold condition, energy consumption is low, and roasting environmental requirement is low, is easy to control convenient operation, nonstaining property γ-ray emission; PbSO in prepared red lead
4content is more than 97.0wt%, and the PbO content in yellow lead is that more than 99wt% product purity is higher, reaches state-set standard.
Due to technique scheme, this embodiment will be dried lead plaster and obtain tri-lead tetroxide, i.e. red lead through calcining.Red lead is the conventional raw material of a kind of industry, is widely used in and manufactures store battery, glass, pottery and enamel etc., also for making dyestuff and as irreplaceable raw material in oxygenant, the especially heavy-duty coating of some organic syntheses.
Owing to adopting technique scheme, this embodiment obtains dry lead plaster rhombic system plumbous oxide through calcining, be yellow lead, yellow lead can be used as pigment white lead, manufactures the intermediate raw material of lead soap, metallurgical solubility promoter, paint drier, ceramic raw material, thiofide, sterilant, lead salt stabilizer for plastics, lead glass industrial raw material, lead salts industry, also can be used for the manufacture of Chinese medicine, the Storage Battery Industry in China and radiation-proof rubber goods, be widely used.
Therefore, this embodiment compared with prior art has following positively effect:
(1) technical process of this embodiment is simple, cost is lower, conversion rate of products is high and purity is higher.
(2) utilization of this embodiment is containing the method for amino material and carbonaceous material desulfurization, and desulfurization degree is high, has reached more than 99%, and by product is worth higher, can be used as nitrogenous fertilizer, manufactures refractory materials, exploits rare earth etc.
(3) this embodiment is utilized low-temperature bake, has avoided the generation of waste gas, environmentally safe; Compare with pyrotic smelting, reduced reaction environment conditional request, reduced cost of investment.
(4) the final product plumbous oxide of this embodiment (red lead and yellow lead) is widely used, the huge market demand, and market value is higher, and economic benefits comparison is considerable.
Therefore, this embodiment has the advantages that technical process is simple, raw materials consumption is few, the rate of recovery is high and product purity is high.
Claims (5)
1. take the preparation method of the plumbous oxide that lead plaster is main raw material in refuse battery, it is characterized in that the preparation process of described method is:
Step 1, waste lead accumulator is broken, sorting, obtains scrap lead cream;
Step 2, described scrap lead cream is added in retort, then add containing amino material, the lead sulfate in scrap lead cream is 1 ︰ (2 ~ 10) with the amino amount of substance ratio containing in amino material; Then add water and adjust liquid-solid ratio to (1 ~ 10) ︰ 1 stirs 0.5 ~ 5h under normal temperature condition, finally adds carbonaceous material to carry out desulfurization, and desulfurization time is 0.5 ~ 10h, and solid-liquid separation obtains desulfurization lead plaster and filtrate;
Step 3, by described filtrate evaporative crystallization, obtain by product ammonium sulfate, then the evaporated liquor in evaporation and crystal process be cooled to room temperature, be transported to recycle in step 2; Water is by described desulfurization lead plaster washing to neutral, and the desulfurization lead plaster after washing is dry 1 ~ 24h under 60 ~ 120 ℃ of conditions, obtains dry lead plaster;
Step 4, by described dry lead plaster 400 ℃ of temperature > and≤calcine 1 ~ 10h under the condition of 500 ℃, obtain tri-lead tetroxide, obtain red lead; Maybe by dry lead plaster 500 ℃ of temperature > and≤calcine 1 ~ 10h under the condition of 650 ℃, obtain plumbous oxide, obtain yellow lead;
Step 5, the carbonic acid gas that calcining in step 4 is produced are delivered to step 2, recycle.
2. preparation method of take the plumbous oxide that lead plaster is main raw material in refuse battery according to claim 1, is characterized in that described is one or both in ammoniacal liquor, urea, quadrol, diethylamine and triethylamine containing amino material.
3. preparation method of take the plumbous oxide that lead plaster is main raw material in refuse battery according to claim 1, is characterized in that described carbonaceous material is one or both in carbonic acid gas, volatile salt, bicarbonate of ammonia.
4. take according to claim 1 the preparation method of the plumbous oxide that lead plaster is main raw material in refuse battery, it is characterized in that the main chemical compositions of described scrap lead cream is: PbSO
4content is 50 ~ 65wt%, PbO
2content is 25 ~ 35wt%, and PbO content is 4 ~ 10wt%, and Pb content is 1 ~ 6wt%.
5. take the plumbous oxide that lead plaster is main raw material in refuse battery, it is characterized in that described plumbous oxide be according to described in any one in claim 1 ~ 4, take the preparation method of the plumbous oxide that lead plaster is main raw material in refuse battery prepared take the plumbous oxide that lead plaster is main raw material in refuse battery.
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