CN111170359A - Device and process for preparing red lead from desulfurized lead - Google Patents
Device and process for preparing red lead from desulfurized lead Download PDFInfo
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- CN111170359A CN111170359A CN201811347921.XA CN201811347921A CN111170359A CN 111170359 A CN111170359 A CN 111170359A CN 201811347921 A CN201811347921 A CN 201811347921A CN 111170359 A CN111170359 A CN 111170359A
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- 229910000003 Lead carbonate Inorganic materials 0.000 description 38
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 35
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 29
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- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
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- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
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- 238000007670 refining Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
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- 150000002611 lead compounds Chemical class 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- ZEZOXEBSNSBSGZ-UHFFFAOYSA-N 2-aminoacetic acid;lead Chemical compound [Pb].NCC(O)=O ZEZOXEBSNSBSGZ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 208000037806 kidney injury Diseases 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a device and a process for preparing red lead by desulfurized lead, which comprises the following steps: (1) adding the crushed desulfurized lead plaster and 1-5M amino acid solution into a leaching tank according to the solid-to-liquid ratio of 1: 10-3: 1, adding 10-150% of hydrogen peroxide containing 10-40% of the specific gravity of the desulfurized lead plaster, heating to 40-80 ℃, stirring for 2-4 hours, complexing lead, carrying out solid-liquid separation after the reaction is finished to obtain filtrate and filter cake, and transferring the filtrate into a liquid storage tank for further treatment. The method has the advantages that the desulfurized lead is complexed by adopting the amino acid, so that the extraction of the lead is improved, other complexed metal impurities in the complexed lead are further removed, the extraction purity of the lead is further improved, meanwhile, the complexed lead solution is recycled through the reduction of carbon dioxide, the calcined tail gas is purified and then recycled, the pollution to the environment is reduced, meanwhile, the consumption of raw materials is effectively reduced, the production and processing cost is reduced, and the recovery rate is improved in an environment-friendly manner.
Description
Technical Field
The invention relates to preparation of lead oxide, in particular to a device and a process for preparing red lead by using desulfurized lead.
Background
With the rapid development of industry and the continuous increase of market demand, lead-acid storage batteries are used as starting power supplies of automobiles, ships and the like, standby power supplies of telecom mobile, power plants and the like, power supplies of submarines, electric vehicles and the like, and energy storage power supplies of solar energy and wind energy independent power generation systems, show more and more bright prospects in new material application, and the current yield reaches 24000 kilo VAh. With the technical progress of advanced lead-acid storage batteries, super batteries and the like, the application in the field of new energy automobiles such as lead-acid hybrid power and the like has more obvious cost advantage. The lead reserves and the basic static guarantee years of the reserves in 2003 are 21 years and 43 years respectively, the lead resource is increasingly exhausted, and the recovery of the secondary lead becomes a necessary way for realizing the sustainable development of the lead industry.
The recovery of the secondary lead mainly comes from lead-acid storage battery pole plates, cable armors, pipelines, lead bullets and lead plates, wherein the waste lead-acid storage batteries account for more than 85 percent. According to statistics, by the end of 2010, 67 ten thousand tons of automobile waste storage batteries and 90 ten thousand tons of electric vehicle waste storage batteries are generated in China every year, and if industries such as communication, ships and the like are considered, the quantity of the waste storage batteries is more. However, in the current recovery process, lead-containing waste gas, waste liquid and waste residue are inevitably generated and enter the body through the skin, digestive tract and respiratory tract to be compatible with various organs, so that anemia, nerve dysfunction and kidney injury are caused, and even cancers are induced. Therefore, the efficient, clean and pollution-free recovery of the lead-acid storage battery is realized, the resource problem is solved, the waste is changed into the valuable, the environmental problem is solved, and the lead-acid storage battery is a significant and remote subject.
At present, the treatment process of lead-acid storage batteries at home and abroad is to crush and sort the lead-acid storage batteries and separate out waste electrolyte, grid, organic matters and lead plaster. Wherein: the waste electrolyte is discharged or recycled after further treatment; the grid mainly takes lead and alloy as main energy to be independently recycled; organic matters such as polypropylene plastics can be recycled as byproducts; the lead plaster is mainly a slurry-like substance formed after the active substance on the pole plate is charged and discharged, and the main components of the lead plaster are lead sulfate, lead dioxide, lead oxide, lead and the like. Because the lead plaster contains a large amount of lead sulfate and lead oxides with different valence states exist, the recycling of the lead plaster becomes a research focus of the recycling of the waste lead-acid battery, and the recycling is mainly carried out by a pyrogenic process, a wet process or a dry-wet combined process.
A large amount of sulfur dioxide gas and lead dust pollution can be generated in the pyrogenic process recovery process, the smelting temperature is too high, and the energy consumption is high; in wet or combined wet and dry recovery, lead sulfate is usually converted into easily-treated lead carbonate, and the commonly used desulfurizing agent is sodium carbonate, ammonium carbonate or ammonium bicarbonate, which has certain disadvantages: the sodium carbonate is strong base and weak acid salt, the pH value is high and is not easy to adjust, so that part of converted lead salt is dissolved, and the economic value of the byproduct sodium sulfate is not high; ammonium carbonate and ammonium bicarbonate are unstable and easy to decompose, the desulfurization rate is reduced, and the investment cost is increased. In addition, in the process of converting lead sulfate into lead carbonate by using the desulfurization conversion agent, lead sulfate in lead plaster is often wrapped by new lead carbonate particles and cannot continue to react (about 5% of PbSO4 generally remains in the converted lead plaster), so that the lead plaster is not desulfurized completely, and the problems of unqualified sulfur emission and troublesome lead product recovery process are brought to subsequent treatment. The recovered products of the lead plaster of the waste lead-acid storage battery mainly comprise lead, lead oxide, lead nitrate, lead chloride, tribasic lead sulfate and the like. The patent technology of 'a method for preparing lead oxide by waste lead-acid storage batteries' (CN 101514395A) provides a method for obtaining lead oxide by oxalic acid reduction, nitric acid dissolution, ammonium carbonate conversion, nitric acid dissolution, ammonia water precipitation and lead hydroxide roasting; the patent technology of 'a method for preparing lead nitrate and lead oxide from waste lead storage battery lead plaster' (CN 101857919A) provides a method for obtaining lead oxide by ammonium carbonate conversion, hydrogen peroxide reduction, nitric acid leaching, sodium hydroxide precipitation and lead hydroxide roasting; the patent technology of 'a recycling method of lead plaster in waste lead storage batteries' (CN 102306855A) provides a method for obtaining lead oxide by ammonium bicarbonate conversion, lead dioxide roasting decomposition and lead carbonate roasting decomposition; the patent technology of 'a method for preparing lead compound nano powder applied to the recovery and manufacture of lead-acid storage batteries' (CN 102689922A) provides a method for converting lead in lead plaster into soluble lead salt or lead hydroxide, and then correspondingly adding alkali or acid and one of salts to convert the lead salt into the lead compound nano powder; a process for preparing nano-lead compound from the lead paste of waste lead-acid accumulator (CN 102820496A) includes dissolving in acetic acid, reducing in hydrogen peroxide, and calcining lead acetate crystal to obtain nano-lead oxide.
From the above, although the method for preparing lead oxide by using waste lead-acid storage batteries is complete at one step, the method still has the following defects: in the process of preparing the red lead from the desulfurized diachylon, the raw materials are consumed too much, the lead cannot be leached out completely, the production and preparation cost is increased, the recovery rate is low, and the overstocked capital is large.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a device and a process for preparing red lead by desulfurized lead, which can reduce the cost and improve the product purity.
The technical scheme of the invention is as follows: a device for preparing red lead by desulfurized lead comprises a leaching tank, a purifying tank, a carbonization tank, a pump, a fan, a conveying pipe, a kiln calcining furnace and a solid-liquid separator, wherein the solid-liquid separator comprises a first solid-liquid separator, a second solid-liquid separator and a third solid-liquid separator; the leaching tank is connected with the first solid-liquid separator through a conveying pipe, and the solution after solid-liquid separation is conveyed to the purification tank through the conveying pipe; the purification tank is connected with the second solid-liquid separator through a conveying pipe, and the solution after solid-liquid separation is conveyed into the carbonization tank; the carbonization tank is connected with the third solid-liquid separator, filter cakes obtained after solid-liquid separation are washed and dried and are sent to the kiln calciner, tail gas generated by the kiln calciner is conveyed to the carbonization tank through a fan and a conveying pipe for waste utilization, filtrate returns to the leaching tank through a conveying pipeline for recycling, and pumps are arranged on the conveying pipe.
Further, all be equipped with agitating unit, feed inlet, heater, observation hole and pH valve thermometer on leaching jar, purifying tank and the carbomorphism jar, agitating unit is equipped with the inside of the jar body, the top of the jar body is located with the observation hole to the feed inlet, leach jar cyclic utilization and locate the side of the jar body.
Furthermore, the stirring device is driven by a motor, and the rotating speed is 200-2000 rpm.
Further, the heater is a resistance heater or an electromagnetic heater.
Furthermore, a solid-liquid separator feeding hole and a solid-liquid separator observation hole are formed in the solid-liquid separator.
And further, conveying the filter cake to washing and drying equipment for drying through a conveying device, and returning the washed washing water and the filtrate separated by the third solid-liquid separator to the leaching tank for recycling.
Further, the solid-liquid separator is a membrane filter press.
Further, the solution after solid-liquid separation is pumped into a liquid storage tank for temporary storage for later use.
A device and a process for preparing red lead by desulfurized lead comprise the following steps:
(1) adding the crushed desulfurized lead plaster and 1-5M amino acid solution into a leaching tank according to the solid-to-liquid ratio of 1: 10-3: 1, adding 10-150% of hydrogen peroxide containing 10-40% of the specific gravity of the desulfurized lead plaster, heating to 40-80 ℃, stirring for 2-4 hours, complexing lead, carrying out solid-liquid separation after the reaction is finished to obtain filtrate and filter cake, and transferring the filtrate into a liquid storage tank for further treatment;
(2) transferring the filtrate in the reservoir in the step (1) to a purification tank, adding lead powder according to 2-8 times of the mass fraction of copper in the solution to remove copper in the complex lead solution, controlling the temperature at 45-80 ℃, stirring for 15-60 minutes, performing solid-liquid separation after the reaction is finished to obtain filtrate and filter cake copper slag, and transferring the filtrate to a reservoir for further treatment;
(3) pumping the filtrate in the liquid storage tank in the step (2) into a carbonization tank, introducing gas at normal temperature, stopping introducing gas when the pH value of the slurry is reduced to 6-7, performing solid-liquid separation after the reaction is finished to obtain filtrate and a filter cake, washing the filter cake, then sending the filter cake to a drying process, returning the washed water to the filtrate in the step, transferring the filtrate into the liquid storage tank together, and recycling the water after returning to the step (1);
(4) and (4) transferring the filter cake dried in the step (3) to a kiln calcining furnace, calcining at the temperature of 350-500 ℃ for dust collection, and introducing the calcined tail gas into the step (3) for recycling.
Further, the filter cake in the step (1) is mainly plastic in the lead plaster, crushed materials of the partition paper and a small amount of unleached lead and other metal impurities, the filter cake is washed once by clear water and then sent to a lead refinery for recycling, and washing liquid is added into the filtrate obtained after the reaction in the step (1) is finished and subjected to solid-liquid separation.
Further, the amino acid in the step (1) is one or more of glycine, serine, threonine, cysteine, tyrosine, asparagine and glutamine.
Further, in the step (2), 99% of lead powder is added according to 5 times of the mass fraction of copper in the solution to remove the copper in the complex lead solution, the temperature is controlled at 60 ℃, and the stirring time is 30 minutes.
And (3) further, washing the filter cake copper slag in the step (2), and then packaging and selling the washed filter cake copper slag.
Further, stopping aeration when the pH value of the slurry in the step (3) is reduced to 6.5, wherein the gas is a purified gas containing carbon dioxide.
Further, the cake described in step (3) was washed with one time of water, and the washing water was returned to step (1) together with the filtrate in step (3).
Further, the filter cake in the step (4) is dried at the temperature of 150-200 ℃ until the water content is less than or equal to 1 percent of the lead carbonate powder.
Further, the calcining dust collection in the step (4) adopts a cloth bag to collect dust, and the dust is red lead.
Further, the solid-liquid separation in the steps (1) to (3) adopts a membrane filter press to carry out the solid-liquid separation.
Compared with the prior art, the invention has the following characteristics:
1. the method has the advantages that the extraction of the lead is improved by complexing the desulfurized lead with the amino acid, other complexed metal impurities in the complexed lead are further removed, the extraction purity of the lead is further improved, and meanwhile, the complexed lead solution is repeatedly utilized after being reduced by carbon dioxide, so that the production cost is effectively reduced, the extraction purity of the lead is effectively improved, and the extraction efficiency is improved.
2. The tail gas after calcination is purified and then is introduced into the step (3) to be utilized, so that the pollution to the environment is reduced, the consumption of raw materials is effectively reduced, and the production and processing cost is reduced.
3. The preparation process of the red lead is ingenious in design and simple to operate, the purity of the red lead is effectively improved, meanwhile, part of intermediate substances are recycled, the production cost is effectively reduced, the environment is protected, and the recovery rate is improved.
The detailed structure of the present invention will be further described with reference to the accompanying drawings and the detailed description.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic view of an apparatus for preparing red lead from desulfurized lead in example 1.
1-feed inlet of leaching tank, 2-observation hole of leaching tank, 3-leaching tank, 4-stirring device, 5-pH value thermometer, 6-pump, 7-waste residue, 8-feed inlet of solid-liquid separator, 9-observation hole of solid-liquid separator, 10-first solid-liquid separator, 11-feed inlet of purifying tank, 12-purifying tank, 13-second solid-liquid separator, 14-metal impurity, 15-carbonization tank, 16-third solid-liquid separator, 17-conveyer, 18-washing and drying equipment, 19-kiln calcining furnace, 20-fan, 21-dust collection and 22-reservoir.
Detailed Description
Example 1
As shown in fig. 1: a device for preparing red lead by desulfurized lead comprises a leaching tank 3, a purification tank 12, a carbonization tank 15, a pump 6, a fan 20, a conveying pipe, a kiln calcining furnace 19, a liquid storage tank 22 and solid-liquid separators, wherein each solid-liquid separator comprises a first solid-liquid separator 10, a second solid-liquid separator 13 and a third solid-liquid separator 16.
The crushed desulfurized lead is put into a leaching tank 3 from a feed inlet 1 of the leaching tank, an amino acid solution is added at the same time, a stirrer is driven by a motor to stir, the lead in the desulfurized lead is completely complexed with amino acid, the reaction condition in the leaching tank 3 can be observed through an observation hole 2 of the leaching tank, the leaching tank 3 is connected with a first solid-liquid separator 10 through a conveying pipe, a solution pump 6 which is well complexed in the leaching tank 3 is put into the first solid-liquid separator 10 for solid-liquid separation, the separated waste residue 7 can be further returned to the furnace, and the separated solution is conveyed into a liquid storage tank 22 through the conveying pipe to be transferred into a purifying tank 12.
And (3) putting high-purity lead powder from a feed inlet 11 in the purification tank 12, replacing other metals in the solution, pumping the solution in the purification tank 12 into a second solid-liquid separator 13 through a pump 6 and a conveying pipe, carrying out solid-liquid separation, recovering the separated metal impurities 14 again, conveying the separated solution into a liquid storage tank 22, and transferring the solution into the carbonization tank 15 for further treatment.
Introducing purified carbon dioxide gas into a carbonization tank 15 to regenerate amino acid, connecting the carbonization tank 15 with a third solid-liquid separator 16, conveying a filter cake after solid-liquid separation to washing and drying equipment 18 through a conveyer 17 for drying, pumping washed washing water and filtrate separated by the third solid-liquid separator 16 into a liquid storage tank 22 together to be transferred back to a leaching tank 3 for recycling, conveying the washed and dried filter cake to a kiln calcining furnace 19, conveying tail gas generated by the kiln calcining furnace 19 to the carbonization tank 15 through a fan 20 and a conveying pipe for waste utilization, returning the separated solution to the leaching tank 3 through the conveying pipe for recycling, and arranging pumps 6 on the conveying pipes.
The leaching tank 3, the purifying tank 12 and the carbonization tank 15 are all provided with a stirring device 4, a feeding hole, a heater, an observation hole and a pH value thermometer 5, the stirring device 4 is arranged inside the tank body, the stirring device 4 is driven by a motor, and the rotating speed is 200-2000 rpm; the heating device is arranged at the bottom of the tank body or on the inner wall of the tank body, and the heater is a resistance heater or an electromagnetic heater; the feed inlet and the observation hole are arranged at the top of the tank body, and the leaching tank 3 is circularly utilized and arranged on the side surface of the tank body.
The solid-liquid separator is provided with a solid-liquid separator feeding hole 8 and a solid-liquid separator observation hole 9 for adding other materials and observing the solid-liquid separation condition in the solid-liquid separator.
The solid-liquid separators are all membrane filter presses, so that the filtering effect is outstanding, solid-liquid separation is facilitated, and the efficiency is improved.
The device for preparing the red lead by using the desulfurized lead comprises the following steps:
(1) adding the crushed desulfurized lead plaster and 3M glycine solution into a leaching tank 3 according to the solid-to-liquid ratio of 1:6, adding 300 kg of 21% hydrogen peroxide into each ton of desulfurized lead plaster, heating to 70 ℃, stirring for 3 hours, complexing lead, pumping the reacted slurry into a membrane filter press for solid-liquid separation, pumping the filtrate which is the glycine lead complexing solution into a reservoir 22 for later use, wherein filter cakes mainly comprise plastics in the lead plaster, crushed substances of the partition paper and a small amount of undissolved lead and other metal impurities, washing once by using clear water, and then delivering the filter cakes to a lead refinery for recycling.
(2) Pumping the lead glycinate complexing solution in the liquid storage tank 22 in the step (1) into a purification tank 12, adding 99% of lead powder according to 5 times of the mass fraction of copper in the solution to remove the copper in the lead glycinate complexing solution, controlling the temperature at 60 ℃, stirring for 30 minutes, pumping the slurry into a diaphragm filter press for liquid-solid separation after the reaction is finished, wherein a filter cake is copper-containing slag, washing, packaging and selling, and transferring the filtrate which is the lead glycinate purifying solution into the liquid storage tank 22 for further treatment.
(3) Pumping the amino acid lead purified liquid in the liquid storage tank in the step (2) into a carbonization tank 15, introducing gas containing 2% by volume of carbon dioxide at normal temperature, stopping introducing gas when the pH value of the slurry is reduced to 6.5, carbonizing the solution of lead glycinate in the slurry, precipitating the lead into lead carbonate, regenerating glycine, carrying out solid-liquid separation on the slurry by using a diaphragm filter press, washing a lead carbonate filter cake by using one time of water, then sending the washed lead carbonate filter cake to a drying process, transferring the washing water and the filtrate in the step into the liquid storage tank 22, and returning the washing water to the step (1) for recycling.
(4) And (3) sending the lead carbonate filter cake obtained in the step (3) into flash evaporation drying equipment, drying at the temperature of 180 ℃ until the content of lead carbonate powder is less than or equal to 1%, then conveying the lead carbonate powder into a rotary kiln calcining furnace 19 by using a pipeline, calcining at the temperature of 350-500 ℃ to obtain red lead powder, packaging after collecting dust 21 by using a cloth bag, and conveying carbon dioxide tail gas obtained after collecting dust by using the cloth bag to the step (3) for carbonizing the lead glycinate solution.
Example 2
A device and a process for preparing red lead by desulfurized lead comprise the following steps:
(1) adding the crushed desulfurized lead plaster and 4M glycine solution into a leaching tank 3 according to the solid-to-liquid ratio of 1:5, adding 300 kg of 25% hydrogen peroxide into each ton of desulfurized lead plaster, heating to 70 ℃, stirring for 3 hours, complexing lead, pumping the reacted slurry into a membrane filter press for solid-liquid separation, pumping the filtrate which is the lead glycinate complexing solution into a reservoir 22 for later use, washing filter cakes which are mainly plastics in the lead plaster, crushed substances of the partition paper and a small amount of undissolved lead and other metal impurities once by using clear water, and then delivering the filter cakes to a lead refinery for recycling.
(2) Pumping the lead glycinate complexing solution in the liquid storage tank 22 in the step (1) into a purification tank 12, adding 99% of lead powder according to 4 times of the mass fraction of copper in the solution to remove the copper in the lead glycinate complexing solution, controlling the temperature at 60 ℃, stirring for 30 minutes, pumping the slurry into a diaphragm filter press for liquid-solid separation after the reaction is finished, wherein a filter cake is copper-containing slag, washing, packaging and selling, and transferring the filtrate which is the lead glycinate purifying solution into the liquid storage tank 22 for further treatment.
(3) Pumping the amino acid lead purified liquid in the liquid storage tank 22 in the step (2) into a carbonization tank 16, introducing gas containing 4% of carbon dioxide at normal temperature, stopping introducing gas when the pH value of the slurry is reduced to 6.5, carbonizing the solution of lead glycinate in the slurry, precipitating the lead into lead carbonate, regenerating glycine, carrying out solid-liquid separation on the slurry by using a diaphragm filter press, washing a lead carbonate filter cake by using one time of water, then sending the washed lead carbonate filter cake to a drying process, pumping the washing water and the filtrate in the step into the liquid storage tank 22, and returning the washing water to the step (1) for recycling.
(4) And (3) sending the lead carbonate filter cake obtained in the step (3) into flash evaporation drying equipment, drying at the temperature of 180 ℃ until the content of lead carbonate powder is less than or equal to 1%, then conveying the lead carbonate powder into a rotary kiln calcining furnace 19 by using a pipeline, calcining at the temperature of 400 ℃ to obtain red lead powder, collecting dust 21 by using a cloth bag, packaging, and conveying carbon dioxide tail gas collected by using the cloth bag to the step (3) for carbonizing the lead glycinate solution.
Example 3
Taking a by-product washed off in the acid leaching process in the manufacturing stage of a positive plate of a lead-acid battery production company in Hunan, crushing and desulfurizing the by-product, and analyzing to obtain a lead-containing component and a lead-containing content which are respectively as follows: the Pb content was 13.5%, the PbO content was 21.4%, and the PbCO3 content was 44.6%. The treatment process is as follows:
(1) adding the crushed desulfurized lead plaster and 4M glycine solution into a leaching tank 3 according to the solid-to-liquid ratio of 1:6, adding 300 kg of 21% hydrogen peroxide into each ton of desulfurized lead plaster, heating to 70 ℃, stirring for 3 hours, complexing lead, pumping the reacted slurry into a membrane filter press for solid-liquid separation, transferring the filtrate, namely the lead glycinate complexing solution, into a liquid storage tank 22 for later use, washing filter cakes, mainly comprising plastics in the lead plaster, crushed substances of the partition board paper, a small amount of undissolved lead and other metal impurities, by using clear water, and then delivering the filter cakes to a lead refinery for recycling.
(2) Pumping the lead glycinate complexing solution in the liquid storage tank 22 in the step (1) into a purification tank 12, adding 99% of lead powder according to 4 times of the mass fraction of copper in the solution to remove the copper in the lead glycinate complexing solution, controlling the temperature at 60 ℃, stirring for 30 minutes, pumping the slurry into a diaphragm filter press for liquid-solid separation after the reaction is finished, wherein a filter cake is copper-containing slag, washing, packaging and selling, and transferring the filtrate which is the lead glycinate purifying solution into the liquid storage tank 22 for further treatment.
(3) Pumping the amino acid lead purified liquid in the liquid storage tank 22 in the step (2) into a carbonization tank 16, introducing gas containing 4% of carbon dioxide at normal temperature, stopping introducing gas when the pH value of the slurry is reduced to 6.5, carbonizing the solution of lead glycinate in the slurry, precipitating the lead into lead carbonate, regenerating glycine, carrying out solid-liquid separation on the slurry by using a diaphragm filter press, washing a lead carbonate filter cake by using one time of water, then sending the washed lead carbonate filter cake to a drying process, transferring the washing water and the filtrate in the step into the liquid storage tank 22, and returning the washing water to the step (1) for recycling.
(4) And (3) sending the lead carbonate filter cake obtained in the step (3) into flash evaporation drying equipment, drying at the temperature of 180 ℃ until the content of lead carbonate powder is less than or equal to 1%, then conveying the lead carbonate powder into a rotary kiln calcining furnace 19 by using a pipeline, calcining at the temperature of 400 ℃ to obtain red lead powder, collecting dust 21 by using a cloth bag, packaging, and conveying carbon dioxide tail gas collected by using the cloth bag to the step (3) for carbonizing the lead glycinate solution.
The invention directly processes the lead plaster of the waste lead-acid storage battery by a wet method to produce the red lead without the processes of reduction lead smelting and refining, the processing cost of producing the red lead by each ton of the lead plaster of the waste lead-acid storage battery is reduced by 50 percent, the energy consumption standard coal is reduced by 60 percent, the metal recovery rate reaches 98.5 percent, and the collected red lead powder is analyzed to obtain the red lead powder with the purity of 99.91 percent and the content of impurity copper of 20 ppm. Therefore, the production cost and the consumption of raw materials are effectively reduced, the purity of the red lead preparation is effectively improved, and the recovery rate is higher.
Example 4
Taking a by-product washed off in the acid leaching process in the manufacturing stage of a positive plate of a lead-acid battery production company in Hunan, crushing and desulfurizing the by-product, and analyzing to obtain a lead-containing component and a lead-containing content which are respectively as follows: the Pb content was 12.5%, the PbO content was 18.4%, and the PbCO3 content was 45.6%. The treatment process is as follows:
(1) adding the crushed desulfurized lead plaster and 5M glycine solution into a leaching tank 3 according to the solid-to-liquid ratio of 1:6, adding 300 kg of 21% hydrogen peroxide into each ton of desulfurized lead plaster, heating to 70 ℃, stirring for 3 hours, complexing lead, pumping the reacted slurry into a membrane filter press for solid-liquid separation, transferring the filtrate, namely the lead glycinate complexing solution, into a liquid storage tank 22 for later use, washing filter cakes, mainly comprising plastics in the lead plaster, crushed substances of the partition board paper, a small amount of undissolved lead and other metal impurities, by using clear water, and then delivering the filter cakes to a lead refinery for recycling.
(2) Pumping the lead glycinate complexing solution in the liquid storage tank 22 in the step (1) into a purification tank 12, adding 99% of lead powder according to 5 times of the mass fraction of copper in the solution to remove the copper in the lead glycinate complexing solution, controlling the temperature at 60 ℃, stirring for 30 minutes, pumping the slurry into a diaphragm filter press for liquid-solid separation after the reaction is finished, wherein a filter cake is copper-containing slag, washing, packaging and selling, and pumping the filtrate into the liquid storage tank 22 for further treatment as the lead glycinate purified liquid.
(3) Pumping the amino acid lead purified liquid in the liquid storage tank 22 in the step (2) into a carbonization tank 16, introducing gas containing 3% of carbon dioxide at normal temperature, stopping introducing gas when the pH value of the slurry is reduced to 6.5, carbonizing the solution of lead glycinate in the slurry, precipitating the lead into lead carbonate, regenerating glycine, carrying out solid-liquid separation on the slurry by using a diaphragm filter press, washing a lead carbonate filter cake by using one time of water, then sending the washed lead carbonate filter cake to a drying process, pumping the washing water and the filtrate in the step into the liquid storage tank 22, and returning the washing water to the step (1) for recycling.
(4) And (3) sending the lead carbonate filter cake obtained in the step (3) into flash evaporation drying equipment, drying at the temperature of 180 ℃ until the content of lead carbonate powder is less than or equal to 1%, then conveying the lead carbonate powder into a rotary kiln calcining furnace 19 by using a pipeline, calcining at the temperature of 450 ℃ to obtain red lead powder, packaging after collecting dust 21 by using a cloth bag, and conveying carbon dioxide tail gas obtained after collecting dust by using the cloth bag to the step (3) for carbonizing the lead glycinate solution.
The invention directly processes the lead plaster of the waste lead-acid storage battery by a wet method to produce the red lead without the processes of reduction lead smelting and refining, the processing cost of producing the red lead by each ton of the lead plaster of the waste lead-acid storage battery is reduced by 56 percent, the energy consumption standard coal is reduced by 64 percent, the metal recovery rate reaches 99.2 percent, and the collected red lead powder has the purity of 99.94 percent and the content of impurity copper of 18ppm by analysis. Therefore, the production cost and the consumption of raw materials are effectively reduced, the purity of the red lead preparation is effectively improved, and the recovery rate is higher.
Example 5
A valve-regulated sealed lead-acid battery with the specification of 12V and 55Ah on the market is taken and crushed and separated to obtain lead paste and a waste sulfuric acid solution. The lead paste is desulfurized and then analyzed to obtain lead-containing components with the Pb content of 9.6%, the PbO content of 14.5%, the PbO2 content of 34.8% and the PbCO3 content of 38.7%. The treatment process is as follows:
(1) adding the crushed desulfurized lead plaster and 5M glycine solution into a leaching tank 3 according to the solid-to-liquid ratio of 1:7, adding 350 kg of 24% hydrogen peroxide into each ton of desulfurized lead plaster, heating to 70 ℃, stirring for 3 hours, complexing lead, pumping the slurry after the reaction into a membrane filter press for solid-liquid separation, transferring the filtrate, namely the lead glycinate complexing solution, into a liquid storage tank 22 for later use, washing filter cakes, mainly comprising plastic in the lead plaster, crushed substances of partition paper, a small amount of undissolved lead and other metal impurities, by using clear water, and then delivering the filter cakes to a lead refinery for recycling.
(2) Pumping the lead glycinate complexing solution in the liquid storage tank 22 in the step (1) into a purification tank 12, adding 99% of lead powder according to 4 times of the mass fraction of copper in the solution to remove the copper in the lead glycinate complexing solution, controlling the temperature at 60 ℃, stirring for 30 minutes, pumping the slurry into a diaphragm filter press for liquid-solid separation after the reaction is finished, wherein a filter cake is copper-containing slag, washing, packaging and selling, and pumping the filtrate into the liquid storage tank 22 for later use as the lead glycinate purified liquid.
(3) Pumping the amino acid lead purified liquid in the liquid storage tank 22 in the step (2) into a carbonization tank 16, introducing gas containing 5% by volume of carbon dioxide at normal temperature, stopping introducing gas when the pH value of the slurry is reduced to 6.5, carbonizing the solution of lead glycinate in the slurry, precipitating the lead into lead carbonate, regenerating glycine, carrying out solid-liquid separation on the slurry by using a diaphragm filter press, washing a lead carbonate filter cake by using one time of water, and then sending the lead carbonate filter cake to a drying process, wherein the washing water and the filtrate in the step are pumped into the liquid storage tank 22 together to be returned to the step (1) for recycling.
(4) And (3) sending the lead carbonate filter cake obtained in the step (3) into flash evaporation drying equipment, drying at the temperature of 160 ℃ until the content of lead carbonate powder is less than or equal to 1%, then conveying the lead carbonate powder into a rotary kiln calcining furnace 19 by using a pipeline, calcining at the temperature of 400 ℃ to obtain red lead powder, packaging after collecting dust 21 by using a cloth bag, and conveying carbon dioxide tail gas obtained after collecting dust by using the cloth bag to the step (3) for carbonizing the lead glycinate solution.
The invention directly processes the lead plaster of the waste lead-acid storage battery by a wet method to produce the red lead without the processes of reduction lead smelting and refining, the processing cost of producing the red lead by each ton of the lead plaster of the waste lead-acid storage battery is reduced by 54 percent, the energy consumption standard coal is reduced by 65 percent, the metal recovery rate reaches 99.3 percent, and the collected red lead powder has the purity of 99.95 percent and the content of impurity copper of 19ppm by analysis. Therefore, the production cost and the consumption of raw materials are effectively reduced, the purity of the red lead preparation is effectively improved, and the recovery rate is higher.
The preferred embodiments of the present invention have been described in detail above, but it is apparent that the present invention is not limited to the above embodiments. Within the scope of the technical idea of the invention, many equivalent modifications can be made to the technical solution of the invention, and these equivalent modifications are all within the protection scope of the invention. In addition, it should be noted that the respective technical features described in the above-described embodiments may be separately and independently combined as long as they are within the technical concept of the present invention.
Claims (10)
1. A device for preparing red lead by desulfurized lead comprises a leaching tank, a purifying tank, a carbonization tank, a pump, a fan, a conveying pipe, a kiln calcining furnace and a solid-liquid separator, wherein the solid-liquid separator comprises a first solid-liquid separator, a second solid-liquid separator and a third solid-liquid separator; the leaching tank is connected with the first solid-liquid separator through a conveying pipe, and the solution after solid-liquid separation is conveyed to the purification tank through the conveying pipe; the purification tank is connected with the second solid-liquid separator through a conveying pipe, and the solution after solid-liquid separation is conveyed into the carbonization tank; the method is characterized in that:
the carbonization tank is connected with the third solid-liquid separator, filter cakes obtained after solid-liquid separation are washed and dried and are sent to the kiln calciner, tail gas generated by the kiln calciner is conveyed to the carbonization tank through a fan and a conveying pipe for waste utilization, filtrate returns to the leaching tank through a conveying pipeline for recycling, and pumps are arranged on the conveying pipe.
2. The device for preparing red lead according to the desulfurized lead according to claim 1, wherein the leaching tank, the purification tank and the carbonization tank are respectively provided with a stirring device, a feed inlet, a heater, an observation hole and a pH value thermometer, the stirring device is arranged in the tank body, the feed inlet and the observation hole are arranged at the top of the tank body, and the leaching tank is arranged on the side surface of the tank body in a recycling manner.
3. The apparatus for preparing red lead by desulfurizing lead according to claim 2, wherein the stirring device (4) is driven by a motor and has a rotation speed of 200-2000 rpm; the heater is a resistance heater or an electromagnetic heater.
4. The device for preparing red lead by desulfurizing lead according to claim 1, wherein the solution after solid-liquid separation is pumped into a liquid storage tank for temporary storage; the solid-liquid separator is provided with a solid-liquid separator feeding hole and a solid-liquid separator observation hole; the solid-liquid separator is a membrane filter press.
5. The device for preparing red lead by desulfurizing lead according to claim 1, wherein the filter cake is conveyed to a washing and drying device for drying by a conveyer, and the washed washing water and the filtrate separated by the third solid-liquid separator are returned to the leaching tank for recycling.
6. A device and a process for preparing red lead by desulfurized lead are characterized by comprising the following steps:
(1) adding the crushed desulfurized lead plaster and 1-5M amino acid solution into a leaching tank according to the solid-to-liquid ratio of 1: 10-3: 1, adding 10-150% of hydrogen peroxide containing 10-40% of the specific gravity of the desulfurized lead plaster, heating to 40-80 ℃, stirring for 2-4 hours, complexing lead, carrying out solid-liquid separation after the reaction is finished to obtain filtrate and filter cake, and transferring the filtrate into a liquid storage tank for further treatment;
(2) transferring the filtrate in the reservoir in the step (1) to a purification tank, adding lead powder according to 2-8 times of the mass fraction of copper in the solution to remove copper in the complex lead solution, controlling the temperature at 45-80 ℃, stirring for 15-60 minutes, performing solid-liquid separation after the reaction is finished to obtain filtrate and filter cake copper slag, and transferring the filtrate to a reservoir for further treatment;
(3) pumping the filtrate in the liquid storage tank in the step (2) into a carbonization tank, introducing gas at normal temperature, stopping introducing gas when the pH value of the slurry is reduced to 6-7, performing solid-liquid separation after the reaction is finished to obtain filtrate and a filter cake, washing the filter cake, then sending the filter cake to a drying process, returning the washed water to the filtrate in the step, transferring the filtrate into the liquid storage tank together, and recycling the water after returning to the step (1);
(4) and (4) transferring the filter cake dried in the step (3) to a kiln calcining furnace, calcining at the temperature of 350-500 ℃ for dust collection, and introducing the calcined tail gas into the step (3) for recycling.
7. The device and the process for preparing red lead by desulfurizing lead according to claim 6, wherein the filter cake in step (1) is mainly plastic in lead plaster, crushed substance of partition paper and a small amount of unlysed lead and other metal impurities, and is washed once by clear water and then sent to a lead refinery for recycling, and the washing liquid is added into the filtrate of solid-liquid separation after the reaction in step (1); the amino acid is one or more of glycine, serine, threonine, cysteine, tyrosine, asparagine and glutamine.
8. The device and the process for preparing the red lead by desulfurizing lead according to claim 6, wherein 99% of lead powder is added in the step (2) according to 5 times of the mass fraction of copper in the solution to remove the copper in the complex lead solution, the temperature is controlled at 60 ℃, and the stirring time is 30 minutes; and washing the filter cake copper slag, and then packaging and selling the filter cake copper slag.
9. The apparatus and process for preparing red lead by desulfurizing lead according to claim 6, wherein the aeration is stopped when the pH value of the slurry is reduced to 6.5 in step (3), and the gas is a purified gas containing carbon dioxide; washing the filter cake with one time of water, and returning the washing water and the filtrate obtained in the step (3) to the step (1); drying the filter cake in the step (4) at the temperature of 150-200 ℃ until the water content is less than or equal to 1 percent; and (4) collecting dust by adopting a cloth bag in the calcining dust collection process, wherein the dust is the red lead.
10. The device and the process for preparing red lead by desulfurizing lead according to any one of claims 6 to 9, wherein the solid-liquid separation in the steps (1) to (3) is performed by a membrane filter press.
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| CN112694119A (en) * | 2020-12-09 | 2021-04-23 | 超威电源集团有限公司 | Preparation method of red lead |
| CN113526546A (en) * | 2021-07-08 | 2021-10-22 | 超威电源集团有限公司 | System and method for preparing battery-grade lead oxide by clean conversion of waste lead paste |
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| CN112694119A (en) * | 2020-12-09 | 2021-04-23 | 超威电源集团有限公司 | Preparation method of red lead |
| CN113526546A (en) * | 2021-07-08 | 2021-10-22 | 超威电源集团有限公司 | System and method for preparing battery-grade lead oxide by clean conversion of waste lead paste |
| CN113526546B (en) * | 2021-07-08 | 2023-09-08 | 安徽超威电源有限公司 | System and method for preparing battery-grade lead oxide through clean conversion of waste lead paste |
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Application publication date: 20200519 |