CN107768759B - Method for preparing tribasic lead sulfate from lead oxide waste - Google Patents
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
FromA method for preparing tribasic lead sulfate from lead oxide waste belongs to the technical field of clean recovery of effective resources. Which comprises the following steps: a. and (3) vulcanization process: the lead oxide waste is subjected to a sulfurization treatment to convert the lead-containing components thereof to PbSO4A solid; b. and (3) complexing: the above-mentioned PbSO-containing solution is mixed with4Dissolving the solid in a complexing agent solution to obtain a lead-containing solution and filter residue; c. and (3) crystallization process: and (3) carrying out crystallization reaction on the lead-containing solution to respectively obtain a tribasic lead sulfate product and a complexing agent solution. The method can be widely applied to lead oxide waste materials from various sources, has clean and energy-saving process, reduces the production cost of tribasic lead sulfate while changing the lead oxide waste materials into valuables, and has high application value in the lead resource industry.
Description
Technical Field
The invention belongs to the technical field of clean recovery of effective resources, and particularly relates to a method for treating lead oxide waste, in particular to a method for preparing tribasic lead sulfate from lead oxide waste.
Background
Lead is one of the commonly used metals, and its yield is the fourth place in non-ferrous metals. According to different sources of lead resources, the lead resources are generally divided into primary resources and secondary resources, namely lead ores and secondary lead. The current proven reserves of lead worldwide are reported to be used on the existing production scale, with a service life of only 10-12 years. With the increasingly depleted natural lead resources, secondary lead resources become the main raw material for realizing the sustainable development of the lead industry. The raw materials of the secondary lead mainly come from the polar plates of the waste lead-acid storage batteries, cable armoring, pipelines, lead bullets and lead plates, wherein the waste lead-acid storage batteries account for more than 85 percent. In the waste lead-acid storage battery recovery technology, the treatment of lead plaster is the key. The lead plaster is mainly a slurry-like substance formed after the active substance on the polar plate is charged and discharged, wherein PbSO4About 40-50% by mass of PbO2The mass fraction is about 28-35%, the mass fraction of PbO is about 9-12%, and the mass fraction of Pb is about 4-11%. After the waste lead plaster is washed by water to primarily remove partial impurities, different methods are utilized to desulfurize and reduce, and corresponding fine processing is carried out to obtain the required refined lead, basic lead sulfate, lead chloride, lead oxide and the like.
The basic lead sulfate mainly comprises tribasic lead sulfate (abbreviated as 3BS) and tetrabasic lead sulfate (abbreviated as 4BS), wherein the tribasic lead sulfate is widely applied to the plastic industry, has the advantages of excellent heat resistance, electric insulation, light stability, no color change and the like, has a heat stabilizing effect on polyvinyl chloride, and is widely applied to polyvinyl chloride insulating materials, paint pigments, wires, cables and additives for improving the performance of batteries so as to prepare lead-acid storage batteries and the like. The 3BS is used as an additive and is added into the lead plaster according to 3% of the mass of the lead plaster to manufacture the positive plate which is assembled into a battery, and a charge and discharge test is carried out. With the rapid development of economy, the use amount of polyvinyl chloride plastics, storage batteries and the like is increased, the demand for tribasic lead sulfate is increased, and the aim of recycling resources becomes the focus of attention of researchers at present.
At present, the conventional process flow, such as a lead oxide method and a lead blue method, is mostly adopted for preparing tribasic lead sulfate. The two processes have the advantages that the adopted raw material is pure lead without purification and impurity removal, so the process flow is simpler, but the defects of higher raw material price and high production cost exist. How to reduce the price of raw materials and thus the production cost becomes the key for preparing tribasic lead sulfate.
Disclosure of Invention
The invention aims to provide a novel method for preparing tribasic lead sulfate, which utilizes high-value utilization of waste containing lead oxide, thereby reducing the preparation cost and environmental pollution.
Based on the above purpose, the preparation method of tribasic lead sulfate provided by the invention comprises the following steps:
a. and (3) vulcanization process: the lead oxide waste is subjected to a sulfurization treatment to convert the lead-containing components thereof to PbSO4A solid;
b. and (3) complexing: the above-mentioned PbSO-containing solution is mixed with4Dissolving the solid in a complexing agent solution to obtain a lead-containing solution and filter residue;
c. and (3) crystallization process: and (3) carrying out crystallization reaction on the lead-containing solution, namely carrying out decompression and cooling operation, and respectively obtaining a tribasic lead sulfate product and a complexing agent solution.
In the step a, during the vulcanization process, the lead oxide waste material needs to be vulcanized by using a sulfuric acid solution, so that a lead-containing component in the lead oxide waste material reacts with the sulfuric acid solution to generate lead sulfate, wherein the main reaction formula is as follows:
PbO+H2SO4＝PbSO4+H2O (1)
in the sulfuration process, the concentration of the sulfuric acid is generally controlled to be 0.1-18mol/L, the preferred concentration is 1-7mol/L, the most preferred concentration is 2-6mol/L, the reaction temperature is generally controlled to be 0-110 ℃, the reaction time is generally 1-300min, and the stirring speed is 10-1000 r/min. After the lead oxide waste is subjected to sulfation treatment, solid-liquid separation is carried out to obtain PbSO4Crude product and sulfuric acid mother liquor.
Generally, the lead oxide scrap contains impurities such as metallic lead, lead dioxide, lead perchlorate, and lead sulfide, in addition to lead oxide. Thus, when other lead-containing constituents are also present in the lead oxide waste, they can be converted to lead sulphate by a sulphidation reaction. For example Pb, PbO2、Pb(ClO4)2The sulfurization reaction with PbS is as follows:
Pb+H2SO4＝PbSO4+H2 (2)
PbO2+H2SO4＝PbSO4+H2O+1/2O2 (3)
Pb(ClO4)2+H2SO4＝PbSO4+2HClO4 (4)
PbS+H2SO4＝PbSO4+H2S (5)
although the reaction (5) is a reaction with a weak equilibrium, it is preferable in the present invention to accelerate the reaction rate on the one hand and to increase the reaction yield on the other hand by adding a vulcanization accelerator during the vulcanization. The vulcanization accelerator is mainly selected from any one or more of the following chemical components (1) amine accelerators, (2) acetic acid accelerators and (3) metal salt accelerators.
Further preferably:
(1) amine accelerators: one or more of ethylenediamine, methylamine, propylamine, propylenediamine, 2-methylpropylamine and the like.
(2) Acetic acid accelerator: acetic acid, fluoroacetic acid, chloroacetic acid, phenylacetic acid and the like.
(3) Metal salt accelerator: copper sulfate, ferrous sulfate, cobalt sulfate, tin sulfate, silver sulfate, mercurous sulfate, nickel sulfate, zinc sulfate, chromium sulfate, manganese sulfate and the like.
Respectively taking an amine accelerator, an acetic acid accelerator and a metal salt accelerator, and mixing according to the weight ratio of (0-1) to (0-10) to (0-100) to obtain the composite vulcanization accelerator, wherein three values in the weight ratio cannot be zero at the same time. The weight percentage content of the compound vulcanization accelerator in the sulfuric acid is controlled to be 0.1-30%, wherein the weight percentage content is preferably 0.5-15%, and the weight percentage content is more preferably 1-10%.
In the above vulcanization process of the present invention, it is further preferred to use air as a reaction co-promoter, wherein the flow rate of blown air is 0.001 to 1L/s, preferably 0.01 to 0.5L/s, per liter of the reaction liquid.
In the presence of the above vulcanization accelerator and synergistic accelerator, the reaction formulae of the above (2) and (5) can be expressed as:
Pb+1/2O2+H2SO4＝PbSO4+H2O (2)
PbS+1/2O2+H2SO4＝PbSO4+H2O+S (5)
the research shows that: because the density of the lead is higher, the air is taken as the vulcanization accelerator, and the disturbance and suspension of bubbles exist in the vulcanization reaction process, so that the effective stirring effect and the oxidation effect are achieved, and the vulcanization process of the lead-containing material is accelerated.
After the sulfuration process, the lead-containing component in the lead oxide waste reacts with the sulfuric acid solution to generate a crude lead sulfate product.
In the complexing process of the step b, the crude lead sulfate product needs to be subjected to complexing reaction treatment by using a complexing agent solution, so that the lead sulfate in the crude lead sulfate product reacts with the complexing agent solution to be dissolved in the complexing agent solution, and the aim of separating the lead sulfate from impurities is fulfilled.
The complexing agent is A + B type, wherein A is selected from an aqueous solution of alkaline gas, and B is selected from one of ammonium salt, alicyclic amine or amide.
The alkaline gas is preferably selected from ammonia, phosphine, methylamine, dimethylamine or trimethylamine; wherein the ammonium salt is preferably selected from ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium sulfite, ammonium bisulfate, or ammonium nitrate; wherein the alicyclic amine is preferably selected from triethylenediamine, diethylenetriamine, hexamethylenetetramine or hexamethyleneimine; wherein the amide is preferably selected from formamide, acetamide, propionamide or butyramide.
The concentration of A in the complexing agent solution in the step b is 1.0-30.0 mol/L, preferably 5.0-25.0 mol/L, and more preferably 8.0-15.0 mol/L. The concentration of B is 1.0mol/L-10.0 mol/L.
By NH3·H2O+(NH4)2SO4As an example of a complexing agent solution, the main reaction formula is as follows:
2PbSO4+2NH3·H2O＝(NH4)2SO4+Pb2(OH)2SO4 (6)
(NH4)2SO4+Pb2(OH)2SO4+6NH3＝2[Pb(NH3)4]SO4+2H2O (7)
during the complexation reaction, NH3·H2The molar concentration of O is 1.0mol/L to 30.0mol/L, preferably 5.0mol/L to 25.0mol/L, and more preferably 8.0mol/L to 15.0 mol/L. (NH)4)2SO4The molar concentration of (b) is 1.0mol/L-10.0 mol/L. The reaction temperature is generally controlled at 0-110 ℃, the reaction time is generally 1-300min, and the stirring speed is 10-1000 r/min. After the complex reaction of the crude lead sulfate, the solid-liquid separation is carried out to obtain the lead-containing complex [ Pb (N)H3)4]SO4And insoluble impurities.
In the complexing reaction process of the present invention, it is further preferable to introduce a corresponding alkaline gas into the complexing agent solution to promote the lead-containing complex [ Pb (NH)3)4]SO4Generating; wherein the flow rate of the corresponding alkaline gas is 0.001-1L/s for each liter of reaction liquid, and the preferred flow rate is 0.01-0.5L/s.
The research shows that: due to Pb2(OH)2SO4The density of the lead-containing solution is high, the introduced alkaline gas has disturbance of bubbles in the complexing reaction process, so that the lead-containing solution is effectively stirred, and the complexing process of the lead-containing solution is accelerated.
In the step c of crystallization, the lead-containing complex [ Pb (NH) according to the invention3)4]SO4The solution of (2) is subjected to a decompression operation and a cooling operation. Lead-containing complexes [ Pb (NH)3)4]SO4The solution is decompressed to remove the alkaline gas, and the alkaline gas can be returned to the complexing process for recycling.
And cooling the lead-containing solution after the alkaline gas is removed to separate out tribasic lead sulfate crystals, and simultaneously obtaining a complexing agent solution containing ammonium sulfate, wherein the solution can be recycled as the complexing agent solution in the complexing process. The main reaction formula of the crystallization process is as follows:
4[Pb(NH3)4]SO4+4H2O＝3(NH4)2SO4+10NH3+(PbO)3·PbSO4·H2O (8)
in the crystallization reaction process, the reaction pressure is generally controlled to be (-0.01MPa) - (-0.1MPa), the reaction temperature is generally controlled to be 0-60 ℃, the reaction time is generally 1-600min, and the stirring speed is 10-1000 r/min. Lead-containing solution [ Pb (NH)3)4]SO4After crystallization reaction, solid-liquid separation is carried out to obtain tribasic lead sulfate products and a recyclable complexing agent solution.
Drawings
Figure 1 is a schematic diagram of a process flow for the preparation of tribasic lead sulphate from lead oxide waste.
Detailed Description
Hereinafter, exemplary embodiments will be described in more detail, but the present invention is not limited to the following examples.
The invention provides a novel method for preparing tribasic lead sulfate, which utilizes high-value load utilization of waste containing lead oxide, thereby reducing the preparation cost and environmental pollution.
Specifically, the invention firstly carries out the vulcanization treatment on the lead oxide waste material through the vulcanization process, so that the lead-containing component in the lead oxide waste material is converted into the lead-containing PbSO4A solid; then the PbSO is added through a complexing process4Dissolving the solid in a complexing agent solution to obtain a lead-containing solution and filter residue; and finally, carrying out crystallization reaction on the lead-containing solution in a crystallization process to respectively obtain a tribasic lead sulfate product and a complexing agent solution.
The invention also provides a method for preparing lead in lead oxide-containing waste into [ Pb (NH) in the process of preparing tribasic lead sulfate3)4]SO4A method of complexing. Specifically, the lead oxide waste refers to any one of lead paste in waste lead-acid batteries, acid leaching byproducts of positive plates in the manufacturing of lead-acid batteries, flue dust containing lead oxide or lead oxide ore, lead oxide-containing waste in the production of other fields, and the like. The waste material containing lead oxide reacts with sulfuric acid under the action of the compound vulcanization accelerator to be converted into lead sulfate, and the obtained lead sulfate reacts with a complexing agent solution in the complexing process to generate a lead-containing complex [ Pb (NH)3)4]SO4The solution of (1). Finally, lead-containing complex [ Pb (NH)3)4]SO4The solution is decompressed and cooled to finally obtain the tribasic lead sulfate product.
In one embodiment, the simultaneous preparation of [ Pb (NH) is illustrated by the example of recovering lead from lead mud containing lead oxide from lead-acid batteries of Hubei to produce tribasic lead sulfate3)4]SO4A method of complexing. The whole process comprises the following steps: carrying out a sulfurization reaction process on lead mud containing lead oxide and the subsequent processA complex reaction process and a crystallization reaction process.
And (3) a vulcanization reaction process:
the raw material in the process of the sulfuration reaction is lead mud containing lead oxide, and the lead in the lead mud exists in the form of a mixture of lead and lead oxide through physical and chemical measurement. In this process, the rationale for the sulfidation reaction is: pb and PbO in lead mud containing lead oxide can react with sulfuric acid under the action of the compound vulcanization accelerator to be converted into lead sulfate, so that the lead-containing raw material can be converted into PbSO to the maximum extent4And the recovery rate of the lead-containing raw material in the lead oxide waste is improved.
The vulcanization reaction process comprises the following steps:
(I) reacting lead mud containing lead oxide with a mixed solution of sulfuric acid and a compound vulcanization accelerator to enable Pb and PbO in the lead mud containing lead oxide to generate lead sulfate, wherein the concentration of the sulfuric acid is 0.1-18mol/L, the weight percentage content of the compound vulcanization accelerator in the sulfuric acid is controlled to be 0.1-30%, and the reaction temperature is 0-110 ℃. Preferably, an acetic acid solution with a sulfuric acid concentration of 3mol/L and a concentration of 2.5mol/L is used as a reaction promoter, and 0.1L of air is blown in during the reaction as a reaction synergistic promoter, and the reaction temperature is 50 ℃.
In the reaction of step (I), H2SO4It may be the waste sulfuric acid in the waste battery, the additional sulfuric acid, or a mixture of the waste sulfuric acid and the additional sulfuric acid. The acetic acid solution is the main promoter of the reaction and air is the synergistic promoter of the reaction.
The specific reaction is as follows:
PbO+H2SO4＝PbSO4+H2O
Pb+1/2O2+H2SO4＝PbSO4+H2O
the solution system in step (I) after the reaction includes lead sulfate, sulfuric acid, acetic acid, lead acetate and other impurities in the lead slime.
(II) carrying out filter pressing or centrifugal separation on the solution system in the step (I) to obtain a crude lead sulfate product and a mother solution containing sulfuric acid, acetic acid and lead acetate. And (5) the obtained lead sulfate crude product is ready for use.
The process of the complex reaction:
the raw material in the process of the complex reaction is the crude lead sulfate product obtained in the process of the sulfuration reaction. In the process, the crude lead sulfate is mixed with added complexing agent solution (NH)3·H2O+(NH4)2SO4) Reaction to generate lead-containing complex [ Pb (NH)3)4]SO4. In this process, the basic principle of the complexation reaction is: PbSO4Easily dissolved in complexing agent solution containing alkaline gas and PbSO4The solubility therein is closely related to the concentration of the alkaline gas. Therefore, the solution containing the alkaline gas complexing agent with higher concentration is selected to dissolve the crude lead sulfate product, PbSO4Can be dissolved in the water quickly and sufficiently, thereby realizing the separation from other impurities.
Specifically, the complexation reaction process actually comprises two consecutive reactions:
(1) the reaction between lead sulfate and ammonia, the reaction formula can be represented as:
2PbSO4+2NH3·H2O＝(NH4)2SO4+Pb2(OH)2SO4
(2) newly generated Pb2(OH)2SO4And (NH)4)2SO4The solution reacts, ammonia gas is introduced at the same time, and [ Pb (NH) is generated by the reaction3)4]SO4Thereby obtaining a catalyst containing [ Pb (NH)3)4]SO4、(NH4)2SO4And NH3·H2The reaction formula of the mixed solution of O can be represented as:
(NH4)2SO4+Pb2(OH)2SO4+6NH3＝2[Pb(NH3)4]SO4+2H2O
control of NH during reaction3·H2The concentration of O is 1.0mol/L-30.0mol/L, (NH)4)2SO4The concentration of (b) is 1.0mol/L to 10.0 mol/L. Wherein, for each liter of reaction liquid, the flow of the corresponding alkaline gas is 0.001-1L/s. The reaction temperature is 0-110 DEG CThe reaction time is 1-300 min. Preferably, NH3·H2The concentration of O is 12.0mol/L, (NH)4)2SO4The concentration of (A) is 4.0mol/L, the flow rate of the alkaline gas is 0.3L/s, the reaction temperature is 45 ℃, and the reaction time is 30 min.
The crystallization reaction process:
the raw material of the crystallization reaction process is a lead-containing complex [ Pb (NH) obtained in the complexation reaction process3)4]SO4The solution of (1). The solution is decompressed to fully remove ammonia gas in the solution, so that tribasic lead sulfate is generated by reaction, and the removed ammonia gas can be returned to the complexing process for recycling. And then cooling to separate out tribasic lead sulfate crystals and obtain a complexing agent solution containing ammonium sulfate, wherein the solution can be recycled. In this process, the basic principle of the crystallization reaction is: the lead-containing complex [ Pb (NH) is removed by utilizing the characteristic that ammonia gas is easily volatilized under low pressure3)4]SO4The solution of (2) is subjected to a pressure reduction operation and the temperature of the solution is lowered to precipitate crystals of the tribasic lead sulfate produced.
Specifically, the main reaction formula of the crystallization reaction process is as follows:
4[Pb(NH3)4]SO4+4H2O＝3(NH4)2SO4+10NH3+(PbO)3·PbSO4·H2O
in the crystallization reaction process, the reaction pressure is controlled to be (-0.01MPa) - (-0.1MPa), the reaction temperature is controlled to be 0-60 ℃, the reaction time is 1-600min, and the stirring speed is 10-1000 r/min. Preferably, the reaction pressure is-0.08 MPa, the reaction temperature is 30 ℃, the reaction time is 300min, and the stirring speed is 200 r/min.
The method for preparing tribasic lead sulfate adopted by the invention has the following advantages:
compared with the prior art for preparing tribasic lead sulfate, the process disclosed by the invention is more energy-saving and environment-friendly, and the process conditions are milder. The whole preparation process is a wet process without a high-temperature roasting treatment process. Therefore, the method is an environment-friendly and economic wet method for preparing tribasic lead sulfate.
And the complexing agent solution can be recycled. The method fully utilizes the characteristics that alkaline gas is easily dissolved in water under high pressure and is volatile under low pressure, can remove the alkaline gas through decompression operation in the crystallization process, and obtains the solution of the complexing agent component B while crystallizing and separating out tribasic lead sulfate through cooling operation. The obtained solution of the alkaline gas and the complexing agent component B can be recycled as a complexing agent solution.
In conclusion, the invention provides a new method for preparing tribasic lead sulfate from lead oxide waste, and the method is an energy-saving and environment-friendly wet process.
Example 1
Waste valve-controlled sealed lead-acid batteries with the specifications of 12V and 55Ah in the market are crushed and separated by a conventional method to obtain lead paste and a waste sulfuric acid solution. The lead paste is obtained by traditional chemical titration analysis, wherein the lead-containing component and the content of the lead-containing component are respectively 9.8% of Pb content, 15.6% of PbO content and PbO content2Content 33.7% and PbSO4The content was 39.8%. Then adding the lead plaster into a sulfuric acid solution for carrying out a vulcanization reaction, wherein the treatment process is as follows:
(1) and (3) vulcanization process: 1.0kg of the lead plaster was charged into a 10L vulcanization reactor, and 7.0L of a 6.0mol/L sulfuric acid solution was added to the reactor, together with 0.2L of a 2.5mol/L acetic acid solution as a reaction accelerator. 0.1L of air is blown in during the reaction process to be used as a synergistic promoter of the reaction, and the reaction is stirred for 2 hours at the constant temperature of 50 ℃, wherein the stirring speed is 350 r/min. The mixture obtained after the reaction was filtered and separated to obtain 1.18kg of PbSO4Crude product and sulfuric acid mother liquor. Wherein the PbSO4The crude product was analyzed and found to be 99.5% PbSO4And a very small amount of insoluble impurities. The sulfuric acid mother liquor is recycled as the next vulcanization process solution, and the PbSO is added4The crude product is transferred to the subsequent complexing process for treatment.
(2) And (3) complexing: the PbSO is added4Transferring the crude product into a 10L complexing reactor containing 5.0L NH3·H2O-(NH4)2SO4The solution being a complexing solution in which NH3·H2The O concentration is 8.0mol/L, (NH)4)2SO4The concentration was 6.0 mol/L. 0.2L of ammonia gas is blown in as a reaction promoter in the reaction process, and the reaction is stirred for 20min at the constant temperature of 50 ℃, and the stirring speed is 400 r/min. And then carrying out solid-liquid separation on the reaction mixture to obtain filter residue containing a small amount of insoluble impurities and a lead-containing solution.
(3) And (3) crystallization process: and transferring the obtained lead-containing solution into a reduced pressure reactor, continuously reacting for 1h under the pressure of-0.1 MPa to obtain the deaminated lead-containing solution and ammonia gas, and returning the ammonia gas to the complexing process for recycling. Transferring the obtained deaminated lead-containing solution into a cooling reactor, reacting at 30 ℃, stirring at a speed of 450r/min, and carrying out solid-liquid separation after 6 hours to obtain a tribasic lead sulfate product and a complexing agent solution, wherein the complexing agent solution is returned to the complexing process for recycling.
Through calculation, 0.96kg of tribasic lead sulfate product is finally prepared by the process flow, the purity of the tribasic lead sulfate product is 99.93 percent, and the comprehensive recovery rate of lead is 99.23 percent.
Example 2
2kg of a material containing lead oxide from a certain mining company in Zhejiang, is crushed into powder by a ball mill, and the lead oxide (PbO) is mainly 75 percent through physical and chemical measurement, and the rest is ferric oxide and clay. Then adding the material containing lead oxide into a sulfuric acid solution for carrying out a vulcanization reaction, wherein the treatment process is as follows:
(1) and (3) vulcanization process: 2kg of the lead oxide-containing material was charged into a 10L vulcanization reactor, and 5.0L of a 6.0mol/L sulfuric acid solution was added to the reactor, together with 0.2L of a 2.3mol/L propylamine solution as a reaction accelerator. 0.15L of air is blown in during the reaction process to be used as a synergistic promoter of the reaction, and the reaction is stirred for 1.5h at the constant temperature of 60 ℃, wherein the stirring speed is 300 r/min. Filtering and separating the mixture obtained after the reaction to obtain 2.04kg of PbSO4Crude product and sulfuric acid mother liquor. Wherein the PbSO4The crude product was analyzed and found to be 99.6% PbSO4And a very small amount of insoluble impurities. Taking the sulfuric acid mother liquor as the next vulcanization processRecycling the solution and simultaneously using the PbSO4The crude product is transferred to the subsequent complexing process for treatment.
(2) And (3) complexing: the PbSO is added4Transferring the crude product into a 10L complexing reactor containing 5.0L NH3·H2O-NH4HSO4The solution is used as complexing agent solution, wherein NH3·H2O concentration is 8.5mol/L, NH4HSO4The concentration was 6.5 mol/L. 0.25L of ammonia gas is blown in as a reaction promoter in the reaction process, and the reaction is carried out for 25min under the constant temperature of 40 ℃ with the stirring speed of 380 r/min. And then carrying out solid-liquid separation on the reaction mixture to obtain filter residue containing a small amount of insoluble impurities and a lead-containing solution.
(3) And (3) crystallization process: and transferring the obtained lead-containing solution into a reduced pressure reactor, continuously reacting for 1.5h under the pressure of-0.08 MPa to obtain the deaminated lead-containing solution and ammonia gas, and returning the ammonia gas to the complexing process for recycling. Transferring the obtained deaminated lead-containing solution into a cooling reactor, reacting at 25 ℃, stirring at a speed of 430r/min, reacting for 5 hours, and performing solid-liquid separation to obtain a tribasic lead sulfate product and a complexing agent solution, wherein the complexing agent solution is returned to the complexing process for recycling.
Through calculation, 1.66kg of tribasic lead sulfate product is finally prepared by the process flow, the purity of the tribasic lead sulfate product is 99.95 percent, and the comprehensive recovery rate of lead is 99.85 percent.
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 Henan, and obtaining lead-containing components and contents in the by-product through traditional chemical titration analysis, wherein the lead-containing components and the contents are respectively as follows: 9.2% of Pb, 18.2% of PbO, and PbSO4The content was 35.6% and the moisture content was 36.1%. The by-product is then added to a sulfuric acid solution to carry out a sulfidation reaction. The treatment process is as follows:
(1) and (3) vulcanization process: 1.0kg of by-products washed off in the acid spraying process in the manufacturing stage of the positive plate is added into a 10L vulcanization reactor, 5.0L of sulfuric acid solution with the concentration of 3.5mol/L is added into the reactor, and 0.3L of ethylenediamine solution with the concentration of 2.3mol/L is added into the reactor as the reactionThe accelerator of (1). 0.16L of air was bubbled in during the reaction as a synergistic promoter for the reaction. Stirring and reacting for 2.5h at the constant temperature of 65 ℃, wherein the stirring speed is 330 r/min. Filtering and separating the mixture obtained after the reaction to obtain 0.74kg of PbSO4Crude product and sulfuric acid mother liquor. Wherein the PbSO4The crude product was analyzed and found to be 99.4% PbSO4And a very small amount of insoluble impurities. The sulfuric acid mother liquor is recycled as the next vulcanization process solution, and the PbSO is added4The crude product is transferred to the subsequent complexing process for treatment.
(2) And (3) complexing: the PbSO is added4Transferring the crude product into a 10L complexing reactor, and taking 3.0L methylamine-triethylenediamine solution as a complexing agent solution, wherein the concentration of methylamine is 10.0mol/L, and the concentration of triethylenediamine is 6.0 mol/L. In the reaction process, 0.23L of methylamine is blown in as a reaction promoter, and the reaction is carried out for 15min under the constant temperature of 45 ℃ with the stirring speed of 360 r/min. And then carrying out solid-liquid separation on the reaction mixture to obtain filter residue containing a small amount of insoluble impurities and a lead-containing solution.
(3) And (3) crystallization process: and transferring the obtained lead-containing solution into a reduced pressure reactor, continuously reacting for 1.0h under the pressure of-0.09 MPa to obtain the de-methylamine lead-containing solution and methylamine, and returning the methylamine to the complexing process for recycling. Transferring the obtained de-methylamine lead-containing solution into a cooling reactor, reacting at 35 ℃, stirring at the speed of 410r/min for 5.5h, and carrying out solid-liquid separation to obtain a tribasic lead sulfate product and a complexing agent solution, wherein the complexing agent solution is returned to the complexing process for recycling.
Through calculation, 0.60kg of tribasic lead sulfate product is finally prepared by the process flow, the purity of the tribasic lead sulfate product is 99.96%, and the comprehensive recovery rate of lead is 99.16%.
Example 4
2.5kg of lead oxide-containing material of a mining company in Hubei province was pulverized into powder by a ball mill, and the powder was mainly 8.5% of lead (Pb) and 86% of lead oxide (PbO) in physical and chemical tests, with the balance being clay. Then adding the material containing lead oxide into a sulfuric acid solution for carrying out a vulcanization reaction, wherein the treatment process is as follows:
(1) and (3) vulcanization process: 2.5kg of the lead oxide-containing material was charged into a 10L vulcanization reactor, and 3.8L of a sulfuric acid solution having a concentration of 3.5mol/L was added to the reactor, together with 20.0g of tin sulfate as a reaction accelerator. 0.18L of air was bubbled in during the reaction as a synergistic promoter for the reaction. Stirring and reacting for 3 hours at the constant temperature of 55 ℃, wherein the stirring speed is 310 r/min. The mixture obtained after the reaction was filtered and separated to obtain 3.24kg of PbSO4Crude product and sulfuric acid mother liquor. Wherein the PbSO4The crude product was analyzed and found to be 99.7% PbSO4And a very small amount of insoluble impurities. The sulfuric acid mother liquor is recycled as the next vulcanization process solution, and the PbSO is added4The crude product is transferred to the subsequent complexing process for treatment.
(2) And (3) complexing: the PbSO is added4Transferring the crude product into a 10L complexing reactor, and taking 4.0L trimethylamine-formamide solution as a complexing agent solution, wherein the trimethylamine concentration is 9.0mol/L, and the formamide concentration is 3.5 mol/L. In the reaction process, 0.26L of trimethylamine is blown in as a reaction promoter, and the reaction is stirred for 25min at the constant temperature of 40 ℃, wherein the stirring speed is 330 r/min. And then carrying out solid-liquid separation on the reaction mixture to obtain filter residue containing a small amount of insoluble impurities and a lead-containing solution.
(3) And (3) crystallization process: and transferring the obtained lead-containing solution into a reduced pressure reactor, continuously reacting for 1.5h under the pressure of-0.1 MPa to obtain the de-trimethylamine lead-containing solution and trimethylamine, and returning the trimethylamine to the complexing process for recycling. Transferring the obtained lead-containing solution after the trimethylamine removal into a cooling reactor, reacting at the temperature of 20 ℃, stirring at the speed of 420r/min, reacting for 6.5 hours, and carrying out solid-liquid separation to obtain a tribasic lead sulfate product and a complexing agent solution, wherein the complexing agent solution is returned to the complexing process for recycling.
Through calculation, 2.64kg of tribasic lead sulfate product is finally prepared by the process flow, the purity of the tribasic lead sulfate product is 99.97%, and the comprehensive recovery rate of lead is 99.80%.
Example 5
Taking waste valve-controlled sealed lead-acid batteries with the commercial specifications of 12V and 12Ah through a conventional methodCrushing and separating to obtain lead plaster and waste sulfuric acid solution. The lead paste is obtained by traditional chemical titration analysis, wherein the lead-containing component and the content of the lead-containing component are respectively 16.9% of Pb content, 11.2% of PbO content and PbO content235.6% and PbSO4The content was 34.1%. Then adding the lead plaster into a sulfuric acid solution for carrying out a vulcanization reaction, wherein the treatment process is as follows:
(1) and (3) vulcanization process: 1.0kg of the lead plaster is added into a 10L vulcanization reactor, 7.0L of sulfuric acid solution with the concentration of 6.0mol/L is added into the reactor, and 0.1L of solution composed of two components of propane diamine and acetic acid is added as a composite vulcanization accelerator for reaction, wherein the concentration of the propane diamine is 1.5mol/L, and the concentration of the acetic acid is 1.0 mol/L. 0.15L of air is blown in during the reaction process to be used as a synergistic promoter of the reaction, and the reaction is stirred for 1.5h at the constant temperature of 70 ℃, wherein the stirring speed is 400 r/min. The mixture obtained after the reaction was filtered and separated to obtain 1.20kg of PbSO4Crude product and sulfuric acid mother liquor. Wherein the PbSO4The crude product was analyzed and found to be 99.1% PbSO4And a very small amount of insoluble impurities. The sulfuric acid mother liquor is recycled as the next vulcanization process solution, and the PbSO is added4The crude product is transferred to the subsequent complexing process for treatment.
(2) And (3) complexing: the PbSO is added4Transferring the crude product into a 10L complexing reactor, and taking 5.0L ammonia water-acetamide solution as a complexing solution, wherein the concentration of the ammonia water is 8.5mol/L, and the concentration of the acetamide is 6.5 mol/L. 0.25L of ammonia gas is blown in as a reaction promoter in the reaction process, and the reaction is stirred for 40min at the constant temperature of 45 ℃, wherein the stirring speed is 350 r/min. And then carrying out solid-liquid separation on the reaction mixture to obtain filter residue containing a small amount of insoluble impurities and a lead-containing solution.
(3) And (3) crystallization process: and transferring the obtained lead-containing solution into a reduced pressure reactor, continuously reacting for 1.5h under the pressure of-0.1 MPa to obtain the deaminated lead-containing solution and ammonia gas, and returning the ammonia gas to the complexing process for recycling. Transferring the obtained deaminated lead-containing solution into a cooling reactor, reacting at 25 ℃, stirring at a speed of 350r/min, reacting for 8 hours, and performing solid-liquid separation to obtain a tribasic lead sulfate product and a complexing agent solution, wherein the complexing agent solution is returned to the complexing process for recycling.
Through calculation, 0.97kg of tribasic lead sulfate product is finally prepared by the process flow, the purity of the tribasic lead sulfate product is 99.82%, and the comprehensive recovery rate of lead is 99.49%.
Example 6
Taking 2kg of lead mud containing lead oxide from some lead-acid batteries of Zhejiang, and mainly measuring 68.3 percent of lead oxide (PbO) and 17.4 percent of lead sulfate (PbSO) through physical and chemical measurement4) And 12.9% water. Then adding the lead mud containing lead oxide into a sulfuric acid solution for carrying out a vulcanization reaction, wherein the treatment process is as follows:
(1) and (3) vulcanization process: 2kg of lead mud containing lead oxide is added into a 10L vulcanization reactor, 6.0L of sulfuric acid solution with the concentration of 5.5mol/L is added into the reactor, and 0.2L of solution consisting of two components of 2-methylpropylamine and manganese sulfate is added as a composite vulcanization accelerator for reaction, wherein the concentration of 2-methylpropylamine is 1.2mol/L, and the concentration of manganese sulfate is 0.5 mol/L. 0.18L of air is blown in during the reaction process to be used as a synergistic promoter of the reaction, and the reaction is stirred for 1.0h at the constant temperature of 80 ℃, wherein the stirring speed is 450 r/min. Filtering and separating the mixture obtained after the reaction to obtain 2.20kg of PbSO4Crude product and sulfuric acid mother liquor. Wherein the PbSO4The crude product was analyzed and found to be 99.3% PbSO4And a very small amount of insoluble impurities. The sulfuric acid mother liquor is recycled as the next vulcanization process solution, and the PbSO is added4The crude product is transferred to the subsequent complexing process for treatment.
(2) And (3) complexing: the PbSO is added4Transferring the crude product into a 10L complexing reactor, and taking 5.0L dimethylamine-ammonium bisulfate solution as a complexing agent solution, wherein the concentration of dimethylamine is 8.0mol/L, and the concentration of ammonium bisulfate is 6.0 mol/L. 0.30L of dimethylamine is blown in as a reaction promoter in the reaction process, and the reaction is stirred for 30min at the constant temperature of 55 ℃, and the stirring speed is 260 r/min. And then carrying out solid-liquid separation on the reaction mixture to obtain filter residue containing a small amount of insoluble impurities and a lead-containing solution.
(3) And (3) crystallization process: and transferring the obtained lead-containing solution into a reduced pressure reactor, continuously reacting for 2.0h under the pressure of-0.08 MPa to obtain the de-dimethylamine lead-containing solution and dimethylamine, and returning the dimethylamine to the complexing process for recycling. Transferring the obtained lead-containing solution after the dimethylamine removal into a cooling reactor, wherein the reaction temperature is 20 ℃, the stirring rate is 300r/min, and after 7 hours of reaction, a tribasic lead sulfate product and a complexing agent solution can be obtained through solid-liquid separation, wherein the complexing agent solution is returned to the complexing process for recycling.
Through calculation, 1.79kg of tribasic lead sulfate product is finally prepared by the process flow, the purity of the tribasic lead sulfate product is 99.56 percent, and the comprehensive recovery rate of lead is 99.04 percent.
Example 7
Taking lead slag generated in the production process of a certain lead-acid battery company, and obtaining lead-containing components and lead contents in the lead slag through traditional chemical titration analysis, wherein the lead contents are respectively as follows: pb content of 11.6%, PbO content of 27.1% and PbO2The content was 59.3%. The by-product is then added to a sulfuric acid solution to carry out a sulfidation reaction. The treatment process is as follows:
(1) and (3) vulcanization process: 1.5kg of the lead slag is added into a 10L vulcanization reactor, 6.5L of sulfuric acid solution with the concentration of 5.5mol/L is added into the reactor, and 0.25L of solution consisting of two components of chloroacetic acid and tin sulfate is added as a composite vulcanization accelerator for reaction, wherein the concentration of chloroacetic acid is 2.0mol/L, and the concentration of tin sulfate is 1.5 mol/L. 0.20L of air was bubbled in during the reaction as a synergistic promoter for the reaction. Stirring and reacting for 2.0h at the constant temperature of 75 ℃, wherein the stirring speed is 400 r/min. Filtering and separating the mixture obtained after the reaction to obtain 1.93kg of PbSO4Crude product and sulfuric acid mother liquor. Wherein the PbSO4The crude product was analyzed and found to be 99.2% PbSO4And a very small amount of insoluble impurities. The sulfuric acid mother liquor is recycled as the next vulcanization process solution, and the PbSO is added4The crude product is transferred to the subsequent complexing process for treatment.
(2) And (3) complexing: the PbSO is added4Transferring the crude product into a 10L complexing reactor, and using 5.0L dimethylamine-diethylenetriamine solution as complexing agent solution, wherein the concentration of dimethylamine is 8.0mol/L, and the concentration of diethylenetriamine isIt was 7.0 mol/L. 0.15L of dimethylamine is blown in as a reaction promoter in the reaction process, and the reaction is stirred for 25min at the constant temperature of 40 ℃, and the stirring speed is 280 r/min. And then carrying out solid-liquid separation on the reaction mixture to obtain filter residue containing a small amount of insoluble impurities and a lead-containing solution.
(3) And (3) crystallization process: and transferring the obtained lead-containing solution into a reduced pressure reactor, continuously reacting for 1.5h under the pressure of-0.08 MPa to obtain the de-dimethylamine lead-containing solution and dimethylamine, and returning the dimethylamine to the complexing process for recycling. Transferring the obtained lead-containing solution after the dimethylamine removal into a cooling reactor, wherein the reaction temperature is 15 ℃, the stirring speed is 200r/min, and after 8 hours of reaction, a tribasic lead sulfate product and a complexing agent solution can be obtained through solid-liquid separation, wherein the complexing agent solution is returned to the complexing process for recycling.
Through calculation, 1.57kg of tribasic lead sulfate product is finally prepared by the process flow, the purity of the tribasic lead sulfate product is 99.91 percent, and the comprehensive recovery rate of lead is 99.06 percent.
Example 8
Taking lead plaster produced in the production process of a certain lead-acid battery company, and obtaining lead-containing components and lead-containing contents in the lead plaster through traditional chemical titration analysis, wherein the lead-containing components and the lead-containing contents are respectively as follows: pb content of 8.2%, PbO content of 35.8% and PbSO4The content was 53.6%. Then the lead plaster is added into a sulfuric acid solution for carrying out a vulcanization reaction. The treatment process is as follows:
(1) and (3) vulcanization process: 3kg of the lead plaster is added into a 10L vulcanization reactor, 6.0L of sulfuric acid solution with the concentration of 6.0mol/L is added into the reactor, and 0.30L of solution consisting of three components of ethylenediamine, acetic acid and tin sulfate is added as a composite vulcanization accelerator for reaction, wherein the concentration of the ethylenediamine is 1.5mol/L, the concentration of the acetic acid is 2.0mol/L, and the concentration of the tin sulfate is 2.0 mol/L. 0.35L of air was bubbled in during the reaction as a synergistic promoter for the reaction. Stirring and reacting for 2h at the constant temperature of 80 ℃, wherein the stirring speed is 200 r/min. The mixture obtained after the reaction was filtered and separated to obtain 3.42kg of PbSO4Crude product and sulfuric acid mother liquor. Wherein the PbSO4The crude product was analyzed and found to be 99.3% PbSO4And a very small amount of insoluble impurities.The sulfuric acid mother liquor is recycled as the next vulcanization process solution, and the PbSO is added4The crude product is transferred to the subsequent complexing process for treatment.
(2) And (3) complexing: the PbSO is added4Transferring the crude product into a 10L complexing reactor, and taking 5.0L ammonia water-hexamethylenetetramine solution as a complexing agent solution, wherein the concentration of the ammonia water is 8.5mol/L, and the concentration of the hexamethylenetetramine is 7.5 mol/L. 0.40L of ammonia gas is blown in as a reaction promoter in the reaction process, and the reaction is carried out for 15min under the condition of constant temperature of 35 ℃ and the stirring speed is 300 r/min. And then carrying out solid-liquid separation on the reaction mixture to obtain filter residue containing a small amount of insoluble impurities and a lead-containing solution.
(3) And (3) crystallization process: and transferring the obtained lead-containing solution into a reduced pressure reactor, continuously reacting for 2.0h under the pressure of-0.1 MPa to obtain the de-ammonia gas lead-containing solution and ammonia gas, and returning the ammonia gas to the complexing process for recycling. And transferring the obtained lead-containing solution after ammonia gas removal into a cooling reactor, wherein the reaction temperature is 30 ℃, the stirring speed is 200r/min, and after 5 hours of reaction, a tribasic lead sulfate product and a complexing agent solution can be obtained through solid-liquid separation, wherein the complexing agent solution is returned to the complexing process for recycling.
Through calculation, 2.78kg of tribasic lead sulfate product is finally prepared by the process flow, the purity of the tribasic lead sulfate product is 99.86%, and the comprehensive recovery rate of lead is 99.12%.
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 method for preparing tribasic lead sulfate from lead oxide waste is characterized by comprising the following steps:
a. vulcanizationThe process is as follows: the lead oxide waste is subjected to a sulfurization treatment to convert the lead-containing components thereof to PbSO4The solid of (4);
b. and (3) complexing: the above-mentioned PbSO-containing solution is mixed with4Dissolving the solid in a complexing agent solution to obtain a lead-containing solution and filter residue;
c. and (3) crystallization process: carrying out crystallization reaction on the lead-containing solution, namely carrying out decompression and cooling operation to respectively obtain a tribasic lead sulfate product and a complexing agent solution;
b, carrying out vulcanization treatment by using a sulfuric acid solution in the vulcanization process of the step a, and reacting a lead-containing component in the vulcanization process with the sulfuric acid solution to generate lead sulfate;
in the complexing process of the step B, the complexing agent is A + B type, wherein A is selected from an aqueous solution of alkaline gas, B is selected from one of ammonium salt, alicyclic amine or amide, and the alkaline gas is selected from ammonia gas, phosphine, methylamine, dimethylamine or trimethylamine; the concentration of A in the complexing agent solution is 1.0mol/L-10.0 mol/L; in the complexing reaction process, corresponding alkaline gas is introduced into the complexing agent solution to promote the lead-containing complex [ Pb (NH)3)4]SO4Generating; wherein, for each liter of reaction liquid, the flow of the corresponding alkaline gas is 0.001-1L/s;
adding a vulcanization accelerator in the vulcanization process, wherein the vulcanization accelerator is selected from any two or more of the following chemical components (1) amine accelerators, (2) acetic acid accelerators and (3) metal salt accelerators, the amine accelerators, the acetic acid accelerators and the metal salt accelerators are respectively taken and mixed according to the weight ratio of (0-1) to (0-10) to (0-100) to obtain a composite vulcanization accelerator, and at least two numerical values in the weight ratio are not zero; the weight percentage content of the compound vulcanization accelerator in the sulfuric acid is controlled to be 0.1-30 percent;
in the vulcanization process of the step a, air is selected as a reaction synergistic accelerator, wherein the flow rate of blown air is 0.001-1L/s for each liter of reaction liquid;
in the step c, the lead-containing solution is subjected to decompression operation and cooling operation, the alkaline gas in the lead-containing solution is removed through the decompression operation, and the alkaline gas is returned to the complexing process for circulationRing use; cooling the lead-containing solution after the alkaline gas is removed to separate out tribasic lead sulfate crystals, and simultaneously obtaining a complexing agent solution containing ammonium sulfate, wherein the solution can be recycled as the complexing agent solution in the complexing process; the reaction pressure is controlled to be (-0.01MPa) - (-0.1MPa), the reaction temperature is controlled to be 0-60 ℃, and the lead-containing solution [ Pb (NH) ]3)4]SO4After crystallization reaction, solid-liquid separation is carried out to obtain tribasic lead sulfate products and a recyclable complexing agent solution.
2. The method for preparing tribasic lead sulfate from lead oxide waste according to claim 1, wherein the sulfuric acid concentration is controlled to 0.1 to 18mol/L, and the reaction temperature is controlled to 0 to 110 ℃; after the lead oxide waste is subjected to sulfation treatment, solid-liquid separation is carried out to obtain PbSO4Crude product and sulfuric acid mother liquor.
3. A method for preparing tribasic lead sulfate from lead oxide scrap according to claim 1, characterized in that the sulfuric acid concentration is controlled to 1 to 7 mol/L.
4. A method for preparing tribasic lead sulfate from lead oxide scrap according to claim 1, characterized in that the sulfuric acid concentration is controlled to 2-6 mol/L.
5. A method for preparing tribasic lead sulfate from lead oxide scrap according to claim 1,
(1) the amine accelerator is selected from one or more of ethylenediamine, methylamine, propylamine, propylenediamine and 2-methylpropylamine;
(2) the acetic acid promoter is selected from one or more of acetic acid, fluoroacetic acid, chloroacetic acid and phenylacetic acid;
(3) the metal salt accelerator is selected from one or more of copper sulfate, ferrous sulfate, cobalt sulfate, tin sulfate, silver sulfate, mercurous sulfate, nickel sulfate, zinc sulfate, chromium sulfate and manganese sulfate.
6. A method for preparing tribasic lead sulfate from lead oxide scrap according to claim 1, characterized in that the content of the composite vulcanization accelerator in sulfuric acid is controlled to be between 0.5 and 15% by weight.
7. A method for preparing tribasic lead sulfate from lead oxide waste according to claim 1, characterized in that the content of the composite vulcanization accelerator in sulfuric acid is controlled to be between 1 and 10% by weight.
8. A method for the preparation of tribasic lead sulphate from lead oxide waste material according to claim 1 characterised in that the flow rate of the blast air is 0.01-0.5L/s.
9. A process according to claim 1, wherein the ammonium salt in the complexation in step b is selected from ammonium carbonate, ammonium bicarbonate, ammonium sulphate, ammonium sulphite, ammonium bisulphate or ammonium nitrate; wherein the alicyclic amine is selected from triethylenediamine, diethylenetriamine, hexamethylenetetramine or hexamethyleneimine; wherein the amide is selected from formamide, acetamide, propionamide or butyramide.
10. A method for preparing tribasic lead sulfate from lead oxide scrap according to claim 1, wherein the flow rate of the alkaline gas introduced is 0.01 to 0.5L/s per liter of the reaction solution.
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| CN102642866A (en) * | 2012-05-04 | 2012-08-22 | 大连交通大学 | Method for recycling waste lead-acid storage battery and producing tribasic lead sulfate |
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| CN105197988A (en) * | 2015-11-02 | 2015-12-30 | 扬州大学 | Ammonia process separation and refinement method of lead sulfate |
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| CN1830804A (en) * | 2006-03-22 | 2006-09-13 | 湖南大学 | Method of preparing tribasic lead sulphate using lead mud in waste lead battery |
| CN102642866A (en) * | 2012-05-04 | 2012-08-22 | 大连交通大学 | Method for recycling waste lead-acid storage battery and producing tribasic lead sulfate |
| CN103526016A (en) * | 2012-07-02 | 2014-01-22 | 张超 | Method for recovering lead-containing raw material by using wet process |
| CN105197988A (en) * | 2015-11-02 | 2015-12-30 | 扬州大学 | Ammonia process separation and refinement method of lead sulfate |
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