CN101823761B - Wet chemical recovery method of lead and zinc in burning solid products - Google Patents
Wet chemical recovery method of lead and zinc in burning solid products Download PDFInfo
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- CN101823761B CN101823761B CN2010101822039A CN201010182203A CN101823761B CN 101823761 B CN101823761 B CN 101823761B CN 2010101822039 A CN2010101822039 A CN 2010101822039A CN 201010182203 A CN201010182203 A CN 201010182203A CN 101823761 B CN101823761 B CN 101823761B
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Abstract
The invention discloses a wet chemical recovery method of lead and zinc in burning solid products, which comprises the following steps of: firstly, using a sodium hydroxide solution for washing fly ash to generate lead hydroxide and zinc hydroxide precipitate; removing chloride ions through being dissolved in water; then, making the precipitate washed in the last work procedure react with sulfuric acid; making the lead hydroxide react with the sulfuric acid to generate lead sulfate precipitate; dissolving the zinc hydroxide into the sulfuric acid to generate a zinc sulfate solution so that the lead and zinc separation can be realized; then, making the obtained solution react with a sodium hydroxide solution; and making the zinc sulfate react with hydroxide to generate zinc hydroxide precipitate for separating out the zinc. The invention can effectively separate out the heavy metal of lead and zinc in the fly ash, can reduce the environment pollution while realize the effect of changing waste materials into resources, and is particularly applicable to the fly ash generated by burning solid waste materials with high lead and zinc content and burning ash of other fuel after the enrichment.
Description
Technical field
The invention belongs to solid waste and handle and the resource recycling field, relate to the wet chemical recovery method of plumbous and zinc in the solid product, be particularly useful for fusion flying dust use plumbous and that zinc content is higher.
Background technology
Usually all contain a certain amount of metal in the fuel.With the average content of metallic lead in fuel is example; Content is about 0.1-15ppm in the coal, and content is about 2ppm in the oil, and content is up to 100-500ppm in the municipal solid wastes; Derived solid fuel content is about 200ppm; Content is 16ppm in the biomass, common sludge content 102-216ppm, and domestic sludge content is about 55-88ppm.In combustion processes, these metallic elements are through process enrichments in certain part solid combustion product such as high-temperature gasifications, cryogenic condensation.Although sometimes enrichment degree is very high, metal content also has bigger gap apart from the requirement of metal smelting smelting industry feed stock for blast furnace in the raw material, and the too high levels of harmful chlorine element wherein, so can not directly be used for smelting.
According to ore reserve and recovery rate in the world at present, plumbous mineral products with zinc will be exhausted by quilt in less than the time in 30 years, so be necessary this metalloid recycling.Having several method to come that the plumbous zinc metal in the burning solid products is carried out further enrichment at present handles.A kind of method is after lead and zinc are converted into muriate, utilizes the difference gasification of its vaporization temperature and zero pour to separate, and this method needs high temperature, and energy expenditure is very big.Another kind is to adopt sodium-acetate and nitrocalcite that lead is reclaimed, and utilizes ammonium acetate and nitric acid that zinc is reclaimed, and this method is because the agents useful for same price comparison is high, so expense is high, uneconomical.
Summary of the invention
The object of the present invention is to provide in a kind of burning solid products wet chemical recovery method plumbous and zinc, this method not only can the harmful chlorine element of effective elimination, can also plumbous and zinc separation and concentration be made it to become the feed stock for blast furnace of suitable Metal smelting.
The wet chemical recovery method of lead and zinc in the burning solid products provided by the invention, its step comprises:
(1) dechlorination operation:
Burning solid products and water are stirred; Utilize mass percent concentration in reactor drum, flying dust to be washed earlier for the sodium hydroxide solution of 10-50%; Generate the precipitation of hydroxide of plumbous and zinc; Cl ions is soluble in water, through filtering the plumbous zinc oxyhydroxide of solid is separated with cl ions in the solution;
(2) plumbous recovery process:
The deposition that the dechlorination operation obtains is mixed, stirred with water; The sulphuric acid soln that adds concentration of volume percent then and be 5-20% reacts in reactor drum; Lead oxide hydrate and sulfuric acid reaction generate the lead sulfate deposition; The zinc hydroxide vitriolization generates solution of zinc sulfate, realizes separating of plumbous and zinc through filtering;
(3) zinc recovery process:
With plumbous recovery process gained solution and mass percent concentration is that the sodium hydroxide solution of 10-50% reacts in reactor drum, and zinc sulfate and oxyhydroxide reaction generate the zinc hydroxide deposition, filter the solid chemical compound that obtains zinc;
(4) drying process:
With plumbous recovery process and zinc recovery process gained solid dehydration after drying.
The present invention through the burning solid by product respectively with the reaction of sodium hydroxide and dilute sulphuric acid; Remove its contained chlorine element; Lead and zinc are separated and enrichment, are made it to become the qualified raw material of lead-zinc smelting, realize that solid waste handles innoxious the time resource utilization.
Description of drawings
The operation synoptic diagram that Fig. 1 implements for the present invention;
Fig. 2 for the pH of dechlorination operation and alkali addition over time;
Fig. 3 be the Pb recovery process pH through the time change;
Fig. 4 be Zn recovery process pH and alkali addition over time.
Embodiment
As shown in Figure 1, the implementation step of the inventive method is following
(1) dechlorination operation: solid product and water are stirred, utilize sodium hydroxide solution that flying dust is washed earlier, the MCl+NaOH → MOH that reacts ↓+Na
++ Cl
-, generating precipitation of hydroxide plumbous and zinc, cl ions is soluble in water, through filtering solid lead zinc oxyhydroxide is separated with cl ions in the solution.
(2) plumbous recovery process: deposition and water that operation (1) is cleaned stir, and add the dilution heat of sulfuric acid reaction then, the Pb that reacts (OH)
2+ H
2SO
4→ PbSO
4↓+2H
2O, Zn (OH)
2+ H
2SO
4→ Zn
2++ SO
2-+ 2H
2O.Lead oxide hydrate and sulfuric acid reaction generate the lead sulfate deposition, and the zinc hydroxide vitriolization generates solution of zinc sulfate, thereby realize separating of plumbous and zinc through filtering.
(3) zinc recovery process: with operation (2) gained solution and sodium hydroxide solution reaction, Zn reacts
2++ 2NaOH → Zn (OH)
2↓+2Na
+, zinc sulfate and oxyhydroxide reaction generate the zinc hydroxide deposition, filter the solid chemical compound that obtains zinc.
(4) drying process: operation (2) and operation (3) gained solid are dehydrated, can obtain qualified lead-zinc smelting starting material.
The mass percent concentration scope of used sodium hydroxide solution is 10%-50% in step (1) and the step (3), and 20-30% is preferable.The concentration of volume percent scope of used sulphuric acid soln is 5%-20% in the step (2), and 8-12% is preferable.The whisking appliance stirring intensity is＞20rpm, and faster effect is good more, but power consumption and equipment attrition increase, and it is good being no more than 1000rpm.Operation (1), operation (2) and operation (3) reaction times are 2-20 minute, reach balance usually in 4-6 minute or get into the sluggish zone.The pH value of operation (1) is adjusted between the 9-10, and wherein 9.1 is good; The pH value of operation (2) is adjusted between the 2-3, and 2.5 is preferred values, can not surpass 3, surpasses 3 sedimentary lead and begins once more to separate out; The pH value of operation (3) is adjusted between the 8-9, and 8.5 is good.Through the adjustment operating parameters, can reach the recovery preferably.
Below through by embodiment the present invention being described in further detail, but following examples only are illustrative, and protection scope of the present invention does not receive the restriction of these embodiment.
Instance 1:
Product to a kind of incineration of refuse flyash fusing system carries out the recovery of plumbous and zinc according to the present invention, and former grey measurement result sees Table 1.
The composition of table 1 fusion flying dust 1
The first step, the dechlorination operation.The main purpose of this step is to let plumbous and zinc entering residue, and useless element such as chlorine gets into filtrating.Get fusion flying dust 50kg, put into cylindrical reactor vessel, add water 500kg; Utilize mechanical stirrer to stir, rotating speed 300rpm becomes to stir and just adds mass concentration and be 25% NaOH solution 7.848L; Monitor the variation of pH value of solution value while stirring, 20 minutes reaction times.The pH of dechlorination operation and alkali addition are seen Fig. 2 over time.Deposition is filtered then, obtains wet residue quality 63.38kg, knows that through surveying water ratio its butt quality is 31.32kg.Behind the composition test to filtrating and residue, material balance calculation result shows that elements such as 100% chlorine element and most of Na, k, Ca get into filtrating, and 100% zinc and 85% lead get into residue.
Second step, plumbous recovery process.This operation purpose is to let most of lead transfer to residue, and most of zinc gets into filtrating.The first step chlorine is removed the clean wet residue of operation put into cylindrical reactor, add water 281.14kg.Utilize mechanical stirrer to stir, rotating speed 300rpm becomes to stir and just adds volumetric concentration and be 10% H
2SO
4Solution 141.4L monitors the variation of pH value of solution value, 10 minutes reaction times while stirring.The pH of plumbous recovery process sees Fig. 3 over time.Deposition is filtered then, obtains wet residue quality 47.0kg, knows that through surveying water ratio its butt quality is 15.7kg.Behind the composition test to filtrating and residue, material balance calculation result shows that elements such as zinc get into filtrating, plumbous, SiO
2, Al
2O
3, FeO and other compositions get in the residue.
The 3rd step, the zinc recovery process.The purpose of this step is exactly that the zinc in the filtrating is extracted with the solid mode.Second filtrating of filtering gained is put into cylindrical reactor.Utilize mechanical stirrer to stir, rotating speed 300rpm, the change stirring just adds mass concentration and is 25%NaOH solution 23.5L, and the variation of monitoring pH value of solution value, 20 minutes reaction times are stirred in the limit.The pH of zinc recovery process sees Fig. 4 over time.Deposition is filtered then, obtains wet residue quality 100.2kg, knows that through surveying water ratio its butt quality is 11.8kg.
The 4th step, drying process.With plumbous recovery process and the further filter-press dehydration of zinc recovery process gained wet slag, dry rich lead materials 15.7kg, the content of Pb+Zn is 13.3%; Rich zinc material 11.8kg, the content of Pb+Zn is 34.6%.The total yield of Pb is 82.8%, and the total yield of Zn is 59.9%.
Instance 2:
Product to a kind of incineration of refuse flyash fusing system carries out the recovery of plumbous and zinc according to the present invention, and former grey measurement result sees Table 1.
The composition of table 2 fusion flying dust 2
The first step, the dechlorination operation.The main purpose of this step is to let plumbous and zinc entering residue, and useless element such as chlorine gets into filtrating.Get fusion flying dust 50kg, put into cylindrical reactor vessel, add water 500kg, utilize mechanical stirrer to stir, rotating speed 300rpm becomes stirring and just adds 25%NaOH solution 5.191L, monitors the variation of pH value of solution value while stirring, 5 minutes reaction times.Deposition is filtered then, obtains wet residue quality 117.9kg, knows that through surveying water ratio its butt quality is 29.43kg.Behind the composition test to filtrating and residue, material balance calculation result shows that elements such as 100% chlorine element and most of Na, k, Ca get into filtrating, and 100% zinc and 87% lead get into residue.
Second step, plumbous recovery process.This operation purpose is to let most of lead transfer to residue, and most of zinc gets into filtrating.The first step chlorine is removed the clean wet residue of operation put into cylindrical reactor, add water 205.83kg.Utilize mechanical stirrer to stir, rotating speed 300rpm, the limit is stirred and is just added 10%H
2SO
4Solution 81.73L, 8 minutes reaction times.Deposition is filtered then, obtains wet residue quality 50.62kg, knows that through surveying water ratio its butt quality is 14.3kg.Behind the composition test to filtrating and residue, material balance calculation result shows that elements such as zinc get into filtrating, plumbous, SiO
2, Al
2O
3, FeO and other compositions get in the residue.
The 3rd step, the zinc recovery process.The purpose of this step is exactly that the zinc in the filtrating is extracted with the solid mode.Second filtrating of filtering gained is put into cylindrical reactor.Utilize mechanical stirrer to stir, rotating speed 300rpm becomes stirring and just adds 25%NaOH solution 15.9L, 5 minutes reaction times.Deposition is filtered then, obtains wet residue quality 186.9kg, knows that through surveying water ratio its butt quality is 19.1kg.
The 4th step, drying process.With plumbous recovery process and the further filter-press dehydration of zinc recovery process gained wet slag, dry rich lead materials 14.3kg, the content of Pb+Zn is 12.5%; Rich zinc material 19.1.1kg, the content of Pb+Zn is 24.8%.The recovery 84.9% that Pb is total, the recovery of Zn are 69.0%.
Instance 3-13
Used flying dust in the instance 1 is handled with present method, and the result under the different operating parameter is as shown in the table.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment and accompanying drawing.So everyly do not break away from the equivalence of accomplishing under the disclosed spirit of the present invention or revise, all fall into the scope of the present invention's protection.
Claims (1)
1. the wet chemical recovery method of plumbous and zinc in the burning solid products is characterized in that this method comprises the steps:
(1) dechlorination operation:
Burning solid products and water are stirred; Utilize mass percent concentration in reactor drum, flying dust to be washed earlier for the sodium hydroxide solution of 10-50%; Generate the precipitation of hydroxide of plumbous and zinc; Cl ions is soluble in water, through filtering the plumbous zinc oxyhydroxide of solid is separated with cl ions in the solution; The pH value of solution is adjusted to 9-10 in the reactor drum;
(2) plumbous recovery process:
The deposition that the dechlorination operation obtains is mixed, stirred with water; The sulphuric acid soln that adds concentration of volume percent then and be 5-20% reacts in reactor drum; Lead oxide hydrate and sulfuric acid reaction generate the lead sulfate deposition; The zinc hydroxide vitriolization generates solution of zinc sulfate, realizes separating of plumbous and zinc through filtering; The concentration of volume percent of used sulphuric acid soln is 8-12%, and the pH value of solution is whole between the 2-3 in the reactor drum;
(3) zinc recovery process:
With plumbous recovery process gained solution and mass percent concentration is that the sodium hydroxide solution of 10-50% reacts in reactor drum, and zinc sulfate and oxyhydroxide reaction generate the zinc hydroxide deposition, filter the solid chemical compound that obtains zinc; The mass percent concentration of used sodium hydroxide solution is 20-30%, and the pH value of solution is adjusted between the 8-9 in the reactor drum;
(4) drying process:
With plumbous recovery process and zinc recovery process gained solid dehydration after drying;
Step (1), step (2) and step (3) reaction times are 2-20 minute; In step (1) and the step (2), the whisking appliance stirring intensity is all greater than 20rpm.
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|---|---|---|---|
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| CN2010101822039A CN101823761B (en) | 2010-05-26 | 2010-05-26 | Wet chemical recovery method of lead and zinc in burning solid products |
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| CN101823761B true CN101823761B (en) | 2012-05-23 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250815A (en) * | 1998-10-09 | 2000-04-19 | 刘帅安 | Full-wet process for pre-treating lead-zinc ore |
| CN101456636A (en) * | 2008-12-26 | 2009-06-17 | 扬州大学 | Recovery treatment method of sewage water resource for wire rope enterprise |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250815A (en) * | 1998-10-09 | 2000-04-19 | 刘帅安 | Full-wet process for pre-treating lead-zinc ore |
| CN101456636A (en) * | 2008-12-26 | 2009-06-17 | 扬州大学 | Recovery treatment method of sewage water resource for wire rope enterprise |
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