CN103436704B - A kind of method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic - Google Patents
A kind of method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic Download PDFInfo
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- CN103436704B CN103436704B CN201310412554.8A CN201310412554A CN103436704B CN 103436704 B CN103436704 B CN 103436704B CN 201310412554 A CN201310412554 A CN 201310412554A CN 103436704 B CN103436704 B CN 103436704B
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Abstract
The present invention relates to a kind of method reclaiming non-ferrous metal from discarded denitrating catalyst, relate to a kind of method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic specifically.The method mainly comprises the steps: catalyst powder breakdown mill, adds hydrogen peroxide and makes partial oxidation vanadium form pervanadic acid, filter and obtain filter cake and the filtrate containing pervanadic acid; Again filter after filtrate heating and obtain V
2o
5, new filtrate and hydrogen peroxide mixed cycle use; In filter cake, add alkali lye, stirring heating, residue vanadium leaches with metavanadate form, and tungsten leaches with metatungstate form, filters and obtains metavanadate and metatungstate mixing solutions; In mixing solutions, add ammonium salt separate out ammonium metavanadate precipitate, filter further and obtain ammonium meta-vanadate filter cake and the third filtrate, the third filtrate adds concentrated acid and separates out wolframic acid precipitation.The inventive method and technique are simple, low without the need to roasting, energy consumption when leaching metavanadate and wolframic acid, solid-liquid reaction contacts, vanadium and tungsten recovery rate high.
Description
Technical field
The present invention relates to a kind of method reclaiming non-ferrous metal from discarded denitrating catalyst, relate to a kind of method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic specifically, belong to nonferrous metals recycling technical field.
Background technology
Oxynitride (NO
x) being acknowledged as one of air primary pollution source, source comprises combustion product gases and vehicle exhaust.Monoblock type vanadium Ti-base catalyst has been widely used in NO in flue gas or tail gas
xremove, by selective catalysis NH
3reductive NO
xfor N
2carry out NO
xremove.This catalyzer is with TiO
2for carrier (usually accounting for the 80-90% of total mass), V
2o
5for active ingredient (accounting for 1-2%), WO
3or MoO
2for co catalysis composition (accounting for 5-10%).In denitration engineering, catalyzer initial cost accounts for the 30-50% of gross investment usually.
The operating temperature range of vanadium titanium based denitration catalyst is 310 ~ 420 DEG C, be equivalent to the flue-gas temperature of boiler economizer outlet, therefore, selective-catalytic-reduction denitrified (SCR) reactor is directly installed between boiler economizer and air preheater usually, i.e. so-called high dirt decoration form.Although this decoration form is conducive to SCR, reaction is carried out, and the activity of catalyzer is higher, and the dust concentration in the interval flue gas of this layout is high, and catalyzer is washed away with basic metal intoxicating phenomenon serious by dust.In addition, boiler working condition change sometimes causes economizer exit flue-gas temperature too high, causes sintering of catalyst.Therefore, the activity of vanadium Ti-base catalyst extends with working time and reduces gradually, when catalyst activity reduction is then difficult to meet the requirement of environmental protection to denitration rate after to a certain degree, and now then should more catalyst changeout.The work-ing life of vanadium Ti-base catalyst is generally about 3 years, except the consumption of ammonia in SCR working cost, then and the cost of mainly more catalyst changeout.
Catalyst deactivation is divided into reversibility poisoning and deactivation and irreversible poisoning and deactivation.The former can regenerate by mending the measures such as vanadium after blowback ash disposal, washing, pickling, and make catalyzer denitration rate return to original more than 90% and re-use, expense is the 20-30% of whole replacement charge.But have by damaged and need discarded in the non-renewable or regenerative process of a large amount of SCR denitration, estimates after 2018, China discards SCR catalyst every year and reaches 7.8 ten thousand tons.Directly discarded SCR denitration not only causes environmental pollution, and causes the waste of Prospects of Rare Metal Vanadium and tungsten.The navajoite of occurring in nature enrichment and tungsten ore are few, and add the year by year increase of the development of science and technology in recent years to vanadium and tungsten demand, cause its price to rise steadily, the secondary resource making full use of vanadium and tungsten is paid attention to make up its country that obtained in short supply.Discarded SCR catalyst amount is large, is the very important rare metal secondary resource of a class.From discarded SCR denitration, reclaim vanadium and tungsten, the pollution to environment can be avoided, valuable resource can be saved again and bring considerable economic benefit.Mostly the waste catalyst recovery patent that can retrieve at present is the Hydrobon catalyst for petrochemical industry, because its composition, character and inactivation all have bigger difference with SCR catalyst, therefore, be difficult to be directly used in the recycling being applied to discarded SCR denitration.About the Patents of discarded vanadium titanium base SCR denitration synthetical recovery non-ferrous metal is few, CN101921916A discloses one and " from SCR denitration, reclaims the method for tungstic oxide and ammonium meta-vanadate ", and it is by catalyzer and Na
2cO
3mixing, pulverize after carry out high-temperature roasting, then agitation leach in hot water, cross filter cake (being mainly titanate) and add sulfuric acid, again filter, wash, obtain TiO after roasting
2; Filter the filtrate obtained and obtain V through steps such as separation, roastings
2o
5, MoO
3and WO
3." from SCR denitration, reclaiming the method for tungstic oxide and ammonium meta-vanadate " that CN102557142A discloses also is add Na by after break-up of catalyst
2cO
3high-temperature roasting, then adds warm water and leaches NaVO
3and NaWO
4, add ammonium salt and separate out ammonium metavanadate precipitate, after surplus solution evaporation, calcining, obtain WO
3.Above method all continues to use the method extracting vanadium from navajoite, namely adds sodium salt high-temperature roasting, causes energy consumption high, and solid catalyst contacts poor with solid sodium carbonate, cause that reactivity is between the two poor, vanadium and tungsten recovery rate low.
Summary of the invention
The object of the present invention is to provide a kind of method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic, the method technique is simple, have the rate of recovery high, save energy consumption, environmental protection, the outstanding feature such as with low cost.Wherein, vanadium recovery can reach 90%, tungsten recovery rate can reach more than 80%.
For achieving the above object, the method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic provided by the invention, comprises the steps:
(1) method of generally adopt pulverizing, grinding, sieving, makes particle diameter and is less than 100 object catalyst fineses, to eliminate the internal diffusion in subsequent solution impregnation by catalyzer;
(2) in the catalyst fines in described step (1), add hydrogen peroxide solution, fully stir, churning time is generally 0.5-3h; Then filter and obtain filtrate and filter cake; In this process, at a middle or low price the vanadium of state and tungsten are substantially oxidized as V catalyzer
2o
5and WO
3, so that hydrogen peroxide reclaims vanadium and follow-up alkaline leaching reclaims vanadium and tungsten.The principle that hydrogen peroxide reclaims vanadium is V
2o
5with H
2o
2reaction generates pervanadic acid (V
2o
5+ 2H
2o
2→ 2HVO
4+ H
2o), the pervanadic acid filtrate obtained containing residue hydrogen peroxide is filtered;
In this step, the concentration of hydrogen peroxide solution is generally 5-30wt%.H in hydrogen peroxide solution
2o
25-15:1 is about with the mol ratio of vanadium in catalyzer.
(3) pH value regulating filtrate in described step (2) is 3.5-6, and then heat, Heating temperature is preferably 40-70 DEG C, until separate out precipitation in filtrate, namely pervanadic acid is decomposed into V
2o
5(2HVO
4→ V
2o
5↓+O
2↑+H
2o), V
2o
5from solution, natural sedimentation is separated out, and filters and obtains solid V
2o
5with new filtrate; Regulate pH in this process and control Heating temperature all in order to suppress the decomposing hydrogen dioxide solution in filtrate, to recycle.
Hydrogen peroxide solution in new filtrate in this step and step (2) can mixed cycle use.
(4) add alkali lye in the filter cake obtained in described step (2), heat and stir, Heating temperature is generally 50-100 DEG C, and the heated and stirred time is about 0.5-3h.Vanadium can be reclaimed further on the one hand like this, reclaim tungsten on the other hand.Then collecting by filtration filtrate, obtains the mixing solutions of metavanadate and metatungstate.
Alkali lye is generally NaOH, KOH or both mixing solutionss, selects NaOH for alkali lye, then the following reaction of main generation in this process, obtains sodium metavanadate and metatungstic acid sodium mixing solutions, collecting by filtration filtrate.
V
2O
5+2NaOH→2NaVO
3+H
2O
WO
3+2NaOH→Na
2WO
4+H
2O
In this step, the concentration of alkali lye is 0.2 ~ 10wt%.The ratio of filter cake and alkali lye is 1g:1-15ml.
(5) pH value regulating mixing solutions in described step (4) is 8-10, by V:NH
4 +mol ratio be that 1:2 ~ 1:4 adds ammonium salt, separate out precipitation after filter, obtain ammonium meta-vanadate filter cake; Then in this filtrate, W:H is pressed
+mol ratio be 1:3 ~ 1:6 add concentrated acid separate out wolframic acid precipitation.Described concentrated acid is generally concentrated hydrochloric acid or the vitriol oil.
Wolframic acid also can obtain WO through further roasting
3.
Its principal reaction equation is as follows:
NaVO
3+NH
4Cl→NH
4VO
3↓+NaCl
Na
2WO
4+2HCl→H
2WO
4↓+NaCl
(NH
4)
2WO
4+2HCl→H
2WO
4↓+NH
4Cl
H
2WO
4→WO
3+H
2O↑
In described step (3) and (5), the method for adjust ph adds hydrochloric acid or sulfuric acid regulates.
Tool of the present invention has the following advantages:
(1) the lower valency vanadium containing a great deal of in useless vanadium Ti-base catalyst, as VO
2and V
2o
3, because Low Valent Vanadium is insoluble in alkali lye, when therefore only adopting alkali collection vanadium, vanadium recovery is low.First the present invention adopts hydrogen peroxide oxidation Low Valent Vanadium, simultaneously original the and V that generates
2o
5change into pervanadic acid and reclaim, then adopting alkaline leaching, to reclaim V further
2o
5, reclaim WO simultaneously
3.The two-step approach that the present invention adopts reclaims vanadium, and vanadium recovery reaches more than 90%.
(2) with the catalyzer of existing patent report and Na
2cO
3baking mixed method is compared, and the method adopted when the present invention obtains metavanadate and wolframic acid all not higher than 100 DEG C, therefore saves energy consumption.
(3) catalyzer of existing patent report and Na
2cO
3baking mixed method is solid-solid reaction, usually contact Gu solid poor, speed of reaction is low, therefore the rate of recovery of vanadium and tungsten is low, and the present invention adopts is liquid-solid reaction extraction vanadium and tungsten, and liquid-solid contact is good, speed of reaction is fast, and therefore the rate of recovery of vanadium and tungsten is high.Wherein, vanadium recovery can reach 90%, tungsten recovery rate can reach more than 80%.
(4) hydrogen peroxide adopted in the present invention recycles, and waste liquid is few, cost is low, environmental protection.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1
It is 100-120 object powder that particle diameter is chosen in broken for the vanadium titanium base waste denitration catalyst of tungstenic, grinding, screening.20wt% hydrogen peroxide is added, wherein H in catalyst fines
2o
2be 15:1 with the mol ratio of vanadium in catalyzer, fully stir 1 hour, the part vanadium in catalyzer and H
2o
2reaction generates pervanadic acid, filters and obtains filter cake (1) and the pervanadic acid filtrate (1) containing hydrogen peroxide.In filtrate (1), add HCl regulate its pH value to 5.5, be then heated to 40 DEG C, constant temperature certain hour makes pervanadic acid be decomposed into V
2o
5, filter and obtain V
2o
5precipitation and filtrate (2), filtrate (2) and hydrogen peroxide mixed cycle use.In filter cake (1), add 4wt%NaOH solution, wherein solid-to-liquid ratio 1g/10ml, be then heated to 60 DEG C, constant temperature stirring reaction 1 hour, filter afterwards and obtain containing NaVO
3and Na
2wO
4mixing solutions.By this mixing solutions with after HCl adjust ph to 9, add NH
4cl solution, control V:NH
4 +mol ratio be 1:2, stir after certain hour and staticly settle, filter and obtain NH
4vO
3with filtrate (3), in filtrate (3), add concentrated hydrochloric acid, control W:H
+mol ratio be 1:3, stir after certain hour and leave standstill, Precipitation wolframic acid, filter and obtain solid wolframic acid.
Detect through inductively coupled plasma atomic emission spectrometry instrument (ICP-OES), the rate of recovery of V is the rate of recovery of 93%, W is 85%.
Embodiment 2
It is 100-120 object powder that particle diameter is chosen in broken for the vanadium titanium base waste denitration catalyst of tungstenic, grinding, screening, adds 5wt% hydrogen peroxide, wherein H in catalyst fines
2o
2be 10:1 with the mol ratio of vanadium in catalyzer, fully stir 3 hours, the part vanadium in catalyzer and H
2o
2reaction generates pervanadic acid, filters and obtains filter cake (1) and the pervanadic acid filtrate (1) containing hydrogen peroxide.H is added in filtrate (1)
2sO
4regulate its pH value to 4.0, be then heated to 70 DEG C, constant temperature certain hour makes pervanadic acid be decomposed into V
2o
5, filter and obtain V
2o
5precipitation and filtrate (2), filtrate (2) and hydrogen peroxide mixed cycle use.In filter cake (1), add 10wt%KOH solution, wherein solid-to-liquid ratio 1g/1ml, be heated to 100 DEG C, constant temperature stirring reaction 0.5 hour, filter afterwards and obtain containing NaVO
3and Na
2wO
4mixing solutions.Adopt sulphuric acid soln to regulate the pH value to 8 of mixing solutions, then add NH
4cl solution, control V:NH
4 +mol ratio be 1:4, stir after certain hour and staticly settle, filter and obtain NH
4vO
3with filtrate (3), in filtrate (3), add the vitriol oil, control W:H
+mol ratio be 1:4, stir after certain hour and leave standstill, Precipitation wolframic acid, filter and obtain solid wolframic acid, wolframic acid obtains WO in 210 DEG C of roastings
3.
Detect through ICP-OES, the rate of recovery of V is the rate of recovery of 93%, W is 84%.
Embodiment 3
It is 100-120 object powder that particle diameter is chosen in broken for the vanadium titanium base waste denitration catalyst of tungstenic, grinding, screening, adds 30wt% hydrogen peroxide, wherein H in catalyst fines
2o
2be 15:1 with the mol ratio of vanadium in catalyzer, fully stir 0.5 hour, the part vanadium in catalyzer and H
2o
2reaction generates pervanadic acid, filters and obtains filter cake (1) and the pervanadic acid filtrate (1) containing hydrogen peroxide.H is added in filtrate (1)
2sO
4regulate its pH value to 3.5, be then heated to 50 DEG C, constant temperature certain hour makes pervanadic acid be decomposed into V
2o
5, filter and obtain V
2o
5precipitation and filtrate (2), filtrate (2) and hydrogen peroxide mixed cycle use.In filter cake (1), add 0.2wt%KOH solution, wherein solid-to-liquid ratio 1g/5ml, be heated to 50 DEG C, constant temperature stirring reaction 3 hours, filter afterwards and obtain containing NaVO
3and Na
2wO
4mixing solutions.Adopt sulphuric acid soln to regulate the pH value to 10 of mixing solutions, then add NH
4cl solution, control V:NH
4 +mol ratio be 1:3, stir after certain hour and staticly settle, filter and obtain NH
4vO
3with filtrate (3), in filtrate (3), add the vitriol oil, control W:H
+mol ratio be 1:5, stir after certain hour and leave standstill, Precipitation wolframic acid, filter and obtain solid wolframic acid.
Detect through ICP-OES, the rate of recovery of V is the rate of recovery of 90%, W is 81%.
Embodiment 4
It is 100-150 object powder that particle diameter is chosen in broken for the vanadium titanium base waste denitration catalyst of tungstenic, grinding, screening, adds 10wt% hydrogen peroxide, wherein H in catalyst fines
2o
2be 5:1 with the mol ratio of vanadium in catalyzer, fully stir 2 hours, the part vanadium in catalyzer and H
2o
2reaction generates pervanadic acid, filters and obtains filter cake (1) and the pervanadic acid filtrate (1) containing hydrogen peroxide.H is added in filtrate (1)
2sO
4regulate its pH value to 6, be then heated to 50 DEG C, constant temperature certain hour makes pervanadic acid be decomposed into V
2o
5, filter and obtain V
2o
5precipitation and filtrate (2), filtrate (2) and hydrogen peroxide mixed cycle use.In filter cake (1), add 1wt%KOH solution, wherein solid-to-liquid ratio 1g/2.5ml, be heated to 70 DEG C, constant temperature stirring reaction 2 hours, filter afterwards and obtain containing NaVO
3and Na
2wO
4mixing solutions.Adopt sulphuric acid soln to regulate the pH value to 9 of mixing solutions, then add NH
4cl solution, control V:NH
4 +mol ratio be 1:2, stir after certain hour and staticly settle, filter and obtain NH
4vO
3with filtrate (3), in filtrate (3), add the vitriol oil, control W:H
+mol ratio be 1:6, stir after certain hour and leave standstill, Precipitation wolframic acid, filter and obtain solid wolframic acid, wolframic acid obtains WO in 210 DEG C of roastings
3.
Detect through ICP-OES, the rate of recovery of V is the rate of recovery of 92%, W is 83%.
Embodiment 5
It is 100-120 object powder that particle diameter is chosen in broken for the vanadium titanium base waste denitration catalyst of tungstenic, grinding, screening, adds 5wt% hydrogen peroxide, wherein H in catalyst fines
2o
2be 10:1 with the mol ratio of vanadium in catalyzer, fully stir 2 hours, the part vanadium in catalyzer and H
2o
2reaction generates pervanadic acid, filters and obtains filter cake (1) and the pervanadic acid filtrate (1) containing hydrogen peroxide.In filtrate (1), add HCl regulate its pH value to 4, be then heated to 50 DEG C, constant temperature certain hour makes pervanadic acid be decomposed into V
2o
5, filter and obtain V
2o
5precipitation and filtrate (2), filtrate (2) and hydrogen peroxide mixed cycle use.In filter cake (1), add 5wt%KOH solution, wherein solid-to-liquid ratio 1g/1ml, be heated to 70 DEG C, constant temperature stirring reaction 2 hours, filter afterwards and obtain containing NaVO
3and Na
2wO
4mixing solutions.Adopt sulphuric acid soln to regulate the pH value to 9 of mixing solutions, then add NH
4cl solution, control V:NH
4 +mol ratio be 1:2, stir after certain hour and staticly settle, filter and obtain NH
4vO
3with filtrate (3), in filtrate (3), add the vitriol oil, control W:H
+mol ratio be 1:3, stir after certain hour and leave standstill, Precipitation wolframic acid, filter and obtain solid wolframic acid, wolframic acid obtains WO in 210 DEG C of roastings
3.
Detect through ICP-OES, the rate of recovery of V is the rate of recovery of 92%, W is 84%.
The above, be only preferred embodiment of the present invention, and can not limit the interest field of the present invention with this, the equivalent variations done according to the claims in the present invention, still belongs to the scope that the present invention is contained.
Claims (9)
1. from the vanadium titanium base waste denitration catalyst of tungstenic, reclaim a method for vanadium and tungsten, comprise the steps:
(1) catalyzer is made particle diameter and be less than 100 object catalyst fineses;
(2) in the catalyst fines in described step (1), add hydrogen peroxide solution, fully stir, then filter and obtain filtrate and filter cake;
(3) filtrate in described step (2) is processed, until separate out precipitation in filtrate, filter and obtain V
2o
5with new filtrate;
(4) add alkali lye in the filter cake obtained in described step (2), heat and stir, then collecting by filtration filtrate, obtaining the mixing solutions of metavanadate and metatungstate;
(5) pH value regulating mixing solutions in described step (4) is 8-10, adds ammonium salt, filters, obtain ammonium meta-vanadate filter cake after separating out precipitation; Then add concentrated acid in the filtrate in this step and separate out wolframic acid precipitation;
It is characterized in that the pH value being adjustment filtrate to filtrate process in described step (3) is 3.5-6, then heat at 40-70 DEG C.
2. the method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic according to claim 1, it is characterized in that in described step (2), the concentration of hydrogen peroxide solution is 5-30wt%.
3. the method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic according to claim 1 and 2, is characterized in that in described step (2), H in hydrogen peroxide solution
2o
2be 5-15:1 with the mol ratio of vanadium in catalyzer.
4. the method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic according to claim 1, is characterized in that, in described step (2), churning time is 0.5-3h.
5. the method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic according to claim 1, is characterized in that the new filtrate in described step (3) and the hydrogen peroxide solution mixed cycle in step (2) use.
6. the method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic according to claim 1, it is characterized in that in described step (4), the concentration of alkali lye is 0.2 ~ 10wt%; Alkali lye is NaOH, KOH or both mixing solutionss.
7. the method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic according to claim 1, it is characterized in that in described step (4), the ratio of filter cake and alkali lye is 1g:1-10ml.
8. the method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic according to claim 1, it is characterized in that, in described step (4), Heating temperature is 50-100 DEG C, the heated and stirred time is 0.5-3h.
9. the method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic according to claim 1, is characterized in that in described step (3) and (5), and the method for adjust ph adds hydrochloric acid or sulfuric acid adjustment.
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| CN115869938B (en) * | 2023-03-08 | 2023-04-28 | 国能龙源环保有限公司 | Treatment method of waste denitration catalyst, preparation method of denitration catalyst and application of denitration catalyst |
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| CN103160690A (en) * | 2011-12-14 | 2013-06-19 | 虹京环保有限公司 | Method for recovering metal oxide from SCR denitration waste catalyst |
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