CN106435197B - A kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device and technique - Google Patents
A kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device and technique Download PDFInfo
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- CN106435197B CN106435197B CN201611127614.1A CN201611127614A CN106435197B CN 106435197 B CN106435197 B CN 106435197B CN 201611127614 A CN201611127614 A CN 201611127614A CN 106435197 B CN106435197 B CN 106435197B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/1254—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using basic solutions or liquors
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/1259—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching treatment or purification of titanium containing solutions or liquors or slurries
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device and technique, it uses NaOH solution, the tungsten of SCR denitration dead catalyst, vanadium is leached into leachate, and titanium is stayed in leached mud, realizes the separation of tungsten, vanadium and titanium；Then using the tungsten and vanadium in alkaline extraction technique separation leachate；Refined again by processes such as crystallization, dehydration, drying, obtain the ammonium paratungstate and ammonium metavanadate for meeting national standard high-purity, while obtain byproduct Ti-enriched slag.The present invention can reclaim the valuable metal in SCR denitration dead catalyst, can obtain the ammonium paratungstate and ammonium metavanadate for meeting the high-purity of national standard, while obtain byproduct Ti-enriched slag.
Description
Technical field
The invention belongs to industrial solid castoff processing technology field, is related at a kind of SCR denitration dead catalyst recycling
Reason technology, and in particular to a kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device and technique.
Background technology
Selective catalytic reduction (SCR) is the mainstream technology of current thermal power plant denitrating flue gas, is current denitration effect
Rate highest, it is the most ripe, using most denitration technologies.The technology is widely used with TiO2For carrier, with WO3、V2O5Etc. rare
Metal oxide is the catalyst of active component.
SCR denitration is after use in a few years, and its activity decrease is to a certain degree, it is impossible to meets that SCR denitration will
Ask, so as to be regenerated or be changed.Regeneration can extend the service life of catalyst, but catalyst eventually can be because of structure
Damage etc. reason can not it is indefinite regeneration and discard.SCR denitration dead catalyst is a kind of environmentally harmful pollutant, by
It is included in《National Hazard waste register》, but this dead catalyst contains the valuable metals such as tungsten, vanadium and titanium.Existing market main flow
Contain WO in SCR denitration3About 2~10%, V2O5About 1%~5%, TiO2About 70~90%, from the angle of resource reclaim,
SCR denitration dead catalyst is a kind of precious resources, and considerable economic benefit can be produced by reclaiming tungsten, vanadium and titanium therein, simultaneously
Through processing dead catalyst by dangerous solid waste be changed into tungsten, vanadium, titanium product reuse, there is good environmental benefit.
Recovery to valuable metal in SCR denitration dead catalyst, foreign countries starting more early, such as U.S., Germany and Japan, mesh
First tungsten, vanadium is entered leachate using " oxidizing roasting-alkali leaching " as previous, then mainly use ion-exchange or acid extract
Extraction tungsten is followed the example of, the above method has the shortcomings of wastewater discharge is big, reagent consumption is high.These technologies relatively fall behind, and study carefully
Its reason, on the one hand it is due to that China's tungsten ore reserves rank first in the world, the smelting technique of China's tungsten is in a leading position ground in the world
Position；On the other hand, for tungsten ore, the total amount of SCR denitration dead catalyst tungstenic accounts for smaller.
Domestic waste catalyst recovery industry is started late, and the recovery concern to SCR denitration dead catalyst is less.Chinese invention
Patent application CN104384167A, CN104772318A disclose it is a kind of first with it is acid-leaching vanadium-extracted, extract tungsten substep with alkali again and carry
The SCR denitration waste catalyst recovery method of tungsten vanadium is taken, not only acid-base reagent consumption is big for this method, and leaching rate is relatively low.
Chinese invention patent application CN103160690B, CN103484678A discloses a kind of first extracted with alkali and takes tungsten vanadium, uses ammonium again
Salt and concentrated acid precipitate the SCR denitration waste catalyst recovery method of ammonium metavanadate and wolframic acid from leachate respectively, and this method is not
Substantial amounts of acid is only consumed, and tungsten vanadium is easily coprecipitated, causes inferior separating effect, product yield low.Chinese patent
CN104862485A discloses one kind and first passes through Roasting And Leaching extraction tungsten vanadium, then tungsten is extracted from leachate by acid extract
SCR denitration waste catalyst recovery method, tungsten vanadium separating effect is preferable, but acid extract is to the poor removal effect of the impurity such as P, Si,
And leachate need to consume substantial amounts of acid in alkalescence, regulation pH value, acid-base neutralization produces substantial amounts of waste water.Two methods are first led to below
Cross leaching while extract tungsten vanadium, then with traditional precipitation method or acid extract separating tungsten vanadium, although leaching rate is higher, in tungsten vanadium
Shortcomings during separation.
Chinese invention patent application CN104263946A is disclosed a kind of given up using alkaline extraction technique from SCR denitration and is catalyzed
The method that tungsten, vanadium and titanium are reclaimed in agent, first passes through Na2CO3Sintering+water logging extracts tungsten vanadium simultaneously, then using alkaline extraction successively
Tungsten, vanadium are extracted, titanium, which stays in, obtains rich-titanium material in leached mud, realize the separation of tungsten, vanadium, titanium.Alkaline extraction can be in alkaline bar
Separating for the impurity such as tungsten, the separation of vanadium and tungsten, vanadium and P, Si is realized under part simultaneously, tungsten vanadium in traditional separation method is overcome and separates
With the deficiencies of impurity-eliminating effect is poor, acid-base reagent consumption is big, wastewater flow rate is big, still, this method uses Na2CO3The side of sintering+water logging
Formula leaches tungsten vanadium, and sintering process power consumption is more and produces a small amount of waste gas, sinters alkali used and is difficult to reuse, tungsten in gained leachate
Vanadium concentration is relatively low, is still needed to before follow-up alkalescence extraction tungsten, extraction vanadium using a small amount of acid-base reagent regulation pH value, and consumes a part of soda acid examination
Agent.
Chinese invention patent application CN104760998A discloses a kind of tungstenic solution based on SCR denitration dead catalyst
Tungsten recovery method, it extracts tungsten using alkaline extraction from the alkali immersion liquid of SCR denitration dead catalyst, the ammonium metatungstate finally given
Or the purity of tungstic acid can reach more than 98%, but this method only reclaims to tungsten, one side SCR denitration dead catalyst
In vanadium, the valuable metal such as titanium be not fully used, the poisonous gold such as vanadium are contained in the raffinate of another aspect alkaline extraction
Category, it is improper conduct oneself well to put can produce new pollution sources.As can be seen here, alkaline extraction has compared to conventional method on tungsten vanadium separating effect
Very big lifting, but existing process clean energy-saving and tungsten, vanadium, titanium resource synthetical recovery in terms of still suffer from deficiency.
In summary, for SCR denitration dead catalyst valuable metal recovery, deposited at present in denitration waste catalyst recovery technique
In problems with：
1st, acid-base reagent consumption is big, leaching rate is low；
2nd, tungsten vanadium low separation efficiency, impurity-eliminating effect be poor, acid-base neutralization produces a large amount of waste water；
3、Na2CO3The power consumption of sintering+water logging is high, produce sintered discharge gas, that alkali is difficult to tungsten vanadium concentration in reuse, leachate is low；
4th, the recovery and purification of tungsten, three kinds of vanadium, titanium valuable metals can not be realized simultaneously.
The content of the invention
It is an object of the invention to provide a kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device and work
Skill, it can obtain meeting state using the valuable metal in NaOH leachings+alkaline extraction technique recovery SCR denitration dead catalyst
The ammonium paratungstate and ammonium metavanadate of the high-purity of family's standard, while obtain byproduct Ti-enriched slag.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device, the device include NaOH leaching systems, alkali
Property extracting system and product purification system；Wherein,
The NaOH leaching systems are used for the separation for realizing tungsten, vanadium and titanium, and it includes raw material tank, the high pressure leaching being sequentially connected
Go out kettle, band filter and the first dryer, the raw material tank is used to give up to the SCR denitration after deashing is broken inputted in it
Catalyst fines be sufficiently mixed with NaOH and water and forms it into mixed serum, and the high pressure leaching kettle is used to make the mixing slurry
Liquid is reacted under certain temperature and pressure to leach tungsten, vanadium, and the band filter is used to wash the slurries of reaction
With filtering to obtain tungstenic, the leachate of vanadium and leached mud containing titanium dioxide, the outlet of the band filter and raw material tank
Entrance connect so that tungstenic, the leachate of vanadium are back in raw material tank, first dryer is used for containing titanium dioxide
Leached mud carries out drying and processing and obtains Ti-enriched slag；
The alkaline extraction system is used to realize the separation of tungsten and vanadium, its extraction tank for including being sequentially connected, sink and
Be stripped groove, the extraction tank is used to making the leachate for the tungstenic, vanadium that band filter obtains and blank organic phase reacts with
Rich tungsten organic phase and rich vanadium raffinate are obtained, the sink is used to carry out pure water, the back extraction groove to rich tungsten organic phase
For reacting the rich tungsten organic phase after washing and back washing agent to obtain rich tungsten strip liquor and blank organic phase；
The product purification system be used for purifying high-purity ammonium paratungstate and ammonium metavanadate, it include tungsten subsystem processed with
Vanadium subsystem processed, the tungsten subsystem processed includes ion exchange column, evaporative crystallization kettle and the second dryer being sequentially connected, described
Ion exchange column is used to carry out deeply removing vanadium to the rich tungsten strip liquor that back extraction groove obtains, and the evaporative crystallization kettle is used for through depth
Except the rich tungsten strip liquor after vanadium is crystallized to obtain ammonium para-tungstate crystal thing, second dryer is used for ammonium paratungstate knot
Brilliant thing carries out drying and processing and obtains ammonium paratungstate, and the neutralization that the vanadium subsystem processed includes being sequentially connected is reacted except silicon kettle, precipitation
Kettle and the 3rd dryer, described neutralize removes silicon except the rich vanadium raffinate that silicon kettle is used to obtain extraction tank carries out precipitation, described heavy
Vanadium reactor is used for except the rich vanadium raffinate after silicon is precipitated to obtain ammonium metavanadate precipitate thing, the 3rd dryer is used
Ammonium metavanadate is obtained in carrying out drying and processing to ammonium metavanadate precipitate thing.
By above-mentioned technical proposal, the outlet of the sink is also connected with the entrance neutralized except silicon kettle, for making washings
Flow into neutralize and remove in silicon kettle.
By above-mentioned technical proposal, the outlet of the back extraction groove is also connected with the entrance of extraction tank, for making blank organic phase
It is back in extraction tank and is recycled.
By above-mentioned technical proposal, the outlet of the ion exchange column is also connected with the entrance neutralized except silicon kettle, for making to remove
Vanadium liquid is flowed into neutralize and removed in silicon kettle.
Accordingly, the present invention also provides a kind of SCR denitration dead catalyst valuable metal alkaline extraction based on said apparatus
Recovery process, comprise the following steps：
S1, NaOH are leached：SCR denitration dead catalyst powder after deashing is broken mixes with NaOH and water in raw material tank
Form mixed serum after uniformly to enter in high pressure leaching kettle, high pressure leaching kettle, which provides certain temperature and pressure, occurs the mixed serum
To leach tungsten, vanadium, reacted slurries obtain tungstenic, the leachate of vanadium and containing titanium dioxide through band filter separation of solid and liquid for reaction
The leached mud of titanium, the leached mud containing titanium dioxide obtain high titanium slag after the first drying machine drying, and tungstenic, the leachate of vanadium return
Leached in raw material tank；
S2, alkaline extraction：Tungstenic, the leachate of vanadium and the blank organic phase in input extraction tank obtained in step S1 is direct
Contact carries out multitple extraction tungsten, obtains rich tungsten organic phase and rich vanadium raffinate, and rich tungsten organic phase enters more through pure water in sink
After stage countercurrent washing, the multistage back extraction tungsten of progress is contacted with the back washing agent in back extraction groove, obtains rich tungsten strip liquor and blank organic phase；
S3, product purification：After the rich tungsten strip liquor obtained in step S2 is by ion exchange column deeply removing vanadium, tied in evaporation
Crystallization obtains ammonium para-tungstate crystal thing in brilliant kettle, and ammonium para-tungstate crystal thing obtains meeting national standard after the second drying machine drying
Ammonium paratungstate, the rich vanadium raffinate obtained in step S2, which enters to neutralize, to be removed after precipitation removes silicon in silicon kettle, in precipitation reactor
Precipitation obtains ammonium metavanadate precipitate thing, and ammonium metavanadate precipitate thing obtains the inclined vanadium for meeting national standard after the 3rd drying machine drying
Sour ammonium.
By above-mentioned technical proposal, in step S1, raw material tank reclaimed water and the mass ratio of SCR denitration dead catalyst powder are
150%~350%, the addition of sodium hydroxide when leaching first for SCR denitration dead catalyst powder quality 10%~
40%th, return leach when for SCR denitration dead catalyst powder quality 5%~20%.
By above-mentioned technical proposal, in step S1, the reaction temperature in high pressure leaching kettle is 180~320 DEG C, reaction pressure
It is 1~4h for 1.0~2.5MPa, reaction time.
By above-mentioned technical proposal, in step S2, each component and each component percent by volume of the blank organic phase are extraction
Take agent:Polarity improver:Diluent=10%~60%:10%~30%:10%~60%, wherein, extractant CO3 2-Season
Ammonium salt class or HCO3 -The one or two of quaternary ammonium salt, polarity improver are higher alcohols, and diluent is kerosene, blank organic phase with
Tungstenic, the flow-rate ratio of leachate of vanadium are 1/1~5/1, and the extraction series of extraction tank is 2~12 grades.
By above-mentioned technical proposal, in step S2, rich tungsten organic phase and the flow-rate ratio of pure water are 4/1~8/ in the sink
1, washing series is 2~10 grades.
By above-mentioned technical proposal, in step S2, the back washing agent be 2.0~3.5mol/L ammonium hydrogen carbonate and 0.5~
The flow-rate ratio of the mixed solution of 1.5mol/L ammoniacal liquor, rich tungsten organic phase and back washing agent is 1/1~5/1, and back extraction series is 5~18
Level.
The present invention, have the advantages that：
1st, the present invention leaches the separation for realizing tungsten, vanadium and titanium using NaOH solution, by the tungsten of SCR denitration dead catalyst, vanadium
Leach into leachate, and titanium is stayed in leached mud, can efficiently leach tungsten, vanadium, it is not necessary to it is calcined, thus roasting will not be produced
Waste gas, roasting power consumption is saved, avoids TiO2Reacted in roasting process and alkali, the height for meeting national standard can be obtained
Titanium slag, and the leachate of tungstenic, vanadium can return to leaching, recycling for water and alkali is simply realized, is lifted in leachate
The concentration of tungsten, vanadium, more conducively follow-up alkaline extraction and product purification；
2nd, the present invention can realize the separation of tungsten and vanadium and point of the impurity such as tungsten and P, Si simultaneously by alkaline extraction tungsten
From obtaining the sodium tungstate solution and sodium vanadate solution of high-purity, finally give the ammonium paratungstate and metavanadic acid for meeting national standard
Ammonium product, three kinds of tungsten, vanadium, titanium valuable metals are recycled simultaneously, produce good economic benefit, and extract the circulation of organic phase
Utilize, reduce further process costs, be adapted to industrialized production；
3rd, the present invention uses the group technology of NaOH leachings+alkaline extraction, and leachate need not adjust pH, can directly enter
Row alkaline extraction, it is not necessary to the free alkali added in a large amount of acid neutralization leachates, so as to avoid producing largely containing inorganic salts
Waste water.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing：
Fig. 1 is the structural representation of the embodiment of the present invention.
In figure：1- raw material tanks, 2- high pressure leaching kettles, 3- band filters, 4 first dryers, 5- extraction tanks, 6- washings
Groove, 7- back extraction grooves, 8- ion exchange columns, 9- evaporative crystallization kettles, the dryers of 10- second, 11-, which is neutralized, removes silicon kettle, 12- precipitations reaction
Kettle, the dryers of 13- the 3rd.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not
For limiting the present invention.
In the preferred embodiment, a kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device, such as
Shown in Fig. 1, the device includes NaOH leaching systems, alkaline extraction system and product purification system；Wherein,
NaOH leaching systems are used for the separation for realizing tungsten, vanadium and titanium, and its raw material tank 1 for including being sequentially connected, high pressure leach
Kettle 2, the dryer 4 of band filter 3 and first, raw material tank 1, which is used to give up to the SCR denitration after deashing is broken inputted in it, urges
Agent powder be sufficiently mixed with NaOH and water and forms it into mixed serum, and high pressure leaching kettle 2 is used to make the mixed serum exist
Reacted under certain temperature and pressure to leach tungsten, vanadium, band filter 3 be used to the slurries of reaction are washed and filtered with
Tungstenic, the leachate of vanadium and the leached mud containing titanium dioxide are obtained, the outlet of band filter 3 is connected with the entrance of raw material tank 1
So that the leachate of tungstenic, vanadium is back in raw material tank 1, the first dryer 4 is used to dry the leached mud containing titanium dioxide
Dry-cure obtains Ti-enriched slag；
Alkaline extraction system is used to realize the separation of tungsten and vanadium, its extraction tank 5 for including being sequentially connected, sink 6 and instead
Extract groove 7, tungstenic, the leachate of vanadium and the blank organic phase that extraction tank 5 is used to obtain band filter 3 react to obtain
Rich tungsten organic phase and rich vanadium raffinate, sink 6 are used to carry out rich tungsten organic phase pure water, and back extraction groove 7 is used for washing
Rich tungsten organic phase afterwards reacts to obtain rich tungsten strip liquor and blank organic phase with back washing agent；
Product purification system is used for the ammonium paratungstate and ammonium metavanadate of purifying high-purity, and it includes tungsten subsystem processed and vanadium processed
Subsystem, tungsten subsystem processed include ion exchange column 8, the dryer 10 of evaporative crystallization kettle 9 and second being sequentially connected, ion exchange
Post 8 is used to carry out deeply removing vanadium to the rich tungsten strip liquor that back extraction groove 7 obtains, and evaporative crystallization kettle 9 is used for after deeply removing vanadium
Rich tungsten strip liquor is crystallized to obtain ammonium para-tungstate crystal thing, and the second dryer 10 is used to dry ammonium para-tungstate crystal thing
Dry-cure obtains ammonium paratungstate, and the neutralization that vanadium subsystem processed includes being sequentially connected is dried except silicon kettle 11, precipitation reactor 12 and the 3rd
Dry machine 13, neutralize and remove silicon except the rich vanadium raffinate that silicon kettle 11 is used to obtain extraction tank 5 carries out precipitation, precipitation reactor 12 is used for
To being precipitated except the rich vanadium raffinate after silicon to obtain ammonium metavanadate precipitate thing, the 3rd dryer 13 is used to sink to ammonium metavanadate
Starch carries out drying and processing and obtains ammonium metavanadate.
In a preferred embodiment of the invention, as shown in figure 1, the outlet of sink 6 is also with neutralizing the entrance except silicon kettle 11
Connection, neutralized for flowing into washings except in silicon kettle.
In a preferred embodiment of the invention, as shown in figure 1, entrance of the outlet of back extraction groove 7 also with extraction tank 5 is connected,
Recycled for making blank organic phase be back in extraction tank.
In a preferred embodiment of the invention, as shown in figure 1, the outlet of ion exchange column 8 is also with neutralizing except silicon kettle 11
Entrance connects, for making to remove in silicon kettle except vanadium liquid flows into neutralize.
A kind of SCR denitration dead catalyst valuable metal alkaline extraction recovery process based on said apparatus, as shown in figure 1,
Comprise the following steps：
S1, NaOH are leached：SCR denitration dead catalyst powder after deashing is broken mixes with NaOH and water in raw material tank 1
Mixed serum is formed after closing uniformly to enter in high pressure leaching kettle 2, high pressure leaching kettle 3 provides certain temperature and pressure (higher temperature
And pressure) mixed serum is reacted to leach tungsten, vanadium, reacted slurries obtain through the separation of solid and liquid of band filter 3
Tungstenic, the leachate of vanadium and the leached mud containing titanium dioxide, the leached mud containing titanium dioxide obtain after the drying of the first dryer 4
High titanium slag, tungstenic, the leachate of vanadium are returned and leached in raw material tank 1；
S2, alkaline extraction：Tungstenic, the leachate of vanadium and the blank organic phase in input extraction tank 5 obtained in step S1
Directly contact carries out multitple extraction tungsten, obtains rich tungsten organic phase and rich vanadium raffinate, and rich tungsten organic phase enters in sink 6 through pure
After the washing of water multi-stage countercurrent, the multistage back extraction tungsten of progress is contacted with the back washing agent in back extraction groove 7, obtaining rich tungsten strip liquor and blank has
Machine phase；
S3, product purification：After the rich tungsten strip liquor obtained in step S2 is by the deeply removing vanadium of ion exchange column 8, evaporating
Crystallization obtains ammonium para-tungstate crystal thing in crystallization kettle 9, and ammonium para-tungstate crystal thing obtains meeting state after the drying of the second dryer 10
The ammonium paratungstate of family's standard, the rich vanadium raffinate obtained in step S2, which enters to neutralize, to be removed after precipitation removes silicon in silicon kettle 11, in precipitation
Precipitation obtains ammonium metavanadate precipitate thing in reactor 12, and ammonium metavanadate precipitate thing obtains meeting state after the drying of the 3rd dryer 13
The ammonium metavanadate of family's standard.
In a preferred embodiment of the invention, as shown in figure 1, in step S1, the reclaimed water of raw material tank 1 and the useless catalysis of SCR denitration
The mass ratio of agent powder is 150%~350%, and the addition of sodium hydroxide is SCR denitration dead catalyst powder when leaching first
End quality 10%~40%, return leach when for SCR denitration dead catalyst powder quality 5%~20%.
In a preferred embodiment of the invention, as shown in figure 1, in step S1, the reaction temperature in high pressure leaching kettle 2 is
180~320 DEG C, reaction pressure be 1.0~2.5MPa, the reaction time be 1~4h.
In a preferred embodiment of the invention, as shown in figure 1, in step S2, each component and each component of blank organic phase
Percent by volume is extractant:Polarity improver:Diluent=10%~60%:10%~30%:10%~60%, wherein,
Extractant is CO3 2-Quaternary ammonium salt or HCO3 -The one or two of quaternary ammonium salt, polarity improver are higher alcohols, and diluent is coal
The flow-rate ratio of oil, blank organic phase and tungstenic, the leachate of vanadium is 1/1~5/1, and the extraction series of extraction tank is 2~12 grades.
In a preferred embodiment of the invention, as shown in figure 1, in step S2, rich tungsten organic phase and pure water in sink 6
Flow-rate ratio is 4/1~8/1, and washing series is 2~10 grades.
In a preferred embodiment of the invention, as shown in figure 1, in step S2, back washing agent is 2.0~3.5mol/L bicarbonates
The flow-rate ratio of the mixed solution of ammonium and 0.5~1.5mol/L ammoniacal liquor, rich tungsten organic phase and back washing agent is 1/1~5/1, is stripped series
For 5~18 grades.
The present invention in specific application, as shown in figure 1, carrying out according to the following steps：
S1, NaOH are leached：SCR denitration dead catalyst contains 5.04% WO3, 2.98% V2O5With 86.47% TiO2,
Deashing is carried out to it and is ground into powder, adds the 500kg denitration dead catalyst powder into raw material tank by conveying worm,
100kg sodium hydroxides and 1500L water are added, stirs to form slurries, slurries are delivered to high pressure leaching kettle, high pressure leaching through pump
Go out kettle and be provided with steam-heating system, leach 2h at 300 DEG C of temperature, tungsten, vanadium and NaOH react and be leached, reacted
Slurries are transported to band filter and are washed and filtered, and obtain tungstenic, the leachate of vanadium and the leached mud containing titanium dioxide, leaching
Go out liquid to be back in raw material tank, add 500kg denitration dead catalyst powder and 50kg sodium hydroxides, leach dead catalyst powder again
End, return 5 times, to lift the concentration of tungsten and vanadium in leachate, while recycling for water and alkali is realized, in obtained leachate
WO containing 73.50g/L3With 44.20g/L V2O5, leachate enters the further separating tungsten of alkaline extraction system and vanadium, leached mud
Drying obtains the level Four high titanium slag 2880kg for meeting national standard；
S2, alkaline extraction：Leachate and the blank organic phase (sulphur of 50%N263+25% sec-octyl alcohols+25% from step S1
Change kerosene) (organic phase is transformed into CO before extraction3 2-And HCO3 -Mixed type) enter extraction tank together, extraction tank makes two with stirring
Mutually separated after rapid mixing, the volume flow ratio for adjusting organic phase and leachate is 1/1, carries out 8 grades of extraction tungsten, obtained raffinate
WO of the liquid containing 1.10g/L3With 43.71g/L V2O5, obtained rich tungsten organic phase enters sink, adjusts organic phase and pure water
Flow-rate ratio is 6/1, carries out 3 grades of washings, rich tungsten organic phase and back washing agent (2mol/L NH after washing4HCO3+1mol/L
NH4OH back extraction groove) is entered together, back extraction groove makes two-phase be separated after mixing rapidly, adjust organic phase and back washing agent with stirring
Volume flow ratio is 3/1, carries out 8 grades of back extraction tungsten, and obtained strip liquor contains WO3 216.98g/L、V2O51.32g/L, obtain
Blank organic phase is back to extraction tank recycling, and rich tungsten strip liquor and rich vanadium raffinate prepare high-purity into product purification system
Spend ammonium paratungstate and ammonium metavanadate；
S3, product purification：After strip liquor from step S2 is by ion exchange column deeply removing vanadium, in evaporative crystallization kettle
Ammonium paratungstate is crystallized, drying obtains 0 grade of ammonium paratungstate product 110kg for meeting national standard, the raffinate from step S2, led to
After neutralization is crossed except precipitation removes silicon in silicon kettle, to precipitate ammonium metavanadate, drying obtains meeting state for ammonium salt precipitation in precipitation reactor
98 grades of ammonium metavanadate product 51kg of family's standard.
The present invention uses NaOH solution first, and the tungsten of SCR denitration dead catalyst, vanadium are leached into leachate, and titanium stays
In leached mud, the separation of tungsten, vanadium and titanium is realized；Then alkaline extraction separating tungsten and vanadium are used；Finally by essences such as crystallization, drying
Process processed, the high-purity ammonium paratungstate and ammonium metavanadate for meeting national standard are obtained, while obtain byproduct Ti-enriched slag.
It should be appreciated that for those of ordinary skills, can according to the above description be improved or converted,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (8)
1. a kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device, it is characterised in that the device soaks including NaOH
Go out system, alkaline extraction system and product purification system；Wherein,
The NaOH leaching systems are used for the separation for realizing tungsten, vanadium and titanium, and its raw material tank for including being sequentially connected, high pressure leach
Kettle, band filter and the first dryer, the raw material tank, which is used to give up to the SCR denitration after deashing is broken inputted in it, urges
Agent powder be sufficiently mixed with NaOH and water and forms it into mixed serum, and the high pressure leaching kettle is used to make the mixed serum
Reacted under certain temperature and pressure to leach tungsten, vanadium, the band filter be used to carrying out the slurries of reaction washing and
Filtering to obtain tungstenic, the leachate of vanadium and leached mud containing titanium dioxide, the outlet of the band filter and raw material tank
Entrance connects so that tungstenic, the leachate of vanadium are back in raw material tank, and first dryer is used for the leaching containing titanium dioxide
Progress drying and processing of slagging tap obtains Ti-enriched slag；
The alkaline extraction system is used for the separation for realizing tungsten and vanadium, and it includes the extraction tank, sink and back extraction being sequentially connected
Groove, tungstenic, the leachate of vanadium and the blank organic phase that the extraction tank is used to obtain band filter react to obtain
Rich tungsten organic phase and rich vanadium raffinate, the sink are used to carry out rich tungsten organic phase pure water, and the back extraction groove is used for
Rich tungsten organic phase after washing and back washing agent are reacted to obtain rich tungsten strip liquor and blank organic phase；
The product purification system is used for the ammonium paratungstate and ammonium metavanadate of purifying high-purity, and it includes tungsten subsystem processed and vanadium processed
Subsystem, the tungsten subsystem processed include ion exchange column, evaporative crystallization kettle and the second dryer being sequentially connected, the ion
Exchange column is used to carry out deeply removing vanadium to the rich tungsten strip liquor that back extraction groove obtains, and the evaporative crystallization kettle is used for through deeply removing vanadium
Rich tungsten strip liquor afterwards is crystallized to obtain ammonium para-tungstate crystal thing, and second dryer is used for ammonium para-tungstate crystal thing
Carry out drying and processing and obtain ammonium paratungstate, the vanadium subsystem processed include the neutralization that is sequentially connected except silicon kettle, precipitation reactor and
3rd dryer, described neutralize remove silicon except the rich vanadium raffinate that silicon kettle is used to obtain extraction tank carries out precipitation, and the precipitation is anti-
Kettle is answered to be used for except the rich vanadium raffinate after silicon is precipitated to obtain ammonium metavanadate precipitate thing, the 3rd dryer is used for pair
Ammonium metavanadate precipitate thing carries out drying and processing and obtains ammonium metavanadate.
2. SCR denitration dead catalyst valuable metal alkaline extraction retracting device according to claim 1, it is characterised in that
The outlet of the sink is also connected with the entrance neutralized except silicon kettle, is removed for making washings flow into neutralization in silicon kettle.
3. SCR denitration dead catalyst valuable metal alkaline extraction retracting device according to claim 1, it is characterised in that
The outlet of the back extraction groove is also connected with the entrance of extraction tank, is made for making blank organic phase be back in extraction tank to carry out circulation
With.
4. SCR denitration dead catalyst valuable metal alkaline extraction retracting device according to claim 1, it is characterised in that
The outlet of the ion exchange column is also connected with the entrance neutralized except silicon kettle, for making to remove in silicon kettle except vanadium liquid flows into neutralize.
5. a kind of SCR denitration dead catalyst valuable metal alkaline extraction based on device any one of Claims 1-4 returns
Knock off skill, it is characterised in that comprise the following steps：
S1, NaOH are leached：SCR denitration dead catalyst powder after deashing is broken is well mixed with NaOH and water in raw material tank
Form mixed serum afterwards to enter in high pressure leaching kettle, high pressure leaching kettle, which provides certain temperature and pressure, makes the mixed serum react
To leach tungsten, vanadium, reacted slurries obtain tungstenic, the leachate of vanadium and containing titanium dioxide through band filter separation of solid and liquid
Leached mud, the leached mud containing titanium dioxide obtain high titanium slag after the first drying machine drying, and tungstenic, the leachate of vanadium return to raw material
Leached in groove；
S2, alkaline extraction：Tungstenic, the leachate of vanadium obtained in step S1 directly contacts with blank organic phase in input extraction tank
Multitple extraction tungsten is carried out, obtains rich tungsten organic phase and rich vanadium raffinate, rich tungsten organic phase enters inverse through pure water multistage in sink
After stream washing, the multistage back extraction tungsten of progress is contacted with the back washing agent in back extraction groove, obtains rich tungsten strip liquor and blank organic phase, its
In, the back washing agent is the mixed solution of 2.0~3.5mol/L ammonium hydrogen carbonate and 0.5~1.5mol/L ammoniacal liquor, rich tungsten organic phase
Flow-rate ratio with back washing agent is 1/1~5/1, and back extraction series is 5~18 grades, each component of the blank organic phase and each group split
Product percentage is extractant:Polarity improver:Diluent=10%~60%:10%~30%:10%~60%, wherein, extractant is
CO3 2-Quaternary ammonium salt or HCO3 -The one or two of quaternary ammonium salt, polarity improver are higher alcohols, and diluent is kerosene, and blank has
Machine phase and the flow-rate ratio of tungstenic, the leachate of vanadium are 1/1~5/1, and the extraction series of extraction tank is 2~12 grades；
S3, product purification：After the rich tungsten strip liquor obtained in step S2 is by ion exchange column deeply removing vanadium, in evaporative crystallization kettle
Middle crystallization obtains ammonium para-tungstate crystal thing, and ammonium para-tungstate crystal thing obtains meeting the secondary of national standard after the second drying machine drying
Ammonium tungstate, the rich vanadium raffinate obtained in step S2, which enters to neutralize, to be removed after precipitation removes silicon in silicon kettle, is precipitated in precipitation reactor
Ammonium metavanadate precipitate thing is obtained, ammonium metavanadate precipitate thing obtains the metavanadic acid for meeting national standard after the 3rd drying machine drying
Ammonium.
6. SCR denitration dead catalyst valuable metal alkaline extraction recovery process according to claim 5, it is characterised in that
In step S1, the mass ratio of raw material tank reclaimed water and SCR denitration dead catalyst powder is 150%~350%, the addition of sodium hydroxide
It is the 10%~40% of the quality of SCR denitration dead catalyst powder when leaching first, when returning and leaching is the useless catalysis of SCR denitration
The 5%~20% of the quality of agent powder.
7. SCR denitration dead catalyst valuable metal alkaline extraction recovery process according to claim 5, it is characterised in that
In step S1, the reaction temperature in high pressure leaching kettle is 180~320 DEG C, reaction pressure is 1.0~2.5MPa, the reaction time
For 1~4h.
8. SCR denitration dead catalyst valuable metal alkaline extraction recovery process according to claim 5, it is characterised in that
In step S2, rich tungsten organic phase and the flow-rate ratio of pure water are 4/1~8/1 in the sink, and washing series is 2~10 grades.
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| CN107699695A (en) * | 2017-10-13 | 2018-02-16 | 北京工业大学 | It is a kind of that tungsten, the method for vanadium are reclaimed from useless SCR denitration |
| CN110015686A (en) * | 2018-01-08 | 2019-07-16 | 神华集团有限责任公司 | Titanium slag recycles the method for titanium dioxide and the method from denitrating catalyst recycling tungsten, titanium and vanadium |
| CN109022794B (en) * | 2018-06-24 | 2020-09-08 | 聊城市鲁西化工工程设计有限责任公司 | Process and device for recovering precious metals in waste catalyst |
| CN111422907B (en) * | 2019-04-22 | 2021-05-25 | 中国科学院过程工程研究所 | Method and system for producing ammonium paratungstate by alkaline extraction |
| CN111001185A (en) * | 2019-12-27 | 2020-04-14 | 昆明弘承商贸有限公司 | Efficient extraction method suitable for food slurry |
| CN111646498A (en) * | 2020-06-11 | 2020-09-11 | 华北电力大学 | Method for recovering mixed ammonium salt and lead titanate from waste SCR denitration catalyst |
| CN112342392B (en) * | 2020-10-27 | 2022-04-15 | 江西理工大学 | Method for respectively recovering titanium, tungsten and vanadium from waste denitration catalyst |
| CN112374541A (en) * | 2020-11-12 | 2021-02-19 | 甘肃盈华环保科技有限公司 | Method for recycling ammonium paratungstate by using waste SCR catalyst |
| CN117551879B (en) * | 2024-01-11 | 2024-03-29 | 中国科学院过程工程研究所 | Method for recycling vanadium and tungsten by using waste SCR catalyst |
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| CN103526031B (en) * | 2013-10-09 | 2014-12-24 | 北京科技大学 | Recovery method for SCR waste flue gas denitration catalyst |
| CN104263946B (en) * | 2014-10-10 | 2016-07-27 | 武汉凯迪电力环保有限公司 | A kind of method reclaiming tungsten, vanadium, titanium from SCR denitration dead catalyst |
| CN104862485B (en) * | 2015-05-22 | 2017-08-18 | 中科过程（北京）科技有限公司 | A kind of vanadium of useless vanadium tungsten system SCR catalyst, tungsten separation and method of purification |
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| CN106119544B (en) * | 2016-06-22 | 2018-03-09 | 中电恒德环保投资有限公司 | A kind of method that titanium slag, tungsten and vanadic salts are extracted from discarded SCR catalyst |
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