CN106521160B - A kind of vanadium extraction from discarded SCR catalyst and the method for preparing activation titanium silicon tungsten powder - Google Patents
A kind of vanadium extraction from discarded SCR catalyst and the method for preparing activation titanium silicon tungsten powder Download PDFInfo
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- 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
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J38/00—Regeneration or reactivation of catalysts, in general
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- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
- B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
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Abstract
The invention discloses a kind of separation failure vanadium from discarded SCR catalyst and the method available for the activation titanium silicon tungsten powder for manufacturing new denitrating catalyst is prepared, to discarded SCR catalyst pretreatment, wet pulverizing adds in oxalic acid solution and carry out Leach reaction into slurries；The titanium slag powder and pressing filtering liquid of the isolated tungstenic silicon of press filtration, rear cleaning activate and are finely ground into Ti-Si nano tungsten powder；Pressing filtering liquid is separated, recycling oxalic acid returns to Leach reaction, adds in oxidant to separating liquid, carries out precipitation reaction, obtains ammonium metavanadate precipitate, be isolated by filtration to obtain ammonium metavanadate solid.The present invention is reacted under normal temperature condition using oxalic acid, and failure vanadic salts can be isolated from SCR catalyst, using acid to carrying out the processing such as fine grinding after other activation of component, obtains the raw material that new denitrating catalyst can be used for prepare.Technology investment requirement of the present invention is low, and low energy consumption, effectively solves the problems, such as SCR catalyst harmless treatment, realizes resource reutilization.
Description
Technical field
The present invention relates to waste catalyst utilization technology fields more particularly to one kind to carry from discarded SCR catalyst
Vanadium and the method for preparing activation titanium silicon tungsten powder.
Background technology
2014 Nian8Yue State Ministry of Environmental Protection formally issue《On the notice for strengthening waste flue gas denitration catalyst supervision》With
《Waste flue gas denitration catalyst hazardous waste business licence guidelines for examination》, waste flue gas denitration catalyst (vanadium titanium system) is included into danger
Dangerous waste is managed, and is classified as《National Hazard waste register》In " the other wastes of HW49 classes " (2016 new to promulgate
Regulation is changed to HW50).
The mounting means of SCR denitration generally use " 2+1 ", normal SCR denitration service life are 2 years
Left and right started to go out useless SCR denitration generation living in the 3rd year.Denitrating catalyst inactivation one of the main reasons is to urge
Vanadic anhydride in agent is converted into sulfate etc. by sulfur dioxide in flue gas and loses catalytic action.And since physics is former
Cause, such as block, be sintered and cause the inactivation of other components (titanium dioxide, tungstic acid etc.) can be by cleaning, being acidified
Method reactivates.
The SCR denitration that national about 1.8 hundred million kilowatts of units are installed before to 2015,2012 is whole
Into the stage of replacement, useless SCR denitration generates quantity and guards estimation in or so 10 ten thousand steres/year, and since 2016,
The amount for SCR denitration of all giving up caused by about 1,000,000,000 kilowatts of units will be stepped up, and by 2017, may be reached every year
To 30 ten thousand steres (200,000 tons or so), so substantial amounts of hazardous waste can give national soil and water body to bring sizable environment
It threatens.
At present, useless SCR denitration is recycled, it is that disposal is discarded to extract useful metal material therein
The usual way of SCR denitration.The main method of recycling is exactly that discarded SCR is taken off by various physics, chemical method
Useful component (titanium, vanadium, tungsten etc.), which extracts, in denox catalyst recycles.
Both at home and abroad the disclosed patented method that metal oxide is recycled from waste flue gas denitration catalyst largely use with
Lower technique：After carrying out high temperature preroast processing after first waste flue gas denitration catalyst is crushed, it is proportionally added into highly basic and mixes, powder
It is broken, then carry out high-temperature roasting.Agglomerate puts into leaching in hot water after crushing.Gained titanate adds in sulfuric acid, filtered, water
It the modes such as washes, hydrolyze, roasting and obtaining TiO2.Filtrate after leaching adds sulphur acid for adjusting pH value, adds excessive ammonium salt precipitation vanadium.It will
The NH being obtained by filtration4VO3Through pyrolytic, V is made2O5Finished product.Filtrate after precipitation vanadium adds salt acid for adjusting pH value, adds calcium
Salt precipitates tungsten, filtering gained CaWO4WO can be obtained with HCl treatment is fired again3.Since these methods need repeatedly at high temperature
Roasting is high to equipment requirement to obtain the output object of high-purity, and investment is big, and high energy consumption is of high cost.
The present invention proposes a kind of at low cost, low energy consumption harmlessness disposing gives up denitrating catalyst, and from discarded SCR catalyst
Vanadium extraction and the method for preparing activation titanium silicon tungsten powder.
The content of the invention
(1) the technical problem to be solved in the present invention is to provide a kind of approach at low cost, low energy consumption：It is catalyzed from discarded SCR
Failure vanadium is extracted in agent and activates titanium silicon tungsten powder and makes the method that raw catelyst prepares raw material；This method not only solves
The problem of SCR catalyst harmless treatment, more realizes the recycling of resource.
(2) technical solution
The purpose of the present invention is what is be achieved through the following technical solutions：
The method that the vanadium extraction provided by the invention from discarded SCR catalyst prepares activation titanium silicon tungsten powder, comprises the following steps：
1) pre-processed to remove adsorbed impurity to discarding SCR catalyst；
2) pretreated discarded SCR catalyst is subjected to wet pulverizing to the slurries of presetting granularity；
3) discarded SCR catalyst and oxalic acid solution are inserted in reaction kettle, it is small to be stirred to react 3-4 at 40-80 DEG C of temperature
When, postcooling；
4) product after cooling will be reacted and carry out press filtration isolated titanium slag and pressing filtering liquid after removing vanadium；
5) by except after vanadium titanium slag be placed in sulfuric acid solution and be acidified, clean to obtain and activate siliceous, tungsten titanium slag powder；
6) except after vanadium titanium slag powder Ti-Si nano tungsten powder obtained by further grinding be used as raw catelyst raw material；
7) pressing filtering liquid is separated by ion exchange, the oxalic acid solution flowed through returns to leaching section, and concentration and separation vanadium are molten
Liquid；
8) by the isolated oxidized reaction treatment of vanadium solution, add in ammonium chloride and vanadium ion is precipitated, at press filtration
Manage isolated ammonium metavanadate finished product.
Further, the pretreatment include by discarded SCR catalyst carry out water leaching and immersion, ultrasonic cleaning, acidifying and
Washing process；Acidifying activation is carried out to available composition, the impurity is flyash and coke button.
Further, the slurries that the wet pulverizing is formed are the slurries that granularity is 180-325 mesh.
Further, it is described except vanadium titanium slag powder through the following steps that realize：
Catalyst slurry and concentration are inserted for 4-9% (mass volume ratio) oxalic acid solution in reaction kettle, the slurries with
Oxalic acid solution volume ratio is 1: 4-5, be stirred to react at 40-80 DEG C of temperature 3-4 it is small when, make wherein vanadic anhydride composition reaction
Be dissolved as vanadyl oxalate, reach except vanadium purpose, postcooling, reacting product after cooling, to carry out press filtration isolated except after vanadium
Titanium slag and pressing filtering liquid；
To obtain except after vanadium titanium slag be placed in the sulfuric acid solution that concentration is 2-3% (mass volume ratio) and cleaned, live
To change 10-20 minutes, the sulfuric acid solution is 1: 5 with the mass ratio except titanium slag after vanadium, then is cleaned 10-20 minutes with deionized water,
It is isolated by filtration to obtain titanium slag powder and the impurity filtrate after removing vanadium activated containing titanium dioxide and tungstic acid；The titanium after removing vanadium
Ground-slag is pie.
Further, the Ti-Si nano tungsten powder is through the following steps that form：
Titanium slag powder adds water that solid-liquid mass ratio is made for 1: 1 slurries and then by wet method eddy flow fine powder machine progress two after vanadium will be removed
Grade grinding obtains 6000-8000 purposes except vanadium titanium valve；Vanadium titanium valve will be removed at powder drying machine and high speed Depolymerizing thrasher
Reason, obtains Ti-Si nano tungsten powder.
Further, the formation of the ammonium metavanadate finished product, is realized according to following steps：
Separating treatment carries out the pressing filtering liquid by ion exchange resin device, oxalic acid is by returning and being soaked for vanadic salts
Go out；Vanadyl oxalate is adsorbed on resin simultaneously；
Concentration is that the sulfuric acid solution of 9-10% (mass volume ratio) elutes resin, obtains vanadyl oxalate and sulphur
Sour vanadyl mixed solution, wherein vanadium ingredient are concentrated；And with concentration it is 9-10% (mass volume ratio) sodium hydroxide solution tune
Save pH value so that pH value is between 5-6；
The mixed solution of vanadyl oxalate and vanadic sulfate after neutralization adds in sodium peroxydisulfate and is aoxidized, and obtains sodium vanadate
Solution；
It is that 1: 2 ratio adds in the ammonium chloride that concentration is 3-4% (mass volume ratio) in mass ratio into sodium vanadate solution
Solution, and obtain ammonium metavanadate precipitate when reaction 1-2 is small at a temperature of 70-80 DEG C；
Product after reaction is subjected to press filtration processing, is separated by filtration to obtain ammonium metavanadate solid.
Further, the press filtration processing is to carry out press filtration processing to ammonium metavanadate precipitate by plate and frame filter press,
It is cleaned in pressure-filtering process using deionized water.
(3) advantageous effect
Compared with the prior art and product, the present invention has the following advantages：
The extraction failure vanadic anhydride provided by the invention from discarded SCR catalyst is simultaneously produced available for new denitration catalyst
The method of the activation Ti-Si nano tungsten powder of agent manufacture.This method includes：Discarded SCR catalyst is pre-processed, Ran Houjin
Into slurries, addition oxalic acid solution is reacted row wet pulverizing in slurries, passes through the isolated tungstenic of plate and frame filter press press filtration
The titanium slag powder and pressing filtering liquid of silicon, titanium slag powder is placed in sulfuric acid solution and is acidified, cleaned, then is passed through after being cleaned with deionized water
The nanoscale powder material activated is made for manufacturing new denitrating catalyst in wet method super-fine milling machine.By ion interchange unit to described
Pressing filtering liquid is separated, and the oxalic acid isolated carries out reuse, and the separating liquid containing vanadyl oxalate is added in sodium peroxydisulfate oxidation, is used
Ammonium chloride solution does precipitating reagent and carries out precipitation reaction, obtains ammonium metavanadate precipitate, passes through the isolated ammonium metavanadate solid of press filtration.
Compared with the prior art, the advantage of the invention is that：
1) since the present invention is without multiple calcination at high temperature, need to only be carried out under room temperature or lower temperature by acid
Leach reaction can isolate failure vanadic salts from SCR catalyst, effectively solve asking for SCR catalyst harmless treatment
Topic.
2) present invention does not extract the titanium dioxide and tungstic acid not by Poisoning Effect, but passes through acidleach, water
Wash and etc. recover its activity, achieve the purpose that resource reutilization.
3) the most techniques of the present invention have been prevented dust harzard, have been reduced worker's working strength, met using wet processing
The requirement of clean manufacturing.
4) this method need to only use some conventional raw materials such as alkali, acid, and cheap, extraction cost is low.
5) it is generated except vanadium post activation titanium slag (TiO according to this method2Content is 80% or so), by wet ground,
Not only grain size and specific surface area meet raw catelyst and prepare requirement, and in being prepared containing raw catelyst necessary silicon and tungsten into
Divide, greatly reduce the manufacture cost of raw catelyst.
6) present invention uses oxalic acid to overcome and carried out using sodium hydroxide solution as leaching acid in vanadium leaching process
The sodium ion brought when alkali leaches to removing titanium slag after vanadium pollutes.
7) ammonium metavanadate (effective content is 85% or so) that the present invention generates can not only be used for needed in prepared by raw catelyst
Vanadic salts source, and can become vanadium smelter quality raw materials.
8) ion exchange resin device that the present invention uses not only recycled oxalic acid, but also the oxalic acid oxygen to leaching
Vanadium is concentrated, and substantially reduces the consumption of oxalic acid and ammonium chloride or ammonium carbonate, reduces wastewater treatment intensity.
9) industrial water in the present invention, with acid can realize recyclings, reduce cost, reduce and pollute.
10) present invention process is simple, low for equipment requirements, and low energy consumption, and production cost is low, non-secondary pollution, and recycling is effective
Ingredient is more, easy to utilize.
Description of the drawings
Fig. 1 is that the vanadium extraction from discarded SCR catalyst of the present invention prepares the method flow diagram of titanium silicon tungsten powder.
Specific embodiment
Understand for the ease of those of ordinary skill in the art and implement the present invention, below in conjunction with the accompanying drawings and specific embodiment
The present invention is described in further detail.
The principle of method provided in this embodiment is as described below：SCR denitration denitration efficiency after prolonged use
The basic reason of reduction is active ingredient therein：The poisoning of vanadic anhydride, among these in existing flue gas potassium sodium arsenic and
Sulfide composition forms vanadate with vanadic anhydride, more there is the process that pentavalent vanadium is converted into tetravalence sulfate, and the latter accounts for mistake
Imitate 60% or so of vanadic anhydride.And the ingredients such as titanium dioxide, tungstic acid are passing through abundant acidleach, are washing in denitrating catalyst
It can recover original function after washing.
Therefore, the mode for the recycling to SCR denitration of giving up that the present invention takes is exactly：It will wherein be failed with oxalic acid
Vanadic anhydride propose, using further acidifying activation process and fine grinding breakdown process, obtain meeting raw catelyst making
The activation powder of the physical parameters such as the grain size needed and specific surface area requirement, then adds in new active ingredient, again sintering system
The standby new denitrating catalyst with catalysis.
The present embodiment provided during vanadium extraction obtains the process of raw catelyst raw material from discarded SCR catalyst,
The chemical principle being related to is as follows：
3H2C2O4+V2O5=2VOC2O4+3H2O+2CO2↑
2VOC2O4+3Na2S2O8+4H2O=2NaVO3+2Na2SO4+4CO2↑+4H2SO4
NaVO3+NH4Cl=NH4VO3↓+NaCl
As shown in the figure, Fig. 1, which is the vanadium extraction from discarded SCR catalyst of the present invention, prepares the method flow of activation titanium silicon tungsten powder
Figure, the method that the vanadium extraction provided in this embodiment from discarded SCR catalyst prepares activation titanium silicon tungsten powder, comprises the following steps：
Embodiment 1
1) pre-processed to remove adsorbed impurity to discarding SCR catalyst；The pretreatment is included discarded SCR
Catalyst carries out water leaching and immersion, ultrasonic cleaning, acidifying and washing process；This method can be to denitrating catalyst upper flue gas
The poisoning element such as potassium sodium arsenic brought is cleaned, and tentatively recovers titanium dioxide, the function of tungstic acid.The impurity is powder
Coal ash and coke button.
2) pretreated discarded SCR catalyst is subjected to wet pulverizing to the slurries of presetting granularity；The wet pulverizing
The slurries of formation are the slurries that granularity is 180 mesh.
3) oxalic acid solution that concentration is 4% (mass volume ratio), and discarded SCR catalyst and grass are added in the slurries
The mass ratio of acid solution is 1: 4, be stirred to react in a kettle at 80 DEG C of temperature 3-4 it is small when, make wherein vanadic anhydride into
Point be dissolved as vanadyl oxalate, reach except vanadium purpose, postcooling；
4) it is isolated except titanium slag powder and pressing filtering liquid after vanadium by plate and frame filter press press filtration that product after cooling will be reacted, it should
Pressing filtering liquid is the mixed solution of the oxalic acid solution containing vanadyl oxalate and excess；
5) by except after vanadium titanium slag be placed in sulfuric acid solution and cleaned, be re-activated to obtain siliceous, tungsten titanium slag powder；The work
Change titanium slag powder through the following steps that realize：
To obtain except after vanadium titanium slag be placed in the sulfuric acid solution that concentration is 2-3% (mass volume ratio) and be acidified, clearly
It washes 10-20 minutes, the sulfuric acid solution is 1: 5 with the mass ratio except titanium slag after vanadium, then is cleaned 10-20 minutes with deionized water,
Pass through isolated titanium silicon tungsten ground-slag and the impurity filtrate after removing vanadium containing titanium dioxide and tungstic acid activated of press filtration；It is described
Except titanium silicon tungsten ground-slag is pie after vanadium.
6) except after vanadium titanium silicon tungsten slag Ti-Si nano tungsten powder obtained by further grinding be used as raw catelyst raw material；It is described
Ti-Si nano tungsten powder is through the following steps that form：
Titanium slag powder adds deionized water that solid-liquid mass ratio is made as 1: 1 slurries after vanadium will be removed, and then passes through wet method eddy flow fine powder
Machine carries out two level grinding, and obtaining 6000 mesh, (D90 is 2.5 μm；D50 is 0.8 μm) except titanium slag powder after vanadium；
7) above-mentioned 8000 mesh is contained except titanium valve enters powder drying machine after vanadium and high speed Depolymerizing thrasher is handled
Water rate is less than 1.5% Ti-Si nano tungsten powder.
8) 4) pressing filtering liquid is handled by ion exchange resin device, it is molten to recycle the oxalic acid in the pressing filtering liquid
Liquid, while concentrate the concentration of vanadyl oxalate in the solution.
9) concentration be 9-10% (mass volume ratio) sulfuric acid solution resin is eluted, obtain vanadyl oxalate and
Vanadic sulfate mixed solution, wherein vanadium ingredient are concentrated；And with concentration it is 9-10% (mass volume ratio) sodium hydroxide solution
Adjust pH value so that pH value is between 5-6；
10) mixed solution of the vanadyl oxalate after 9) neutralizing and vanadic sulfate adds in sodium peroxydisulfate and is aoxidized, and obtains
Sodium vanadate solution；Add in ammonium chloride to vanadium ion precipitate, by press filtration from isolated ammonium metavanadate solid；The metavanadic acid
The formation of ammonium solid is realized according to following steps：
It is that 1: 2 ratio adds in the ammonium chloride that concentration is 3-4% (mass volume ratio) by volume into sodium vanadate solution
Solution, and obtain ammonium metavanadate precipitate when reaction 1-2 is small at a temperature of 70-80 DEG C；
Product after reaction is subjected to press filtration processing, is separated by filtration to obtain ammonium metavanadate solid.
The press filtration processing is to carry out press filtration processing to ammonium metavanadate precipitate by plate and frame filter press, in pressure-filtering process
It is middle to be cleaned using deionized water.
Embodiment 2
The present embodiment provides similar embodiment 1 the vanadium extraction from discarded SCR catalyst prepare activation titanium silicon tungsten powder method,
Specifically include following steps：
1) pre-processed to remove adsorbed impurity to discarding SCR catalyst；The pretreatment is included discarded SCR
Catalyst carries out water leaching and immersion, ultrasonic cleaning, acidifying and washing process；This method can be to denitrating catalyst upper flue gas
The poisoning element such as potassium sodium arsenic brought is cleaned, and tentatively recovers titanium dioxide, the function of tungstic acid.The impurity is powder
Coal ash and coke button.
2) pretreated discarded SCR catalyst is subjected to wet pulverizing to the slurries of certain particle size, such as granularity is 325
Purpose slurries；
3) oxalic acid solution that mass percent concentration is 9% (mass volume ratio), and discarded SCR are added in the slurries
The mass ratio of catalyst and oxalic acid solution is 1: 4, be stirred to react in a kettle at 40 DEG C of temperature 3.5 it is small when, make wherein five
V 2 O ingredient is dissolved as vanadyl oxalate, reaches except vanadium purpose, postcooling；
4) it is isolated except titanium slag powder and pressing filtering liquid after vanadium by plate and frame filter press press filtration that product after cooling will be reacted, it should
Pressing filtering liquid is the mixed solution of the oxalic acid solution containing vanadyl oxalate and excess；
5) by except after vanadium titanium slag be placed in sulfuric acid solution and cleaned, be re-activated to obtain siliceous, tungsten titanium slag powder；The work
Change titanium slag powder through the following steps that realize：
To obtain except after vanadium titanium slag be placed in the sulfuric acid solution that concentration is 1.5% (mass volume ratio) and carry out cleaning activation
15 minutes, sulfuric acid solution was 1: 4 with the mass ratio except titanium slag after vanadium, then is cleaned 16 minutes with deionized water, is isolated by filtration
Activated containing titanium dioxide and tungstic acid etc. except titanium slag powder and impurity filtrate after vanadium；
6) except after vanadium titanium silicon tungsten slag Ti-Si nano tungsten powder obtained by further grinding be used as raw catelyst raw material；It is described
Ti-Si nano tungsten powder is through the following steps that form：By aqueous mass ratio be 40% or so except after vanadium titanium slag powder add water
1: 1 slurries of solid-to-liquid ratio are made, three-level grinding is then carried out by wet method eddy flow fine powder machine, obtaining 8000 mesh, (D90 is 2 μm；D50
For 0.6 μm) Ti-Si nano tungsten powder.
7) above-mentioned 8000 mesh is contained except titanium valve enters powder drying machine after vanadium and high speed Depolymerizing thrasher is handled
Water rate is less than 1.5% Ti-Si nano tungsten powder.
8) ion exchange resin device is crossed to handle the 4) pressing filtering liquid, it is molten to recycle the oxalic acid in the pressing filtering liquid
Liquid, while concentrate the concentration of vanadyl oxalate in the solution.
9) concentration be 9-10% (mass volume ratio) sulfuric acid solution resin is eluted, obtain vanadyl oxalate and
Vanadic sulfate mixed solution, wherein vanadium ingredient are concentrated；And with concentration it is 9-10% (mass volume ratio) sodium hydroxide solution
Adjust pH value so that pH value is between 5-6；
10) mixed solution of the vanadyl oxalate after 9) neutralizing and vanadic sulfate adds in sodium peroxydisulfate and is aoxidized, and obtains
Sodium vanadate solution；Add in ammonium chloride to vanadium ion precipitate, by press filtration from isolated ammonium metavanadate solid；The metavanadic acid
The formation of ammonium solid is realized according to following steps：
It is that 1: 2 ratio adds in the ammonium chloride that concentration is 3-4% (mass volume ratio) by volume into sodium vanadate solution
Solution, and obtain ammonium metavanadate precipitate when reaction 1-2 is small at a temperature of 70-80 DEG C；
Product after reaction is subjected to press filtration processing, is separated by filtration to obtain ammonium metavanadate solid.
The press filtration processing is to carry out press filtration processing to ammonium metavanadate precipitate by plate and frame filter press, in pressure-filtering process
It is middle to be cleaned using deionized water.
The method used in both examples above is difference that is different according to the active princlple in dead catalyst and using
Disposal options.Two kinds of disposal options are applicable in most of useless denitrating catalysts.Each step of two ways is described as follows：
In pre-treatment step, the pretreatment can include method well known in the art, such as discarded SCR is catalyzed
Agent carries out the processing such as water leaching and immersion, ultrasonic cleaning, drum bubbling -cleaning, acidifying and washing；This method can be to denitration catalyst
The poisoning element such as potassium sodium arsenic that agent upper flue gas is brought carries out cleaning removal, and tentatively recovers the work of titanium dioxide, tungstic acid
Property.
In oxalic acid Leaching Vanadium step, the oxalic acid leaches the process of useless vanadium, can be adopted according to dead catalyst composition difference
Vanadium ingredient therein is leached with different concentration of oxalic acid and different reaction temperatures.Herein wherein, oxalic acid both as acid into
Row reaction, while reducing agent is also served as, pentavalent vanadium can be made to be converted into tetravalence vanadium, oxalic acid Leaching Vanadium is the key that this method institute
.
In wet pulverizing step, the wet pulverizing may be employed method well known in the art and realize.It is i.e. described wet
Method crushing is the process of comminuted solids material using water or its solution as medium；Solid active ingredient, auxiliary agent and water are added in together
Atomizer mill is crushed to certain fineness and forms.
In press filtration separating step, the plate and frame filter press can be arbitrary plate and frame filter press available on the market；It is logical
It is pie to cross the titanium slag powder that plate and frame filter press press filtration obtains.It is of course also possible to it (for example is centrifuged using other species filter presses
Machine etc.) separation of solid and liquid is carried out, titanium slag powder can also be other shapes.
In reactivation step is acidified, described carries out cleaning reactivation using dilute sulfuric acid to titanium slag after removing vanadium, thoroughly extensive
The activity of multiple titanium dioxide and tungstic acid can also use other acid or the combination of different acid to carry out；In addition, use deionization
Water cleans obtained thick titanium slag powder.
In fine powder drying steps, the superfine grinding is to carry out series and parallel fine grinding using wet method eddy flow fine powder machine, can
To be level-one or two level, even more multistage, which is the key that obtain nanoscale except vanadium titanium silicon tungsten powder.
In fine powder drying steps, the drying and high speed Depolymerizing thrasher are the quality assurances for producing nanoscale raw material.
May suitable dispersant and surfactant be added according to product demand in segmentation process simultaneously.
In ionic energy transfer step, weak acid may be employed in the ion exchange process or strong acidic ion exchanges tree
Fat is more than 90% to the rate of recovery that the oxalic acid solution in pressing filtering liquid recycles, although may contain in the oxalic acid solution after separation
Vanadyl oxalate ingredient not to be adsorbed, but still fully recovering is to leaching step.
In ionic energy transfer step, the ion exchange process exists to the adsorption rate of pressing filtering liquid mesoxalic acid vanadyl
85-95%, the concentration of the vanadyl oxalate that pickling is isolated in the solution can improve 10-20 times.It is eluted due to the use of acid solution, elution
It in liquid in addition to containing vanadyl oxalate, can also contain the sour vanadyl that elution acid is formed, also have part oxalic acid and elution acid.In described
Specific method with reaction treatment can be：Concentration is that the sodium hydroxide solution of 9-10% (mass volume ratio) is molten with mixing
Liquid is mixed, and is carried out neutralization reaction, is made the pH value of the mixed solution between 5-6.
In vanadic salts settling step, the vanadium ammonium coprecipitation mode can use various ammonium salt (carbonic acid according to actual conditions
Ammonium, ammonium chloride, ammonium hydroxide etc.) vanadic salts neutralized is precipitated.And filter press can be used to carry out press filtration processing, obtain inclined vanadium
Sour ammonium solid；It is cleaned in pressure-filtering process using deionized water.
In above-mentioned processing step, the various waste liquids of generation, such as impurity filtrate, spent caustic solution, waste acid liquor, cleaning
Waste liquid afterwards etc. will all be recycled into waste water processing station, and wherein spent caustic solution and waste acid liquor can also mix or single
It solely carries out neutralization reaction and is used for wastewater treatment process.
By the obtained Ti-Si nano tungsten powder of method provided by the invention, meet grain necessary to prepared by raw catelyst
The essential components such as the physical parameters such as footpath and specific surface area and titanium dioxide and tungstic acid need to only rejoin new appropriate
Nano titanium dioxide powder and ammonium metavanadate solution, then through workshop sections such as sintering, you can qualified new denitrating catalyst is made.
The ammonium metavanadate solid that the present embodiment obtains, by drying, pack can be supplied to downstream raw catelyst factory
As vanadic anhydride additive, and it is provided to raw material of the vanadium Tungsten smelting factory as high quality.
Those skilled in the art can make various modifications to described specific embodiment
Or supplement or substitute in a similar way, for those of ordinary skill in the art, do not departing from present inventive concept
Under the premise of, without departing from scope defined in the present invention, it is within the scope of protection of the invention.
Claims (5)
1. the method that vanadium extraction prepares activation titanium silicon tungsten powder from discarded SCR catalyst, which is characterized in that comprise the following steps：
1) pre-processed to remove adsorbed flyash impurity to discarding SCR catalyst；
2) pretreated discarded SCR catalyst is subjected to wet pulverizing to the slurries of presetting granularity；
3) catalyst slurry and oxalic acid solution are inserted in reaction kettle, be stirred to react at 40-80 DEG C of temperature 3-4 it is small when, afterwards
Cooling；
4) product after cooling will be reacted and carry out press filtration isolated titanium slag and pressing filtering liquid after removing vanadium；
5) titanium slag is placed in sulfuric acid solution and is acidified after removing vanadium, and cleaning is siliceous, tungsten after activate to remove vanadium titanium slag powder；
6) except after vanadium titanium slag powder Ti-Si nano tungsten powder obtained by further grinding be used as raw catelyst raw material；
7) pressing filtering liquid is separated by ion exchange, the oxalic acid solution return to step 3 flowed through), concentration and separation vanadium solution；
8) by the isolated oxidized reaction treatment of vanadium solution, add in ammonium chloride and vanadium ion is precipitated, pass through press filtration processing point
From obtaining ammonium metavanadate solid；
Wherein, pass through step 3) -5) obtained except vanadium titanium slag powder through the following steps that realize：
Catalyst slurry and concentration are inserted for 4-9% oxalic acid solutions in reaction kettle, 3-4 is stirred to react at 40-80 DEG C of temperature
Hour, make wherein vanadic anhydride ingredient reaction be dissolved as vanadyl oxalate, reach except vanadium purpose, postcooling, will reaction cooling
It is isolated except titanium slag and pressing filtering liquid after vanadium that product afterwards carries out press filtration；
To obtain except after vanadium titanium slag be placed in the sulfuric acid solution that concentration is 2-3% and be acidified, clean 10-20 minutes；It is described
Concentration is mass volume ratio, and the sulfuric acid solution is 1 with the mass ratio except vanadium titanium slag:5, then clean 10-20 with deionized water
Minute, be isolated by filtration activated containing titanium dioxide and tungstic acid except vanadium post activation titanium slag powder and impurity are filtered
Liquid；It is described except after vanadium titanium slag powder be pie,
Wherein, step 7) -8 is passed through) the ammonium metavanadate solid that is obtained is through the following steps that realize：
The pressing filtering liquid is handled by ion exchange resin device, oxalic acid is by returning and being leached for vanadic salts；Simultaneously will
Vanadyl oxalate and sour vanadyl are adsorbed on resin；
Concentration is that the sulfuric acid solution of 9-10% elutes resin, obtains vanadyl oxalate and vanadic sulfate mixed solution,
Wherein vanadium ingredient is concentrated；It is that 9-10% sodium hydroxide solutions adjust pH value with concentration, solution ph is made to be between 5-6；
The mixed solution of vanadyl oxalate and vanadic sulfate after neutralization adds in sodium peroxydisulfate and is aoxidized, and it is molten to obtain sodium vanadate
Liquid；
It is 1 in mass ratio into sodium vanadate solution:2 ratio adds in the ammonium chloride solution that concentration is 3-4%, and at 70-80 DEG C
At a temperature of react 1-2 it is small when obtain ammonium metavanadate precipitate, the concentration is mass volume ratio；
Product after reaction is subjected to press filtration processing, is separated by filtration to obtain ammonium metavanadate solid.
2. the method that the vanadium extraction according to claim 1 from discarded SCR catalyst prepares activation titanium silicon tungsten powder, feature exist
In the pretreatment includes discarded SCR catalyst carrying out water leaching and immersion, ultrasonic cleaning, acidifying and washing process；It is described
Impurity is flyash and coke button.
3. the method that the vanadium extraction according to claim 1 from discarded SCR catalyst prepares activation titanium silicon tungsten powder, feature exist
In the slurries that the wet pulverizing is formed are 180-325 mesh for granularity, and solid content is 50% slurries.
4. the method that the vanadium extraction according to claim 1 from discarded SCR catalyst prepares activation titanium silicon tungsten powder, feature exist
In, the Ti-Si nano tungsten powder through the following steps that be formed：
Titanium slag powder adds deionized water that solid-liquid mass ratio is made as 1 after vanadium will be removed：1 slurries, then by wet method eddy flow fine powder machine into
Row multilevel grinding obtains 6000-8000 purposes except titanium silicon tungsten powder after vanadium；Titanium silicon tungsten powder is in powder drying machine and high speed after vanadium being removed
Depolymerizing thrasher is handled, and obtains nanoscale activated titanium silicon tungsten powder.
5. the method that the vanadium extraction according to claim 1 from discarded SCR catalyst prepares activation titanium silicon tungsten powder, feature exist
In the press filtration processing is to carry out press filtration processing to ammonium metavanadate precipitate by plate and frame filter press, is made in pressure-filtering process
It is cleaned with deionized water.
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| CN107519945A (en) * | 2017-06-08 | 2017-12-29 | 河北威达蓝海环保科技有限公司 | A kind of handling process of wide temperature range denitrating catalyst raw material |
| CN107860639B (en) * | 2017-09-30 | 2020-04-28 | 中国科学院生态环境研究中心 | Hydrofluoric acid-free titanium dioxide digestion and separation method |
| CN108893624B (en) * | 2018-06-20 | 2020-12-11 | 江苏龙净科杰环保技术有限公司 | Recovery system and recovery method for recovering titanium-tungsten powder from waste SCR (Selective catalytic reduction) catalyst |
| CN108910955A (en) * | 2018-07-04 | 2018-11-30 | 安徽思凯瑞环保科技有限公司 | A method of titanium tungsten powder is manufactured using discarded SCR denitration |
| CN110923458A (en) * | 2019-12-29 | 2020-03-27 | 江苏龙清环境技术有限公司 | Method for preparing titanium-tungsten powder by recycling waste SCR catalyst |
| CN111455186B (en) * | 2020-06-08 | 2022-08-30 | 江苏美东环境科技有限公司 | Method for preparing vanadium pentoxide by treating vanadium-containing waste sulfuric acid catalyst through two-step method |
| CN112110482B (en) * | 2020-08-13 | 2022-07-15 | 北京华电光大环境股份有限公司 | Method for recovering nano strontium titanate and high-purity tungsten slag from waste SCR denitration catalyst |
| CN112516994B (en) * | 2020-10-30 | 2023-10-20 | 苏州西热节能环保技术有限公司 | Method for preparing regenerated powder by using waste SCR catalyst and regenerated powder |
| CN114534706B (en) * | 2022-01-17 | 2023-04-21 | 北京科技大学 | Method for preparing titanium-silicon carrier by recycling waste denitration catalyst |
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Denomination of invention: A Method for Extracting Vanadium from Waste SCR Catalysts and Preparing Activated Titanium Silicon Tungsten Powder Effective date of registration: 20230630 Granted publication date: 20180529 Pledgee: Chuzhou Puhui Financing Guarantee Co.,Ltd. Pledgor: ANHUI SCR ENVIRONMENTAL TECHNOLOGY CO.,LTD. Registration number: Y2023980047121 |