CN107904403A - A kind of method of vanadium titanium system denitration dead catalyst comprehensive reutilization - Google Patents

A kind of method of vanadium titanium system denitration dead catalyst comprehensive reutilization Download PDF

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CN107904403A
CN107904403A CN201711043706.6A CN201711043706A CN107904403A CN 107904403 A CN107904403 A CN 107904403A CN 201711043706 A CN201711043706 A CN 201711043706A CN 107904403 A CN107904403 A CN 107904403A
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dead catalyst
water
fine grinding
vanadium
sodium
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CN107904403B (en
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高建军
张俊
王�锋
王海风
林万舟
严定鎏
齐渊洪
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Gangyan Sheng Hua Polytron Technologies Inc
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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
    • 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
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    • 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
    • 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
    • C22B34/34—Obtaining molybdenum
    • C22B34/345—Obtaining molybdenum from spent catalysts
    • 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
    • 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
    • C22B7/001—Dry processes
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P10/20—Recycling

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Abstract

A kind of method of vanadium titanium system denitration dead catalyst comprehensive reutilization, dead catalyst is subjected to water quenching with the high-temperature fusant after sodium carbonate mixing high-temperature roasting, vitreum is made, filtrate and filter residue is obtained by filtration by water logging is carried out after vitreum fine grinding, the filtrate is used to extract vanadium oxide, tungsten oxide and molybdenum oxide, and the filter residue is used to prepare titanium dioxide.The present invention realizes whole recyclings of valuable element in dead catalyst, and obtained product can directly return to the preparation for denitrating catalyst, multiple element can recycle at the same time, titanium dioxide product can finally especially be directly obtained to the recycling of titanium elements, this method, its purity can reach more than 99.0%, eliminate the process of sulfuric acid process recycling, with the characteristics of environmental friendly, synthetical recovery cost is low, and value of the product is high.

Description

A kind of method of vanadium titanium system denitration dead catalyst comprehensive reutilization
Technical field
The present invention relates to denitration spent catalyst recovery field, especially a kind of vanadium titanium system denitration dead catalyst integrates back Receive the method utilized.
Background technology
Vanadium titanium system denitrating catalyst can at relatively low temperature, with NH3It is reducing agent by NOxIt is reduced to free of contamination N2And H2O, NH3With O2Redox hardly occur, so as to improve N2Selectivity, save NH3Cost.Vanadium titanium system takes off Containing valuable metals such as titanium, tungsten, molybdenum, vanadium in nitre dead catalyst, the pollution for not only resulting in air, water body, soil is directly abandoned, Soil vegetative cover and human health are seriously endangered, and causes the waste of metals resources.According to current titanium dioxide, five oxidations two The market price of vanadium, tungsten oxide and molybdenum oxide etc., recycles denitration dead catalyst, not only can be with comprehensive reutilization These oxides, and there is good economic benefit.
China denitrating flue gas environmental protection standard implement it is later, into just having come into effect denitrating flue gas skill from power plant since the new century Art.With the implementation of environmental protection policy and regulation, all flue gas NOxEnterprise not up to standard all carries out denitrating flue gas, thus can produce Substantial amounts of denitration dead catalyst.At present, recycling the method for vanadium titanium system dead catalyst mainly has the side such as Dry recovery, hydrometallurgic recovery Method.Patent CN104263946B《Tungsten, vanadium, the method for titanium are recycled in a kind of dead catalyst from SCR denitration》, by dead catalyst powder Broken, incorporation sodium carbonate stirs evenly sintering at high temperature and obtains sintering feed, adds water logging to go out to obtain the sodium salt mixing containing tungsten, vanadium molten Liquid；The selective extraction tungsten under conditions of solution ph is more than 12, extracts the raffinate after tungsten also in the condition that pH is 10~11.5 Lower extracting vanadium, titanium stays obtains rich-titanium material in leaching.Although this method can recycle tungsten and vanadium in dead catalyst, titanium is A kind of primary raw materials, it is impossible to directly utilize.Patent CN103526031B《A kind of recycling side of SCR waste flue gas denitration catalysts Method》, denitrating catalyst is crushed after being handled with preroast, is proportionally added into NaOH solution and is dissolved, solid-liquid is carried out after dissolving Lock out operation, then adds sulfuric acid to gained Chen Ding, through leaching, settling, hydrolyzing, salt treatment, roasting TiO is made2.This method is adopted Recycling tungsten and vanadium are leached with NaOH, TiO is recycled using sulfuric acid process2Although the valuable element in dead catalyst, sulphur can be recycled TiO is made in acid system2Technique acid consumption is big, and environmental pollution is serious.Patent CN101921916B《Recycled from waste flue gas denitration catalyst The method of metal oxide》, high temperature preroast pretreatment is carried out after denitrating catalyst is crushed, is proportionally added into Na2CO3And mix Close, crush progress high-temperature roasting, agglomerate puts into hot water after crushing and is stirred leaching, and gained titanate adds sulfuric acid, warp TiO is made in filtering, washing, roasting2.This patent uses Na2CO3As calcination agent, hot water leaching can recycle tungsten and vanadium, TiO2's The problems such as recycling still uses sulfuric acid process, high there are production cost, and environmental pollution is big.
Denitration spent catalyst recovery and utilizing is at the early-stage in China, and many enterprises and university have carried out denitrating catalyst Research is recycled, these technologies have significant advantage to recycling tungsten, vanadium, but are difficult to recycle the key component in denitrating catalyst TiO2, or recovery process is not environmentally, it is of high cost.
The content of the invention
In view of analyze above, for the deficiency in existing scheme, the catalysis the present invention is intended to provide a kind of vanadium titanium system denitration is given up The method of agent comprehensive reutilization, is given up and catalyst reaction using sodium carbonate, realizes that vanadium in dead catalyst, titanium, tungsten, molybdenum etc. aoxidize Recycled while thing.This method has the characteristics that element organic efficiency is high, added value of product is high, production cost is low.
The purpose of the present invention is mainly achieved through the following technical solutions：
A kind of method of vanadium titanium system denitration dead catalyst comprehensive reutilization, dead catalyst is roasted with sodium carbonate mixing high temperature High-temperature fusant after burning carries out water quenching, and vitreum is made, and filtrate and filter residue is obtained by filtration by water logging is carried out after vitreum fine grinding, institute State filtrate to be used to extract vanadium oxide, tungsten oxide and molybdenum oxide, the filter residue is used to prepare titanium dioxide.
Further, the described method comprises the following steps：
Step 1: the dead catalyst of broken fine grinding is mixed in proportion with sodium carbonate；
Step 2: the mixture in step 1 is carried out high-temperature roasting, mixture melt is obtained；
Step 3: by mixture melt fine grinding after vitreum is made in water quenching, fine grinding powder is made；
Step 4: agitator treating after the fine grinding powder is mixed in proportion with water, filtrate and filter are obtained by filtration by mixed liquor Slag, the filtrate is containing sodium vanadate, sodium tungstate, sodium molybdate, and for extracting vanadium oxide, tungsten oxide and molybdenum oxide, the filter residue is titanium Hydrochlorate precipitates；
Step 5: the filter residue is mixed in proportion with water, the mixed liquor after adjusting pH is placed in reactor and is carried out instead Metatitanic acid precipitation should be obtained to obtain reaction product, after the aged washing of reaction product；
Step 6: the metatitanic acid precipitation prepares titanium dioxide by calcining.
Given up and catalyst high-temperature roasting using sodium carbonate, make the oxide in dead catalyst react to form sodium with sodium carbonate Salt, wherein sodium vanadate, sodium tungstate, sodium molybdate etc. are all soluble easily in water, and sodium titanate is not readily dissolved in water, and titanium elements are realized by water logging With the separation of the element such as vanadium, tungsten, molybdenum, and then realize the oxides such as vanadium in dead catalyst, titanium, tungsten, molybdenum while recycle.
Further, the dead catalyst granularity that fine grinding is crushed in the step 1 is less than 300 μm.
In order to improve the contact area of dead catalyst powder and carbonic acid sodium powder, be conducive to the preparation of mixture melt, accelerate The speed of melt generation is finely ground to less than 300 μm, it is necessary to which dead catalyst is crushed, and improves reaction efficiency.
Further, dead catalyst powder and sodium carbonate are pressed 1 in the step 2:0.7~1:1.4 mass ratio mixes It is even, then mixture melt is made in 1100 DEG C~1400 DEG C high-temperature roastings, roasting time 0.5~5 in mixture when small.
In order to obtain soluble sodium salt, the present invention need to be mixed using sodium carbonate with dead catalyst.In order to obtain sodium vanadate, tungsten Sour sodium, sodium molybdate and Sodium Titanate, it is necessary to control the mass ratio that dead catalyst is mixed with sodium carbonate, its mass ratio it is excessive then no To preferable sodium salt, its mass ratio is too low, causes the waste of sodium carbonate, therefore the quality that dead catalyst is mixed with sodium carbonate Than controlling 1:0.7~1:In the range of 1.4.
In order to carry out natridization reaction, it is necessary to control the calcination temperature of mixture, in the range of 1100~1400 DEG C, sodium Reaction can be smoothed out, while high-temperature roasting can increase the activity of mixture, be conducive to the progress of subsequent reactions, Jin Erti The rate of recovery of high each element.According to the difference of calcination temperature, the length of roasting time can be controlled, when calcination temperature is high, instead Can suitably it shorten between seasonable, when calcination temperature is low, the reaction time can suitably increase.
Further, vitreum is made in the quick water quenching of high temperature mixture melt in the step 3, then utilizes ball milling Vitreum is milled down to less than 150 μm by machine, and fine grinding powder is made.
The step of vitreum is made primarily to increasing the activity of finer abrasive in water quenching, so as to promote follow-up water logging reaction It is quick to carry out.
Further, fine grinding powder is put into 80 DEG C of hot water in the step 4, is stirred, washing and filtering, obtains Filtrate be containing sodium vanadate, sodium tungstate, sodium molybdate lye, filter residue precipitates for titanate, and the ratio of the fine grinding powder and water is 1: 20~1:100.
During water logging, the too low then leaching velocity of temperature of water is slow, and the leaching that water temperature increase is conducive to solute in powder is molten Solution, but temperature is excessive, then and water evaporation is serious, is unfavorable for water logging, therefore water temperature is controlled at 80 DEG C, this temperature is conducive to solute Dissolving is leached, while water is not easy to evaporate.
In order to improve the efficiency of water logging process, it is necessary to control solid-to-liquid ratio, when solid-to-liquid ratio is too low, Leach reaction carries out slow Slowly, with the raising of solid-to-liquid ratio, Leach reaction speed increase, but it is a kind of waste on the contrary that solid-to-liquid ratio is excessive, therefore by step 4 In solid-to-liquid ratio control 1:20~1:In 100 this rational scope.
Further, by titanate precipitation and water in mass ratio 1 in the step 4:10~1:150 are fitted into reactor, Raw material is uniformly mixed by stirring, with pH≤6.0 of inorganic acid-conditioning solution, then by bar of the reactor at 20~100 DEG C 8~48h is kept the temperature under part, solid is washed with water in reaction product after separation of solid and liquid, and metatitanic acid precipitation is made.
Add inorganic acid for adjusting pH value in filter residue solution, sodium titanate can be made to generate metatitanic acid with acid reaction and precipitated, pass through precipitation Ageing can realize that crystal seed is grown up.Inorganic acid is alternative carbonic acid, hydrochloric acid and sulfuric acid etc., selects different acid to obtain Different salting liquids.
Further, the pH value of carbon acid-conditioning solution is used in the step 5.
Ideally carbonic acid in inorganic acid, what sodium titanate was reacted in carbonic acid is sodium carbonate liquor, and solution is by steaming After hair crystallization, it can also return for sodium roasting, the utilization ratio of reagent is high, can further reduce production cost.
Further, metatitanic acid is deposited in 600~1000 DEG C of 1~10h of calcining by the step 6, and titanium dioxide is prepared Titanium.
The present invention has the beneficial effect that：
The present invention provides a kind of method of vanadium titanium system denitration dead catalyst comprehensive reutilization, is given up and is catalyzed using sodium carbonate Agent high-temperature roasting, makes the oxide in dead catalyst react to form sodium salt with sodium carbonate, wherein sodium vanadate, sodium tungstate, sodium molybdate Deng all soluble easily in water, and sodium titanate is not readily dissolved in water, and the separation of the element such as titanium elements and vanadium, tungsten, molybdenum is realized by water logging, and then Recycled while realizing the oxides such as vanadium in dead catalyst, titanium, tungsten, molybdenum.The step of vitreum is made using water quenching come Further increase the activity of finer abrasive, so as to promote the quick progress of follow-up water logging reaction.The recovery method of the present invention has member The features such as plain organic efficiency is high, added value of product is high, production cost is low, gives up in addition, the method can solve the denitration of vanadium titanium system Problem of environmental pollution caused by catalyst is stored up, it is achieved thereby that the synthesis of the oxide such as vanadium, titanium, tungsten, molybdenum is returned in dead catalyst Receive and utilize.The method of the vanadium titanium system denitration dead catalyst comprehensive reutilization of the present invention realizes valuable element in dead catalyst All recycle, and obtained product can directly return to the preparation for denitrating catalyst, and multiple element can be at the same time Recycling, the especially recycling to titanium elements, this method can finally directly obtain titanium dioxide product, its purity can reach More than 99.0%, eliminate sulfuric acid process recycling process, have it is environmental friendly, synthetical recovery cost is low, the high spy of value of the product Point.
Other features and advantages of the present invention will illustrate in the following description, also, part can become from specification Obtain it is clear that or being understood by implementing the present invention.The purpose of the present invention and other advantages can be by the explanations write Specifically noted structure is realized and obtained in book and claims.
Embodiment
The principle of the present invention is explained with reference to embodiment.
The method of vanadium titanium system denitration dead catalyst comprehensive reutilization provided by the present invention mainly includes：By dead catalyst Mixed after broken fine grinding with sodium carbonate and carry out high-temperature roasting；High-temperature fusant after roasting carries out water quenching and vitreum, Ran Houxi is made Mill；Powder after fine grinding carries out water logging filtering, and the filtrate after filtering is used to extract vanadium oxide and tungsten oxide etc.；Filter residue Jia Shui, add Inorganic acid for adjusting pH value, after precipitation is aged, washing filtering obtains metatitanic acid precipitation；Metatitanic acid precipitation is prepared by high-temperature calcination Obtain TiO2.Specifically include following step：
1) fine grinding is crushed：Dead catalyst physics is crushed and is finely ground to less than 300 μm；
2) high-temperature roasting：By dead catalyst powder and Na2CO3By 1:0.7~1:1.4 mass ratio mixes, then will mixing Mixture melt is made in 1100 DEG C~1400 DEG C high-temperature roastings, roasting time 0.5~5 in material when small；
3) water quenching fine grinding：Vitreum is made in the quick water quenching of high temperature mixture melt, then using ball mill by vitreum Less than 150 μm are milled down to, fine grinding powder is made；
4) water logging is filtered：Fine grinding powder is pressed into solid-liquid mass ratio 1:20~1:100 are put into 80 DEG C or so of hot water, are stirred Mix, washing and filtering, obtained filtrate be containing sodium vanadate, sodium tungstate, sodium molybdate lye, filter residue for titanate precipitation；
5) pH value and washing are adjusted：By titanate precipitation and water in mass ratio 1:10~1:150 are fitted into reactor, pass through Raw material is uniformly mixed by stirring, with pH≤6.0 of inorganic acid-conditioning solution, then by reactor under conditions of 20~100 DEG C 8~48h is kept the temperature, solid is washed with water in reaction product after separation of solid and liquid, and metatitanic acid precipitation is made；
6) calcine：Metatitanic acid is deposited in 600~1000 DEG C of 1~10h of calcining, TiO is prepared2。
Specifically, dead catalyst and sodium carbonate high-temperature roasting, mainly make the oxide and sodium carbonate in dead catalyst Reaction forms sodium salt, and wherein sodium vanadate, sodium tungstate, sodium molybdate etc. are all soluble easily in water, and sodium titanate is not readily dissolved in water, so as to pass through The separation of titanium oxide and other oxides is realized in water logging.It is mainly the activity for increasing finer abrasive that vitreum, which is made, in water quenching, so as to promote Quick into water logging reaction carries out.Add inorganic acid for adjusting pH value in filter residue solution, sodium titanate is generated titanium with acid reaction Acid precipitation, can realize that crystal seed is grown up by precipitating ageing.
Dead catalyst has with sodium carbonate high-temperature roasting reaction：
V2O5+3Na2CO3=2Na3VO4+3CO2(g)
WO3+Na2CO3=Na2WO4+CO2(g)
MoO3+Na2CO3=Na2MoO4+CO2(g)
TiO2+Na2CO3=Na2TiO3+CO2(g)
2TiO2+Na2CO3=Na2O*2TiO2+CO2(g)
Wherein, Na3VO4、Na2WO4And Na2MoO4It is highly soluble in water, forms mixed solution, further separation and Extraction V2O5、 WO3And MoO3。Na2TiO3And Na2O*2TiO2Water is insoluble in, forms filter residue, filter residue adds inorganic acid for adjusting pH value, precipitate through washing After ageing, H is made in washing filtering4TiO4Precipitation.
Embodiment 1
The main chemical compositions of vanadium titanium system dead catalyst are following (in mass)：TiO286.2%th, V2O53.4%th, WO37.5%th, MoO32.4%th, other 0.7%.
Processing step is as follows：100kg dead catalyst is milled down to 300 μm, with 140kg powderies Na2CO3It is uniformly mixed, so Afterwards by mixture in 1100 DEG C of high-temperature roastings, when roasting time 5 is small, vitreum is made in roasting material direct-water-quenching, then by glass Body is finely ground to 150 μm, obtains fine grinding powder.Fine grinding powder is pressed into solid-liquid mass ratio 1:50 are put into 80 DEG C or so of hot water, be stirred, Washing and filtering, obtains the lye and titanate precipitation containing sodium vanadate, sodium tungstate and sodium molybdate.Lye is used to extract V2O5、WO3With MoO3, titanate precipitates and water in mass ratio 1:10 are fitted into reactor, are uniformly mixed raw material by stirring, are adjusted with hydrochloric acid The pH of solution is 5.0, reactor is then kept the temperature 48h under conditions of 20 DEG C, reaction product is washed with water after separation of solid and liquid Solid, is made metatitanic acid precipitation.Metatitanic acid is deposited in 1000 DEG C of calcining 1h, and TiO is prepared2, TiO2Purity can reach 99.5% with On.
Embodiment 2
The main chemical compositions of vanadium titanium system dead catalyst are following (in mass)：TiO290.0%th, V2O52.1%th, WO35.5%th, MoO31.4%th, other 1.0%.
Processing step is as follows：100kg dead catalyst is milled down to 100 μm, with 70kg powderies Na2CO3It is uniformly mixed, so Afterwards by mixture in 1400 DEG C of high-temperature roastings, when roasting time 0.5 is small, vitreum is made in roasting material direct-water-quenching, then by glass Glass body is finely ground to 80 μm, obtains fine grinding powder.Fine grinding powder is pressed into solid-liquid mass ratio 1:20 are put into 80 DEG C or so of hot water, are stirred Mix, washing and filtering, obtain the lye and titanate precipitation containing sodium vanadate, sodium tungstate and sodium molybdate.Lye is used to extract V2O5、WO3 And MoO3, titanate precipitates and water in mass ratio 1:50 are fitted into reactor, are uniformly mixed raw material by stirring, with hydrochloric acid tune The pH for saving solution is 4.0, reactor is then kept the temperature 20h under conditions of 80 DEG C, reaction product is washed with water after separation of solid and liquid Solid is washed, metatitanic acid precipitation is made.Metatitanic acid is deposited in 800 DEG C of calcining 2h, and TiO is prepared2, TiO2Purity can reach 99.0% More than.
Embodiment 3
The main chemical compositions of vanadium titanium system dead catalyst are following (in mass)：TiO288.3%th, V2O52.4%th, WO35.5%th, MoO31.4%th, other 2.4%.
Processing step is as follows：100kg dead catalyst is milled down to 80 μm, with 130kg powderies Na2CO3It is uniformly mixed, so Afterwards by mixture in 1300 DEG C of high-temperature roastings, when roasting time 2 is small, vitreum is made in roasting material direct-water-quenching, then by glass Body is finely ground to 60 μm, obtains fine grinding powder.Fine grinding powder is pressed into solid-liquid mass ratio 1:100 are put into 80 DEG C or so of hot water, be stirred, Washing and filtering, obtains the lye and titanate precipitation containing sodium vanadate, sodium tungstate and sodium molybdate.Lye is used to extract V2O5、WO3With MoO3, titanate precipitates and water in mass ratio 1:150 are fitted into reactor, are uniformly mixed raw material by stirring, with sulfuric acid acid The pH for adjusting solution is 6.0, reactor is then kept the temperature 10h under conditions of 80 DEG C, reaction product uses water after separation of solid and liquid Solid is washed, metatitanic acid precipitation is made.Metatitanic acid is deposited in 600 DEG C of calcining 10h, and TiO is prepared2, TiO2Purity can reach More than 99.5%.
In conclusion the present invention provides a kind of method of vanadium titanium system denitration dead catalyst comprehensive reutilization, using carbonic acid Sodium gives up forms sodium salt with catalyst high-temperature roasting, all soluble easily in water using sodium vanadate, sodium tungstate, sodium molybdate etc., and sodium titanate is not Characteristic soluble easily in water, the recycling of the oxides such as vanadium in dead catalyst, titanium, tungsten, molybdenum is realized by water logging.Use water at the same time The step of vitreum is made quench further to increase the activity of finer abrasive, so as to promote the quick progress of follow-up water logging reaction.This Invention realizes whole recyclings of valuable element in dead catalyst, and obtained product can be returned directly for denitration The preparation of catalyst, multiple element can recycle at the same time, especially the recycling to titanium elements, and this method can finally directly obtain Titanium dioxide product, its purity can reach more than 99.0%, eliminate sulfuric acid process recycling process, have it is environmental friendly, it is comprehensive Close the characteristics of cost recovery is low, and value of the product is high.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in, It should be covered by the protection scope of the present invention.

Claims (9)

  1. A kind of 1. method of vanadium titanium system denitration dead catalyst comprehensive reutilization, it is characterised in that by dead catalyst and sodium carbonate Mix the high-temperature fusant after high-temperature roasting and carry out water quenching, vitreum is made, filter is obtained by filtration by water logging is carried out after vitreum fine grinding Liquid and filter residue, the filtrate are used to extract vanadium oxide, tungsten oxide and molybdenum oxide, and the filter residue is used to prepare titanium dioxide.
  2. 2. the method for vanadium titanium system denitration dead catalyst comprehensive reutilization according to claim 1, it is characterised in that the side Method comprises the following steps：
    Step 1: the dead catalyst of broken fine grinding is mixed in proportion with sodium carbonate；
    Step 2: the mixture in step 1 is carried out high-temperature roasting, mixture melt is obtained；
    Step 3: by mixture melt fine grinding after vitreum is made in water quenching, fine grinding powder is made；
    Step 4: agitator treating after the fine grinding powder is mixed in proportion with water, is obtained by filtration filtrate and filter residue, institute by mixed liquor Filtrate is stated containing sodium vanadate, sodium tungstate, sodium molybdate, for extracting vanadium oxide, tungsten oxide and molybdenum oxide, the filter residue sinks for titanate Form sediment；
    Step 5: the filter residue is mixed in proportion with water, will adjust the mixed liquor after pH be placed in reactor reacted with Reaction product is obtained, after the aged washing of reaction product, obtains metatitanic acid precipitation；
    Step 6: the metatitanic acid precipitation prepares titanium dioxide by calcining.
  3. 3. the method for vanadium titanium system denitration dead catalyst comprehensive reutilization according to claim 2, it is characterised in that the step The dead catalyst granularity that fine grinding is crushed in rapid one is less than 300 μm.
  4. 4. the method for vanadium titanium system denitration dead catalyst comprehensive reutilization according to Claims 2 or 3, it is characterised in that institute State dead catalyst powder and sodium carbonate in step 2 by 1:0.7~1:1.4 mass ratio mixes, then by mixture 1100 DEG C~1400 DEG C of high-temperature roastings, mixture melt is made in roasting time 0.5~5 when small.
  5. 5. according to the method for vanadium titanium system denitration dead catalyst comprehensive reutilization described in claim 2-4, it is characterised in that described Vitreum is made in the quick water quenching of high temperature mixture melt in step 3, vitreum is then milled down to 150 μm using ball mill Hereinafter, fine grinding powder is made.
  6. 6. the method for vanadium titanium system denitration dead catalyst comprehensive reutilization according to claim 2, it is characterised in that the step Fine grinding powder is put into 80 DEG C of hot water in rapid four, is stirred, washing and filtering, obtained filtrate is containing sodium vanadate, sodium tungstate, molybdenum The lye of sour sodium, filter residue precipitate for titanate, and the ratio of the fine grinding powder and water is 1:20~1:100.
  7. 7. according to the method for the vanadium titanium system denitration dead catalyst comprehensive reutilization of claim 2 or 6, it is characterised in that institute State titanate precipitation and water in mass ratio 1 in step 5:10~1:150 are fitted into reactor, are mixed raw material by stirring Uniformly, with pH≤6.0 of inorganic acid-conditioning solution, reactor is then kept the temperature into 8~48h under conditions of 20~100 DEG C, is reacted Solid is washed with water in product after separation of solid and liquid, and metatitanic acid precipitation is made.
  8. 8. according to the method for the vanadium titanium system denitration dead catalyst comprehensive reutilization of claim 2 or 6 or 7, it is characterised in that The pH value of carbon acid-conditioning solution is used in the step 5.
  9. 9. the method for vanadium titanium system denitration dead catalyst comprehensive reutilization according to claim 2, it is characterised in that the step Metatitanic acid is deposited in 600~1000 DEG C of 1~10h of calcining by rapid six, and titanium dioxide is prepared.
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