CN106756054A - It is a kind of that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration - Google Patents

It is a kind of that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration Download PDF

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Publication number
CN106756054A
CN106756054A CN201710073321.8A CN201710073321A CN106756054A CN 106756054 A CN106756054 A CN 106756054A CN 201710073321 A CN201710073321 A CN 201710073321A CN 106756054 A CN106756054 A CN 106756054A
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filtrate
filter cake
separated
vanadium
tungsten
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李寒春
丁溪锋
陈镜伊
刘志猛
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BEIJING CALION TECH DEVELOPMENT Co Ltd
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BEIJING CALION TECH DEVELOPMENT Co Ltd
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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
    • 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
    • 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
    • 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
    • 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 method that titanium, tungsten, vanadium are separated and recovered from discarded SCR denitration, comprise the following steps：1) pre-process；2) titanium dioxide is separated；3) silica is separated；4) separating tungsten, vfanadium compound；5) separating tungsten；6) deliming is gone；7) vanadium is separated.Higher according to major product rutile type titanium white, tungstic acid, purity of vanadium pentoxide and the rate of recovery that the inventive method is obtained, byproduct silica and calcium carbonate can serve as resource and utilized, and can solve the problem of current SCR dead catalyst treatment.In addition, the present invention greatly reduces water consume and alkaline consumption by using adverse current or cross-flow operation, while reducing the consumption of medicine added by subsequent technique, economic benefit had not only been economized on resources but also highlighted.It is simple without condition of high voltage, operating procedure in present invention operation.Reduce the requirement to equipment in actual industrial.Furthermore, the present invention is whole to be participated in reacting without organic matter, greatly reduces wastewater treatment difficulty.

Description

It is a kind of that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration
Technical field
The present invention relates to green technology and recycling economy field, more particularly to one kind is divided from discarded SCR denitration From recovery Pd, tungsten, vanadium method.
Background technology
It is main energy sources in coal in China, the nitrogen oxides that its burning is produced can not only form acid rain, also result in chemistry Smog, endangers human health.70% comes from the direct burning of coal in China's nitrogen oxide emission, and power industry is The coal-fired rich and influential family of China, therefore thermal power plant is one of main source of nitride (NOx) discharge.With Ecological Civilization Construction The five in one layout of socialist construction is included, the air pollution that fire coal is caused increasingly causes the attention of government.
Selective catalytic reduction is (referred to as：SCR methods) it is to apply the more ripe technology of most, technology in the world at present, It is considered to have denitration efficiency higher (up to 90%).In SCR device actual motion, alkali metal and arsenic are caused in flue gas Catalyst poisoning, sintering of catalyst, catalyst pores blocking, catalyst abrasion, Water vapor condensation and sulfate and sulphur ammonium mineralization Reduced etc. catalyst activity reduction, life-span can be caused.It is catalyst for the processing mode that the catalyst for failing considers first Regeneration, but spent catalyst can not still recover its activity using regeneration, then can only carry out the renewal of catalyst.At present SCR denitration generally using the mounting means of " 2+1 ", i.e., first installs 2 layers of catalyst, installs the 3rd layer, 3 years after about 3 years additional again The 1st layer of catalyst is changed afterwards, changes one layer of catalyst within hereafter every 2 years.Pushed away according to the SCR catalyst service life of 3 years or so Calculate, the useless denitrating catalyst that will have at least up to ten thousand tons to the year two thousand twenty is produced.
《Coal steam-electric plant smoke denitration engineering legislation-selective catalytic reduction》(HJ562-2010) it is useless to SCR methods in Denitrating catalyst defines harmless treatment mode, i.e., filled after catalyst being crushed.But the useless denitrating catalyst crushing of SCR After filled, on the one hand can take substantial amounts of land resource, increase the cost of enterprise；Another aspect catalyst is using process Central some adsorbed poisonous and harmful substances and some metallic elements contained by itself can be entered due to various effects To natural environment, particularly water body, serious harm is brought to environment；The V that another further aspect SCR catalyst contains in itself2O5、WO3With TiO2All it is valuable resource, useless denitrating catalyst is abandoned and causes various valuable metal resources contained therein to fail back Receive and utilize, the huge waste of efficient resource can be caused.If the mode of separating-purifying can be taken to be reclaimed, can not only produce new Profit growth point, also comply with《People's Republic of China's recycling economy promotion law》In about recycle and resource Industry Model Requirement.Therefore, the recovery of denitrating catalyst, the research and development of innoxious process for treating and realize that industrialized production has urgent society Can demand.
The content of the invention
The technical problems to be solved by the invention are to provide one kind and titanium, tungsten, vanadium are separated and recovered from waste denitration catalyst Method.Major product rutile type titanium white, tungstic acid, purity of vanadium pentoxide and the rate of recovery that the method is obtained compared with Height, byproduct silica and calcium carbonate can serve as resource and utilized.The method has economic results in society very high, Industrialized implementation is higher, can solve the problem of current SCR dead catalyst treatment.
The technical problems to be solved by the invention are achieved through the following technical solutions：
Principle of the invention and key step are as follows：(1) SCR catalyst dedusting pretreatment is discarded.(2) alkaline leaching.(3) Drying and calcining prepares rutile titanium dioxide after leached mud washing.(4) leachate acid adding adds calcium chloride after separating silica, Tungsten and vanadium is set to be precipitated in the form of calcium salt.(5) exhausted water after separating tungsten vanadium carries out Treatment for Reuse.(6) with hydrochloric acid by tungsten vanadium Separation prepares tungstic acid after wolframic acid is produced in compound dissolving.(7) liquid obtained after wolframic acid is separated with sodium carbonate except calcium ion, then Vanadium is separated out in the form of ammonium metavanadate with ammonium chloride and prepare vanadic anhydride again.(8) waste water obtained after ammonium metavanadate is separated Liquid carries out Treatment for Reuse.
Specifically, it is a kind of that titanium, tungsten, the method for vanadium, including following step are separated and recovered from discarded SCR denitration Suddenly：
1) pre-process：Discarded SCR denitration is taken, dedusting, broken, grinding obtain catalyst fines；
2) titanium dioxide is separated：With sodium hydroxide solution leach step 1) catalyst fines, centrifugal filtration, obtain filter cake and Filtrate, filter cake obtains titanium dioxide through washing, dry, calcining；
3) silica is separated：By step 2) pH value of filtrate that obtains is adjusted to 7.5-8.5, stirs 10-30min, centrifugation Filtering, obtains filter cake and filtrate, and filter cake obtains silica through washing, drying；
4) separating tungsten, vfanadium compound：To step 3) calcium chloride and NaOH are added in the filtrate that obtains, regulation filtrate PH value to 10-12, centrifugal filtration obtains filter cake and filtrate, and filtrate processes through Waste Water Treatment and recycles, and filter cake is tungstenic With the calcium salt compound of vanadium；
5) separating tungsten：To step 4) add in the filter cake that obtains 36.5% concentrated hydrochloric acid, adjust to pH≤1, be heated up to 50- 90 DEG C, stirring forms suspension, and centrifugal filtration obtains filter cake and filtrate, and filter cake washing and drying calcines to obtain tungstic acid；
6) deliming is gone：To step 5) filtrate in add sodium carbonate, and adjust the pH to 7-9 of filtrate, centrifugal filtration must be filtered Cake and filtrate, filter cake are calcium carbonate；
7) vanadium is separated：By step 6) filtrate in add ammonium chloride, centrifugal filtration obtains filter cake and filtrate, and filter cake washing is dry It is dry to calcine to obtain vanadic anhydride.
Preferably, in above-mentioned technical proposal, methods described also includes step：
8) circulation prepares vanadic anhydride：Collection step 7) treatment after filtrate, add calcium chloride, collect formed alum acid Calcium, return to step 6) and step 7) circulation prepares vanadic anhydride.
Preferably, in above-mentioned technical proposal, the step 1) catalyst fines be to be prepared by the following：Will be discarded After SCR denitration dust removal process, crush, grind, the SCR powder after grinding is screened through classifying screen, be classified grit number >=100 Mesh, screenings is catalyst fines, and oversize mixes with the discarded SCR denitration after crushing, re-grinds, and sieves, weight Multiple circulation.
Preferably, in above-mentioned technical proposal, the step 2) leaching be to be entered by level Four cross-flow or two stage countercurrent modes Capable leaching, extraction temperature is 100-150 DEG C；The concentration of sodium hydroxide solution is 10%-40%.
Preferably, in above-mentioned technical proposal, the step 2) washing be specially：Filter cake is washed twice, twice The liquid-solid ratio of washing is (5-10)：1, washing temperature is 40-60 DEG C, and the time is 30-50min, and water scouring water can be followed twice Ring is used or as other step water；The condition of calcining is：600-1000 DEG C is calcined 1-3 hours.
Preferably, in above-mentioned technical proposal, the step 2) titanium dioxide be rutile titanium dioxide.
Preferably, in above-mentioned technical proposal, the step 4) it is specially：To NaOH is added in filtrate, when pH value is every When raising 1, then add a calcium chloride, stirring reaction 0.5-1 hours under normal temperature, until the pH value of filtrate is 10-12；Wherein, chlorine The consumption for changing calcium is 0.2-1 times of handled discarded SCR denitration weight, and added calcium chloride should to be made into saturation molten Liquid.
Preferably, in above-mentioned technical proposal, the step 5) in, the condition of calcining is：400-800 DEG C is calcined 1-3 hours.
Preferably, in above-mentioned technical proposal, the step 6) in, the consumption of sodium carbonate is that handled discarded SCR is de- urges 0.2-1 times of agent consumption.
Preferably, in above-mentioned technical proposal, the step 7) in, plus ammonium chloride prepares the operation temperature of ammonium metavanadate and is 70-95 DEG C, the time be 1h, the consumption of ammonium chloride is the 5%-10% of filtrate quality；Vanadic anhydride is prepared by ammonium metavanadate Operating condition is：Heating and calcining is calcined 1-3 hours to 700-850 DEG C.
Above-mentioned technical proposal of the present invention, has the advantages that：
Major product rutile type titanium white, tungstic acid, purity of vanadium pentoxide and recovery that present invention process is obtained Rate is higher.Byproduct silica and calcium carbonate can serve as resource and utilized.Therefore, this technique has society very high Economic benefit, industrialized implementation is higher, can solve the problem of current SCR dead catalyst treatment.
In addition, the present invention greatly reduces water consume and alkaline consumption by using adverse current or cross-flow operation, while reducing follow-up work The consumption of medicine added by skill, had not only economized on resources but also had highlighted economic benefit.Present invention process is in operation without condition of high voltage, and operation Step is simple.Reduce the requirement to equipment in actual industrial.
Furthermore, present invention process is whole to be participated in reacting without organic matter, greatly reduces wastewater treatment difficulty.In the pre- of this technique Processing stage can effectively remove the heavy metal element of Catalyst Adsorption.And toxic element vanadium can be efficiently separated by this technique, accord with Close the discharge standard of vanadium.
Brief description of the drawings
Fig. 1 is the flow chart according to separation and recovery method of the invention.
Specific embodiment
Specific embodiment of the invention is described in detail below, in order to further understand the present invention.
All experimental techniques for using unless otherwise specified, are conventional method in following examples.
Material used, reagent etc. in following examples, unless otherwise specified, can be obtained by commercial sources.
Embodiment 1
1) pre-process：A certain amount of discarded SCR denitration is taken, dedusting, broken, grinding cross 100 mesh sieve, under sieve Thing is catalyst fines.Oversize mixes with the out of stock catalyst of discarded SCR after crushing, and sieves again.
2) titanium dioxide is separated：Above-mentioned catalyst fines 10g, 10% sodium hydroxide solution 50ml are weighed, in 100 DEG C of bars Oil bath 4h under part, centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Filter cake is washed (use water 50ml every time) twice with 100ml water, the time of washing is 30min, temperature every time It it is 60 DEG C, water scouring water can be recycled.
Filter cake after washing is placed in air dry oven, 120 DEG C dry 1h.
Dried filter cake 600 DEG C of calcining 3h in Muffle furnace, obtain rutile titanium dioxide powder.
3) silica is separated：Using 36.5% concentrated hydrochloric acid by step 2) pH value of filtrate that obtains adjusts to 8.5, stirs Mix, stand 10min, centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Filter cake is washed into (method is with step 2), is dried, obtained silica；
4) separating tungsten, vfanadium compound：To step 3) 10g calcium chloride and 2g NaOH, regulation are added in the filtrate that obtains To 10, after reacting 30min in 50 DEG C of water-baths, centrifugal filtration obtains filter cake and filtrate to the pH value of filtrate.Filtrate is colourless liquid, Can further recycle and reuse.
Filter cake is the compound containing artificial schellite, calcium vanadate and calcium hydroxide.
5) separating tungsten：To step 4) add in the filter cake that obtains 36.5% concentrated hydrochloric acid, adjust to pH≤1, be heated up to 50 DEG C, stirring forms suspension, and centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Through washing (method is with step 2), drying, 400 DEG C of calcining 3h obtain tungstic acid to filter cake.
6) deliming is gone：To step 5) 10g sodium carbonate is added in the filtrate that obtains, and the pH of filtrate is adjusted to 7, it was centrifuged Filter, obtains filter cake and filtrate.Filtrate is retained standby next step and is used.Filter cake is calcium carbonate.
7) vanadium is separated：By step 6) filtrate in add ammonium chloride the 5% of filtrate quality (its consumption for), 70 DEG C of reactions 1h, centrifugal filtration obtains filter cake and filtrate.
Filter cake washing (method is with step 2), dry, 700 DEG C of calcining 3h, obtain vanadic anhydride.
Filtrate remains further treatment.
8) circulation prepares vanadic anhydride：Collection step 7) treatment after filtrate, add calcium chloride, collect formed alum acid Calcium precipitate, return to step 6) and step 7) circulation prepares vanadic anhydride.
Detected by weight method, the isolated titanium dioxide 8.58g of method of embodiment 1, the rate of recovery of titanium is up to 98% Above, purity is up to more than 98%, silica 0.385g, tungstic acid 0.227g, vanadic anhydride 0.12.
Embodiment 2
1) pre-process：A certain amount of discarded SCR denitration is taken, dedusting, broken, grinding cross 100 mesh sieve, under sieve Thing is catalyst fines.Oversize mixes with the out of stock catalyst of discarded SCR after crushing, and sieves again.
2) titanium dioxide is separated：Above-mentioned catalyst fines 10g, 40% sodium hydroxide solution 20ml are weighed, in 150 DEG C of bars Oil bath 2h under part, centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Filter cake is washed (use water 20ml every time) twice with 40ml water, the time of washing is 50min every time, and temperature is 40 DEG C, water scouring water can be recycled.
Filter cake after washing is placed in air dry oven, 120 DEG C dry 1h.
Dried filter cake 1000 DEG C of calcining 1h in Muffle furnace, obtain rutile titanium dioxide powder.
3) silica is separated：Using 36.5% concentrated hydrochloric acid by step 2) pH value of filtrate that obtains adjusts to 7.5, stirs Mix, stand 30min, centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Filter cake is washed into (method is with step 2), is dried, obtained silica；
4) separating tungsten, vfanadium compound：To step 3) 2g calcium chloride and 2g NaOH, regulation filter are added in the filtrate that obtains To 12, after reacting 1h in 50 DEG C of water-baths, centrifugal filtration obtains filter cake and filtrate to the pH value of liquid.Filtrate is colourless liquid, can enter one Step recycle and reuse.
Filter cake is the compound containing artificial schellite, calcium vanadate and calcium hydroxide.
5) separating tungsten：To step 4) add in the filter cake that obtains 36.5% concentrated hydrochloric acid, adjust to pH≤1, be heated up to 90 DEG C, stirring forms suspension, and centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Through washing (method is with step 2), drying, 800 DEG C of calcining 1h obtain tungstic acid to filter cake.
6) deliming is gone：To step 5) add 2g sodium carbonate in the filtrate that obtains, and the pH to 9 of filtrate is adjusted, centrifugal filtration, Obtain filter cake and filtrate.Filtrate is retained standby next step and is used.Filter cake is calcium carbonate.
7) vanadium is separated：By step 6) filtrate in add ammonium chloride the 10% of filtrate quality (its consumption for), 95 DEG C of reactions 1h, centrifugal filtration obtains filter cake and filtrate.
Filter cake washing (method is with step 2), dry, 850 DEG C of calcining 1h, obtain vanadic anhydride.
Filtrate remains further treatment.
8) circulation prepares vanadic anhydride：Collection step 7) treatment after filtrate, add calcium chloride, collect formed alum acid Calcium, return to step 6) and step 7) circulation prepares vanadic anhydride.
Detected by weight method, the isolated titanium dioxide 8.53g of method of embodiment 2, the rate of recovery of titanium is up to 98% Above, purity is up to more than 98%, silica 0.39g, tungstic acid 0.225g, vanadic anhydride 0.15.
Embodiment 3
1) pre-process：A certain amount of discarded SCR denitration is taken, dedusting, broken, grinding cross 100 mesh sieve, under sieve Thing is catalyst fines.Oversize mixes with the out of stock catalyst of discarded SCR after crushing, and sieves again.
2) titanium dioxide is separated：Above-mentioned catalyst fines 10g, 20% sodium hydroxide solution 40ml are weighed, in 120 DEG C of bars Oil bath 3h under part, centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Filter cake is washed (use water 35ml every time) twice with 70ml water, the time of washing is 40min every time, and temperature is 50 DEG C, water scouring water can be recycled.
Filter cake after washing is placed in air dry oven, 120 DEG C dry 1h.
Dried filter cake 800 DEG C of calcining 2h in Muffle furnace, obtain rutile titanium dioxide powder.
3) silica is separated：Using 36.5% concentrated hydrochloric acid by step 2) pH value of filtrate that obtains adjusts to 8, stirs Mix, stand 20min, centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Filter cake is washed into (method is with step 2), is dried, obtained silica；
4) separating tungsten, vfanadium compound：To step 3) 6g calcium chloride and 2g NaOH, regulation filter are added in the filtrate that obtains To 11, after reacting 45min in 50 DEG C of water-baths, centrifugal filtration obtains filter cake and filtrate to the pH value of liquid.Filtrate is colourless liquid, can Further recycle and reuse.
Filter cake is the compound containing artificial schellite, calcium vanadate and calcium hydroxide.
5) separating tungsten：To step 4) add in the filter cake that obtains 36.5% concentrated hydrochloric acid, adjust to pH≤1, be heated up to 75 DEG C, stirring forms suspension, and centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Through washing (method is with step 2), drying, 600 DEG C of calcining 2h obtain tungstic acid to filter cake.
6) deliming is gone：To step 5) add 6g sodium carbonate in the filtrate that obtains, and the pH to 8 of filtrate is adjusted, centrifugal filtration, Obtain filter cake and filtrate.Filtrate is retained standby next step and is used.Filter cake is calcium carbonate.
7) vanadium is separated：By step 6) filtrate in add ammonium chloride the 7.5% of filtrate quality (its consumption for), 80 DEG C of reactions 1h, centrifugal filtration obtains filter cake and filtrate.
Filter cake washing (method is with step 2), dry, 770 DEG C of calcining 2h, obtain vanadic anhydride.
Filtrate remains further treatment.
Circulation prepares vanadic anhydride：Collection step 7) treatment after filtrate, add calcium chloride, collect formed alum acid calcium Precipitation, return to step 6) and step 7) circulation prepares vanadic anhydride.
Detected by weight method, the isolated titanium dioxide 8.72g of method of embodiment 31, the rate of recovery of titanium is up to 98% Above, purity is up to more than 98%, silica 0.393g, tungstic acid 0.227g, vanadic anhydride 0.14.
Embodiment 4
1) pre-process：A certain amount of discarded SCR denitration is taken, dedusting, broken, grinding cross 100 mesh sieve, under sieve Thing is catalyst fines.Oversize mixes with the out of stock catalyst of discarded SCR after crushing, and sieves again.
2) titanium dioxide is separated：Above-mentioned catalyst fines 10g is weighed, is leached using level Four cross-flow method, add 10% Sodium hydroxide solution 50ml, the oil bath 2h under the conditions of 150 DEG C, separation of solid and liquid are collected filter cake and continuously add sodium hydroxide solution weight Multiple operation, it is final to obtain filter cake and four filtrates.Merging filtrate is retained standby next step and is used.
Filter cake is washed (use water 50ml every time) twice with 100ml water, the time of washing is 50min, temperature every time It it is 50 DEG C, water scouring water can be recycled.
Filter cake after washing is placed in air dry oven, 120 DEG C dry 1h.
Dried filter cake 800 DEG C of calcining 2h in Muffle furnace, obtain rutile titanium dioxide powder.
3) silica is separated：Using 36.5% concentrated hydrochloric acid by step 2) pH value of filtrate that obtains adjusts to 8, stirs Mix, stand 20min, centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Filter cake is washed into (method is with step 2), is dried, obtained silica；
4) separating tungsten, vfanadium compound：To step 3) 8g calcium chloride and 2g NaOH, regulation filter are added in the filtrate that obtains To 11.5, after reacting 30min in 50 DEG C of water-baths, centrifugal filtration obtains filter cake and filtrate to the pH value of liquid.Filtrate is colourless liquid, Can further recycle and reuse.
Filter cake is the compound containing artificial schellite, calcium vanadate and calcium hydroxide.
5) separating tungsten：To step 4) add in the filter cake that obtains 36.5% concentrated hydrochloric acid, adjust to pH≤1, be heated up to 75 DEG C, stirring forms suspension, and centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Through washing (method is with step 2), drying, 600 DEG C of calcining 2h obtain tungstic acid to filter cake.
6) deliming is gone：To step 5) 10g sodium carbonate is added in the filtrate that obtains, and the pH of filtrate is adjusted to 8, it was centrifuged Filter, obtains filter cake and filtrate.Filtrate is retained standby next step and is used.Filter cake is calcium carbonate.
7) vanadium is separated：By step 6) filtrate in add ammonium chloride the 7.5% of filtrate quality (its consumption for), 90 DEG C of reactions 1h, centrifugal filtration obtains filter cake and filtrate.
Filter cake washing (method is with step 2), dry, 770 DEG C of calcining 2h, obtain vanadic anhydride.
Filtrate remains further treatment.
Circulation prepares vanadic anhydride：Collection step 7) treatment after filtrate, add calcium chloride, collect formed alum acid calcium Precipitation, return to step 6) and step 7) circulation prepares vanadic anhydride.
Detected by weight method, the isolated titanium dioxide 8.73g of method of embodiment 4, the rate of recovery of titanium is up to 98% Above, purity is up to more than 98%, silica 0.395g, tungstic acid 0.312g, vanadic anhydride 0.156.
Embodiment 5
1) pre-process：A certain amount of discarded SCR denitration is taken, dedusting, broken, grinding cross 100 mesh sieve, under sieve Thing is catalyst fines.Oversize mixes with the out of stock catalyst of discarded SCR after crushing, and sieves again.
2) titanium dioxide is separated：Above-mentioned catalyst fines 10g is weighed, is leached using two stage countercurrent methods, it is equal per one-level Using 10% sodium hydroxide solution 100ml, the oil bath 5h under the conditions of 150 DEG C, separation of solid and liquid, filter cake continuously adds NaOH leaching Go out, new catalyst fines is added in filtrate, collect filtrate and filtrate.Filtrate is retained standby next step and is used.
Filter cake is washed (use water 50ml every time) twice with 100ml water, the time of washing is 50min, temperature every time It it is 50 DEG C, water scouring water can be recycled.
Filter cake after washing is placed in air dry oven, 120 DEG C dry 1h.
Dried filter cake 800 DEG C of calcining 2h in Muffle furnace, obtain rutile titanium dioxide powder.
3) silica is separated：Using 36.5% concentrated hydrochloric acid by step 2) pH value of filtrate that obtains adjusts to 8, stirs Mix, stand 20min, centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Filter cake is washed into (method is with step 2), is dried, obtained silica；
4) separating tungsten, vfanadium compound：To step 3) 8g calcium chloride and 2g NaOH, regulation filter are added in the filtrate that obtains To 11.5, after reacting 30min in 50 DEG C of water-baths, centrifugal filtration obtains filter cake and filtrate to the pH value of liquid.Filtrate is colourless liquid, Can further recycle and reuse.
Filter cake is the compound containing artificial schellite, calcium vanadate and calcium hydroxide.
5) separating tungsten：To step 4) add in the filter cake that obtains 36.5% concentrated hydrochloric acid, adjust to pH≤1, be heated up to 75 DEG C, stirring forms suspension, and centrifugal filtration obtains filter cake and filtrate.Filtrate is retained standby next step and is used.
Through washing (method is with step 2), drying, 600 DEG C of calcining 2h obtain tungstic acid to filter cake.
6) deliming is gone：To step 5) 10g sodium carbonate is added in the filtrate that obtains, and the pH of filtrate is adjusted to 8, it was centrifuged Filter, obtains filter cake and filtrate.Filtrate is retained standby next step and is used.Filter cake is calcium carbonate.
7) vanadium is separated：By step 6) filtrate in add ammonium chloride the 7.5% of filtrate quality (its consumption for), 90 DEG C of reactions 1h, centrifugal filtration obtains filter cake and filtrate.
Filter cake washing (method is with step 2), dry, 770 DEG C of calcining 2h, obtain vanadic anhydride.
Filtrate remains further treatment.
Circulation prepares vanadic anhydride：Collection step 7) treatment after filtrate, add calcium chloride, collect formed alum acid calcium Precipitation, return to step 6) and step 7) circulation prepares vanadic anhydride.
Detected by weight method, the isolated titanium dioxide 8.73g of method of embodiment 5, the rate of recovery of titanium is up to 98% Above, purity is up to more than 98%, silica 0.395g, tungstic acid 0.307g, vanadic anhydride 0.147.
Although the present invention is disclosed as above with embodiment, so it is not intended to limit the present invention, any people in the art Member, without departing from the spirit and scope of the present invention, can make a variety of selections and modification, therefore protection model of the invention Enclose and limited by claims and its equivalents.

Claims (10)

1. it is a kind of that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration, it is characterised in that including following step Suddenly：
1) pre-process：Discarded SCR denitration is taken, dedusting, broken, grinding obtain catalyst fines；
2) titanium dioxide is separated：With sodium hydroxide solution leach step 1) catalyst fines, through separation of solid and liquid, obtain filter cake and filter Liquid, filter cake obtains titanium dioxide through washing, dry, calcining；
3) silica is separated：By step 2) pH value of filtrate that obtains is adjusted to 7.5-8.5, stirs 10-30min, separation of solid and liquid, Filter cake and filtrate are obtained, filter cake obtains silica through washing, drying；
4) separating tungsten, vfanadium compound：To step 3) calcium chloride and NaOH are added in the filtrate that obtains, adjust the pH value of filtrate To 10-12, separation of solid and liquid obtains filter cake and filtrate, and filtrate processes through Waste Water Treatment and recycles, and filter cake is tungstenic and vanadium Calcium salt compound；
5) separating tungsten：To step 4) add in the filter cake that obtains 36.5% concentrated hydrochloric acid, adjust to pH≤1, be heated up to 50-90 DEG C, stirring forms suspension, and separation of solid and liquid obtains filter cake and filtrate, and filter cake washing and drying calcines to obtain tungstic acid；
6) deliming is gone：To step 5) filtrate in add sodium carbonate, and adjust the pH to 7-9 of filtrate, centrifugal filtration, obtain filter cake and Filtrate, filter cake is calcium carbonate；
7) vanadium is separated：To step 6) filtrate in add ammonium chloride, centrifugal filtration obtains filter cake and filtrate, and filter cake washing and drying is forged Burn to obtain vanadic anhydride.
2. according to claim 1 that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration, its feature exists In methods described also includes step：
8) circulation prepares vanadic anhydride：Collection step 7) treatment after filtrate, add calcium chloride, collect formed alum acid calcium, Return to step 6) and step 7) circulation prepares vanadic anhydride.
3. according to claim 1 that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration, its feature exists In the step 1) catalyst fines be to be prepared by the following：After by discarded SCR denitration dust removal process, break Broken, grinding, the SCR powder after grinding is screened through classifying screen, is classified grit number >=100 mesh, and screenings is catalyst fines, on sieve Thing mixes with the discarded SCR denitration after crushing, and re-grinds, and sieves, repetitive cycling.
4. according to claim 1 that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration, its feature exists In the step 2) leaching be the leaching carried out by level Four cross-flow or two stage countercurrent modes, extraction temperature is 100-150 ℃；The concentration of sodium hydroxide solution is 10%-40%.
5. according to claim 1 that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration, its feature exists In the step 2) washing be specially：Filter cake is washed twice, the liquid-solid ratio washed twice is (2-5)：1, washing Temperature is 40-60 DEG C, and the time is 30-50min, and water scouring water can be recycled or as other step water twice；Calcining Condition be：600-1000 DEG C is calcined 1-3 hours.
6. according to claim 1 that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration, its feature exists In the step 2) titanium dioxide be rutile titanium dioxide.
7. according to claim 1 that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration, its feature exists In the step 4) it is specially：To NaOH is added in filtrate, when pH value often raises 1, then add a calcium chloride, normal temperature Lower stirring reaction 0.5-1 hours, until the pH value of filtrate is 10-12；Wherein, the consumption of calcium chloride is handled discarded SCR 0.2-1 times of denitrating catalyst weight, and added calcium chloride should be made into saturated solution.
8. according to claim 1 that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration, its feature exists In the step 5) in, the condition of calcining is：400-800 DEG C is calcined 1-3 hours.
9. according to claim 1 that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration, its feature exists In the step 6) in, the consumption of sodium carbonate is 0.2-1 times of handled discarded SCR denitrating catalysts consumption.
10. it is according to claim 1 that titanium, tungsten, the method for vanadium, its feature are separated and recovered from discarded SCR denitration It is, the step 7) in, plus ammonium chloride prepares the operation temperature of ammonium metavanadate for 70-95 DEG C, time are 1h, the use of ammonium chloride Measure the 5%-10% for filtrate quality；The operating condition for preparing vanadic anhydride by ammonium metavanadate is：700-850 DEG C is heated to, Calcining 1-3 hours.
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CN115924926A (en) * 2022-11-22 2023-04-07 辽宁智优环保科技有限公司 Method for efficiently recovering valuable components in waste SCR catalyst
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