CN106756053A - It is a kind of that titanium, the method for tungsten are separated and recovered from discarded SCR denitration - Google Patents
It is a kind of that titanium, the method for tungsten are separated and recovered from discarded SCR denitration Download PDFInfo
- Publication number
- CN106756053A CN106756053A CN201710073315.2A CN201710073315A CN106756053A CN 106756053 A CN106756053 A CN 106756053A CN 201710073315 A CN201710073315 A CN 201710073315A CN 106756053 A CN106756053 A CN 106756053A
- Authority
- CN
- China
- Prior art keywords
- filter cake
- filtrate
- separated
- tungsten
- scr denitration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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 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.Major product rutile type titanium white, tungstic acid purity and the rate of recovery obtained according to the inventive method are higher, and 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
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, the method for tungsten.
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 a kind of separation and recovery titanium, the side of tungsten 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 are higher, secondary
Product silica and calcium carbonate can serve as resource and utilized.The method has economic results in society very high, industry
The implementation of change 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, the method for tungsten are separated and recovered from discarded SCR denitration, comprise the following steps:
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.
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.
Above-mentioned technical proposal of the present invention, has the advantages that:
Major product rutile type titanium white, tungstic acid purity and the rate of recovery that present invention process is obtained are higher.By-product
Product silica and calcium carbonate can serve as resource and utilized.Therefore, this technique has economic results in society very high, work
The implementation of industry 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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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 (7)
1. it is a kind of that titanium, the method for tungsten are separated and recovered from discarded SCR denitration, it is characterised in that to comprise the following steps:
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.
It is 2. according to claim 1 that titanium, the method for tungsten are separated and recovered from discarded SCR denitration, it is characterised in that
The step 1) catalyst fines be to be prepared by the following:After by discarded SCR denitration dust removal process, crush,
Grinding, the SCR powder after grinding is screened through classifying screen, is classified grit number >=100 mesh, and screenings is catalyst fines, oversize
Mix with the discarded SCR denitration after broken, re-grind, sieve, repetitive cycling.
It is 3. according to claim 1 that titanium, the method for tungsten are separated and recovered from discarded SCR denitration, it is characterised in that
The step 2) leaching be the leaching carried out by level Four cross-flow or two stage countercurrent modes, extraction temperature is 100-150 DEG C;Hydrogen
The concentration of sodium hydroxide solution is 10%-40%.
It is 4. according to claim 1 that titanium, the method for tungsten are separated and recovered from discarded SCR denitration, it is characterised in that
The step 2) washing be specially:Filter cake is washed twice, the liquid-solid ratio washed twice is (2-5):1, washing temperature
It is 40-60 DEG C to spend, and the time is 30-50min, and water scouring water can be recycled or as other step water twice;Calcining
Condition is:600-1000 DEG C is calcined 1-3 hours.
It is 5. according to claim 1 that titanium, the method for tungsten are separated and recovered from discarded SCR denitration, it is characterised in that
The step 2) titanium dioxide be rutile titanium dioxide.
It is 6. according to claim 1 that titanium, the method for tungsten are separated and recovered from discarded SCR denitration, it is characterised in that
The step 4) it is specially:To NaOH is added in filtrate, when pH value often raises 1, then add a calcium chloride, stirred under normal temperature
Reaction 0.5-1 hours is mixed, until the pH value of filtrate is 10-12;Wherein, the consumption of calcium chloride is handled discarded SCR denitration
0.2-1 times of catalyst weight, and added calcium chloride should be made into saturated solution.
It is 7. according to claim 1 that titanium, the method for tungsten are separated and recovered from discarded SCR denitration, it is characterised in that
The step 5) in, the condition of calcining is:400-800 DEG C is calcined 1-3 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710073315.2A CN106756053A (en) | 2017-02-10 | 2017-02-10 | It is a kind of that titanium, the method for tungsten are separated and recovered from discarded SCR denitration |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710073315.2A CN106756053A (en) | 2017-02-10 | 2017-02-10 | It is a kind of that titanium, the method for tungsten are separated and recovered from discarded SCR denitration |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106756053A true CN106756053A (en) | 2017-05-31 |
Family
ID=58955800
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710073315.2A Pending CN106756053A (en) | 2017-02-10 | 2017-02-10 | It is a kind of that titanium, the method for tungsten are separated and recovered from discarded SCR denitration |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106756053A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107512734A (en) * | 2017-08-01 | 2017-12-26 | 洛阳理工学院 | A kind of method that tungsten vanadium and titanium dioxide are reclaimed from discarded SCR denitration |
CN111676372A (en) * | 2020-06-17 | 2020-09-18 | 中国电建集团装备研究院有限公司 | Method for refining titanium dioxide in waste catalyst for coal-fired flue gas denitration |
CN115194163A (en) * | 2022-07-15 | 2022-10-18 | 北京科技大学 | Method for preparing titanium-tungsten powder by recovering waste SCR denitration catalyst |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2264478C1 (en) * | 2004-05-26 | 2005-11-20 | Федун Марина Петровна | Method of processing of titanium-silicon containing concentrates |
CN103484678A (en) * | 2013-09-09 | 2014-01-01 | 北京化工大学 | Method for recovering vanadium, tungsten and titanium from waste vanadium-tungsten-titanium-based denitration catalyst |
CN104805298A (en) * | 2015-05-22 | 2015-07-29 | 北京赛科康仑环保科技有限公司 | Method for recovering waste SCR (Selective Catalytic Reduction) denitration catalyst |
CN105648241A (en) * | 2016-03-18 | 2016-06-08 | 昆明冶金研究院 | Method for comprehensively recovering valuable metal including tungsten, vanadium and titanium in waste vanadium, tungsten and titanium denitration catalyst |
CN106048235A (en) * | 2016-08-09 | 2016-10-26 | 河北钢铁股份有限公司承德分公司 | Method for extracting vanadium-tungsten from waste denitration catalyst |
US20160376682A1 (en) * | 2014-03-11 | 2016-12-29 | Korea Institute Of Geoscience And Mineral Resource | Method for recovering vanadium and tungsten from leach solution of waste denitrification catalyst |
-
2017
- 2017-02-10 CN CN201710073315.2A patent/CN106756053A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2264478C1 (en) * | 2004-05-26 | 2005-11-20 | Федун Марина Петровна | Method of processing of titanium-silicon containing concentrates |
CN103484678A (en) * | 2013-09-09 | 2014-01-01 | 北京化工大学 | Method for recovering vanadium, tungsten and titanium from waste vanadium-tungsten-titanium-based denitration catalyst |
US20160376682A1 (en) * | 2014-03-11 | 2016-12-29 | Korea Institute Of Geoscience And Mineral Resource | Method for recovering vanadium and tungsten from leach solution of waste denitrification catalyst |
CN104805298A (en) * | 2015-05-22 | 2015-07-29 | 北京赛科康仑环保科技有限公司 | Method for recovering waste SCR (Selective Catalytic Reduction) denitration catalyst |
CN105648241A (en) * | 2016-03-18 | 2016-06-08 | 昆明冶金研究院 | Method for comprehensively recovering valuable metal including tungsten, vanadium and titanium in waste vanadium, tungsten and titanium denitration catalyst |
CN106048235A (en) * | 2016-08-09 | 2016-10-26 | 河北钢铁股份有限公司承德分公司 | Method for extracting vanadium-tungsten from waste denitration catalyst |
Non-Patent Citations (2)
Title |
---|
唐丁玲: ""废弃SCR催化剂的再利用实验研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
张勇 主编: "《矿业开采可行性分析研究与开采新模式及矿产品分析试验方法技术标准实用手册 第2卷》", 28 February 2005 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107512734A (en) * | 2017-08-01 | 2017-12-26 | 洛阳理工学院 | A kind of method that tungsten vanadium and titanium dioxide are reclaimed from discarded SCR denitration |
CN111676372A (en) * | 2020-06-17 | 2020-09-18 | 中国电建集团装备研究院有限公司 | Method for refining titanium dioxide in waste catalyst for coal-fired flue gas denitration |
CN115194163A (en) * | 2022-07-15 | 2022-10-18 | 北京科技大学 | Method for preparing titanium-tungsten powder by recovering waste SCR denitration catalyst |
CN115194163B (en) * | 2022-07-15 | 2023-05-30 | 北京科技大学 | Method for preparing titanium tungsten powder by recycling waste SCR denitration catalyst |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106756054A (en) | It is a kind of that titanium, tungsten, the method for vanadium are separated and recovered from discarded SCR denitration | |
CN104862485B (en) | A kind of vanadium of useless vanadium tungsten system SCR catalyst, tungsten separation and method of purification | |
CN105648241B (en) | Valuable metal tungsten, vanadium, the method for titanium synthetical recovery in useless vanadium tungsten titanium denitrating catalyst | |
CN109279651B (en) | Method for extracting high-purity titanium dioxide from waste SCR denitration catalyst containing barium and cerium | |
CN106048230B (en) | The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration | |
CN104384167B (en) | A kind of comprehensive reutilization method of discarded titanium-based vanadium system SCR catalyst | |
CN105714118B (en) | A kind of extraction from discarded SCR catalyst reclaims tungsten, the technique of vanadium | |
CN106884090B (en) | A kind of sub-molten salt method that vanadium tungsten titanium recycles entirely in waste denitration catalyst | |
CN108043404B (en) | Catalyst prepared from red mud for removing volatile organic compounds and preparation method thereof | |
CN106756053A (en) | It is a kind of that titanium, the method for tungsten are separated and recovered from discarded SCR denitration | |
CN107699695A (en) | It is a kind of that tungsten, the method for vanadium are reclaimed from useless SCR denitration | |
CN107185554A (en) | A kind of method that useless SCR denitration cleaning is recycled | |
CN107557599A (en) | Tungsten, the method for vanadium are reclaimed in discarded SCR denitration | |
CN106622284A (en) | Recovery and utilization technology of waste titanium-vanadium based SCR catalyst capable of being applied to reproduction | |
CN106521160A (en) | Method for extraction of vanadium from waste SCR catalyst and preparation of activated titanium silicon tungsten powder | |
CN105457491B (en) | A kind of method of discarded fire coal boiler fume denitrating catalyst separation renewable resources | |
CN104071832A (en) | Method for extracting metal oxide from waste SCR (selective catalytic reduction) denitrification catalyst | |
CN104178636A (en) | Method for recovering Ti, V, Mo and Si in SCR (selective catalytic reduction) waste catalyst by combination of activation calcination and acid leaching | |
CN104611564A (en) | Method for recycling metal oxides from waste SCR (selective catalytic reduction) catalyst | |
CN105621483A (en) | Process for reclaiming honeycomb SCR waste catalyst | |
CN109295313B (en) | Method for preparing titanium-tungsten powder by recycling waste SCR denitration catalyst and application | |
CN110218859A (en) | The method of the useless denitrating catalyst valuable element of middle temperature tunnel type solid-state activation extraction | |
CN104789780A (en) | Method for recovering anatase-type titanium tungsten powder from waste vanadium-tungsten-titanium catalyst | |
CN115445604A (en) | Resource recycling method of waste denitration catalyst | |
KR101885917B1 (en) | Method for Rematerializing Waste De-NOx Catalyst Using Organic Acid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |