CN106048230B - The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration - Google Patents
The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B7/007—Wet processes by acid leaching
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
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Abstract
The invention discloses the separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration, belong to waste catalyst recovery technical field.This method comprises the concrete steps that：First by useless SCR catalyst crush drying after with Na2CO3It is well mixed, it is placed in dilute sulfuric acid and is leached after high-temperature roasting；Secondly the W in leachate and V are extracted using the kerosin of tri-n-octyl amine+isodecanol, then separated W and V from extraction organic phase using NaOH as strippant；H is added in most backward stripping solution2SO4PH is adjusted, and adds excessive NH4Cl precipitations, the ammonium metavanadate precipitate that is filtrated to get is fired to obtain V2O5Product；Continue to add sulphur acid for adjusting pH into the secondary filtrate after precipitation, and add excess amount of Ca Cl2Heavy tungsten, the CaWO being filtrated to get4Precipitation obtains WO after chlorohydric acid pickling through roasting3Product.The tungsten that can be realized in useless SCR catalyst and vanadium of the invention efficiently separating and reclaiming, and technique is simple, and pollution is few, has higher engineering application value.
Description
Technical field
The invention belongs to waste catalyst recovery technical field, and in particular in a kind of useless SCR denitration tungsten and
Vanadium separation, the method for recovery.
Background technology
NO caused by fire coalxIt is the main reason for causing acid rain, photochemical fog and depletion of the ozone layer, turns into danger at present
Evil is only second to the Air Pollutants of pellet.Coal-burning power plant is NOxOne of primary discharge source, China nearly 70%
Discharged nitrous oxides both from the burning of coal, at present industrial widely used SCR both at home and abroad
(Selective Catalytic Reduction, write a Chinese character in simplified form SCR) denitration technology controls it, in the presence of catalyst
Utilize reducing agent NH3By the NO in flue gasxReduction turns into harmless N2And H2O, the key reaction being related to are as follows：
4NH3+4NO+O2→4N2+6H2O
2NH3+NO+NO2→2N2+3H2O
8NH3+6NO2→7N2+12H2O
Catalyst is the core of SCR denitration technology, V2O5-WO3/TiO2It is that the SCR denitration that current common commercialization is applied is urged
Agent, influenceed by catalyst activity temperature window, SCR denitration reactor is often arranged in boiler economizer and air preheater
Between high temperature (300~400 DEG C), Gao Chenduan, catalyst in use easily because poisoning, duct block, high temperature sintering
Cause its activity decrease with reasons such as scaling loss, its service life typically only 3~5 years.Country requires in being planned in " 12 "
Mandatory denitrating flue gas, by NOxEmission reduction and SO2Emission reduction targets are equally classified as a new environment constraint index.As flue gas takes off
The propulsion of nitre work is implemented, and the yield of decaying catalyst also gradually increases, it is contemplated that after 2018, the country every year will be continuously steady
3.8 ten thousand tons of useless SCR denitrations are given birth in fixed output quota.Useless SCR catalyst belongs to hazardous solid waste, and directly abandoning can not only take greatly
The soil of amount, also there are serious pollution, the particularly pollution to underground water to environment.Meanwhile the tungsten (W) that contains in catalyst and
Vanadium (V) belongs to rare metal, less and expensive in distributed in nature, is widely used in various industrial processes, has
Very high recycling value.Therefore, valuable metal oxide is reclaimed from useless SCR denitration, preciousness can be saved
Resource, reduces denitration cost, and and can avoids the pollution to environment, has preferable economic benefit and environmental benefit.It is domestic at present
There has been no the technology of special SCR catalyst metal recovery and company, the research for carrying out useless SCR catalyst metal recovery technology has
There are important theory significance and construction value.
It is relatively fewer about the research of vanadium metal and tungsten recovery in SCR denitration of giving up at present, have than more typical：In
State patent CN105200236A discloses a kind of method that W and V is reclaimed from waste flue gas denitration catalyst, and the invention will urge first
Agent is ground to 160~200 mesh, and the concentrated sulfuric acid that concentration is 85%~92%, solid-to-liquid ratio 1 are added into catalyst fines:1.5
It is 1 by the weight of catalyst and water ratio after~1.8 acidolysis:0.5~0.6 ratio adds water and filtered, and obtains filter residue and filtrate is standby
With.Then the filtrate obtained by catalyst acidolysis is heated to 70~100 DEG C and is concentrated into 150~200g/L, by concentrate with
The weight ratio of water is 1：0.8~1 ratio adds water and is hydrolyzed, and hydrolysate filters after carrying out settlement treatment, clear to upper strata
Excessive NH is added in liquid4Cl, and it is 7.5~8.5 to adjust pH, obtains metavanadic acid ammonia precipitation in 50~80 DEG C of reactions, will precipitate
It is calcined after filtering, finally obtains product V2O5.It is anti-that excessive 10~28% ammoniacal liquor are added in filter residue obtained by most backward catalyst acid solution
Should after filter, after the filter residue after filtering is heated to 80~100 DEG C, crystal is dried, forged by obtained order of ammoniumparatungstate crystal
Burn, obtain product WO3.Chinese patent CN104611564A discloses a kind of recovery metal oxide from useless SCR catalyst
Method, the method that the invention uses are：Useless SCR catalyst is crushed to more than 80 mesh first, urged using 3~4 times of water immersion
After agent powder carries out impurity elimination, 3~4 times of 20~30%NaOH solution is added, is heated to 80 DEG C, 1~2h is soaked, adds 1
~2% potassium chlorate will be oxidized to pentavalent vanadium, resulting solution NH in raw material containing tetravalence vanadium4The pH to 1.7 of Cl regulation aqueous phases~
1.8, boil 1~2h and carry out heavy alum, be refining to obtain pure metavanadic acid by adding HCl in the filtrate after separate vanadium, pH value is adjusted
To 4.5~5.0, CaCl is added2Solution, it is settled out CaWO4After filtered, H is made with HCl processing in filter cake2WO4And H2MoO4。
Chinese patent CN101921916A discloses a kind of method that metal oxide is reclaimed from waste flue gas denitration catalyst, flue gas
After carrying out high-temperature roasting pretreatment after denitrating catalyst is broken, Na is proportionally added into2CO3And mix, crush, carry out high-temperature roasting.
Agglomerate puts into leaching in hot water after crushing.Gained titanate adds sulfuric acid, filtered, washing, roasting, can obtain
TiO2.Filtrate after leaching adds sulphur acid for adjusting pH value to add excessive NH to 8.0~9.04Cl precipitations.NH will be filtrated to get4VO3
Through pyrolytic, V is made2O5Finished product.Filtrate after precipitation adds hydrochloric acid regulated value to add CaCl to 4.5~5.02Heavy molybdenum, tungsten.
Filtering gained CaWO4And CaMoO4WO can be obtained with HCl treatment is fired again3With Mo3。
In the above-mentioned methods, Chinese patent CN105200236A, Chinese patent CN104611564A, Chinese patent
CN101921916A separates and recovers metal using chemical precipitation method from useless SCR catalyst leachate, and cost is relatively low, but operates
Process is cumbersome, and metal leaching rate is generally relatively low in catalyst, causes the rate of recovery of metal relatively low, at the same can not realize V, W and
The metal product for efficiently separating and acquiring high-purity of the valuable metals such as Ti.Therefore, study a set of efficient, low cost useless
The process for separating and recovering of tungsten, vanadium in SCR denitration, to realizing the separation of vanadium, tungsten and titanium in useless SCR denitration with returning
The commercial Application of receipts has important value.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide tungsten in a kind of useless SCR denitration
Separation, recovery method with vanadium, to by the tungsten in catalyst and vanadium efficiently extract, separate, to reclaim high-purity
WO3And V2O5Product.
In order to realize above-mentioned technical purpose, the present invention is achieved by the following technical programs.
The separation of tungsten and vanadium, recovery method, are comprised the following steps that in a kind of useless SCR denitration of the present invention：
(1) preparation of acid leaching solution
The a useless SCR denitrations of the dry compressed air purging of cleaning, grind after removing the flying dust of catalyst surface deposition
Clay into power shape, sieved and be baked to not less than 100 the polished standard screens；
B presses sodium carbonate (Na2CO3) and SCR denitration mass ratio be 0.5~1.6:1, by a certain amount of Na2CO3
After being well mixed with step a catalyst fineses, the mixture of gained is calcined 1~5h at a temperature of 700~900 DEG C, obtained
Agglomerate；
Agglomerate obtained by above-mentioned b is placed in 2%~10% (v/v) dilution heat of sulfuric acid by c, while using magnetic agitation
Mode makes the mixture in solution be in suspended state, leach 1 to the W in solid mixture and V at a temperature of 35 DEG C~90 DEG C~
5h, liquid-solid ratio are 5~15:1, finally mixed solution is filtered, obtains the acid leaching solution containing W and V.
(2) in acid leaching solution W and V extraction
The pH to 1.00~3.50 of a pickle liquors obtained by sulfuric acid regulating step (1)；
B takes the pickle liquor obtained in a certain amount of above-mentioned a in separatory funnel, and adding tri-n-octyl amine thereto, (molecular formula is
[CH3(CH2)7]3N, it is abbreviated as R3N the kerosin of)+isodecanol, it is 0.5 to control extractant and the volume ratio of pickle liquor:20~
10:20, concussion separatory funnel makes pickle liquor be well mixed with extractant, and W and V are transferred into organic phase, stand 5~30min
Lower floor's aqueous phase is released afterwards, obtains extracting organic phase.
The concentration of the tri-n-octyl amine is 2%~15% (v/v), and the concentration of the isodecanol is 2%~12%,；
(3) the back extraction separation and recovery of W and V in organic phase is extracted
A is added a certain amount of using certain density NaOH as strippant into the extraction organic phase obtained by step (2)
NaOH solution, W and V is separated into lower floor's aqueous phase from extraction organic phase；
The concentration of the NaOH is 0.25mol/L~1.25mol/L, and the organic phase and NaOH volume ratio are 2:1~
1:4；
B H2SO4After the pH value of aqueous phase is 8 or so obtained by the interim above-mentioned a of regulation, excessive NH is added4Cl, 80
Make vanadium Precipitation in the form of ammonium metavanadate under the conditions of DEG C, be calcined after then sediment is filtered, finally give V2O5Product.
C continues into the secondary filtrate after above-mentioned b precipitations after adding sulphur acid for adjusting pH to be 1.5 or so, adds excessive
CaCl2Heavy tungsten, the CaWO being filtrated to get4Precipitation roasting after chlorohydric acid pickling can obtain WO3Product.
Optimize as one kind, in above-mentioned steps (1)：Na2CO3Mass ratio with SCR denitration is 1.2:1, roasting temperature
Spend for 800 DEG C, roasting time 3h, dilute sulfuric acid concentration is 2% (v/v), liquid-solid ratio 8:1, extraction time 4h.
Optimize as one kind, in above-mentioned steps (2)：The pH of pickle liquor is 2.50, and the volume ratio of extractant and pickle liquor is
1:10, the concentration of tri-n-octyl amine is 12%, and the concentration of isodecanol is 10%, and extraction time of repose is 15min.
Optimize as one kind, in above-mentioned steps (3)：NaOH concentration is 0.75mol/L, organic phase and NaOH volume ratio
For 1:3.
Na in above-mentioned steps (1)2CO3Powder is mixed and is calcined with useless SCR denitration powder, to remove useless urge
Organic matter, oils and carbon deposit thing in agent, while the WO in useless SCR denitration3、V2O5Under the high temperature conditions with Na2CO3
The soluble Na of reaction generation2WO4And NaVO3, the main chemical reactions of generation are as follows：
WO3+Na2CO3→Na2WO4+CO2↑
V2O5+Na2CO3→2NaVO3+CO2↑
In above-mentioned steps (2) extraction process, extractant composition for tri-n-octyl amine+isodecanol kerosin, wherein three just
Octylame is main extractant, and isodecanol is phase modulation agent, and kerosene is diluent.Tri-n-octyl amine is Amberlite LA-2, extraction
Mechanism is mainly anion exchange, when the tungsten in pickle liquor, vanadium extract, tri-n-octyl amine first with the H in solution2SO4
Reaction forms the sulfate of amine, and reaction is as follows：
R3N+H2SO4→R3NH·HSO4
When adjusting the pH value of pickle liquor, the ion existing forms of tungsten and vanadium in the solution are with pickle liquor pH change meeting
A series of changes of generation.Under the conditions of optimal pickle liquor pH is 2.50, tungsten is mainly with W8O26 4-Ionic species is present, extraction process
The key reaction of generation is：
4R3NH·HSO4+W8O26 4-→(R3NH)4·W8O26+4HSO4 -
For vanadium, pickle liquor pH<2.00 when, vanadium is mainly with VO2 +Exist in solution, as pH is increased to by 1.00
During 3.50, vanadium oxygen cation easily is hydrolyzed into vanadium oxygen anion：
2VO2 ++3H2O→H3V2O7 -+3H+
5H3V2O7 -→V10O28 6-+H++7H2O
Therefore under the conditions of optimal pickle liquor pH is 2.50, vanadium is mainly with V10O28 6-Ionic species is present, extraction process hair
Raw key reaction is：
6R3NH·HSO4+V10O28 6-→(R3NH)6·V10O28+6HSO4 -
In above-mentioned steps (3), when being stripped using NaOH to the tungsten in load organic phases and vanadium, generation it is main anti-
It should be：
(R3NH)4·W8O26+16NaOH→4R3N+8Na2WO4+10H2O
(R3NH)6·V10O28+10NaOH→6R3N+10NaVO3+8H2O
Utilizing NH4Cl and CaCl2During precipitation, heavy tungsten, the key reaction of generation is：
WO4 2-+Ca2+→CaWO4↓
VO3 -+NH4 +→NH4VO3↓
The key reaction that artificial schellite and ammonium metavanadate precipitate occur in pickling, roasting process is：
CaWO4+2HCl→H2WO4+CaCl2
Compared with prior art, the present invention has the following technical effect that：
(1) present invention proposes tungsten and vanadium extraction, the method for separation in a kind of useless SCR denitration pickle liquor, pass through to
A certain amount of Na is added in catalyst fines2CO3Mixed, be then once calcined mixture, you can by solid SCR
V and W in denitrating catalyst are converted into the Na of solubility2WO4And NaVO3, then using dilution heat of sulfuric acid to the mixing after roasting
Thing is leached, and makes Na2WO4And NaVO3Dissolving enters liquid phase, realizes the efficient leaching of tungsten and vanadium, and W and V leaching rate are distinguished can
Reach 99.08% and 98.49%,.
(2) present invention uses tri-n-octyl amine isodecanol makees diluent as phase modifier, aviation kerosine for main extractant,
The selectivity of extractant is higher, is formed in extraction process without emulsion and third phase, and interface is limpid, and split-phase is simple to operate, energy
Realize to being extracted while tungsten and vanadium, and the extraction yield of tungsten and vanadium is higher, under the conditions of optimal extraction experiments, the extraction of tungsten and vanadium
Rate can be up to 98.26% and 96.65% respectively.
(3) present invention carries out back extraction experiment using NaOH from the organic phase for loading tungsten, vanadium, and W and V separation are more thorough
Bottom, W are almost stripped completely from organic phase and come out, and the stripping rate that stripping rate is up to 99.99%, V can reach
88.05%, the two kinds of metal product WO produced from strip liquor3And V2O5Purity is higher.
(4) present invention process is simple, and condition is easily controllable, workable, strong to the disposal ability of dead catalyst, cost
Relatively low, high efficiente callback while realizing tungsten and vanadium, the rate of recovery of metal is higher, while extractant reusable edible, right
Environmental pollution is smaller.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the present invention is not limited to following embodiments.
1st, in dead catalyst W and V leaching：
Embodiment 1
A takes useless SCR denitration (the main component V that a run time exceedes 24000h2O5-WO3/TiO2, specifically
Component is as shown in table 1), with the compressed air purging inactivation SCR denitration catalyst that cleaning is dry, deposited with removing catalyst surface
Flying dust, wherein, the operating air pressure of compressed air is 0.5MPa, gas flow 0.5m3/ s, purge time 10min.Grinding
By catalyst grind into powder in alms bowl, then with the sieving of 100 the polished standard screens is not less than, then by catalyst fines in 105 DEG C of temperature
2h is dried under the conditions of degree.
B, which is weighed in step a, dries, the catalyst fines 5g after cooling, adds Na thereto2CO3Solid, Na2CO3With urging
The mass ratio of agent is 0.5, is placed in again in Muffle furnace after being sufficiently mixed, is calcined 3h under 800 DEG C of temperature conditionss, is sintered
Block.
C concentrations are that 2% (v/v) dilution heat of sulfuric acid leaches to the V in step b agglomerates and W, leaching process
Middle to ensure that solid powder is in suspended state by the way of magnetic agitation, it is 8 to control the solid mass ratio of liquid:1, extraction temperature 80
DEG C, extraction time 4h.Then mixed solution is filtered, the aperture that filter membrane is used during suction filtration is 0.45 μm, is obtained
Leachate containing V and W is simultaneously settled to 200mL, and the leaching rate that V, W is calculated is respectively 61.86% and 85.39%.
Embodiment 2
A takes useless SCR denitration (the main component V that a run time exceedes 24000h2O5-WO3/TiO2, specifically
Component is as shown in table 1), with the compressed air purging inactivation SCR denitration catalyst that cleaning is dry, deposited with removing catalyst surface
Flying dust, wherein, the operating air pressure of compressed air is 0.5MPa, gas flow 0.5m3/ s, purge time 10min.Grinding
By catalyst grind into powder in alms bowl, then with the sieving of 100 the polished standard screens is not less than, then by catalyst fines in 105 DEG C of temperature
2h is dried under the conditions of degree.
B, which is weighed in step a, dries, the catalyst fines 5g after cooling, adds Na thereto2CO3Solid, Na2CO3With urging
The mass ratio of agent is 1.2, is placed in again in Muffle furnace after being sufficiently mixed, is calcined 5h under 800 DEG C of temperature conditionss, is sintered
Block.
C concentrations are that 10% (v/v) dilution heat of sulfuric acid leaches to the V in step b agglomerates and W, are leached
Ensure that solid powder is in suspended state by the way of magnetic agitation in journey, it is 5 to control the solid mass ratio of liquid:1, extraction temperature 90
DEG C, extraction time 5h.Then mixed solution is filtered, the aperture that filter membrane is used during suction filtration is 0.45 μm, is obtained
Leachate containing V and W is simultaneously settled to 200mL, and the leaching rate that V, W is calculated is respectively 82.16% and 87.38%.
Embodiment 3
A takes useless SCR denitration (the main component V that a run time exceedes 24000h2O5-WO3/TiO2, specifically
Component is as shown in table 1), with the compressed air purging inactivation SCR denitration catalyst that cleaning is dry, deposited with removing catalyst surface
Flying dust, wherein, the operating air pressure of compressed air is 0.5MPa, gas flow 0.5m3/ s, purge time 10min.Grinding
By catalyst grind into powder in alms bowl, then with the sieving of 100 the polished standard screens is not less than, then by catalyst fines in 105 DEG C of temperature
2h is dried under the conditions of degree.
B, which is weighed in step a, dries, the catalyst fines 5g after cooling, adds Na thereto2CO3Solid, Na2CO3With urging
The mass ratio of agent is 1.2, is placed in again in Muffle furnace after being sufficiently mixed, is calcined 3h under 800 DEG C of temperature conditionss, is sintered
Block.
C concentrations are that 2% (v/v) dilution heat of sulfuric acid leaches to the V in step b agglomerates and W, leaching process
Middle to ensure that solid powder is in suspended state by the way of magnetic agitation, it is 8 to control the solid mass ratio of liquid:1, extraction temperature 80
DEG C, extraction time 4h.Then mixed solution is filtered, the aperture that filter membrane is used during suction filtration is 0.45 μm, is obtained
Leachate containing V and W is simultaneously settled to 200mL, and the leaching rate that V, W is calculated is respectively 98.49% and 99.08%.
2nd, in acid leaching solution W and V extraction
Embodiment 1
(1) preparation of catalyst acid immersion liquid
The preparation method of catalyst acid immersion liquid is the same as the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) in acid leaching solution W and V extraction
The pH to 3.50 of a pickle liquors obtained by sulfuric acid regulating step (1)；
B takes the pickle liquor obtained in the above-mentioned a of 20ml in separatory funnel, adds the coal of tri-n-octyl amine+isodecanol thereto
Oil solution, it is 2 to control extractant and the volume ratio of pickle liquor:20, tri-n-octyl amine concentration is 10% (v/v), and isodecyl determining alcohol is
6% (v/v), concussion separatory funnel make pickle liquor be well mixed with extractant, and W and V are transferred into organic phase, stand 15min
Lower floor's aqueous phase is released afterwards, obtains extracting organic phase, the extraction yield that W and V is calculated is respectively 67.02%, 86.17%.
Embodiment 2
(1) preparation of catalyst acid immersion liquid
The preparation method of catalyst acid immersion liquid is the same as the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) in acid leaching solution W and V extraction
The pH to 2.50 of a pickle liquors obtained by sulfuric acid regulating step (1)；
B takes the pickle liquor obtained in the above-mentioned a of 20ml in separatory funnel, adds the coal of tri-n-octyl amine+isodecanol thereto
Oil solution, it is 2 to control extractant and the volume ratio of pickle liquor:20, tri-n-octyl amine concentration is 12% (v/v), and isodecyl determining alcohol is
10% (v/v), concussion separatory funnel make pickle liquor be well mixed with extractant, and W and V are transferred into organic phase, stand 15min
Lower floor's aqueous phase is released afterwards, obtains extracting organic phase, the extraction yield that W and V is calculated is respectively 98.26%, 96.65%.
Embodiment 3
(1) preparation of catalyst acid immersion liquid
The preparation method of catalyst acid immersion liquid is the same as the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) in acid leaching solution W and V extraction
The pH to 2.50 of a pickle liquors obtained by sulfuric acid regulating step (1)；
B takes the pickle liquor obtained in the above-mentioned a of 20ml in separatory funnel, adds the coal of tri-n-octyl amine+isodecanol thereto
Oil solution, it is 0.5 to control extractant and the volume ratio of pickle liquor:20, tri-n-octyl amine concentration is 10% (v/v), isodecyl determining alcohol
For 6% (v/v), concussion separatory funnel makes pickle liquor be well mixed with extractant, W and V is transferred into organic phase, stands
Lower floor's aqueous phase is released after 10min, obtains extracting organic phase, the extraction yield that W and V is calculated is respectively 96.43%, 84.43%.
3rd, the back extraction separation and recovery of W and V in organic phase is extracted
Embodiment 1
(1) preparation of catalyst acid immersion liquid
The preparation method of catalyst acid immersion liquid is the same as the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) in acid leaching solution W and V extraction
Extract the preparation method of organic phase with " 2, in acid leaching solution W and V extraction " in embodiment 2.
(3) the back extraction separation and recovery of W and V in organic phase is extracted
A is 1mol/L NaOH solution as strippant using concentration, is added into the extraction organic phase obtained by step (2)
NaOH solution, wherein extraction organic phase and NaOH volume ratio are 2:1, W and V is separated under entrance from extraction organic phase
Layer aqueous phase, the stripping rate that W and V is calculated is respectively 89.79%, 37.38%；
B H2SO4After the pH value of aqueous phase is 8 or so obtained by the interim above-mentioned a of regulation, excessive NH is added4Cl, 80
Make vanadium Precipitation in the form of ammonium metavanadate under the conditions of DEG C, 1h is calcined in 500 DEG C of conditions after then sediment is filtered, it is final to obtain
To V2O5Product.
C continues into the secondary filtrate after above-mentioned b precipitations after adding sulphur acid for adjusting pH to be 1.5 or so, adds excess amount of Ca Cl2
Heavy tungsten, the CaWO being filtrated to get4Precipitation is calcined 1h after chlorohydric acid pickling under the conditions of 500 DEG C can obtain WO3Product.
Embodiment 2
(1) preparation of catalyst acid immersion liquid
The preparation method of catalyst acid immersion liquid is the same as the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) in acid leaching solution W and V extraction
Extract the preparation method of organic phase with " 2, in acid leaching solution W and V extraction " in embodiment 2.
(3) the back extraction separation and recovery of W and V in organic phase is extracted
A is 1mol/L NaOH solution as strippant using concentration, is added into the extraction organic phase obtained by step (2)
NaOH solution, wherein extraction organic phase and NaOH volume ratio are 1:2, W and V is separated under entrance from extraction organic phase
Layer aqueous phase, the stripping rate that W and V is calculated is respectively 99.99%, 75.53%；
B H2SO4After the pH value of aqueous phase is 8 or so obtained by the interim above-mentioned a of regulation, excessive NH is added4Cl, 80
Make vanadium Precipitation in the form of ammonium metavanadate under the conditions of DEG C, 1h is calcined in 500 DEG C of conditions after then sediment is filtered, it is final to obtain
To V2O5Product.
C continues into the secondary filtrate after above-mentioned b precipitations after adding sulphur acid for adjusting pH to be 1.5 or so, adds excess amount of Ca Cl2
Heavy tungsten, the CaWO being filtrated to get4Precipitation is calcined 1h after chlorohydric acid pickling under the conditions of 500 DEG C can obtain WO3Product.
Embodiment 3
(1) preparation of catalyst acid immersion liquid
The preparation method of catalyst acid immersion liquid is the same as the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) in acid leaching solution W and V extraction
Extract the preparation method of organic phase with " 2, in acid leaching solution W and V extraction " in embodiment 2.
(3) the back extraction separation and recovery of W and V in organic phase is extracted
A using concentration be 0.75mol/L NaOH solution as strippant, into the extraction organic phase obtained by step (2)
NaOH solution is added, wherein extraction organic phase and NaOH volume ratio are 1:3, by W and V from extraction organic phase in separate into
Enter lower floor's aqueous phase, the stripping rate that W and V is calculated is respectively 99.99%, 88.05%；
B H2SO4After the pH value of aqueous phase is 8 or so obtained by the interim above-mentioned a of regulation, excessive NH is added4Cl, 80
Make vanadium Precipitation in the form of ammonium metavanadate under the conditions of DEG C, 1h is calcined in 500 DEG C of conditions after then sediment is filtered, it is final to obtain
To V2O5Product.
C continues into the secondary filtrate after above-mentioned b precipitations after adding sulphur acid for adjusting pH to be 1.5 or so, adds excess amount of Ca Cl2
Heavy tungsten, the CaWO being filtrated to get4Precipitation is calcined 1h after chlorohydric acid pickling under the conditions of 500 DEG C can obtain WO3Product.
Embodiment 4
(1) preparation of catalyst acid immersion liquid
The preparation method of catalyst acid immersion liquid is the same as the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) in acid leaching solution W and V extraction
Extract the preparation method of organic phase with " 2, in acid leaching solution W and V extraction " in embodiment 2.
(3) the back extraction separation and recovery of W and V in organic phase is extracted
A using the NaOH solution that concentration is 1.5mol/L as strippant, into the extraction organic phase obtained by step (2) plus
Enter NaOH solution, wherein extraction organic phase and NaOH volume ratio are 1:3, W and V is separated into entrance from extraction organic phase
Lower floor's aqueous phase, the stripping rate that W and V is calculated are respectively 99.99%, 83.14%；
B H2SO4After the pH value of aqueous phase is 8 or so obtained by the interim above-mentioned a of regulation, excessive NH is added4Cl, 80
Make vanadium Precipitation in the form of ammonium metavanadate under the conditions of DEG C, 1h is calcined in 500 DEG C of conditions after then sediment is filtered, it is final to obtain
To V2O5Product.
C continues into the secondary filtrate after above-mentioned b precipitations after adding sulphur acid for adjusting pH to be 1.5 or so, adds excess amount of Ca Cl2
Heavy tungsten, the CaWO being filtrated to get4Precipitation is calcined 1h after chlorohydric acid pickling under the conditions of 500 DEG C can obtain WO3Product.
The key component and ratio of table 1, useless SCR denitration
Claims (4)
1. the separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration, it is characterised in that this method include with
Lower step：
(1) preparation of acid leaching solution
A, with the useless SCR denitration of the dry compressed air purging of cleaning, ground after removing the flying dust of catalyst surface deposition
Into powdered, sieved and be baked to not less than 100 the polished standard screens；
B, by sodium carbonate and the catalyst fines in mass ratio 0.5~1.6 obtained by step a:After 1 is well mixed, by the mixed of gained
Compound is calcined 1~5h at a temperature of 700~900 DEG C, obtains agglomerate；
C, the agglomerate obtained by above-mentioned b is placed in the dilution heat of sulfuric acid of volume ratio 2%~10%, liquid-solid ratio is 5~15:1, together
The mode of Shi Caiyong magnetic agitations makes the mixture in solution be in suspended state, and 1~5h is leached to mixture at 35 DEG C~90 DEG C,
Finally mixed solution is filtered, obtains the acid leaching solution containing W and V；
(2) in acid leaching solution W and V extraction
A, with the pH to 1.00~3.50 of sulfuric acid regulating step (1) gained acid leaching solution；
B, the acid leaching solution obtained in above-mentioned a is taken in separatory funnel, and the kerosene for adding tri-n-octyl amine+isodecanol thereto is molten
For liquid as extractant, it is 0.5~10 to control the volume ratio of extractant and acid leaching solution:20, concussion separatory funnel makes acid leaching
Go out liquid to be well mixed with extractant, W and V are transferred into organic phase, release lower floor's aqueous phase after standing 5~30min, extracted
Organic phase；
The volumetric concentration of the tri-n-octyl amine is 2%~15%, and the volumetric concentration of the isodecanol is 2%~12%；(3) extract
W and V back extraction and separation, recovery in organic phase
A, using NaOH as strippant, NaOH solution is added into the extraction organic phase obtained by step (2), by W and V from extraction
Separated in organic phase into lower floor's aqueous phase；
The concentration of the NaOH is 0.25~1.25mol/L, and the extraction organic phase and NaOH volume ratio are 0.25~2:1；
B, H is used2SO4After the pH value for adjusting aqueous phase obtained by above-mentioned a is 8, excessive NH is added4Cl, vanadium is made under the conditions of 80 DEG C with inclined
Vanadic acid ammonium form Precipitation, is calcined after then sediment is filtered, obtains V2O5Product；
C, continue to add H into the secondary filtrate after above-mentioned b precipitations2SO4After regulation pH is 1.5, excess amount of Ca Cl is added2Heavy tungsten, mistake
Filter obtained CaWO4Precipitation is calcined after chlorohydric acid pickling produces WO3Product.
2. the separation of tungsten and vanadium, recovery method in useless SCR denitration as claimed in claim 1, it is characterised in that
In the step (1)：Sodium carbonate and the mass ratio of useless SCR denitration are 1.2:1, sintering temperature is 800 DEG C, roasting time
For 3h, dilute sulfuric acid concentration is 2%, liquid-solid ratio 8:1, extraction time 4h.
3. the separation of tungsten and vanadium, recovery method in useless SCR denitration as claimed in claim 1, it is characterised in that
In the step (2)：With the pH to 2.50 of sulfuric acid regulation acid leaching solution, the volume ratio of extractant and acid leaching solution is 1:
10, the volumetric concentration of tri-n-octyl amine is 12%, and the volumetric concentration of isodecanol is 10%, and extraction time of repose is 15min.
4. the separation of tungsten and vanadium, recovery method in useless SCR denitration as claimed in claim 1, it is characterised in that
In the step (3)：NaOH concentration is 0.75mol/L, and the volume ratio for extracting organic phase and NaOH is 1:3.
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| CN107512734B (en) * | 2017-08-01 | 2019-06-11 | 洛阳理工学院 | A method of recycling tungsten vanadium and titanium dioxide from discarded SCR denitration |
| CN107699695A (en) * | 2017-10-13 | 2018-02-16 | 北京工业大学 | It is a kind of that tungsten, the method for vanadium are reclaimed from useless SCR denitration |
| CN112569926A (en) * | 2019-09-30 | 2021-03-30 | 国家能源投资集团有限责任公司 | Denitration catalyst and method for preparing denitration catalyst from waste denitration catalyst |
| CN112547136B (en) * | 2021-03-01 | 2021-05-11 | 中国科学院过程工程研究所 | Method for adjusting titanium-tungsten carrier pore channel in waste SCR denitration catalyst and application |
| CN113046560B (en) * | 2021-03-08 | 2022-05-03 | 绍兴上虞华电光大环境有限公司 | Method for recovering and obtaining nano-iron tungstate from waste catalyst |
| CN113046562B (en) * | 2021-03-08 | 2022-08-12 | 北京华电光大环境股份有限公司 | Method for recovering tungsten element in waste catalyst |
| CN115255378B (en) * | 2022-06-27 | 2023-07-21 | 北京科技大学 | Preparation method of porous tungsten material with multi-stage pore structure |
| CN115784310B (en) * | 2023-02-06 | 2023-04-14 | 国能龙源环保有限公司 | Method for preparing silicotungstic acid by using waste denitration catalyst and silicotungstic acid obtained by method |
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