CN106048230A - Separating and recovering method for W and V in waste SCR denitration catalyst - Google Patents
Separating and recovering method for W and V in waste SCR denitration catalyst Download PDFInfo
- Publication number
- CN106048230A CN106048230A CN201610520660.1A CN201610520660A CN106048230A CN 106048230 A CN106048230 A CN 106048230A CN 201610520660 A CN201610520660 A CN 201610520660A CN 106048230 A CN106048230 A CN 106048230A
- Authority
- CN
- China
- Prior art keywords
- extraction
- acid
- organic facies
- catalyst
- vanadium
- 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.)
- Granted
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
- 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
-
- 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
- C22B7/007—Wet processes by acid 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a separating and recovering method for W and V in a waste SCR denitration catalyst, and belongs to the technical field of recovery of waste catalysts. The separating and recovering method comprises the specific steps that at first, after being smashed and dried, the SCR catalyst is uniformly mixed with Na2CO3 to obtain a mixture, the mixture is calcined at high temperature to obtain a calcined product, and the calcined product is placed in dilute sulphuric acid to leach W and V; then, W and V in the leachate are extracted with a trioctylamine-isodecanol kerosene solution, and are separated out from an extracted organic phase with NaOH as a back-extractant; next, H2SO4 is added in a back extraction solution to regulate pH, excessive NH4C1 is added to realize vanadium precipitation, and ammonium metavanadate precipitates obtained through filtering are calcined to obtain a V2O5 product; and at last, sulfuric acid is continuously added in a secondary filtrate obtained after vanadium precipitation to regulate pH, excessive CaCl2 is added to realize tungsten precipitation, CaWO4 precipitates obtained through filtering are pickled with hydrochloric acid to obtain a pickled product, and the pickled product is calcined to obtain a WO3 product. The separating and recovering method can realize efficient separation and recovery of W and V in the waste SCR catalyst, the process is simple, the pollution is less, and the separating and recovering method has a relatively high engineering application value.
Description
Technical field
The invention belongs to waste catalyst recovery technical field, be specifically related in a kind of useless SCR denitration tungsten and
The method that vanadium separates, reclaims.
Background technology
The coal-fired NO producedxIt is the main cause causing acid rain, photochemical fog and depletion of the ozone layer, has the most become danger
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, current domestic and international industrial widely used SCR
(Selective Catalytic Reduction, write a Chinese character in simplified form SCR) denitration technology controls it, under the effect of catalyst
Utilize reducing agent NH3By the NO in flue gasxReduction becomes harmless N2And H2O, the dominant response related to is 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, is affected by catalyst activity temperature window, and SCR denitration reactor is often arranged in boiler economizer and air preheater
Between high temperature (300～400 DEG C), Gao Chenduan, catalyst is in use easily because of poisoning, duct blocking, high temperature sintering
Its activity decrease is caused, typically only 3～5 years its service life with the reason such as scaling loss.Country's requirement in " 12 " plan
Mandatory denitrating flue gas, by NOxReduce discharging and SO2Emission reduction targets is equally classified as a new environment constraint index.Along with flue gas takes off
Nitre work propelling implement, the generation amount of decaying catalyst the most gradually increases, it is contemplated that after 2018, domestic annual will be the most steady
The raw 3.8 ten thousand tons of useless SCR denitration of fixed output quota.Useless SCR catalyst belongs to hazardous solid waste, directly abandons and not only can take greatly
, also there are serious pollution, the particularly pollution to subsoil water in the soil of amount 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
The highest recycling is worth.Therefore, from useless SCR denitration, reclaim valuable metal oxide, preciousness can be saved
Resource, reduces denitration cost, is avoided that again the pollution to environment, has preferable economic benefit and environmental benefit.The most domestic
Not yet there are technology and the company of special SCR catalyst metal recovery, carry out the research tool of useless SCR catalyst metal recovery technology
There are important theory significance and construction value.
The research reclaimed about vanadium metal and tungsten in useless SCR denitration at present is relatively fewer, has than more typical: in
State's patent CN105200236A discloses a kind of method reclaiming W and V from waste flue gas denitration catalyst, and first this invention will urge
Agent is ground to 160～200 mesh, adds the concentrated sulphuric acid that concentration is 85%～92% in catalyst fines, and solid-to-liquid ratio is 1:1.5
～1.8 after acidolysis, added water in the ratio that weight ratio is 1:0.5～0.6 of catalyst with water and filtered, obtaining filtering residue and filtrate is standby
With.Then the filtrate obtained by catalyst acidolysis be heated to 70～100 DEG C and be concentrated into 150～200g/L, by concentrated solution with
The weight ratio of water is that the ratio addition water of 1:0.8～1 is hydrolyzed, and hydrolyzate filters after carrying out settlement treatment, clear to upper strata
Liquid adds the NH of excess4Cl, and to regulate pH be 7.5～8.5, obtains metavanadic acid ammonia precipitation 50～80 DEG C of reactions, will precipitation
It is calcined after filtration, finally obtains product V2O5.Filtering residue obtained by the most backward catalyst acid solution adds excess 10～28% ammonia is anti-
Filter after should, after the filtering residue after filtration is heated to 80～100 DEG C, the order of ammoniumparatungstate crystal obtained, crystal is dried, forges
Burn, obtain product WO3.Chinese patent CN104611564A discloses and a kind of reclaims metal-oxide from the useless SCR catalyst
Method, the method that this invention uses is: first useless SCR catalyst is crushed to more than 80 mesh, uses the water soaking of 3～4 times to urge
After agent powder carries out roguing, add the 20～30%NaOH solution of 3～4 times, be heated to 80 DEG C, soak 1～2h, add 1
～2% potassium chlorate raw material will be oxidized to pentavalent vanadium, gained solution NH containing tetravalence vanadium4Cl regulation aqueous phase pH to 1.7～
1.8, boil 1～2h and carry out heavy vitriol, be refining to obtain pure metavanadic acid by, the filtrate after separating vanadium adds HCl, pH value is adjusted
To 4.5～5.0, add CaCl2Solution, is settled out CaWO4After filter, H is made in filter cake HCl process2WO4And H2MoO4。
Chinese patent CN101921916A discloses a kind of method reclaiming metal-oxide from waste flue gas denitration catalyst, useless flue gas
After carrying out high-temperature roasting pretreatment after denitrating catalyst is broken, it is proportionally added into Na2CO3And mix, pulverize, carry out high-temperature roasting.
Agglomerate puts into leaching in hot water after pulverizing.Gained titanate adds sulphuric acid, through filtration, washing, roasting, available
TiO2.Filtrate after leaching adds sulfur acid for adjusting pH value to 8.0～9.0, adds excess NH4Cl precipitation.NH will be filtrated to get4VO3
Through pyrolytic, prepare V2O5Finished product.Filtrate after precipitation adds hydrochloric acid regulated value to 4.5～5.0, adds CaCl2Heavy molybdenum, tungsten.
Filter gained CaWO4And CaMoO4With HCl treatment the most fired WO3With Mo3。
In the above-mentioned methods, Chinese patent CN105200236A, Chinese patent CN104611564A, Chinese patent
CN101921916A all uses chemical precipitation method to separate and recover metal from useless SCR catalyst leachate, and cost is relatively low, but operation
Process is cumbersome, and in catalyst, metal leaching rate is the most on the low side, and the response rate causing metal is relatively low, cannot realize simultaneously V, W and
The high efficiency separation of the valuable metals such as Ti also acquires highly purified metal product.Therefore, study a set of efficiently, low cost useless
The process for separating and recovering of tungsten, vanadium in SCR denitration, to realizing in useless SCR denitration the separation of vanadium, tungsten and titanium and returning
The commercial Application received has important value.
Summary of the invention
For overcoming the deficiencies in the prior art, it is an object of the invention to provide tungsten in a kind of useless SCR denitration
Separation with vanadium, recovery method, to efficiently extracting the tungsten in catalyst and vanadium, separate, in order to reclaim highly purified
WO3And V2O5Product.
In order to realize above-mentioned technical purpose, the present invention is achieved by the following technical programs.
Tungsten and the separation of vanadium, recovery method in a kind of useless SCR denitration of the present invention, specifically comprise the following steps that
(1) preparation of acid leaching solution
The useless SCR denitration of compressed air purging that a is dried by cleaning, grinds after removing the flying dust of catalyst surface deposition
Grinds powder, with sieving not less than the standard screen of 100 mesh and being baked to；
B presses sodium carbonate (Na2CO3) and the mass ratio of SCR denitration be 0.5～1.6:1, by a certain amount of Na2CO3
After mixing homogeneously with step a catalyst fines, by the mixture of gained roasting 1～5h at a temperature of 700～900 DEG C, obtain
Agglomerate；
The agglomerate of above-mentioned b gained is placed in 2%～10% (v/v) dilution heat of sulfuric acid by c, uses magnetic agitation simultaneously
Mode makes the mixture in solution be suspended state, at a temperature of 35 DEG C～90 DEG C in solid mixture W and V leach 1～
5h, liquid-solid ratio is 5～15:1, finally mixed solution is carried out sucking filtration, obtains the acid leaching solution containing W and V.
(2) extraction of W and V in acid leaching solution
The a pH to 1.00～3.50 of sulphuric acid regulating step (1) gained pickle liquor；
B takes the pickle liquor obtained in a certain amount of above-mentioned a in separatory funnel, and (molecular formula is to be added thereto to tri-n-octyl amine
[CH3(CH2)7]3N, is abbreviated as R3The kerosin of N)+isodecanol, control the volume ratio of extractant and pickle liquor be 0.5:20～
10:20, concussion separatory funnel makes pickle liquor mix homogeneously with extractant, W and V transitions into organic facies, stands 5～30min
Rear releasing lower floor aqueous phase, is extracted organic facies.
The concentration of described tri-n-octyl amine is 2%～15% (v/v), and the concentration of described isodecanol is 2%～12%,；
(3) in extraction organic facies, the back extraction of W with V separates and reclaims
A, using certain density NaOH as strippant, adds a certain amount of in the extraction organic facies of step (2) gained
NaOH solution, separates entrance lower floor aqueous phase from extraction organic facies by W and V；
The concentration of described NaOH is 0.25mol/L～1.25mol/L, the volume ratio of described organic facies and NaOH be 2:1～
1:4；
B H2SO4After the interim pH value regulating above-mentioned a gained aqueous phase is about 8, add the NH of excess4Cl, 80
Make vanadium with ammonium metavanadate form Precipitation under the conditions of DEG C, then by roasting after precipitate filtration, finally give V2O5Product.
C continues to add after sulfur acid for adjusting pH is about 1.5 in the secondary filtrate after above-mentioned b precipitation, add excess
CaCl2Heavy tungsten, the CaWO being filtrated to get4Precipitation after chlorohydric acid pickling roasting WO3Product.
As one optimization, in above-mentioned steps (1): Na2CO3It is 1.2:1 with the mass ratio of SCR denitration, roasting temperature
Degree is 800 DEG C, and roasting time is 3h, and dilute sulfuric acid concentration is 2% (v/v), and liquid-solid ratio is 8:1, and extraction time is 4h.
As one optimization, in above-mentioned steps (2): the pH of pickle liquor is 2.50, extractant with the volume ratio of 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.
As one optimization, in above-mentioned steps (3): the concentration of NaOH is 0.75mol/L, organic facies and the volume ratio of NaOH
For 1:3.
Na in above-mentioned steps (1)2CO3Powder carries out mixing with useless SCR denitration powder and roasting, to remove useless urging
Organic matter, oils and carbon deposit thing in agent, give up the WO in SCR denitration simultaneously3、V2O5Under the high temperature conditions with Na2CO3
Reaction generates the Na of solubility2WO4And NaVO3, the main chemical reactions of generation is as follows:
WO3+Na2CO3→Na2WO4+CO2↑
V2O5+Na2CO3→2NaVO3+CO2↑
In above-mentioned steps (2) extraction process, extractant consists of the kerosin of tri-n-octyl amine+isodecanol, and 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 predominantly anion exchange, when the tungsten in pickle liquor, vanadium are extracted, tri-n-octyl amine first with the H in solution2SO4
Reaction forms the sulfate of amine, reacts as follows:
R3N+H2SO4→R3NH·HSO4
When regulating the pH value of pickle liquor, tungsten and vanadium ion existing forms in the solution is along with the change meeting of pickle liquor pH
There is a series of change.Under the conditions of optimal pickle liquor pH is 2.50, tungsten is mainly with W8O26 4-Ionic species exists, extraction process
The dominant response occurred is:
4R3NH·HSO4+W8O26 4-→(R3NH)4·W8O26+4HSO4 -
For vanadium, < when 2.00, vanadium is mainly with VO for pickle liquor pH2 +Exist in solution, along with 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 exists, and extraction process is sent out
Raw dominant response is:
6R3NH·HSO4+V10O28 6-→(R3NH)6·V10O28+6HSO4 -
In above-mentioned steps (3), when utilizing NaOH that the tungsten in load organic phases and vanadium are carried out back extraction, generation main anti-
Should be:
(R3NH)4·W8O26+16NaOH→4R3N+8Na2WO4+10H2O
(R3NH)6·V10O28+10NaOH→6R3N+10NaVO3+8H2O
Utilizing NH4Cl and CaCl2During precipitation, heavy tungsten, the dominant response of generation is:
WO4 2-+Ca2+→CaWO4↓
VO3 -+NH4 +→NH4VO3↓
The dominant response 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) during the present invention proposes a kind of useless SCR denitration pickle liquor tungsten and vanadium extraction, separate method, by
Catalyst fines adds a certain amount of Na2CO3Mix, then mixture is carried out a roasting, can be by solid SCR
V and W in denitrating catalyst is converted into the Na of solubility2WO4And NaVO3, then use dilution heat of sulfuric acid to the mixing after roasting
Thing leaches, and makes Na2WO4And NaVO3Dissolve and enter liquid phase, it is achieved tungsten and the efficient leaching of vanadium, the leaching rate of W and V respectively can
Reach 99.08% and 98.49%,.
(2) present invention uses tri-n-octyl amine to be main extractant, and isodecanol makees diluent as phase modifier, aerial kerosene,
The selectivity of extractant is higher, is formed without emulsion and third phase in extraction process, and interface is limpid, and split-phase is simple to operate, energy
Realize extracting while tungsten and vanadium, and the extraction yield of tungsten and vanadium is higher, under the conditions of optimal extraction experiments, tungsten and the extraction of vanadium
Rate can be up to 98.26% and 96.65% respectively.
(3) present invention utilizes NaOH to carry out back extraction experiment from the organic facies loading tungsten, vanadium, W with V separates more thorough
The end, W almost by completely from organic facies back extraction out, stripping rate is up to 99.99%, the stripping rate of 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 tungsten and vanadium can be realized, the response rate of metal is higher, simultaneously extractant reusable edible, right
Environmental pollution is less.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not limited to following embodiment.
1, the leaching of W and V in dead catalyst:
Embodiment 1
A takes the operation time useless SCR denitration more than 24000h and (is mainly composed of V2O5-WO3/TiO2, specifically
Component is as shown in table 1), the compressed air purging inactivation SCR denitration catalyst being dried by cleaning, to remove catalyst surface deposition
Flying dust, wherein, compressed-air actuated operating air pressure is 0.5MPa, and gas flow is 0.5m3/ s, purge time is 10min.Grinding
By catalyst grind into powder in alms bowl, then sieve with not less than the standard screen of 100 mesh, then by catalyst fines 105 DEG C of temperature
2h is dried under the conditions of degree.
B weighs in step a dries, cool down after catalyst fines 5g, be added thereto to Na2CO3Solid, Na2CO3With urge
The mass ratio of agent is 0.5, is placed in Muffle furnace after being sufficiently mixed again, and under 800 DEG C of temperature conditionss, roasting 3h, is sintered
Block.
C concentration is that V and W in step b agglomerate is leached by the dilution heat of sulfuric acid of 2% (v/v), leaching process
The mode of middle employing magnetic agitation guarantees that pressed powder is suspended state, and controlling liquid-solid mass ratio is 8:1, and extraction temperature is 80
DEG C, extraction time is 4h.Then mixed solution being carried out sucking filtration, the aperture using filter membrane during sucking filtration is 0.45 μm, obtains
Leachate containing V and W is also settled to 200mL, and the leaching rate being calculated V, W is respectively 61.86% and 85.39%.
Embodiment 2
A takes the operation time useless SCR denitration more than 24000h and (is mainly composed of V2O5-WO3/TiO2, specifically
Component is as shown in table 1), the compressed air purging inactivation SCR denitration catalyst being dried by cleaning, to remove catalyst surface deposition
Flying dust, wherein, compressed-air actuated operating air pressure is 0.5MPa, and gas flow is 0.5m3/ s, purge time is 10min.Grinding
By catalyst grind into powder in alms bowl, then sieve with not less than the standard screen of 100 mesh, then by catalyst fines 105 DEG C of temperature
2h is dried under the conditions of degree.
B weighs in step a dries, cool down after catalyst fines 5g, be added thereto to Na2CO3Solid, Na2CO3With urge
The mass ratio of agent is 1.2, is placed in Muffle furnace after being sufficiently mixed again, and under 800 DEG C of temperature conditionss, roasting 5h, is sintered
Block.
C concentration is that V and W in step b agglomerate is leached by the dilution heat of sulfuric acid of 10% (v/v), leaches
The mode using magnetic agitation in journey guarantees that pressed powder is suspended state, and controlling liquid-solid mass ratio is 5:1, and extraction temperature is 90
DEG C, extraction time is 5h.Then mixed solution being carried out sucking filtration, the aperture using filter membrane during sucking filtration is 0.45 μm, obtains
Leachate containing V and W is also settled to 200mL, and the leaching rate being calculated V, W is respectively 82.16% and 87.38%.
Embodiment 3
A takes the operation time useless SCR denitration more than 24000h and (is mainly composed of V2O5-WO3/TiO2, specifically
Component is as shown in table 1), the compressed air purging inactivation SCR denitration catalyst being dried by cleaning, to remove catalyst surface deposition
Flying dust, wherein, compressed-air actuated operating air pressure is 0.5MPa, and gas flow is 0.5m3/ s, purge time is 10min.Grinding
By catalyst grind into powder in alms bowl, then sieve with not less than the standard screen of 100 mesh, then by catalyst fines 105 DEG C of temperature
2h is dried under the conditions of degree.
B weighs in step a dries, cool down after catalyst fines 5g, be added thereto to Na2CO3Solid, Na2CO3With urge
The mass ratio of agent is 1.2, is placed in Muffle furnace after being sufficiently mixed again, and under 800 DEG C of temperature conditionss, roasting 3h, is sintered
Block.
C concentration is that V and W in step b agglomerate is leached by the dilution heat of sulfuric acid of 2% (v/v), leaching process
The mode of middle employing magnetic agitation guarantees that pressed powder is suspended state, and controlling liquid-solid mass ratio is 8:1, and extraction temperature is 80
DEG C, extraction time is 4h.Then mixed solution being carried out sucking filtration, the aperture using filter membrane during sucking filtration is 0.45 μm, obtains
Leachate containing V and W is also settled to 200mL, and the leaching rate being calculated V, W is respectively 98.49% and 99.08%.
2, the extraction of W and V in acid leaching solution
Embodiment 1
(1) preparation of catalyst acid immersion
The preparation method of catalyst acid immersion is with the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) extraction of W and V in acid leaching solution
The a pH to 3.50 of sulphuric acid regulating step (1) gained pickle liquor；
B takes the pickle liquor obtained in the above-mentioned a of 20ml in separatory funnel, is added thereto to the coal of tri-n-octyl amine+isodecanol
Oil solution, the volume ratio controlling extractant and pickle liquor is 2:20, and tri-n-octyl amine concentration is 10% (v/v), and isodecanol concentration is
6% (v/v), concussion separatory funnel makes pickle liquor mix homogeneously with extractant, W and V transitions into organic facies, stands 15min
Rear releasing lower floor aqueous phase, is extracted organic facies, and the extraction yield being calculated W and V is respectively 67.02%, 86.17%.
Embodiment 2
(1) preparation of catalyst acid immersion
The preparation method of catalyst acid immersion is with the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) extraction of W and V in acid leaching solution
The a pH to 2.50 of sulphuric acid regulating step (1) gained pickle liquor；
B takes the pickle liquor obtained in the above-mentioned a of 20ml in separatory funnel, is added thereto to the coal of tri-n-octyl amine+isodecanol
Oil solution, the volume ratio controlling extractant and pickle liquor is 2:20, and tri-n-octyl amine concentration is 12% (v/v), and isodecanol concentration is
10% (v/v), concussion separatory funnel makes pickle liquor mix homogeneously with extractant, W and V transitions into organic facies, stands 15min
Rear releasing lower floor aqueous phase, is extracted organic facies, and the extraction yield being calculated W and V is respectively 98.26%, 96.65%.
Embodiment 3
(1) preparation of catalyst acid immersion
The preparation method of catalyst acid immersion is with the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) extraction of W and V in acid leaching solution
The a pH to 2.50 of sulphuric acid regulating step (1) gained pickle liquor；
B takes the pickle liquor obtained in the above-mentioned a of 20ml in separatory funnel, is added thereto to the coal of tri-n-octyl amine+isodecanol
Oil solution, the volume ratio controlling extractant and pickle liquor is 0.5:20, and tri-n-octyl amine concentration is 10% (v/v), isodecanol concentration
Being 6% (v/v), concussion separatory funnel makes pickle liquor mix homogeneously with extractant, W and V transitions into organic facies, stands
Releasing lower floor's aqueous phase after 10min, be extracted organic facies, the extraction yield being calculated W and V is respectively 96.43%, 84.43%.
3, in extraction organic facies, the back extraction of W with V separates and reclaims
Embodiment 1
(1) preparation of catalyst acid immersion
The preparation method of catalyst acid immersion is with the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) extraction of W and V in acid leaching solution
The preparation method of extraction organic facies is with embodiment 2 in " 2, the extraction of W and V in acid leaching solution ".
(3) in extraction organic facies, the back extraction of W with V separates and reclaims
The a NaOH solution using concentration as 1mol/L, as strippant, adds in the extraction organic facies of step (2) gained
NaOH solution, wherein extraction organic facies is 2:1 with the volume ratio of NaOH, is separated under entrance by W and V from extraction organic facies
Layer aqueous phase, the stripping rate being calculated W and V is respectively 89.79%, 37.38%；
B H2SO4After the interim pH value regulating above-mentioned a gained aqueous phase is about 8, add the NH of excess4Cl, 80
Make under the conditions of DEG C vanadium with ammonium metavanadate form Precipitation, at 500 DEG C of condition roasting 1h after then precipitate being filtered, final
To V2O5Product.
C continues to add after sulfur acid for adjusting pH is about 1.5 in the secondary filtrate after above-mentioned b precipitation, add excess amount of Ca Cl2
Heavy tungsten, the CaWO being filtrated to get4Precipitation after chlorohydric acid pickling under the conditions of 500 DEG C roasting 1h WO3Product.
Embodiment 2
(1) preparation of catalyst acid immersion
The preparation method of catalyst acid immersion is with the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) extraction of W and V in acid leaching solution
The preparation method of extraction organic facies is with embodiment 2 in " 2, the extraction of W and V in acid leaching solution ".
(3) in extraction organic facies, the back extraction of W with V separates and reclaims
The a NaOH solution using concentration as 1mol/L, as strippant, adds in the extraction organic facies of step (2) gained
NaOH solution, wherein extraction organic facies is 1:2 with the volume ratio of NaOH, is separated under entrance by W and V from extraction organic facies
Layer aqueous phase, the stripping rate being calculated W and V is respectively 99.99%, 75.53%；
B H2SO4After the interim pH value regulating above-mentioned a gained aqueous phase is about 8, add the NH of excess4Cl, 80
Make under the conditions of DEG C vanadium with ammonium metavanadate form Precipitation, at 500 DEG C of condition roasting 1h after then precipitate being filtered, final
To V2O5Product.
C continues to add after sulfur acid for adjusting pH is about 1.5 in the secondary filtrate after above-mentioned b precipitation, add excess amount of Ca Cl2
Heavy tungsten, the CaWO being filtrated to get4Precipitation after chlorohydric acid pickling under the conditions of 500 DEG C roasting 1h WO3Product.
Embodiment 3
(1) preparation of catalyst acid immersion
The preparation method of catalyst acid immersion is with the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) extraction of W and V in acid leaching solution
The preparation method of extraction organic facies is with embodiment 2 in " 2, the extraction of W and V in acid leaching solution ".
(3) in extraction organic facies, the back extraction of W with V separates and reclaims
The a NaOH solution using concentration as 0.75mol/L is as strippant, in the extraction organic facies of step (2) gained
Adding NaOH solution, wherein the volume ratio of extraction organic facies and NaOH is 1:3, W and V is separated from extraction organic facies into
Entering lower floor's aqueous phase, the stripping rate being calculated W and V is respectively 99.99%, 88.05%；
B H2SO4After the interim pH value regulating above-mentioned a gained aqueous phase is about 8, add the NH of excess4Cl, 80
Make under the conditions of DEG C vanadium with ammonium metavanadate form Precipitation, at 500 DEG C of condition roasting 1h after then precipitate being filtered, final
To V2O5Product.
C continues to add after sulfur acid for adjusting pH is about 1.5 in the secondary filtrate after above-mentioned b precipitation, add excess amount of Ca Cl2
Heavy tungsten, the CaWO being filtrated to get4Precipitation after chlorohydric acid pickling under the conditions of 500 DEG C roasting 1h WO3Product.
Embodiment 4
(1) preparation of catalyst acid immersion
The preparation method of catalyst acid immersion is with the embodiment 3 in " 1, the preparation of dead catalyst pickle liquor ".
(2) extraction of W and V in acid leaching solution
The preparation method of extraction organic facies is with embodiment 2 in " 2, the extraction of W and V in acid leaching solution ".
(3) in extraction organic facies, the back extraction of W with V separates and reclaims
The a NaOH solution using concentration as 1.5mol/L, as strippant, adds in the extraction organic facies of step (2) gained
Entering NaOH solution, wherein extraction organic facies is 1:3 with the volume ratio of NaOH, and from extraction organic facies, W and V is separated entrance
Lower floor's aqueous phase, the stripping rate being calculated W and V is respectively 99.99%, 83.14%；
B H2SO4After the interim pH value regulating above-mentioned a gained aqueous phase is about 8, add the NH of excess4Cl, 80
Make under the conditions of DEG C vanadium with ammonium metavanadate form Precipitation, at 500 DEG C of condition roasting 1h after then precipitate being filtered, final
To V2O5Product.
C continues to add after sulfur acid for adjusting pH is about 1.5 in the secondary filtrate after above-mentioned b precipitation, add excess amount of Ca Cl2
Heavy tungsten, the CaWO being filtrated to get4Precipitation after chlorohydric acid pickling under the conditions of 500 DEG C roasting 1h WO3Product.
Table 1, the key component of useless SCR denitration and ratio
Claims (4)
1. tungsten and the separation of vanadium, recovery method in a useless SCR denitration, it is characterised in that the method comprise with
Lower step:
(1) preparation of acid leaching solution
A, the useless SCR denitration of compressed air purging being dried by cleaning, grind after removing the flying dust of catalyst surface deposition
Powdered, with sieving not less than the standard screen of 100 mesh and being baked to；
B, sodium carbonate is mixed homogeneously with the catalyst fines in mass ratio 0.5～1.6:1 of step a gained after, mixed by gained
Compound is roasting 1～5h at a temperature of 700～900 DEG C, obtains agglomerate；
C, being placed in the dilution heat of sulfuric acid of volume ratio 2%～10% by the agglomerate of above-mentioned b gained, liquid-solid ratio is 5～15:1, with
The mode of Shi Caiyong magnetic agitation makes the mixture in solution be suspended state, at 35 DEG C～90 DEG C to mixture leach 1～
5h, finally mixed solution is carried out sucking filtration, obtain the acid leaching solution containing W and V；
(2) extraction of W and V in acid leaching solution
A, the pH to 1.00～3.50 of use sulphuric acid regulating step (1) gained acid leaching solution；
B, taking the acid leaching solution obtained in above-mentioned a in separatory funnel, the kerosene being added thereto to tri-n-octyl amine+isodecanol is molten
Liquid is as extractant, and the volume ratio controlling extractant and acid leaching solution is 0.5～10:20, and concussion separatory funnel makes acid leaching
Go out liquid to mix homogeneously with extractant, W and V is transitioned into organic facies, release lower floor's aqueous phase after standing 5～30min, be extracted
Organic facies；
The volumetric concentration of described tri-n-octyl amine is 2%～15%, and the volumetric concentration of described isodecanol is 2%～12%；(3) extraction
The back extraction of W and V and separation, recovery in organic facies
A, using NaOH as strippant, in the extraction organic facies of step (2) gained add NaOH solution, by W and V from extraction
Organic facies is separated entrance lower floor aqueous phase；
The concentration of described NaOH is 0.25～1.25mol/L, and described extraction organic facies is 0.25～2:1 with the volume ratio of NaOH；
B, use H2SO4Regulate after the pH value of above-mentioned a gained aqueous phase is 8, add the NH of excess4Cl, makes vanadium with partially under the conditions of 80 DEG C
Ammonium vanadate form Precipitation, roasting after then precipitate being filtered, obtain V2O5Product；
C, secondary filtrate after above-mentioned b precipitation continue to add H2SO4After regulation pH is 1.5, add excess amount of Ca Cl2Heavy tungsten, mistake
The CaWO that filter obtains4Precipitation roasting after chlorohydric acid pickling i.e. obtains WO3Product.
2. tungsten and the separation of vanadium, recovery method in useless SCR denitration as claimed in claim 1, it is characterised in that
In described step (1): sodium carbonate is 1.2:1 with the mass ratio of useless SCR denitration, and sintering temperature is 800 DEG C, roasting time
For 3h, dilute sulfuric acid concentration is 2%, and liquid-solid ratio is 8:1, and extraction time is 4h.
3. tungsten and the separation of vanadium, recovery method in useless SCR denitration as claimed in claim 1, it is characterised in that
In described step (2): with the pH to 2.50 of sulphuric acid regulation acid leaching solution, extractant is 1 with the volume ratio of acid leaching solution:
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. tungsten and the separation of vanadium, recovery method in useless SCR denitration as claimed in claim 1, it is characterised in that
In described step (3): the concentration of NaOH is 0.75mol/L, extraction organic facies is 1:3 with the volume ratio of NaOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610520660.1A CN106048230B (en) | 2016-07-01 | 2016-07-01 | The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610520660.1A CN106048230B (en) | 2016-07-01 | 2016-07-01 | The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106048230A true CN106048230A (en) | 2016-10-26 |
| CN106048230B CN106048230B (en) | 2017-12-19 |
Family
ID=57201888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610520660.1A Active CN106048230B (en) | 2016-07-01 | 2016-07-01 | The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106048230B (en) |
Cited By (9)
| 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 |
| CN107557599A (en) * | 2017-07-20 | 2018-01-09 | 北京世纪地和控股有限公司 | Tungsten, the method for vanadium are reclaimed in 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 |
| CN112547136A (en) * | 2021-03-01 | 2021-03-26 | 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 |
| 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 |
| CN113046560A (en) * | 2021-03-08 | 2021-06-29 | 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 |
| CN113046562A (en) * | 2021-03-08 | 2021-06-29 | 北京华电光大环境股份有限公司 | Method for recovering tungsten element in waste catalyst |
| CN115255378A (en) * | 2022-06-27 | 2022-11-01 | 北京科技大学 | Preparation method of porous tungsten material with multistage pore structure |
| CN115784310A (en) * | 2023-02-06 | 2023-03-14 | 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789550A (en) * | 2014-01-26 | 2014-05-14 | 郝喜才 | Method for recovering vanadium, potassium and silicon from waste vanadium catalyst |
| CN104611564A (en) * | 2013-11-01 | 2015-05-13 | 沈阳远大环境工程有限公司 | Method for recycling metal oxides from waste SCR (selective catalytic reduction) catalyst |
| CN104760998A (en) * | 2015-04-27 | 2015-07-08 | 苏州华电北辰环保技术有限公司 | Tungsten recycling method of tungsten-containing solution based on wasted SCR 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 |
| EP2940162A1 (en) * | 2014-04-30 | 2015-11-04 | Tropinon Enterprises Ltd. | Reuse of titanium-based catalysts |
| CN105274341A (en) * | 2015-11-10 | 2016-01-27 | 安徽工业大学 | Method for leaching metallic vanadium and metallic tungsten in waste selective catalytic reduction (SCR) denitration catalyst |
-
2016
- 2016-07-01 CN CN201610520660.1A patent/CN106048230B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611564A (en) * | 2013-11-01 | 2015-05-13 | 沈阳远大环境工程有限公司 | Method for recycling metal oxides from waste SCR (selective catalytic reduction) catalyst |
| CN103789550A (en) * | 2014-01-26 | 2014-05-14 | 郝喜才 | Method for recovering vanadium, potassium and silicon from waste vanadium catalyst |
| EP2940162A1 (en) * | 2014-04-30 | 2015-11-04 | Tropinon Enterprises Ltd. | Reuse of titanium-based catalysts |
| CN104760998A (en) * | 2015-04-27 | 2015-07-08 | 苏州华电北辰环保技术有限公司 | Tungsten recycling method of tungsten-containing solution based on wasted SCR 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 |
| CN105274341A (en) * | 2015-11-10 | 2016-01-27 | 安徽工业大学 | Method for leaching metallic vanadium and metallic tungsten in waste selective catalytic reduction (SCR) denitration catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 郝喜才等: "从废钒催化剂酸浸液中萃取钒", 《湿法冶金》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107557599A (en) * | 2017-07-20 | 2018-01-09 | 北京世纪地和控股有限公司 | Tungsten, the method for vanadium are reclaimed in discarded SCR denitration |
| 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 |
| 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 |
| CN112547136A (en) * | 2021-03-01 | 2021-03-26 | 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 |
| 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 |
| CN113046560A (en) * | 2021-03-08 | 2021-06-29 | 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 |
| CN113046562A (en) * | 2021-03-08 | 2021-06-29 | 北京华电光大环境股份有限公司 | Method for recovering tungsten element in waste catalyst |
| CN115255378A (en) * | 2022-06-27 | 2022-11-01 | 北京科技大学 | Preparation method of porous tungsten material with multistage pore structure |
| CN115784310A (en) * | 2023-02-06 | 2023-03-14 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106048230B (en) | 2017-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106048230B (en) | The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration | |
| CN109750156B (en) | Method for recovering vanadium, tungsten/molybdenum and titanium elements from waste SCR denitration catalyst | |
| CN104263946B (en) | A kind of method reclaiming tungsten, vanadium, titanium from SCR denitration dead catalyst | |
| CN103436704B (en) | A kind of method reclaiming vanadium and tungsten from the vanadium titanium base waste denitration catalyst of tungstenic | |
| CN102936039B (en) | Recovery process of honeycomb type selective catalytic reduction (SCR) waste catalyst containing tungsten, vanadium and titanium | |
| CN104831075B (en) | A kind of vanadium of useless vanadium molybdenum system SCR catalyst, molybdenum are separated and method of purification | |
| CN104118911B (en) | A kind of method reclaiming tungstic oxide in discarded SCR catalyst completely | |
| WO2021017940A1 (en) | Method for hazard-free treatment of sludge from spent solution of mixed acids after acid washing of stainless steel | |
| CN104862485B (en) | A kind of vanadium of useless vanadium tungsten system SCR catalyst, tungsten separation and method of purification | |
| CN104178636B (en) | A kind of activation burning reclaims Ti in SCR spent catalyst, V, Mo, the method for Si in conjunction with acidic leaching | |
| CN106521160B (en) | A kind of vanadium extraction from discarded SCR catalyst and the method for preparing activation titanium silicon tungsten powder | |
| CN107699695A (en) | It is a kind of that tungsten, the method for vanadium are reclaimed from useless SCR denitration | |
| CN103526031A (en) | Recovery method for SCR waste flue gas denitration catalyst | |
| CN105969991A (en) | Method for extracting titanium, vanadium and tungsten metallic oxide from failed SCR catalyst | |
| CN107185554A (en) | A kind of method that useless SCR denitration cleaning is recycled | |
| CN105274341A (en) | Method for leaching metallic vanadium and metallic tungsten in waste selective catalytic reduction (SCR) denitration catalyst | |
| CN105838885B (en) | A kind of comprehensive reutilization method of useless SCR catalyst | |
| CN106011503A (en) | Method for recycling tungsten, vanadium and titanium from SCR waste catalysts | |
| WO2023246080A1 (en) | Method for recycling industrial waste salt and waste denitration catalyst | |
| CN105648241A (en) | Method for comprehensively recovering valuable metal including tungsten, vanadium and titanium in waste vanadium, tungsten and titanium denitration catalyst | |
| CN104611564A (en) | Method for recycling metal oxides from waste SCR (selective catalytic reduction) catalyst | |
| CN104071832A (en) | Method for extracting metal oxide from waste SCR (selective catalytic reduction) denitrification catalyst | |
| CN110218859A (en) | The method of the useless denitrating catalyst valuable element of middle temperature tunnel type solid-state activation extraction | |
| CN110724836B (en) | Method for extracting vanadium from waste SCR denitration catalyst by taking iron salt as roasting additive | |
| CN106011478A (en) | Method for separating and extracting Ti from waste SCR denitration catalyst in metatitanic acid form |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |