CN109750156A - A method of recycling vanadium, tungsten/molybdenum and titanium elements from discarded SCR denitration - Google Patents
A method of recycling vanadium, tungsten/molybdenum and titanium elements from discarded SCR denitration Download PDFInfo
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Abstract
The invention belongs to nonferrous metals recycling fields, and in particular to a method of vanadium, tungsten/molybdenum and titanium elements are recycled from discarded SCR denitration.Vanadium, tungsten/molybdenum and titanium elements recovery method of the present invention include waste catalyst pretreatment, element sepatation, element purification and element recycling step, pass through specific recovery process, realize the high efficiente callback of vanadium in discarded SCR denitration, tungsten/molybdenum and several high added value elements of titanium (tungsten and molybdenum chemical property are very close, this technique has same effect tungsten and molybdenum element).Recovery process has that the rate of recovery is high, product purity is excellent, the simple and easy advantages such as low with input cost, in denitrating flue gas industry waste catalyst element recycling field market value with higher.
Description
Technical field
The invention belongs to nonferrous metals recycling fields, and in particular to one kind from discarded SCR denitration recycle vanadium,
The method of tungsten/molybdenum and titanium elements.
Background technique
With the continuous improvement of environmental consciousness, in addition to coal-burning power plant, the industries smoke pollution such as steel, cement, waste incineration
The limitation for NOx emission concentration has been introduced sequentially into object discharge standard.Currently, as domestic main flume denitration technology, SCR
Denitration technology is widely used in the NOx emission control of different industries flue gas.SCR denitration is the pass of SCR denitration technology
Key, severe working environment cause its service life usually to only have 2-3, and activity declines and can not pass through what regeneration techniques restored
Catalyst will eventually become discarded SCR denitration.Discarded SCR denitration is a kind of special solid waste, tool
There are following characteristics:
(1) hypertoxicity.Discarded SCR denitration not only itself contains B grades of inorganic extremely toxic substance V2O5And heavy metal oxidation
Object WO3Or MoO3, the hypertoxicities element such as As, Hg, Pb in flue gas can be also absorbed in use, these toxic elements enter ring
Border will bring huge harm.
(2) yield is big.According to dependency number it is estimated that 2021 are only discarded SCR denitration that thermal power plant generates every year just
It is up to 110,000 m3More than.With the continuous expansion of SCR denitration technical application range, the production of the discarded SCR denitration in the country
Amount will constantly increase, and the reasonable disposition of a large amount of discarded SCR denitrations will be the following stern challenge.
(3) high added value ingredient is more.It is sufficiently expensive to produce the raw materials used price of SCR denitration.Ammonium metatungstate valence
Lattice are always at 200,000 yuan/ton or so, and the price of ammonium heptamolybdate is also at 100,000 yuan/ton or more, and ammonium metavanadate is due to source of goods deficiency,
500,000 yuan/ton have been even up to when price highest.In addition, titanium dioxide price used in production SCR denitration also reaches
1.5 ten thousand yuan/ton or more.
(4) it is more difficult to recycle, and High efficiency recovery lacks.SCR denitration, which is removed, contains V2O5、WO3/MoO3And TiO2Outside,
SiO can be then introduced using shaping assistant in process of production2、Al2O3With the ingredients such as CaO, and flue gas can be also absorbed in use process
The multiple elements such as middle sulphur, alkali metal, phosphorus, arsenic, mercury, lead, complicated ingredient undoubtedly produce the vanadium, tungsten/molybdenum and titanium of recycling high-purity
Product increase certain difficulty；In addition, WO in discarded SCR denitration3Or MoO3Content is often less than 5wt%, and V2O5Contain
Amount is even in 1wt% hereinafter, this is a greatly challenge for element recovery rate.Currently, domestic not yet for discarded vanadium
Titanium system SCR denitration vanadium, the mature technology of tungsten/molybdenum and titanium elements recycling and relevant unit.
For the above feature, the High efficiency recovery scheme of vanadium, tungsten/molybdenum and several high added value elements of titanium is developed, in ring
Border protection and resource-effective etc. all have highly important meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of from discarded SCR denitration recycles the side of vanadium, tungsten/molybdenum and titanium elements
Method.The present invention is directed to the existence form and chemical characteristic of each component in discarded SCR denitration, passes through specific recovery process
Realize efficiently separating, purify and recycling for vanadium, tungsten/molybdenum and titanium elements.
The method provided according to the present invention, method includes the following steps:
(1) pretreatment of SCR denitration is discarded
1. being directed to flat discarded SCR denitration: catalyst surface dust stratification is blown away, by the modes such as shaking or tapping
Separate catalyst with metal otter board；Collect and roast the catalyst to fall off, then catalyst is sufficiently crushed to 200 mesh with
Under.
2. for cellular discarded SCR denitration: blowing away the partial loose dust stratification blocked in catalyst duct, then
Catalyst is subjected to calcination process；Soot blowing again, residue becomes loose dust stratification after removing roasting；Finally, catalyst is abundant
It is crushed to 200 mesh or less.
(2) titanium elements and vanadium, the separation of tungsten/molybdenum element
By the Na of waste catalyst powder and certain mass obtained by above-mentioned steps (1)2CO3Or NaOH be uniformly mixed, then plus
Enter suitable water to continue to stir, further strengthens the uniformity and contact of hybrid solid；After drying, roasting hybrid solid is burnt
Agglomeration；Agglomerate is crushed to 200 mesh hereinafter, being leached repeatedly under the conditions of heating and stirring with NaOH solution, obtains NaVO3、
Na2WO4/Na2MoO4、Na2SiO3、NaAlO2Ti-enriched slag precipitating and first comprising vanadium, tungsten/molybdenum etc. is obtained by filtration in equal soluble sodium salts
The solution of element.
(3) recycling of titanium elements
Ti-enriched slag is crushed to 200 mesh hereinafter, being 80-95% concentrated sulfuric acid solution in 140-180 DEG C of heating with concentration and stirring
Ti-enriched slag is dissolved under the conditions of mixing, and obtains titaniferous slurries；Stop stirring, keeps heat aging 2-5h；It is dropped after curing to temperature
When to 100 DEG C or less, 5% dilution heat of sulfuric acid is added, clarification diluted Ti solution is then obtained by filtration；The deionization for being 3-6 times by quality
Water and titanium liquid are preheated to 90-98 DEG C, titanium liquid are slowly uniformly added into deionized water in 15-30min, titanium liquid is just added
When there is white precipitate, then gradually become colourless transparent solution；Boil solution to there are a large amount of white precipitates, stop heating and
Stirring reopens stirring after standing 30min and 2-4h is boiled in heating, this process requires supplementation with moisture to keep liquor capacity phase
To stabilization；Finally TiO is obtained through filtering, washing, drying and roasting recycling2。
(4) vanadium, the separation of tungsten/molybdenum element and purification
Above-mentioned steps (2) acquired solution pH value is adjusted to 8-11 with 5% dilution heat of sulfuric acid, and heated solution is stirred to 60-90 DEG C
0.5-3h is mixed, the impurity elements such as the silicon, aluminium, calcium of hydrolytic precipitation is filtered to remove, obtains clear solution；With in extractant extraction solution
Tungsten/molybdenum element obtains tungstenic/molybdenum organic phase；It is then stripped tungsten/molybdenum element in organic phase, obtains tungstenic/molybdenum solution.
Surplus solution pH value extracts vanadium with extractant, obtains organic containing vanadium to 0.5-2.0 after adjusting extraction tungsten/molybdenum
Phase；It is then stripped vanadium in organic phase, is obtained containing vanadium solution.
(5) tungsten/molybdenum element recycling
It is evaporated tungstenic/molybdenum solution obtained by above-mentioned steps (4), 750 DEG C of roastings remove step (4) and adjust the impurity that pH value introduces
Element sulphur；Under the conditions of being stirred at room temperature, roasting obtained solid is dissolved with ammonia spirit, then heating is boiled until surplus solution is rigid
Just covering container bottom；It is fully cooled, the wolframic acid ammonium salt/dimolybdate salt being precipitated in solution is obtained by filtration, through ethyl alcohol cleaning, drying
With WO is obtained after roasting3/MoO3Solid.
(6) recycling of vanadium
It is evaporated containing vanadium solution obtained by above-mentioned steps (4), at room temperature, is slowly added into dilute hydrochloric acid solution until solid is completely molten
Solution, obtains clear solution；Oxidizing agent solution is added dropwise into solution, solution is made to become stable rufous；It is dilute with same concentrations
Hydrochloric acid solution adjusts pH value to 1.0-3.0, boils solution, continues to boil 1h after there is red precipitate；Through filtering, water after cooling
It washes, dry and roasting obtains V2O5Solid.
Preferably, in the step (1), discarded SCR denitration is that the superseded vanadium titanium system of industrial smoke denitration urges
Agent, carrier TiO2, active constituent V2O5, catalyst promoter WO3Or MoO3。
Preferably, in the step (1), maturing temperature is 450-650 DEG C, calcining time 2-12h.
Preferably, in the step (2), Na used2CO3Or the amount of NaOH is carried out by sodium element and titanium elements molar ratio
It is quantitative, molar ratio Na:Ti=(1.5-3): 1.
Preferably, in the step (2), maturing temperature is 650-800 DEG C, calcining time 3-10h.
Preferably, in the step (2), NaOH solution concentration is 1-3mol/L, and leaching temperature is 60-90 DEG C, leaching
Number is 2-4 times, and every not good liquor stereoplasm amount ratio is (4-10): 1, leaching time 2-6h.
Preferably, in the step (3), TiO in titaniferous slurries2Concentration is 200-300g/L, clarifies TiO in diluted Ti solution2
Concentration is 100-150g/L.
Preferably, in the step (3), drying temperature is 60-90 DEG C, drying time 2-12h；Maturing temperature is
450-750 DEG C, calcining time 3-6h.
Preferably, in the step (4), for extract tungsten/molybdenum element extractant by effective component, phase modifier and
Diluent composition.Wherein effective component is secondary carbon primary amine (N1923) or three octyl tertiary amines (N235), and volume accounts for 5-20%；Phase
Regulator is tributyl phosphate or isooctanol, and volume accounts for 5%-20%；Diluent is sulfonated kerosene, and volume accounts for 60%-90%；Extraction
Taking series is 2-5 grades, and every grade of organic phase and tungstenic/molybdenum solution volume ratio are 1:(3-5).
Preferably, in the step (4), be stripped tungsten/molybdenum element used in stripping agent be ammonium hydroxide, ethanol amine, ammonium chloride or
Ammonium bicarbonate solution, concentration 1-5mol/L；Being stripped series is 2-5 grades, and every grade of organic phase and stripping agent liquor capacity ratio are 1:
(3-5)。
Preferably, in the step (4), the extractant effective component for extracting vanadium is three octyl tertiary amines
(N235) or di-(2-ethylhexyl)phosphoric acid ester (P204), volume accounts for 5-20%；Phase modifier is that sec-octyl alcohol or certain herbaceous plants with big flowers alcohol, volume account for
5-20%；Diluent is sulfonated kerosene, and volume accounts for 60-90%；Extracting series is 2-5 grades, every grade of organic phase and body containing vanadium solution
Product is than being 1:(3-5).
Preferably, in the step (4), being stripped stripping agent used in vanadium is dust technology or hydrogen peroxide solution, concentration
For 0.5-2.0mol/L；Being stripped series is 2-5 grades, and every grade of organic phase and stripping agent liquor capacity ratio are 1:(3-5).
Preferably, in the step (5), ammonia spirit concentration used is 10-30%, and it is (4-8) that liquid, which consolidates mass ratio: 1.
Preferably, in the step (5), drying temperature is 60-90 DEG C, drying time 2-12h；Maturing temperature is
450-600 DEG C, calcining time 3-6h.
Preferably, in the step (6), dilute hydrochloric acid solution volumetric concentration used is 2-8%.
Preferably, in the step (6), oxidant used is hydrogen peroxide or dilute nitric acid solution, concentration 0.5-
2.5mol/L。
Preferably, in the step (6), drying temperature is 60-90 DEG C, drying time 2-12h；Maturing temperature is
450-600 DEG C, calcining time 3-6h.
Beneficial effects of the present invention:
The present invention passes through spy using vanadium, tungsten/molybdenum and several high added value elements of titanium in discarded SCR denitration as target
Fixed recovery process realizes the efficient full recycling to object element, and simple for process, secondary pollution is small, vanadium, tungsten/molybdenum and titanium
Element recovery rate is more than 90%, recycling gained V2O5And WO3/MoO3Purity is up to 99.5 or more, TiO2Purity is up to 98.5% or more.
Mainly realized by the following aspects:
(1) many chemical reaction processes involved in recovery method proposed by the present invention, the efficiency of each process are directly closed
It is the rate of recovery to object element.Existence form and chemistry of the present invention according to object element in discarded SCR denitration
Characteristic optimizes experiment condition, promotes each step reaction efficiency, reduce loss of the object element in transfer process as far as possible.Such as
In baking mixed waste catalyst powder and Na2CO3Or when NaOH, by adding water and stirring, optimize hybrid solid the uniformity and
Contact, makes vanadium, tungsten/molybdenum element efficiently switch to soluble sodium salt；And NaOH solution is used in leaching step, can not only dissolve can
Vanadium, the tungsten/molybdenum sodium salt of dissolubility, for not generating the remaining V of sodium salt2O5And WO3/MoO3Also there is certain solute effect, to mention
Vanadium, tungsten/molybdenum element extraction rate are risen；Meanwhile when purifying vanadium, tungsten/molybdenum element, optimal extraction has been determined by exploring
Agent, stripping agent and experiment condition realize the efficient transfer of vanadium, tungsten/molybdenum element between solution, organic phase, stripping agent, damage
Mistake rate is lower than 1%；In addition, using Hydrolyze method in titanium, vanadium recycling step, used in tungsten/molybdenum element recycling step
Crystallisation is boiled, equally there are the advantages such as high-efficient, loss is small, extremely meet the chemical characteristic of object element.
(2) discard SCR denitration in addition to object element vanadium, tungsten/molybdenum and titanium, there is also silicon, aluminium, calcium, barium, magnesium,
The Determination of Multi-Impurities such as sulphur, chlorine, mercury, lead, arsenic, and recovery stage can introduce more impurity elements again, efficiently remove impurity member
Element is the guarantee for recycling product purity.Very efficient removal step is contained in recovery method of the present invention.Purification vanadium, tungsten/
Molybdenum element step, extractant and stripping agent proposed by the present invention have high selectivity for object element, are diverting the aim
The impurity element carried in elementary process is few, to realize the efficient removal of impurity element.By extracting and being stripped, gained
Vanadium, tungsten/molybdenum solution dopant species are few and content is extremely low, are very beneficial to the recycling of succeeding target element；Meanwhile it is proposed by the present invention
Element recovery method is also more suitable for, such as in Hydrolyze method recovery Pd, vanadium, since remaining other impurities element is in the party
It will not be hydrolyzed under method experiment condition, to recycle products obtained therefrom very high purity.And boiling crystallisation recycling tungsten/molybdenum element
Before, the purpose of high-temperature roasting is removing element sulphur, this is because a large amount of element sulphurs are introduced during front, and element sulphur is not
It is easily completely removed by extraction and back extraction, therefore can make in the solid of subsequent cooling precipitation that sulfur-containing impurities are not pure by high-temperature roasting
Du Genggao；In addition, waste catalyst pre-treatment step soot blowing, roasting, and hydrolysis except silicon, aluminium and etc. be all conducive to mention
Rise the purity of recycling product.
(3) vanadium provided by the present invention, tungsten/molybdenum and titanium recovery method be divided into pretreatment, element sepatation, element purification and
Element recycles four-stage, and method is clearly simple, and agents useful for same and technique easily realize industrial large-scale application, and at
This lower, most commonly seen for denitrating flue gas field V2O5-WO3/TiO2And V2O5-MoO3/TiO2Catalyst is largely effective.
Specific embodiment
The method that the present invention provides a kind of to recycle vanadium, tungsten/molybdenum and titanium elements from discarded SCR denitration, below
In conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
Embodiment 1 describes a kind of method that vanadium, tungsten and titanium elements are recycled from discarded SCR denitration, specifically
Step includes:
(1) pretreatment of SCR denitration is discarded
Certain power plant is taken to discard flat SCR denitration (V2O5-WO3/TiO2), blow away superficial dust, by concussion and
Percussion separates catalyst with metal otter board；The catalyst to fall off is collected, then roasts 12h at 450 DEG C；It will catalysis after roasting
Agent is sufficiently crushed to 200 mesh hereinafter, obtaining waste catalyst powder.
(2) separation of titanium elements and vanadium, wolfram element
By waste catalyst powder and Na2CO3It is uniformly mixed, wherein molar ratio Na:Ti=1.5:1, is then added suitable
Water continues to stir；Sufficiently after drying, 650 DEG C of roasting 10h obtain agglomerate；Agglomerate is crushed to 200 mesh hereinafter, adding at 60 DEG C
Leaching 4 times is repeated with the NaOH solution that concentration is 1mol/L under heat and stirring condition, every not good liquor stereoplasm amount ratio is 10:1, when leaching
Between be 2h；Ti-enriched slag precipitating and the simultaneously solution containing vanadium, wolfram element is obtained by filtration.
(3) recycling of titanium elements
Ti-enriched slag is crushed to 200 mesh hereinafter, the concentrated sulfuric acid solution for being 80% with concentration is in 180 DEG C of heating and stirring conditions
Lower dissolution Ti-enriched slag, obtains TiO2Concentration is the titaniferous slurries of 200g/L；Stop stirring, keeps heat aging 5h；Curing terminates
Afterwards when temperature is down to 100 DEG C or less, 5% dilution heat of sulfuric acid is added, TiO is obtained by filtration2Concentration is the dilute titanium of clarification of 100g/L
Liquid；The deionized water and titanium liquid for taking 3 times of quality are preheated to 90 DEG C, and titanium liquid is slowly uniformly added into 15min to deionization
In water, titanium liquid obtains colourless transparent solution after all adding；Boil solution, when there are a large amount of white precipitates, stop heating and
Stirring reopens stirring after standing 30min and 2h is boiled in heating, this process requires supplementation with moisture to keep liquor capacity opposite
Stablize；Deposit is obtained by filtration, sufficiently most obtains TiO after 450 DEG C of roastings afterwards in 60 DEG C of dry 12h after washing2。
(4) separation and purification of vanadium, wolfram element
Above-mentioned steps (2) acquired solution pH value is adjusted to 8.0 with 5% dilution heat of sulfuric acid, and heated solution is to 60 DEG C, stirring
3h is filtered to remove the impurity elements such as the silicon, aluminium, calcium of hydrolytic precipitation, obtains clear solution.
Wolfram element is extracted with extractant, wherein extractant is by 5% secondary carbon primary amine (N1923), 5% isooctanol and 90% sulfonation
Kerosene composition, extraction series are 5 grades, and every grade of organic phase and water phase volume ratio are 1:3；With the ammonia spirit of 1mol/L from organic phase
Middle back extraction wolfram element obtains tungstenic solution, and back extraction series is 2 grades, and every grade of organic phase and stripping agent volume ratio are 1:5.
Surplus solution pH value extracts vanadium with extractant, wherein extractant is pungent by 5% 3 to 0.5 after adjusting extraction tungsten
Alkyl tertiary amine (N235), 5% sec-octyl alcohol and 90% sulfonated kerosene composition, extraction series are 5 grades, every grade of organic phase and water phase volume
Than for 1:3；It is stripped vanadium from organic phase with the hydrogen peroxide solution of 0.5mol/L, obtains containing vanadium solution, back extraction series is 5
Grade, every grade of organic phase and stripping agent volume ratio are 1:3.
(5) recycling of wolfram element
It is evaporated tungstenic solution obtained by above-mentioned steps (4), 750 DEG C of roasting remaining solids；Under the conditions of being stirred at room temperature, volume is used
The ammonia spirit dissolution roasting obtained solid that concentration is 10%, it is 8:1 that liquid, which consolidates mass ratio,；Then heating is boiled, until remaining molten
Liquid just covers container bottom；It is fully cooled, the ammonium salt for the wolframic acid being precipitated from solution is obtained by filtration, in 60 DEG C after ethyl alcohol cleaning
Dry 12h, most obtains WO through 450 DEG C of roastings afterwards3Solid.
(6) recycling of vanadium
It is evaporated obtained by above-mentioned steps (4) containing vanadium solution, is slowly added into the dilute hydrochloric acid solution that volumetric concentration is 2% at room temperature
Until solid is completely dissolved, clear solution is obtained；The dust technology of 0.5mol/L is slowly added dropwise into solution, solution is made to become stable
Rufous；PH value is adjusted to 1.0 with 2% dilute hydrochloric acid solution, is boiled solution, is continued to boil 1h after there is red precipitate；It is cooling
After hydrolytic precipitation is obtained by filtration, sufficiently washing after in 60 DEG C of dry 12h, most obtain V through 450 DEG C of roastings afterwards2O5Solid.
By embodiment 1, the vanadium rate of recovery recycles gained V up to 92%2O5Purity is 99.65%；Wolfram element recycling
Rate recycles gained WO up to 95%3Purity is 99.70%；The titanium elements rate of recovery recycles gained TiO up to 90%2Purity is
98.90%.
Embodiment 2
The method that examples 2 describe a kind of to recycle vanadium, molybdenum and titanium elements from discarded SCR denitration, specifically
Step includes:
(1) pretreatment of SCR denitration is discarded
Certain power plant is taken to discard flat SCR denitration (V2O5-MoO3/TiO2), superficial dust is blown away, concussion is passed through
And percussion separates catalyst with metal otter board；The catalyst to fall off is collected, then roasts 2h at 650 DEG C；It will be urged after roasting
Agent is sufficiently crushed to 200 mesh hereinafter, obtaining waste catalyst powder.
(2) separation of titanium elements and vanadium, molybdenum element
Waste catalyst powder is uniformly mixed, wherein molar ratio Na:Ti=3:1 with NaOH solid, is then added appropriate
Water continue to stir；Sufficiently after drying, 800 DEG C of roasting 3h obtain agglomerate；Agglomerate is crushed to 200 mesh hereinafter, at 90 DEG C
Leaching 2 times is repeated with the NaOH solution that concentration is 3mol/L under the conditions of heating and stirring, every not good liquor stereoplasm amount ratio is 4:1, leaching
Time is 2h；Ti-enriched slag precipitating and the simultaneously solution containing vanadium, molybdenum element is obtained by filtration.
(3) recycling of titanium elements
Ti-enriched slag is crushed to 200 mesh hereinafter, being 95% concentrated sulfuric acid solution under the conditions of 140 DEG C of heating and stirring with concentration
Ti-enriched slag is dissolved, TiO is obtained2Concentration is the titaniferous slurries of 300g/L；Stop stirring, keeps heat aging 2h；After curing
When temperature is down to 60 DEG C or less, 5% dilution heat of sulfuric acid is added, TiO is obtained by filtration2Concentration is the clarification diluted Ti solution of 150g/L；
The deionized water and titanium liquid for taking 6 times of quality are preheated to 98 DEG C, and titanium liquid is slowly uniformly added into 30min to deionized water
In, titanium liquid obtains colourless transparent solution after all adding；Solution is boiled, when there are a large amount of white precipitates, stops heating and stirs
It mixes, reopens stirring after standing 30min and 4h is boiled in heating, this process requires supplementation with moisture to keep liquor capacity relatively steady
It is fixed；Deposit is obtained by filtration, sufficiently most obtains TiO after 750 DEG C of roastings afterwards in 90 DEG C of dry 2h after washing2。
(4) separation and purification of vanadium, molybdenum element
Above-mentioned steps (2) acquired solution pH value is adjusted to 11 with 5% dilution heat of sulfuric acid, and heated solution is to 90 DEG C, stirring
0.5h is filtered to remove the impurity elements such as the silicon, aluminium, calcium of hydrolytic precipitation, obtains clear solution.
Molybdenum element is extracted with extractant, wherein extractant is by 20% 3 octyl tertiary amine (N235), 20% tributyl phosphate
It is formed with 60% sulfonated kerosene, extraction series is 2 grades, and every grade of organic phase and water phase volume ratio are 1:5；It is molten with the ammonium hydroxide of 5mol/L
Liquid is stripped molybdenum element from organic phase, obtains containing molybdenum solution, back extraction series is 2 grades, and every grade of organic phase is with stripping agent volume ratio
1:3。
Surplus solution pH value extracts vanadium with extractant, wherein extractant is by 20% 2 to 2.0 after adjusting extraction molybdenum
(2- ethylhexyl) phosphate (P204), 20% sec-octyl alcohol and 60% sulfonated kerosene composition, extraction series are 2 grades, and every grade organic
It is mutually 1:5 with water phase volume ratio；It is stripped vanadium from organic phase with the dilute nitric acid solution of 2mol/L, obtains containing vanadium solution, instead
Extracting series is 2 grades, and every grade of organic phase and stripping agent volume ratio are 1:5.
(5) recycling of molybdenum element
It is evaporated obtained by above-mentioned steps (4) containing molybdenum solution, 750 DEG C of roasting remaining solids；Under the conditions of being stirred at room temperature, volume is used
The ammonia spirit dissolution roasting obtained solid that concentration is 30%, it is 4:1 that liquid, which consolidates mass ratio,；Then heating is boiled, until remaining molten
Liquid just covers container bottom；It is fully cooled, the ammonium salt for the molybdic acid being precipitated from solution is obtained by filtration, in 90 DEG C after ethyl alcohol cleaning
Dry 2h, most obtains MoO through 600 DEG C of roastings afterwards3Solid.
(6) recycling of vanadium
It is evaporated obtained by above-mentioned steps (4) containing vanadium solution, is slowly added into the dilute hydrochloric acid solution that volumetric concentration is 8% at room temperature
Until solid is completely dissolved, clear solution is obtained；The hydrogen peroxide solution of 2.5mol/L is slowly added dropwise into solution, becomes solution
Stable rufous；PH value is adjusted to 3.0 with 8% dilute hydrochloric acid solution, is boiled solution, is continued to boil 1h after there is red precipitate；
Cooled and filtered obtains hydrolytic precipitation, sufficiently most obtains V through 600 DEG C of roastings afterwards in 90 DEG C of dry 2h after washing2O5Solid.
By embodiment 2, the vanadium rate of recovery recycles gained V up to 93%2O5Purity is 99.85%；Molybdenum element recycling
Rate recycles gained MoO up to 94%3Purity is 99.80%；The titanium elements rate of recovery recycles gained TiO up to 91%2Purity is
98.95%.
Embodiment 3
Embodiment 3 describes another method that vanadium, tungsten and titanium elements are recycled from discarded SCR denitration, specifically
The step of include:
(1) pretreatment of SCR denitration is discarded
Take the discarded cellular SCR denitration (V of certain power plant2O5-WO3/TiO2), soot blowing processing after, by catalyst in
8h is roasted at 600 DEG C；Catalyst is then sufficiently crushed to 200 mesh hereinafter, obtaining waste catalyst powder by soot blowing again.
(2) separation of titanium elements and vanadium, wolfram element
By waste catalyst powder and Na2CO3It is uniformly mixed, wherein molar ratio Na:Ti=2.5:1, is then added suitable
Water continues to stir；Sufficiently after drying, 800 DEG C of roasting 6h obtain agglomerate；Agglomerate is crushed to 200 mesh hereinafter, adding at 90 DEG C
Leaching 4 times is repeated with the NaOH solution that concentration is 1mol/L under heat and stirring condition, every not good liquor stereoplasm amount ratio is 5:1, when leaching
Between be 2h；Ti-enriched slag precipitating and the simultaneously solution containing vanadium, wolfram element is obtained by filtration.
(3) recycling of titanium elements
Ti-enriched slag is crushed to 200 mesh hereinafter, being 95% concentrated sulfuric acid solution under the conditions of 150 DEG C of heating and stirring with concentration
Ti-enriched slag is dissolved, TiO is obtained2Concentration is the titaniferous slurries of 240g/L；Stop stirring, keeps heat aging 4h；After curing
When temperature is down to 90 DEG C or less, 5% dilution heat of sulfuric acid is added, TiO is obtained by filtration2Concentration is the clarification diluted Ti solution of 120g/L；
The deionized water and titanium liquid for taking 4 times of quality are preheated to 98 DEG C, and titanium liquid is slowly uniformly added into 30min to deionized water
In, titanium liquid obtains colourless transparent solution after all adding；Solution is boiled, when there are a large amount of white precipitates, stops heating and stirs
It mixes, reopens stirring after standing 30min and 3h is boiled in heating, this process requires supplementation with moisture to keep liquor capacity relatively steady
It is fixed；Deposit is obtained by filtration, sufficiently most obtains TiO after 600 DEG C of roastings afterwards in 100 DEG C of dry 8h after washing2。
(4) separation and purification of vanadium, wolfram element
With 5% dilution heat of sulfuric acid adjusting above-mentioned steps (2) acquired solution pH value to 11, heated solution stirs 1h to 70 DEG C,
The impurity elements such as the silicon, aluminium, calcium of hydrolytic precipitation are filtered to remove, clear solution is obtained.
Wolfram element is extracted with extractant, wherein extractant is by 20% secondary carbon primary amine (N1923), 10% isooctanol and 70% sulphur
Change kerosene composition, extraction series is 2 grades, and every grade of organic phase and water phase volume ratio are 1:3；Ethanolamine solutions with 2mol/L are from having
It is stripped wolfram element in machine phase, obtains tungstenic solution, back extraction series is 2 grades, and every grade of organic phase and stripping agent volume ratio are 1:3.
Surplus solution pH value extracts vanadium with extractant, wherein extractant is by 15% 2 to 1.0 after adjusting extraction tungsten
(2- ethylhexyl) phosphate (P204), 15% sec-octyl alcohol and 70% sulfonated kerosene composition, extraction series are 3 grades, and every grade organic
It is mutually 1:3 with water phase volume ratio；It is stripped vanadium from organic phase with the dilute nitric acid solution of 1.5mol/L, obtains containing vanadium solution,
Being stripped series is 3 grades, and every grade of organic phase and stripping agent volume ratio are 1:3.
(5) recycling of wolfram element
It is evaporated tungstenic solution obtained by above-mentioned steps (4), 750 DEG C of roasting remaining solids；Under the conditions of being stirred at room temperature, volume is used
The ammonia spirit dissolution roasting obtained solid that concentration is 30%, it is 8:1 that liquid, which consolidates mass ratio,；Then heating is boiled, until remaining molten
Liquid just covers container bottom；It is fully cooled, the ammonium salt for the wolframic acid being precipitated from solution is obtained by filtration, in 60 DEG C after ethyl alcohol cleaning
Dry 8h, most obtains WO through 550 DEG C of roastings afterwards3Solid.
(6) recycling of vanadium
It is evaporated obtained by above-mentioned steps (4) containing vanadium solution, is slowly added into the dilute hydrochloric acid solution that volumetric concentration is 3% at room temperature
Until solid is completely dissolved, clear solution is obtained；The hydrogen peroxide solution of 1.5mol/L is slowly added dropwise into solution, becomes solution
Stable rufous；PH value is adjusted to 1.5 with 3% dilute hydrochloric acid solution, is boiled solution, is continued to boil 1h after there is red precipitate；
Cooled and filtered obtains hydrolytic precipitation, sufficiently most obtains V through 550 DEG C of roastings afterwards in 70 DEG C of dry 9h after washing2O5Solid.
By embodiment 3, the vanadium rate of recovery recycles gained V up to 95%2O5Purity is 99.95%；Wolfram element recycling
Rate recycles gained WO up to 93%3Purity is 99.79%；The titanium elements rate of recovery recycles gained TiO up to 90%2Purity is
98.83%.
Embodiment 4
Embodiment 4 describes another method that vanadium, molybdenum and titanium elements are recycled from discarded SCR denitration, specifically
The step of include:
(1) pretreatment of SCR denitration is discarded
Take the discarded cellular SCR denitration (V of certain power plant2O5-MoO3/TiO2), soot blowing processing after, by catalyst in
6h is roasted at 650 DEG C；Catalyst is then sufficiently crushed to 200 mesh hereinafter, obtaining waste catalyst powder by soot blowing again.
(2) separation of titanium elements and vanadium, molybdenum element
Waste catalyst powder is uniformly mixed, wherein molar ratio Na:Ti=3:1 with NaOH solid, is then added appropriate
Water continue to stir；Sufficiently after drying, 800 DEG C of roasting 3h obtain agglomerate；Agglomerate is crushed to 200 mesh hereinafter, at 60 DEG C
Leaching 2 times is repeated with the NaOH solution that concentration is 2mol/L under the conditions of heating and stirring, every not good liquor stereoplasm amount ratio is 6:1, leaching
Time is 3h；Ti-enriched slag precipitating and the simultaneously solution containing vanadium, molybdenum element is obtained by filtration.
(3) recycling of titanium elements
Ti-enriched slag is crushed to 200 mesh hereinafter, being 85% concentrated sulfuric acid solution under the conditions of 160 DEG C of heating and stirring with concentration
Ti-enriched slag is dissolved, TiO is obtained2Concentration is the titaniferous slurries of 300g/L；Stop stirring, keeps heat aging 3h；After curing
When temperature is down to 80 DEG C or less, 5% dilution heat of sulfuric acid is added, TiO is obtained by filtration2Concentration is the clarification diluted Ti solution of 150g/L；
The deionized water and titanium liquid for taking 6 times of quality are preheated to 95 DEG C, and titanium liquid is slowly uniformly added into 25min to deionized water
In, titanium liquid obtains colourless transparent solution after all adding；Solution is boiled, when there are a large amount of white precipitates, stops heating and stirs
It mixes, reopens stirring after standing 30min and 3h is boiled in heating, this process requires supplementation with moisture to keep liquor capacity relatively steady
It is fixed；Deposit is obtained by filtration, sufficiently most obtains TiO after 550 DEG C of roastings afterwards in 80 DEG C of dry 9h after washing2。
(4) separation and purification of vanadium, molybdenum element
With 5% dilution heat of sulfuric acid adjusting above-mentioned steps (2) acquired solution pH value to 10, heated solution stirs 3h to 80 DEG C,
The impurity elements such as the silicon, aluminium, calcium of hydrolytic precipitation are filtered to remove, clear solution is obtained.
With extractant extract molybdenum element, wherein extractant by 20% secondary carbon primary amine (N1923), 10% tributyl phosphate and
70% sulfonated kerosene composition, extraction series are 3 grades, and every grade of organic phase and water phase volume ratio are 1:4；With the ammonia spirit of 2mol/L
It is stripped molybdenum element from organic phase, obtains containing molybdenum solution, back extraction series is 3 grades, and every grade of organic phase and stripping agent volume ratio are 1:
4。
Surplus solution pH value extracts vanadium with extractant, wherein extractant is pungent by 20% 3 to 1.0 after adjusting extraction molybdenum
Alkyl tertiary amine (N235), 10% sec-octyl alcohol and 70% sulfonated kerosene composition, extraction series are 3 grades, every grade of organic phase and water phase body
Product is than being 1:3；It is stripped vanadium from organic phase with the hydrogen peroxide solution of 2mol/L, obtains containing vanadium solution, back extraction series is 3
Grade, every grade of organic phase and stripping agent volume ratio are 1:3.
(5) recycling of molybdenum element
It is evaporated obtained by above-mentioned steps (4) containing molybdenum solution, 750 DEG C of roasting remaining solids；Under the conditions of being stirred at room temperature, volume is used
The ammonia spirit dissolution roasting obtained solid that concentration is 30%, it is 4:1 that liquid, which consolidates mass ratio,；Then heating is boiled, until remaining molten
Liquid just covers container bottom；It is fully cooled, the ammonium salt for the molybdic acid being precipitated from solution is obtained by filtration, in 80 DEG C after ethyl alcohol cleaning
Dry 6h, most obtains MoO through 500 DEG C of roastings afterwards3Solid.
(6) recycling of vanadium
It is evaporated obtained by above-mentioned steps (4) containing vanadium solution, is slowly added into the dilute hydrochloric acid solution that volumetric concentration is 4% at room temperature
Until solid is completely dissolved, clear solution is obtained；The dilute nitric acid solution of 1mol/L is slowly added dropwise into solution, solution is made to become steady
Fixed rufous；PH value is adjusted to 1.5 with 4% dilute hydrochloric acid solution, is boiled solution, is continued to boil 1h after there is red precipitate；It is cold
But hydrolytic precipitation is obtained by filtration afterwards, sufficiently most obtains V through 500 DEG C of roastings afterwards in 70 DEG C of dry 8h after washing2O5Solid.
By embodiment 4, the vanadium rate of recovery recycles gained V up to 92%2O5Purity is 99.86%；Molybdenum element recycling
Rate recycles gained MoO up to 92%3Purity is 99.89%；The titanium elements rate of recovery recycles gained TiO up to 91%2Purity is
98.93%.
It should be understood that the above embodiments merely illustrate the technical concept and features of the present invention, its object is to for this field skill
Art personnel understand the contents of the present invention and implement accordingly, and the not exhaustion of specific embodiment can not limit the present invention with this
Protection scope.It is all to be modified or replaced equivalently according to the technique and scheme of the present invention, without departing from technical solution of the present invention
Objective and range, should all cover in scope of the invention as claimed.
Claims (10)
1. a kind of method for recycling vanadium, tungsten/molybdenum and titanium elements from discarded SCR denitration, which is characterized in that including as follows
Step:
(1) pretreatment of SCR denitration is discarded
1. being directed to flat discarded SCR denitration: blowing away catalyst surface dust stratification, make to be catalyzed by shaking or tapping mode
Agent is separated with metal otter board；It collects and roasts the catalyst to fall off, wherein maturing temperature is 450-650 DEG C, calcining time 2-
12h；Catalyst is then sufficiently crushed to 200 mesh or less；
2. for cellular discarded SCR denitration: blowing away the partial loose dust stratification blocked in catalyst duct, will then urge
Agent carries out calcination process；Wherein, maturing temperature is 450-650 DEG C, calcining time 2-12h；Soot blowing again, after removing roasting
Residue becomes loose dust stratification；Finally, catalyst to be sufficiently crushed to 200 mesh or less；
(2) titanium elements and vanadium, the separation of tungsten/molybdenum element
By the Na of above-mentioned steps (1) resulting discarded SCR denitration powder and certain mass2CO3Or NaOH is uniformly mixed,
Suitable water is then added to continue to stir, further strengthens hybrid solid contact area and the uniformity；After drying, roasting mixing is solid
Body obtains agglomerate；Wherein, maturing temperature is 650-800 DEG C, calcining time 3-10h；By agglomerate be crushed to 200 mesh with
Under, it under the conditions of heating and stirring, is leached repeatedly with NaOH solution, Ti-enriched slag precipitating is obtained by filtration and comprising vanadium, tungsten/molybdenum element
Solution；
(3) recycling of titanium elements
Ti-enriched slag precipitating is crushed to 200 mesh hereinafter, being 80-95% concentrated sulfuric acid solution in 140-180 DEG C of heating with concentration
With dissolve Ti-enriched slag under stirring condition, obtain titaniferous slurries；Stop stirring, keeps heat aging 2-5h；To temperature after curing
When degree is down to 100 DEG C or less, 5% dilution heat of sulfuric acid is added, clarification diluted Ti solution is then obtained by filtration；It is 3-6 times for quality to go
Ionized water and titanium liquid are preheated to 90-98 DEG C, titanium liquid are slowly uniformly added into deionized water in 15-30min, titanium liquid is rigid
Occur white precipitate when addition, then gradually becomes colourless transparent solution；Solution is boiled to there are a large amount of white precipitates, stops adding
Heat and stirring reopen stirring after standing 30min and 2-4h are boiled in heating, this process requires supplementation with moisture to keep solution body
Product is relatively stable；Finally TiO is obtained through filtering, washing, drying and roasting recycling2；Wherein, drying temperature is 60-90 DEG C, dry
Time is 2-12h；Maturing temperature is 450-750 DEG C, calcining time 3-6h；
(4) vanadium, the separation of tungsten/molybdenum element and purification
Above-mentioned steps (2) acquired solution pH value is adjusted to 8-11 with 5% dilution heat of sulfuric acid, and heated solution is to 60-90 DEG C, stirring
0.5-3h is filtered to remove the impurity elements such as the silicon, aluminium, calcium of hydrolytic precipitation, obtains clear solution；With in extractant extraction solution
Tungsten/molybdenum element obtains tungstenic/molybdenum organic phase；It is then stripped tungsten/molybdenum element in organic phase, obtains tungstenic/molybdenum solution；
Surplus solution pH value extracts vanadium with extractant, obtains organic phase containing vanadium to 0.5-2.0 after adjusting extraction tungsten/molybdenum；And
It is stripped vanadium in organic phase afterwards, obtains containing vanadium solution；
(5) tungsten/molybdenum element recycling
It is evaporated tungstenic/molybdenum solution obtained by above-mentioned steps (4), 750 DEG C of roastings remove step (4) and adjust the sulfur impurity member that pH value introduces
Element；Under the conditions of being stirred at room temperature, roasting obtained solid is dissolved with ammonia spirit, then heating is boiled until surplus solution just covers
Lid container bottom；It is fully cooled, the wolframic acid ammonium salt/dimolybdate salt being precipitated in solution is obtained by filtration, through ethyl alcohol cleaning, dry and roasting
WO is obtained after burning3/MoO3Solid；Wherein, drying temperature is 60-90 DEG C, drying time 2-12h；Maturing temperature is 450-600
DEG C, calcining time 3-6h；
(6) recycling of vanadium
It is evaporated containing vanadium solution obtained by above-mentioned steps (4), at room temperature, is slowly added into the dilute hydrochloric acid solution that volumetric concentration is 2-8%
Until solid is completely dissolved, clear solution is obtained；Oxidizing agent solution is added dropwise into solution, solution is made to become stable rufous；
PH value is adjusted to 1.0-3.0 with the dilute hydrochloric acid solution of same concentrations, is boiled solution, is continued to boil 1h after there is red precipitate；It is cold
But V is obtained through filtering, washing, drying and roasting afterwards2O5Solid；Wherein, drying temperature is 60-90 DEG C, drying time 2-12h；
Maturing temperature is 450-600 DEG C, calcining time 3-6h.
2. a kind of method that vanadium, tungsten/molybdenum and titanium elements are recycled from discarded SCR denitration according to claim 1,
It is characterized in that, discarding SCR denitration in the step (1) is the superseded vanadium Titanium series catalyst of industrial smoke denitration, carry
Body is TiO2, active constituent V2O5, catalyst aid WO3Or MoO3。
3. a kind of method that vanadium, tungsten/molybdenum and titanium elements are recycled from discarded SCR denitration according to claim 1,
It is characterized in that, Na used in the step (2)2CO3Or the amount of NaOH is quantified by sodium element and titanium elements molar ratio, is rubbed
You are than Na:Ti=(1.5-3): 1.
4. a kind of method that vanadium, tungsten/molybdenum and titanium elements are recycled from discarded SCR denitration according to claim 1,
It is characterized in that, NaOH solution concentration is 1-3mol/L in the step (2), leaching temperature is 60-90 DEG C, and leaching number is 2-
4 times, every not good liquor stereoplasm amount ratio is (4-10): 1, leaching time 2-6h.
5. a kind of method that vanadium, tungsten/molybdenum and titanium elements are recycled from discarded SCR denitration according to claim 1,
It is characterized in that, TiO in titaniferous slurries in the step (3)2Concentration is 200-300g/L, clarifies TiO in diluted Ti solution2Concentration is
100-150g/L。
6. a kind of method that vanadium, tungsten/molybdenum and titanium elements are recycled from discarded SCR denitration according to claim 1,
It is characterized in that, for extracting tungsten/molybdenum element extractant by effective component, phase modifier and diluent in the step (4)
Composition；Wherein effective component is that secondary carbon primary amine or three octyl tertiary amines, volume account for 5-20%；Phase modifier be tributyl phosphate or
Isooctanol, volume account for 5%-20%；Diluent is sulfonated kerosene, and volume accounts for 60%-90%；Extracting series is 2-5 grades, and every grade has
Machine phase and tungstenic/molybdenum solution volume ratio are 1:(3-5).
7. a kind of method that vanadium, tungsten/molybdenum and titanium elements are recycled from discarded SCR denitration according to claim 1,
It is characterized in that, stripping agent used in back extraction tungsten/molybdenum element is ammonium hydroxide, ethanol amine, ammonium chloride or ammonium hydrogencarbonate in the step (4)
Solution, concentration 1-5mol/L；Being stripped series is 2-5 grades, and every grade of organic phase and stripping agent liquor capacity ratio are 1:(3-5).
8. a kind of method that vanadium, tungsten/molybdenum and titanium elements are recycled from discarded SCR denitration according to claim 1,
It is characterized in that, the extractant effective component in the step (4) for extracting vanadium is three octyl tertiary amines or two (2- second
Base hexyl) phosphate, volume accounts for 5-20%；Phase modifier is that sec-octyl alcohol or certain herbaceous plants with big flowers alcohol, volume account for 5-20%；Diluent is sulfonated coal
Oil, volume account for 60-90%；Extracting series is 2-5 grades, and every grade of organic phase and volume ratio containing vanadium solution are 1:(3-5).
9. a kind of method that vanadium, tungsten/molybdenum and titanium elements are recycled from discarded SCR denitration according to claim 1,
It is characterized in that, stripping agent used in back extraction vanadium is dust technology or hydrogen peroxide solution, concentration 0.5- in the step (4)
2.0mol/L；Being stripped series is 2-5 grades, and every grade of organic phase and stripping agent liquor capacity ratio are 1:(3-5).
10. a kind of side for recycling vanadium, tungsten/molybdenum and titanium elements from discarded SCR denitration according to claim 1
Method, which is characterized in that ammonia spirit concentration used is 10-30% in the step (5), and liquid consolidate mass ratio as (4-8): 1.
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