CN106179323A - A kind of vanadium tungsten titanium oxide catalyst and its production and use - Google Patents
A kind of vanadium tungsten titanium oxide catalyst and its production and use Download PDFInfo
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- CN106179323A CN106179323A CN201610514241.7A CN201610514241A CN106179323A CN 106179323 A CN106179323 A CN 106179323A CN 201610514241 A CN201610514241 A CN 201610514241A CN 106179323 A CN106179323 A CN 106179323A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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Abstract
The invention provides a kind of vanadium tungsten titanium oxide catalyst and its production and use, described vanadium tungsten titanium oxide catalyst includes following component by weight/mass percentage composition: vanadic anhydride 5% 25%, Tungstic anhydride. 5% 30% and titanium dioxide 50% 85%；Described vanadic anhydride, Tungstic anhydride. and titanium dioxide uniformly mix, and each oxide crystal particle diameter independently be 1 30nm.Described vanadium tungsten titanium oxide catalyst is used for Selective Catalytic Reduction of NOxCatalytic performance good, even if still can show the catalytic performance of excellence at high-speed environment, operate temperature window width, there is within the temperature range of 150 500 DEG C the most excellent low temperature active, N2Generate selectivity, water resistant, sulfur resistive and thermal stability；And its preparation method is simple.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of vanadium tungsten titanium oxide catalyst and preparation method thereof and use
On the way.
Background technology
Nitrogen oxides (NOx) great environmental problem such as gray haze, acid rain and photochemical fog can be caused, control NOxDischarge
It it is a significant challenge facing of field of environment protection.Since last century the seventies, NH3Selective Catalytic Reduction of NOx(i.e.
NH3-SCR) technology is widely used in the stationary source denitrating flue gas such as coal-burning power plant, Industrial Boiler.Traditional V2O5-WO3/TiO2Catalysis
Agent is applied for many years in stationary source denitration field as a kind of commercial SCR catalyst, and owing to it has the anti-SO of uniqueness2
Poisoning capability, the most still cannot be substituted.Additionally, V2O5-WO3/TiO2Catalyst is also in company with NH3-SCR technology has been introduced in bavin
Oil turbine tail gas NOxCatalytic purification field.Have the shortcomings such as bio-toxicity due to catalytic component based on vanadium, researchers develop
The molecular sieve catalyst of the series transition metal exchanges such as Fe-ZSM-5, Cu-SSZ-13 and Cu-SAPO-34, to it on diesel vehicle
Application substitute.Further, a lot of developed countries have prohibited catalytic component based on vanadium use on motor vehicles.But, right
For a lot of developing countries with China as representative, owing to catalytic component based on vanadium has the anti-SO of excellence2Poisoning capability, and
Cheap, in the environment of oil quality is the most poor, can be the most complete currently without other catalyst systems
Face substitutes catalytic component based on vanadium.It addition, boat diesel engine typically uses heavy oil, propellant composition is complicated, sulfur content is high, vanadio
Catalyst is due to the anti-SO of its excellence2Poisoning capability and stability also become optimal selection.In actual applications, existing vanadium
There is the shortcoming that low temperature active is not enough and temperature window is narrower in base catalyst so that it is by one on suitable environment and denitration efficiency
Fixed restriction.Therefore, catalytic component based on vanadium is improved, improve low temperature active, widen temperature window, raising denitration efficiency with full
The needs of full border application have very important significance.
CN 104162421 A discloses a kind of vanadium tungsten titanium oxide for ammine selectivity catalytic reduction nitrous oxides and urges
The preparation method of agent.Described preparation method is to first pass through sluggish precipitation to prepare tungsten titanium composite oxide as catalysis
Agent carrier, then use infusion process to load barium oxide on tungsten titanium composite oxide, after roasting, obtain vanadium tungsten titanium oxide
Catalyst.Although the catalyst that the method prepares is high temperature resistant, but, its performance need to promote further.
Summary of the invention
The deficiency existed for prior art, it is an object of the invention to provide a kind of vanadium tungsten titanium oxide catalyst and
Preparation method and purposes, described vanadium tungsten titanium oxide catalyst is used for Selective Catalytic Reduction of NOxCatalytic performance good, even if
High-speed environment still can show the catalytic performance of excellence, operates temperature window width, have the most excellent low temperature active,
N2Generate selectivity, water resistant, sulfur resistive and thermal stability.
For reaching this purpose, the present invention by the following technical solutions:
An object of the present invention is to provide a kind of vanadium tungsten titanium oxide catalyst, described vanadium tungsten titanium oxide catalyst
Following component is included: vanadic anhydride 5%-25%, Tungstic anhydride. 5%-30% and titanium dioxide 50%-by weight/mass percentage composition
85%；Described vanadic anhydride, Tungstic anhydride. and titanium dioxide uniformly mix, and described vanadic anhydride, Tungstic anhydride. and
The crystal particle diameter of titanium dioxide independently be 1-30nm.
The vanadium tungsten titanium oxide catalyst that the present invention provides is due to vanadic anhydride therein, Tungstic anhydride. and titanium dioxide
Titanium is dispersed, and active site is more, therefore, its better catalytic activity, operation temperature window width (150-450 DEG C), tool
Have the most excellent low temperature active (when 150 DEG C, NOxConversion ratio up to more than 50%), N2Generation selectivity (when 150 DEG C, can
Reach 100%), water resistant, sulfur resistive and thermal stability.
In described vanadium tungsten titanium oxide catalyst the weight/mass percentage composition of vanadic anhydride can be 8%, 10%, 12%,
15%, 18%, 20% or 22% etc.；The weight/mass percentage composition of Tungstic anhydride. can be 8%, 10%, 12%, 15%, 18%,
20%, 22%, 25% or 28% etc.；The weight/mass percentage composition of titanium dioxide can be 52%, 58%, 63%, 68%, 70%,
75%, 78%, 80% or 83% etc..
The crystal particle diameter of described vanadic anhydride, Tungstic anhydride. and titanium dioxide independently be 1-30nm, as 2nm, 3nm,
5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, 25nm or 28nm etc..When particle diameter is bigger, the active force between three is relatively
Weak, catalytic effect is the best.
An object of the present invention also resides in the preparation method providing a kind of vanadium tungsten titanium oxide catalyst, described preparation side
Method comprises the steps:
(1) vanadium source, tungsten source, titanium source, alternatively cosolvent and solvent are mixed to form mixed solution；
(2) in mixed solution, add slow release precipitator, obtain reaction solution；
(3) raising the temperature of reaction solution, reaction solution reacts, and obtains containing sedimentary solution；
(4) post processing will be carried out containing sedimentary solution, obtain described vanadium tungsten titanium oxide catalyst.
The preparation method of the vanadium tungsten titanium oxide catalyst that the present invention provides is simple, only need to be led in vanadium source, tungsten source and titanium source
Cross slow release precipitator co-precipitation can be prepared by.Described slow release precipitator is owing to can slowly discharge, therefore, and the vanadium tungsten titanyl prepared
In compound catalyst, vanadic anhydride, Tungstic anhydride. and titanium dioxide can be dispersed.
Vanadium in step (1) described vanadium source, the tungsten in tungsten source, the mol ratio of the titanium in titanium source are (0.05-0.15):
(0.05-0.15): 1, as 0.06:0.08:1,0.06:0.09:1,0.06:0.10:1,0.06:0.12:1,0.08:0.12:1,
0.12:0.13:1,0.08:0.14:1 or 0.03:0.12:1.
Preferably, the quality of step (1) described cosolvent is (0.5-3) with the ratio of the quality sum in vanadium source and tungsten source: 1,
Such as 0.6:1,0.8:1,1.0:1,1.5:1,2.0:1,2.5:1 or 2.8:1 etc..
Preferably, the mode of step (1) described mixing is stirring.
Preferably, carry out at being blended in 10-40 DEG C described in step (1), as 12 DEG C, 15 DEG C, 18 DEG C, 20 DEG C, 25 DEG C, 28
DEG C, 30 DEG C, 35 DEG C or 38 DEG C etc. carry out.
Step (1) described vanadium source is in ammonium metavanadate, vanadium oxysulfate, vanadyl oxalate, vanadium tetrachloride or vanadium oxytrichloride
Any one or the combination of at least two.Typical but non-limiting combination such as ammonium metavanadate and vanadium oxysulfate, vanadyl oxalate with
Vanadium tetrachloride, vanadyl oxalate, vanadium tetrachloride and vanadium oxytrichloride, ammonium metavanadate, vanadium oxysulfate and vanadyl oxalate.
Preferably, step (1) described tungsten source is selected from ammonium tungstate and/or ammonium paratungstate.
Preferably, step (1) described titanium source in titanium sulfate, titanium tetrachloride or butyl titanate any one or extremely
The combination of few two kinds.Typical but non-limiting combination such as titanium sulfate and titanium tetrachloride, butyl titanate and titanium sulfate, sulphuric acid
Titanium, titanium tetrachloride and butyl titanate.
Preferably, any one in oxalic acid, acetic acid, nitric acid, sulphuric acid, hydrochloric acid or phosphoric acid of step (1) described cosolvent
Plant or the combination of at least two.Typical but non-limiting combination such as oxalic acid and acetic acid, nitric acid and sulphuric acid, hydrochloric acid and phosphoric acid, second
Acid, nitric acid and sulphuric acid, sulphuric acid, hydrochloric acid and phosphoric acid, oxalic acid, acetic acid, nitric acid and sulphuric acid.
Step (2) the described slow release precipitator any one or at least two in carbamide, ammonium carbonate or ammonium hydrogen carbonate
Combination.Typical but non-limiting combination such as carbamide and ammonium carbonate, carbamide and ammonium hydrogen carbonate, carbamide, ammonium carbonate and bicarbonate
Ammonium.
Preferably, in the vanadium in the mole of step (2) described slow release precipitator and vanadium source, tungsten in tungsten source and titanium source
The ratio of the mole sum of titanium is (5-25): 1, such as 8:1,10:1,12:1,15:1,18:1,20:1 or 22:1 etc..
The temperature of step (3) described rising reaction solution is: raise reaction solution temperature to 65-95 DEG C, as 70 DEG C, 72
DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 85 DEG C, 88 DEG C, 90 DEG C or 93 DEG C etc..
Preferably, step (3) described slow release precipitator reacts under agitation with vanadium source, tungsten source and titanium source.
Preferably, the time of described stirring is 1-25h, such as 2h, 5h, 8h, 10h, 12h, 15h, 18h, 20h or 22h etc., excellent
Elect 10h as.
Step (4) described post processing is: will be precipitated thing containing sedimentary solution solid-liquid separation, then by precipitate
Washing, is dried, roasting.
Preferably, the method for described solid-liquid separation is for filtering and/or centrifugation.
Preferably, described dry temperature is 80-120 DEG C, such as 82,85,88,90,95,100,105,110 or 115 etc..
Preferably, the described dry time is 5-24h, such as 6h, 8h, 10h, 12h, 15h, 18h, 20h or 22h etc..
Preferably, the temperature of described roasting is 400-700 DEG C, as 420 DEG C, 450 DEG C, 480 DEG C, 500 DEG C, 530 DEG C, 550
DEG C, 580 DEG C, 600 DEG C, 630 DEG C, 680 DEG C or 690 DEG C etc..
Preferably, the time of described roasting is 1-24h, such as 2h, 5h, 8h, 10h, 12h, 15h, 18h, 20h or 22h etc..
As preferred technical scheme, described preparation method comprises the steps:
(1) by vanadium source, tungsten source, titanium source, solvent and alternatively cosolvent be mixed to form mixed solution, wherein, described vanadium source
In vanadium, the tungsten in tungsten source, the mol ratio of the titanium in titanium source be (0.05-0.15): (0.05-0.15): 1, the quality of cosolvent
It is (0.5-3) with the ratio of the quality sum in Zhong Hewu source, vanadium source: 1；
(2) in mixed solution, add slow release precipitator, obtain reaction solution, the mole of described slow release precipitator and vanadium
The ratio of the mole sum of the titanium in the vanadium in source, the tungsten in tungsten source and titanium source is (5-25): 1；
(3) temperature raising reaction solution is to 65-95 DEG C and continuously stirred, and reaction solution reacts, after 1-25h,
To containing sedimentary solution；
(4) solid-liquid separation will be carried out containing sedimentary solution, be precipitated thing, precipitate be washed, at 80-120 DEG C
It is dried 5-24h, then at 400-700 DEG C of roasting 1-24h, obtains described vanadium tungsten titanium oxide catalyst.
An object of the present invention also resides in a kind of method providing selective catalyst reduction of nitrogen oxides, described selectivity
The method of catalyzing and reducing nitrogen oxides uses vanadium tungsten titanium oxide catalyst as above as SCR nitrogen oxygen
The catalyst of compound.
The temperature of described selective catalyst reduction of nitrogen oxides is 150-500 DEG C, as 180 DEG C, 200 DEG C, 250 DEG C, 300
DEG C, 350 DEG C, 400 DEG C or 450 DEG C etc., the action pane width of described vanadium tungsten titanium oxide catalyst, can be the temperature of 150-500 DEG C
Catalysis activity is played in the range of degree.
That is, present invention also offers the purposes of vanadium tungsten titanium oxide catalyst as above, it is applied to selectivity and urges
Change nitrogen oxides reduction.
Compared with prior art, the invention have the benefit that
(1) the vanadium tungsten titanium oxide catalyst that the present invention provides is for Selective Catalytic Reduction of NOxCatalysis activity good, and
And operation temperature window width (can use in the range of 150-500 DEG C), it is adaptable to moving source (such as diesel vehicle and boats and ships) tail gas
The applied environment that range of temperature is big；
(2) present invention provide vanadium tungsten titanium oxide catalyst there is the most excellent low temperature active (even can be 200
DEG C used below), can be widely applied to stationary source denitrating flue gas；
(3) even if the vanadium tungsten titanium oxide catalyst of present invention offer is at high-speed environment (200,000h-1Above) still
The catalytic performance of excellence can be shown, be the very efficient SCR catalyst of one；
(4) the vanadium tungsten titanium oxide catalyst that the present invention provides has the most excellent N2Generation selectivity (when 150 DEG C,
Up to 100%)；
(5) the vanadium tungsten titanium oxide catalyst that the present invention provides has extraordinary water resistant, sulfur resistive and thermal stability.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.
Embodiment 1
A kind of vanadium tungsten titanium oxide catalyst, includes following component by weight/mass percentage composition: vanadic anhydride 9%, three oxygen
Change tungsten 12% and titanium dioxide 79%；Described vanadic anhydride, Tungstic anhydride. and titanium dioxide uniformly mix, and five oxidations two
The crystal particle diameter of vanadium, Tungstic anhydride. and titanium dioxide independently be 1-15nm.
The preparation method of described vanadium tungsten titanium oxide catalyst comprises the steps:
Using ammonium metavanadate as vanadium source, using ammonium tungstate as tungsten source, using titanium sulfate as titanium source, oxalic acid as cosolvent,
Carbamide is as slow release precipitator.
It is that 0.05:0.05:1 is to containing cosolvent, (quality of oxalic acid is ammonium metavanadate and wolframic acid according to V:W:Ti mol ratio
The quality sum of ammonium) solvent in add ammonium metavanadate, ammonium tungstate and titanium sulfate, make mixed solution, and be added thereto to
Amount carbamide (mole of carbamide is 10 with the ratio of the mole of V, W and Ti) is as precipitant；Afterwards, under 83 DEG C of water bath condition
Continuous stirring 10h, obtains containing sedimentary solution；Precipitate is carried out sucking filtration and washing, afterwards filter cake is put in 100 DEG C of bakings
Case is dried 12h, finally in Muffle furnace, prepare powder catalyst in 500 DEG C of roasting 3h under air atmosphere, is labeled as catalyst
A。
Embodiment 2
A kind of vanadium tungsten titanium oxide catalyst, includes following component by weight/mass percentage composition: vanadic anhydride 8%, three oxygen
Change tungsten 21% and titanium dioxide 71%；Described vanadic anhydride, Tungstic anhydride. and titanium dioxide uniformly mix, and five oxidations two
The crystal particle diameter of vanadium, Tungstic anhydride. and titanium dioxide independently be 1-15nm.
The preparation method of described vanadium tungsten titanium oxide catalyst is:
Other condition such as embodiment 1 is constant, and changing V:W:Ti mol ratio is 0.05:0.1:1, obtains catalyst and is labeled as B.
Embodiment 3
A kind of vanadium tungsten titanium oxide catalyst, includes following component by weight/mass percentage composition: vanadic anhydride 17%, three oxygen
Change tungsten 11% and titanium dioxide 73%；Described vanadic anhydride, Tungstic anhydride. and titanium dioxide uniformly mix, and five oxidations two
The crystal particle diameter of vanadium, Tungstic anhydride. and titanium dioxide independently be 1-15nm.
The preparation method of described vanadium tungsten titanium oxide catalyst is:
Other condition such as embodiment 1 is constant, and changing V:W:Ti mol ratio is 0.1:0.05:1, obtains described catalyst, mark
It is designated as C.
Embodiment 4
A kind of vanadium tungsten titanium oxide catalyst, includes following component by weight/mass percentage composition: vanadic anhydride 15%, three oxygen
Change tungsten 19% and titanium dioxide 66%；Described vanadic anhydride, Tungstic anhydride. and titanium dioxide uniformly mix, and five oxidations two
The crystal particle diameter of vanadium, Tungstic anhydride. and titanium dioxide independently be 1-15nm.
The preparation method of described vanadium tungsten titanium oxide catalyst is:
Other condition such as embodiment 1 is constant, and changing V:W:Ti mol ratio is 0.1:0.1:1, obtains described catalyst, labelling
For D.
Embodiment 5
A kind of vanadium tungsten titanium oxide catalyst, includes following component by weight/mass percentage composition: vanadic anhydride 14%, three oxygen
Change tungsten 26% and titanium dioxide 60%；Described vanadic anhydride, Tungstic anhydride. and titanium dioxide uniformly mix, and five oxidations two
The crystal particle diameter of vanadium, Tungstic anhydride. and titanium dioxide independently be 5-25nm.
The preparation method of described vanadium tungsten titanium oxide catalyst is:
Other condition such as embodiment 1 is constant, and changing V:W:Ti mol ratio is 0.1:0.15:1, obtains described catalyst, mark
It is designated as E.
Embodiment 6
A kind of vanadium tungsten titanium oxide catalyst, is included by weight/mass percentage composition: vanadic anhydride 19%, Tungstic anhydride. 25%
With titanium dioxide 56%；Described vanadic anhydride, Tungstic anhydride. and titanium dioxide uniformly mix, and vanadic anhydride, three oxygen
The crystal particle diameter changing tungsten and titanium dioxide independently be 5-30nm.
The preparation method of described vanadium tungsten titanium oxide catalyst is:
Other condition such as embodiment 1 is constant, and changing V:W:Ti mol ratio is 0.15:0.15:1, obtains described catalyst, mark
It is designated as F.
Embodiment 7
A kind of vanadium tungsten titanium oxide catalyst, the preparation method of described vanadium tungsten titanium oxide catalyst is:
Other condition such as embodiment 4 is constant, and the change stirring in water bath time is 1h, obtains described catalyst, is labeled as G.
Embodiment 8
A kind of vanadium tungsten titanium oxide catalyst, the preparation method of described vanadium tungsten titanium oxide catalyst is:
Other condition such as embodiment 4 is constant, and the change stirring in water bath time is 3h, obtains described catalyst, is labeled as H.
Embodiment 9
A kind of vanadium tungsten titanium oxide catalyst, the preparation method of described vanadium tungsten titanium oxide catalyst is:
Other condition such as embodiment 4 is constant, and the change stirring in water bath time is 6h, obtains described catalyst, is labeled as I.
Embodiment 10
A kind of vanadium tungsten titanium oxide catalyst, the preparation method of described vanadium tungsten titanium oxide catalyst is:
Other condition such as embodiment 4 is constant, and the change stirring in water bath time is 25h, obtains described catalyst, is labeled as J.
Embodiment 11
A kind of vanadium tungsten titanium oxide catalyst, described catalyst includes following component by weight/mass percentage composition:
Vanadic anhydride 5%, Tungstic anhydride. 30% and titanium dioxide 65%；Described vanadic anhydride, Tungstic anhydride. and two
Titanium oxide uniformly mixes.
The preparation method of described vanadium tungsten titanium oxide catalyst is:
Using ammonium metavanadate as vanadium source, using ammonium tungstate as tungsten source, using titanium sulfate as titanium source, oxalic acid as cosolvent,
Carbamide is as slow release precipitator.
It is that 0.05:0.15:1 is to containing cosolvent (quality of cosolvent and vanadium source and tungsten source according to V:W:Ti mol ratio
The ratio of quality sum is 3:1) solvent in add ammonium metavanadate, ammonium tungstate and titanium sulfate, make mixed solution, and add wherein
Enter excess urea (mole of carbamide is 5:1 with the ratio of the mole of V, W and Ti) as slow release precipitator；Afterwards, at 65 DEG C
Continuous stirring 15h under water bath condition, obtains containing sedimentary solution；Precipitate is carried out sucking filtration and washing, afterwards by filter cake
It is put in 80 DEG C of oven drying 24h, finally in Muffle furnace, prepare powder catalyst in 400 DEG C of roasting 24h under air atmosphere.
Embodiment 12
A kind of vanadium tungsten titanium oxide catalyst, described catalyst includes following component by weight/mass percentage composition:
Vanadic anhydride 25%, Tungstic anhydride. 5% and titanium dioxide 70%；Described vanadic anhydride, Tungstic anhydride. and two
Titanium oxide uniformly mixes.
The preparation method of described vanadium tungsten titanium oxide catalyst is:
Using ammonium metavanadate as vanadium source, using ammonium tungstate as tungsten source, using titanium sulfate as titanium source, hydrochloric acid as cosolvent,
Carbamide is as slow release precipitator.
It is that 0.10:0.05:1 is to containing cosolvent (quality of cosolvent and vanadium source and tungsten source according to V:W:Ti mol ratio
The ratio of quality sum is 0.5:1) solvent in add vanadium source, tungsten source and titanium source, make mixed solution, and be added thereto to excess
Carbamide (mole of carbamide is 25:1 with the ratio of the mole of V, W and Ti) is as slow release precipitator；Afterwards, at 95 DEG C of water-bath bars
Continuous stirring 20h under part, obtains containing sedimentary solution；Precipitate is carried out sucking filtration and washing, afterwards filter cake is put in 120
DEG C oven drying 5h, finally in Muffle furnace, prepare powder catalyst in 700 DEG C of roasting 1h under air atmosphere.
Embodiment 13
A kind of vanadium tungsten titanium oxide catalyst, described catalyst includes following component by weight/mass percentage composition:
Vanadic anhydride 25%, Tungstic anhydride. 25% and titanium dioxide 50%；Described vanadic anhydride, Tungstic anhydride. and two
Titanium oxide uniformly mixes.
The preparation method of described vanadium tungsten titanium oxide catalyst is:
Using vanadium tetrachloride and vanadium oxytrichloride as vanadium source, using ammonium paratungstate as tungsten source, make with titanium sulfate and titanium tetrachloride
For titanium source, nitric acid and oxalic acid as cosolvent, ammonium hydrogen carbonate is as slow release precipitator.
It is that 0.12:0.10:1 is to containing cosolvent (quality in cosolvent and vanadium source and tungsten source according to V:W:Ti mol ratio
The ratio of quality sum be 2:1) solvent in add vanadium source, tungsten source and titanium source, make mixed solution, and be added thereto to excess
Ammonium hydrogen carbonate (mole of ammonium hydrogen carbonate is 15:1 with the ratio of the mole of V, W and Ti)；Afterwards, connect under 80 DEG C of water bath condition
Continuous stirring 5h, obtains containing sedimentary solution；Precipitate is carried out sucking filtration and washing, afterwards filter cake is put in 100 DEG C of baking ovens
It is dried 12h, finally in Muffle furnace, prepare powder catalyst in 600 DEG C of roasting 15h under air atmosphere.
Embodiment 14
A kind of vanadium tungsten titanium oxide catalyst, described catalyst includes following component by weight/mass percentage composition:
Vanadic anhydride 8%, Tungstic anhydride. 7% and titanium dioxide 85%；Described vanadic anhydride, Tungstic anhydride. and dioxy
Change titanium uniformly to mix.
The preparation method of described vanadium tungsten titanium oxide catalyst is:
Using vanadium oxysulfate as vanadium source, using ammonium tungstate and ammonium paratungstate as tungsten source, using butyl titanate as titanium source, phosphorus
Acid is as cosolvent, and ammonium carbonate is as slow release precipitator.
It is that 0.06:0.05:1 is to containing cosolvent (quality of phosphoric acid and vanadium source and the matter in tungsten source according to V:W:Ti mol ratio
The ratio of amount sum is 2:1) solvent in add vanadium source, tungsten source and titanium source, make mixed solution, and be added thereto to excess carbonic acid
Ammonium (mole of ammonium carbonate is 15:1 with the ratio of the mole of V, W and Ti)；Afterwards, continuous stirring under 80 DEG C of water bath condition
5h, obtains containing sedimentary solution；Precipitate is carried out sucking filtration and washing, afterwards filter cake is put in 100 DEG C of oven dryings
12h, finally in Muffle furnace, prepare powder catalyst in 600 DEG C of roasting 15h under air atmosphere.
Comparative example 1
0.61g oxalic acid, 0.064g ammonium metavanadate and 0.55g ammonium tungstate are dissolved in 100mL deionized water, then molten to mixing
Liquid adds 5g TiO2Dust carrier, is sufficiently stirred for more than 1h, then mixed serum is carried out rotary evaporation and fully waves to moisture
Sending out, and dry 12h under 100 DEG C of air atmospheres, finally roasting 5h under 500 DEG C of air atmospheres, obtains comparative catalyst 1%
V2O5-10%WO3/TiO2, it is labeled as K.
Comparative example 2
A kind of vanadium tungsten titanium oxide catalyst (being labeled as L), is included by weight/mass percentage composition: vanadic anhydride 9%, three oxygen
Change tungsten 12% and titanium dioxide 79%；Described vanadic anhydride, Tungstic anhydride. and titanium dioxide uniformly mix, and state five oxidations two
The particle diameter of vanadium, Tungstic anhydride. and titanium dioxide independently be 50nm.
Application examples 1
Prepared sample A, B, C, D, E, F, G, H, I, J, K and L are carried out tabletting, grinds, sieve, take 40-60 mesh granule
Fixed bed reactors carry out NH3Selective Catalytic Reduction of NOx(NH3-SCR) investigation of reactivity.
The usage amount of catalyst is 0.12mL, consisting of of reaction mixture gas: [NO]=[NH3]=500ppm, [O2]=
5%, N2Making Balance Air, total gas flow rate is 400mL/min, and air speed is 200,000h-1, reaction temperature 150-450 DEG C.NO and
NH3And by-product N2O、NO2Nicolet Antaris IGS infrared gas analyser is all utilized to measure.NOxConversion ratio and N2Generate
Selectivity is shown in Tables 1 and 2 respectively.
As shown in Table 1, under same reaction conditions, the low temperature NH of catalyst A, B, C, D, E, F in the present invention3-SCR activity is bright
Aobvious higher than traditional vanadium tungsten titanium oxide catalyst K, and the high temperature active of A, B, E is also above tradition vanadium tungsten titanium oxide catalysis
Agent.As shown in Table 2, in the present invention, catalyst A, B, C, D, E, F also have higher N2Generate selectivity.Therefore, institute of the present invention
The vanadium tungsten titanium oxide catalyst provided has the most excellent catalytic performance.
The NO of the different sample of table 1xConversion ratio
The N of the different sample of table 22Selectivity
From the activity of catalyst G, H, I, D, J in table 1, when the stirring in water bath time is 1h, 3h, 6h, 10h, prepared
The activity of catalyst improves constantly with stirring in water bath time lengthening, and extends to 25h from 10h, and catalyst activity does not occur
Significant change.Therefore, the optimal stirring in water bath time in preparation process is about 10h.
Application examples 2
Choose catalyst D and test the reaction velocity impact on catalyst SCR activity.Adjust catalyst in application examples 1
Usage amount is 0.24mL, so that reaction velocity reduces to 100,000h-1。NOxConversion ratio is as shown in table 3.
Table 3 reaction velocity is 100,000h-1Time catalyst D NOxConversion ratio
The NO of catalyst D in contrast table 3 and table 1xConversion ratio, finds that reducing reaction velocity can improve the catalysis of catalyst
Activity.It is 100,000h in air speed-1Time, catalyst D has broader operation temperature window and more preferable low temperature active, even may be used
To realize the NO of more than 95% under the conditions of 200 DEG CxConversion ratio.
Application examples 3
Choose catalyst A-F, it is tested SO2Impact on catalyst SCR activity.At 250 DEG C to described in application examples 1
Reaction atmosphere in be passed through 100ppm SO2, all there is not reduction phenomenon, shows the present invention in the 48h inner catalyst activity in test
The vanadium tungsten titanium oxide catalyst provided has the most excellent anti-SO2Poisoning performance.
Time actually used, catalyst is placed in exhaust pipe way, sprays into reducing agent in the upstream of catalyst and tail gas mixes
Closing, reducing agent uses ammonia or carbamide (available ammonia after hydrolysis), and reducing agent consumption is the 0.8-1.2 of nitrogen oxide in tail gas
Times, can be by NO in the widest temperature window under excess oxygenxIt is reduced to N2And H2O, is provided simultaneously with the N of excellence2Generate and select
Property and sulfur resistive water repelling property.
Described tail gas is preferably moving source gas containing nitrogen oxide, such as diesel vehicle and ship tail gas, or stationary source is nitrogenous
Oxide gas, such as coal-burning power plant and industrial furnace flue gas.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. a vanadium tungsten titanium oxide catalyst, it is characterised in that described vanadium tungsten titanium oxide catalyst presses weight/mass percentage composition
Including following component: vanadic anhydride 5%-25%, Tungstic anhydride. 5%-30% and titanium dioxide 50%-85%；Described five oxygen
Change two vanadium, Tungstic anhydride. and titanium dioxide uniformly to mix, and the crystal of described vanadic anhydride, Tungstic anhydride. and titanium dioxide
Particle diameter independently be 1-30nm.
2. the preparation method of a vanadium tungsten titanium oxide catalyst, it is characterised in that described preparation method comprises the steps:
(1) vanadium source, tungsten source, titanium source, alternatively cosolvent and solvent are mixed to form mixed solution；
(2) in mixed solution, add slow release precipitator, obtain reaction solution；
(3) raising the temperature of reaction solution, reaction solution reacts, and obtains containing sedimentary solution；
(4) post processing will be carried out containing sedimentary solution, obtain described vanadium tungsten titanium oxide catalyst.
Preparation method the most according to claim 2, it is characterised in that in vanadium in step (1) described vanadium source, tungsten source
The mol ratio of the titanium in tungsten, titanium source is (0.05-0.15): (0.05-0.15): 1；
Preferably, the quality of step (1) described cosolvent is (0.5-3) with the ratio of the quality sum in vanadium source and tungsten source: 1；
Preferably, the mode of step (1) described mixing is stirring；
Preferably, carry out at being blended in 10-40 DEG C described in step (1).
4. according to the preparation method described in Claims 2 or 3, it is characterised in that step (1) described vanadium source selected from ammonium metavanadate,
Any one or the combination of at least two in vanadium oxysulfate, vanadyl oxalate, vanadium tetrachloride or vanadium oxytrichloride；
Preferably, step (1) described tungsten source is selected from ammonium tungstate and/or ammonium paratungstate；
Preferably, step (1) described titanium source in titanium sulfate, titanium tetrachloride or butyl titanate any one or at least two
The combination planted；
Preferably, step (1) described cosolvent in oxalic acid, acetic acid, nitric acid, sulphuric acid, hydrochloric acid or phosphoric acid any one or
The combination of at least two；
Preferably, step (1) described solvent is water.
5. according to the preparation method one of claim 2-4 Suo Shu, it is characterised in that step (2) described slow release precipitator is selected from
Any one or the combination of at least two in carbamide, ammonium carbonate or ammonium hydrogen carbonate；
Preferably, the mole of step (2) described slow release precipitator and vanadium, the tungsten in tungsten source and the titanium in titanium source in vanadium source
The ratio of mole sum is (5-25): 1.
6. according to the preparation method one of claim 2-5 Suo Shu, it is characterised in that step (3) described rising reaction solution
Temperature is: raise the temperature of reaction solution to 65-95 DEG C；
Preferably, step (3) described slow release precipitator reacts under agitation with vanadium source, tungsten source and titanium source；
Preferably, the time of described stirring is 1-25h, preferably 10h.
7. utilize the preparation method that one of claim 2-6 is described, it is characterised in that step (4) described post processing is: will contain
Sedimentary solution solid-liquid separation, is precipitated thing, then is washed by precipitate, be dried, roasting；
Preferably, the method for described solid-liquid separation is for filtering and/or centrifugation；
Preferably, described dry temperature is 80-120 DEG C；
Preferably, the described dry time is 5-24h；
Preferably, the temperature of described roasting is 400-700 DEG C；
Preferably, the time of described roasting is 1-24h.
8. according to the preparation method one of claim 2-7 Suo Shu, it is characterised in that described preparation method comprises the steps:
(1) by vanadium source, tungsten source, titanium source, solvent and alternatively cosolvent be mixed to form mixed solution, wherein, in described vanadium source
Tungsten in vanadium, tungsten source, the mol ratio of the titanium in titanium source are (0.05-0.15): (0.05-0.15): 1, the quality of cosolvent and vanadium
The ratio of the quality sum in source and tungsten source is (0.5-3): 1；
(2) in mixed solution, add slow release precipitator, obtain in reaction solution, the mole of described slow release precipitator and vanadium source
The ratio of mole sum of vanadium, the tungsten in tungsten source and the titanium in titanium source be (5-25): 1；
(3) temperature raising reaction solution is to 65-95 DEG C and continuously stirred, and reaction solution reacts, and after 5-25h, is contained
There is sedimentary solution；
(4) solid-liquid separation will be carried out containing sedimentary solution, be precipitated thing, precipitate will be washed, be dried at 80-120 DEG C
5-24h, then at 400-700 DEG C of roasting 1-24h, obtain described vanadium tungsten titanium oxide catalyst.
9. the method for a selective catalyst reduction of nitrogen oxides, it is characterised in that use the vanadium tungsten titanyl described in claim 1
Compound catalyst is as the catalyst of selective catalyst reduction of nitrogen oxides.
Method the most according to claim 9, it is characterised in that the temperature of described selective catalyst reduction of nitrogen oxides is
150-500℃。
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| CN106984300A (en) * | 2017-05-26 | 2017-07-28 | 中国科学院生态环境研究中心 | A kind of vanadium titanium oxide catalyst and its production and use |
| CN108236943A (en) * | 2016-12-23 | 2018-07-03 | 中国科学院宁波城市环境观测研究站 | A kind of preparation method of vanadium oxide catalyst |
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| CN108262037A (en) * | 2016-12-30 | 2018-07-10 | 中国科学院宁波城市环境观测研究站 | A kind of vanadium oxide catalyst of low temperature performance excellent and its application |
| CN109364943A (en) * | 2018-12-12 | 2019-02-22 | 辽宁大学 | A kind of efficient cryogenic denitrating catalyst and its preparation method and application |
| CN110124677A (en) * | 2019-06-24 | 2019-08-16 | 江苏浩日朗环保科技有限公司 | Denitrating catalyst and preparation method thereof |
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| CN109364943A (en) * | 2018-12-12 | 2019-02-22 | 辽宁大学 | A kind of efficient cryogenic denitrating catalyst and its preparation method and application |
| CN110124677A (en) * | 2019-06-24 | 2019-08-16 | 江苏浩日朗环保科技有限公司 | Denitrating catalyst and preparation method thereof |
| CN112844370A (en) * | 2020-12-30 | 2021-05-28 | 中国科学院生态环境研究中心 | Vanadium-titanium catalyst and preparation method and application thereof |
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