CN105251477A - High-temperature SCR denitration catalyst in vanadium wide window and preparing method and application of high-temperature SCR denitration catalyst - Google Patents
High-temperature SCR denitration catalyst in vanadium wide window and preparing method and application of high-temperature SCR denitration catalyst Download PDFInfo
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Abstract
The invention discloses a high-temperature SCR denitration catalyst in a vanadium wide window and a preparing method and application of the high-temperature SCR denitration catalyst. According to the catalyst, titanium-tin oxide serves as a carrier, vanadium oxide serves as an active ingredient, tungsten oxide serves as a promoter, TiO2-SnO2 serves as the titanium-tin oxide, V2O5 serves as the vanadium oxide, WO3 serves as the tungsten oxide, and V2O5-WO3/TiO2-SnO2 serves as the promoter. In the catalyst, the mole ratio of the titanium element to the tin element is 1 to 1, the mass of the tungsten oxide accounts for 6-12% of the total mass of the tungsten oxide and the titanium-tin oxide, and the mass of the vanadium oxide accounts for 1% of the mass of the catalyst. Due to the fact that tungsten trioxide is added, the dispersity of V2O5 on the surface of the catalyst is enhanced, the Bronsted acidity of the surface of the catalyst is greatly increased, and thus the denitration efficiency of the catalyst is improved. Meanwhile, the preparing method and application of the catalyst are disclosed.
Description
Technical field
The invention belongs to Flue Gas Denitration Technology of Coal-buming Power Plant field, specifically refer to high temperature SCR denitration and its preparation method and application in the wide window of vanadium system.
Background technology
Have a lot for SCR denitration catalysts kind at present, wherein V
2o
5/ WO
3(MoO
3)/TiO
2(Detitanium-ore-type) catalyst series is SCR industrial catalyst most widely used at present.The temperature window of traditional business denitrating catalyst application is 370-430 DEG C, and power-plant flue gas did not often reach the requirement of denitration temperature window before entering denitrating system, therefore post bake to be carried out to flue gas, add the cost of power-plant flue gas denitration, develop wide temperature window, the catalyst of high denitration rate has just become a problem demanding prompt solution.
It should be noted that traditional V
2o
5/ TiO
2(anatase) catalyst based is the system of a rather unstable, TiO
2(anatase) is a kind of metastable state crystal in titanium oxide, and specific area is less, and when being heated, surface is very easily shunk, and is easily converted into the more stable rutile of thermodynamic state, WO under uniform temperature and pressure condition
3and MoO
3add the conversion contributing to stoping anatase form, but fundamentally cannot to solve the problem, so how to address this problem the place just becoming key.
In recent years, various metals is doped to TiO by much research
2middle formation composite oxide carrier, as TiO
2-ZrO
2deng, to improving TiO
2the mechanical strength of (anatase), specific area, heat endurance and reactivity.TiO
2-ZrO
2solid solution specific area can reach 256.14m
2/ g.ZrO
2interpolation inhibit anatase titanium dioxide TiO
2to rutile TiO
2transformation, enhance TiO
2-ZrO
2heat endurance.Correlative study simultaneously also finds TiO
2-ZrO
2solid solution has powerful acidity, has certain denitration activity (50%), therefore TiO
2-ZrO
2solid solution is the extremely promising denitration catalyst carrier of one.
Summary of the invention
An object of the present invention is to provide high temperature SCR denitration in the wide window of vanadium system, and this catalyst not only will possess stronger high-temperature catalytic activity, and will possess the wide characteristic of temperature window.
This purpose of the present invention realizes by following technical solution: high temperature SCR denitration in the wide window of a kind of vanadium system, it is characterized in that: described catalyst with titanium tin-oxide for carrier, with the oxide of vanadium for active component, with the oxide of tungsten for co-catalyst, described titanium tin-oxide is TiO
2-SnO
2, the oxide of described vanadium is V
2o
5, the oxide of described tungsten is WO
3, described catalyst is V
2o
5-WO
3/ TiO
2-SnO
2, wherein, in described catalyst, the mol ratio of titanium elements and tin element is 1 ︰ 1, and the quality of the oxide of described tungsten accounts for 6 ~ 12% of the oxide of tungsten and the gross mass of titanium tin-oxide, and the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
In catalyst of the present invention, adding of tungstic acid enhances V
2o
5at catalyst surface dispersed, significantly enhance catalyst surface
acid amount, and then improve the denitration efficiency of catalyst.
Two of object of the present invention is to provide the preparation method of high temperature SCR denitration in the wide window of above-mentioned vanadium system, and this preparation method is simple to operate, can obtain high temperature SCR denitration in the wide window of vanadium system.
This purpose of the present invention realizes by following technical solution: the preparation method of high temperature SCR denitration in the wide window of vanadium system, it is characterized in that, the method comprises the steps:
(1) TiO
2-SnO
2the preparation of carrier: utilize coprecipitation to prepare TiO
2-SnO
2carrier, the TiO of preparation
2-SnO
2in carrier, the mol ratio of titanium elements and tin element is 1 ︰ 1, by the TiO of preparation
2-SnO
2carrier is for subsequent use after drying, grinding, calcining successively;
(2) WO
3/ TiO
2-SnO
2preparation: the TiO that step (1) is obtained
2-SnO
2carrier joins in oxalic acid deionized water solution, then adds ammonium tungstate, under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, is warming up to 80 ~ 90 DEG C and continues to stir dipping 4 ~ 5h, after band moisture evaporate to dryness, then obtains WO after drying, grinding, calcining successively
3/ TiO
2-SnO
2catalyst, the ammonium tungstate wherein added and TiO
2-SnO
2the mass ratio of carrier is 6.98 ~ 14.9 ︰ 100, thus makes the quality of the oxide of tungsten account for oxide and the TiO of tungsten
2-SnO
26 ~ 12% of the gross mass of carrier;
(3) V
2o
5-WO
3/ TiO
2-SnO
2the preparation of catalyst: the WO that step (2) is obtained
3/ TiO
2-SnO
2join in oxalic acid deionized water solution, then add ammonium metavanadate, under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, be warming up to 80 ~ 90 DEG C and continue to stir dipping 4 ~ 5h, after moisture evaporate to dryness, obtaining V after drying, grinding, calcining successively
2o
5-WO
3/ TiO
2-SnO
2catalyst, wherein, the ammonium metavanadate added and WO
3/ TiO
2-SnO
2mass ratio be 1.29 ︰ 100, thus make V
2o
5-WO
3/ TiO
2-SnO
2in, the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
In step of the present invention (2), oxalic acid only plays the effect promoting that ammonium tungstate dissolves, and 5g oxalic acid is enough relative to the load capacity being at every turn no more than 2g, and unnecessary oxalic acid can be decomposed into CO by follow-up oil bath link
2and H
2o.In step (3), oxalic acid only plays the effect promoting that ammonium metavanadate dissolves, and 5g oxalic acid is enough relative to the load capacity being at every turn no more than 2g, and unnecessary oxalic acid can be decomposed into CO by follow-up oil bath link
2and H
2o.In the present invention, in described step (1), coprecipitation prepares TiO
2-SnO
2the concrete steps of carrier are: under the condition of ice-water bath, stirring, to volume be 200ml, concentration is drip the TiCl of 9.56ml with the speed of 0.8 ~ 1ml/min while stirring in the stannic chloride pentahydrate deionized water solution of 0.1528g/ml
4, drip NH with the speed of 3 ~ 5ml/min simultaneously
3mass content is that the ammoniacal liquor of 25% ~ 28% is in reactor, until be 9 ~ 10 with the pH that pH test paper records solution in reactor, then leave standstill 12 ~ 14h hypsokinesis and go supernatant liquor to be precipitated thing, spend sediment described in deionized water, and suction filtration, repeated washing until in filtrate inspection do not measure Cl
-till, obtain TiO
2-SnO
2carrier.
To TiCl
4ammoniacal liquor (NH is dropwise dripped with in the solution of stannic chloride pentahydrate
3content is 25% ~ 28%) adjust ph to 9 ~ 10, when dripping ammoniacal liquor with glue head dropper, TiCl
4with can produce in the solution of stannic chloride pentahydrate white " milky " precipitation, when instilling next ammoniacal liquor, observe the position that an ammoniacal liquor drips in the solution, next drip ammoniacal liquor drip position want and upper one stagger, can ensure that diverse location all can form precipitation in the solution like this; In dropping ammoniacal liquor process, continuous glass bar to dip solution in large beaker, survey the pH value of solution until 9 ~ 10 with pH test paper, now stop dripping ammoniacal liquor, obtain white " milky " precipitation, leave standstill 12 ~ 14h, wash, suction filtration.Particularly, spend deionized water, collect the waste liquid of washing precipitation, waste liquid is placed in beaker, check among waste liquid with or without chlorion with the liquor argenti nitratis ophthalmicus of 0.1mol/L, if also have chlorion, continue washing, until without chlorion in silver nitrate inspection waste liquid, the object of this method is to prevent raw material TiCl
4in precipitation, the metal complex of chloride ion-containing is formed with the chlorion symbiosis in stannic chloride pentahydrate, and then the quality of impact precipitation.
In the present invention, the concentration of described step (2) mesoxalic acid deionized water solution is 0.5g/ml, the quality of oxalic acid and TiO
2-SnO
2the quality of carrier is 1 ︰ 1; The concentration of described step (3) mesoxalic acid deionized water solution is 0.5g/ml, the quality of oxalic acid and TiO
2-SnO
2the mass ratio of carrier is 2.5 ︰ 1.
In the present invention, the stirring in described step (1), (2) and (3) is magnetic agitation or mechanical agitation, and stir speed (S.S.) is 20 ~ 30r/s.
In the present invention, the drying condition in described step (1), (2) and (3) is dry 11 ~ 13h at 100 ~ 120 DEG C of temperature.
In the present invention, the calcination condition in described step (1), (2) and (3) is 400 ~ 500 DEG C of temperature lower calcination 3 ~ 4h.The calcining heat of whole preparation process can not higher than 500 DEG C, and when calcining heat is higher than 500 DEG C, titanium dioxide starts have anatase crystal to change to rutile crystal type, unfavorable to reaction.Preferably, the condition of described calcining is calcine 4h at 450 DEG C.
In the present invention, the grinding condition in described step (1), (2) and (3) for being ground to 60 orders, and then be dissolved in deionized water or ammonium tungstate oxalic acid solution in.
Three of object of the present invention is to provide the application of high temperature SCR denitration in thermal power plant in high temperature SCR denitration in the wide window of above-mentioned vanadium system.
Preferably, the temperature range of described middle high temperature is 250 ~ 400 DEG C.
Compared with prior art, in the wide window of vanadium system of the present invention high temperature SCR denitration by adding WO
3, adding of tungstic acid enhances V
2o
5in the dispersiveness of catalyst surface, enhance catalyst surface
acid amount, and then improve the denitration efficiency of catalyst.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.
Fig. 1 is V of the present invention
2o
5(1%)-WO
3(x%)/TiO
2-SnO
2the denitration performance comparison diagram of catalyst series, wherein, x% is respectively 0%, 6%, 9% and 12%;
Fig. 2 is V of the present invention
2o
5(1%)-WO
3(x%)/TiO
2-SnO
2the NH of catalyst series
3-TPD spectrogram, wherein, x% is respectively 0%, 6%, 9% and 12%;
Fig. 3 is V of the present invention
2o
5(1%)-WO
3(x%)/TiO
2-SnO
2the FT-IR spectrogram of catalyst series, wherein, x% is respectively 0%, 6%, 9% and 12%, and (a), (b), (c), (d) represent WO respectively
3be 0%, WO
3be 6%, WO
3be 9% and WO
3it is the FT-IR spectrogram of the catalyst of 12%;
Fig. 4 is V of the present invention
2o
5(1%)/TiO
2-SnO
2the XRD spectra of catalyst;
Fig. 5 is V of the present invention
2o
5(1%)-WO
3(6%)/TiO
2-SnO
2the XRD spectra of catalyst;
Fig. 6 is V of the present invention
2o
5(1%)-WO
3(9%)/TiO
2-SnO
2the XRD spectra of catalyst;
Fig. 7 is V of the present invention
2o
5(1%)-WO
3(12%)/TiO
2-SnO
2the XRD spectra of catalyst.
Detailed description of the invention
Embodiment 1
High temperature SCR denitration in the wide window of a kind of vanadium system, this catalyst is with titanium tin-oxide for carrier, and with the oxide of vanadium for active component, with the oxide of tungsten for co-catalyst, titanium tin-oxide is TiO
2-SnO
2, the oxide of vanadium is V
2o
5, the oxide of tungsten is WO
3, catalyst is V
2o
5-WO
3/ TiO
2-SnO
2, wherein, in catalyst, the mol ratio of titanium elements and tin element is 1 ︰ 1, and the quality of the oxide of tungsten accounts for 6% of the oxide of tungsten and the gross mass of titanium tin-oxide, and the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
The preparation method of above-mentioned catalyst, comprises the steps:
(1) TiO
2-SnO
2the preparation of carrier: use Co deposited synthesis TiO
2-SnO
2solid solution (titanium tin solid solution, Ti-Sn).
With titanium tetrachloride (TiCl
4, density 1.726g/ml) and stannic chloride pentahydrate (SnCl
45H
2o) be raw material, first in fume hood, place 2L large beaker, moved in frozen water by 2L large beaker, insert magnetic stirring apparatus in large beaker, open and stir, mixing speed is 20r/s.30.5677g stannic chloride pentahydrate dissolves by the experimental bench outside fume hood in 25ml beaker, and lysate is proceeded in the large beaker of 2L, add deionized water, add the stannic chloride pentahydrate deionized water solution that rear formation volume is 200ml, concentration is 0.1528g/ml, stir with back and just dropwise instill 9.56ml titanium tetrachloride, often drip interval 10s, to guarantee that titanium tetrachloride solution thoroughly can be hydrolyzed in the solution of stannic chloride pentahydrate.Then NH is dripped
3content be the ammoniacal liquor of 25%, regulate the pH value to 9 of solution in large beaker, in dropping process, should stagger in the two dropping positions of ammoniacal liquor in large beaker solution, front and back, dropwise drip until produce white " milky " precipitation in solution, continuous glass bar dips the solution in large beaker in the process, surveys the pH value of solution with pH test paper, when pH value is 9, stop dripping.By precipitation leave standstill 12 hours, deionized water washing, suction filtration, repeated washing until in filtrate inspection do not measure Cl
-till, obtain TiO
2-SnO
2carrier, the TiO of preparation
2-SnO
2in carrier, the mol ratio of titanium elements and tin element is 1 ︰ 1, by the TiO of preparation
2-SnO
2carrier is for subsequent use after drying, grinding, calcining successively, dries as 100 DEG C of dry 13h in an oven, gets dried solid, pulverize and sieve, get 60 object solids after sieving, calcine 4h and namely obtain titanium tin solid solution, i.e. TiO in Muffle furnace at 400 DEG C
2-SnO
2, wherein, n (Ti)/n (Sn)=1, n is molal quantity.
(2) WO
3/ TiO
2-SnO
2preparation: load ammonium tungstate, calcining obtain WO
3/ TiO
2-SnO
2.
Get TiO prepared by step (1)
2-SnO
2carrier 5g, put into beaker, add in the oxalic acid deionized water solution that volume is 10ml, concentration is 0.5g/ml, then ammonium tungstate is added, oxalic acid only plays the effect promoting that ammonium tungstate dissolves, 5g oxalic acid is enough relative to the load capacity being at every turn no more than 2g, and oxalic acid can be decomposed into CO by follow-up oil bath link
2and H
2o, therefore the concentration of oxalic acid is on reaction not impact, chooses according to actual needs, the ammonium tungstate added and TiO
2-SnO
2the mass ratio of carrier is 6.98 ︰ 100, thus makes the quality of the oxide of tungsten account for oxide and the TiO of tungsten
2-SnO
26% of the gross mass of carrier, by beaker oil bath 5h at 80 DEG C of temperature, stir evaporate to dryness, take out the solid after evaporate to dryness, 100 DEG C of dry 13h, pulverize and sieve in an oven, get 60 object solids after sieving; Calcine 4h at 400 DEG C in Muffle furnace, namely obtain: 6%W/Ti-Sn (i.e. 6%WO
3/ TiO
2-SnO
2), wherein, the WO prepared by 6% representative
3/ TiO
2-SnO
2wO in catalyst
3quality account for WO
3/ TiO
2-SnO
2gross mass percentage by weight be 6%.
In above-mentioned steps (2), by beaker oil bath 5h at 80 DEG C of temperature, also can replace with and first under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, be then warming up to 80 ~ 90 DEG C and continue to stir dipping 4 ~ 5h, reaching same evaporate to dryness effect.
(3) V
2o
5-WO
3/ TiO
2-SnO
2the preparation of catalyst: load ammonium metavanadate, gets the 6%WO prepared
3/ TiO
2-SnO
22g, put into 25ml beaker, add in the oxalic acid deionized water solution that volume is 10ml, concentration is 0.5g/ml, then the ammonium metavanadate of 0.026g is added, oxalic acid only plays the effect promoting that ammonium tungstate dissolves, 5g oxalic acid is enough relative to the load capacity being at every turn no more than 2g, and oxalic acid can be decomposed into CO by follow-up oil bath link
2and H
2o, therefore the concentration of oxalic acid is on reaction not impact, chooses according to actual needs, the ammonium metavanadate added and WO
3/ TiO
2-SnO
2mass ratio be 1.29 ︰ 100, thus make V
2o
5-WO
3/ TiO
2-SnO
2in, the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst, and by beaker oil bath 5h at 80 DEG C of temperature, stir evaporate to dryness, take out the solid after evaporate to dryness, 100 DEG C of dry 13h, pulverize and sieve in an oven, get 60 object solids after sieving; Calcine 4h at 400 DEG C in Muffle furnace, namely obtain V
2o
5-WO
3/ TiO
2-SnO
2catalyst, in this catalyst, the mol ratio of titanium elements and tin element is 1 ︰ 1, and the quality of the oxide of tungsten accounts for 6% of the oxide of tungsten and the gross mass of titanium tin-oxide, and the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
In above-mentioned steps (3), by beaker oil bath 5h at 80 DEG C of temperature, also can replace with and first under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, be then warming up to 80 ~ 90 DEG C and continue to stir dipping 4 ~ 5h, reaching same evaporate to dryness effect.
Embodiment 2
High temperature SCR denitration in the wide window of a kind of vanadium system, this catalyst is with titanium tin-oxide for carrier, and with the oxide of vanadium for active component, with the oxide of tungsten for co-catalyst, titanium tin-oxide is TiO
2-SnO
2, the oxide of vanadium is V
2o
5, the oxide of tungsten is WO
3, catalyst is V
2o
5-WO
3/ TiO
2-SnO
2, wherein, in catalyst, the mol ratio of titanium elements and tin element is 1 ︰ 1, and the quality of the oxide of tungsten accounts for 9% of the oxide of tungsten and the gross mass of titanium tin-oxide, and the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
The preparation method of above-mentioned catalyst, comprises the steps:
(1) TiO
2-SnO
2the preparation of carrier: use Co deposited synthesis TiO
2-SnO
2solid solution (titanium tin solid solution, Ti-Sn).
With titanium tetrachloride (TiCl
4, density 1.726g/ml) and stannic chloride pentahydrate (SnCl
45H
2o) be raw material, first in fume hood, place 2L large beaker, moved in frozen water by 2L large beaker, insert magnetic stirring apparatus in large beaker, open and stir, mixing speed is 25r/s.30.5677g stannic chloride pentahydrate dissolves by the experimental bench outside fume hood in 25ml beaker, and lysate is proceeded in the large beaker of 2L, add deionized water, add the stannic chloride pentahydrate deionized water solution that rear formation volume is 200ml, concentration is 0.1528g/ml, stir with back and just dropwise instill 9.56ml titanium tetrachloride, often drip interval 10s, to guarantee that titanium tetrachloride solution thoroughly can be hydrolyzed in the solution of stannic chloride pentahydrate.Then NH is dripped
3content be the ammoniacal liquor of 26%, regulate the pH value to 9.5 of solution in large beaker, in dropping process, should stagger in the two dropping positions of ammoniacal liquor in large beaker solution, front and back, dropwise drip until produce white " milky " precipitation in solution, continuous glass bar dips the solution in large beaker in the process, surveys the pH value of solution with pH test paper, when pH value is 9.5, stop dripping.By precipitation leave standstill 12 hours, deionized water washing, suction filtration, repeated washing until in filtrate inspection do not measure Cl
-till, obtain TiO
2-SnO
2carrier, the TiO of preparation
2-SnO
2in carrier, the mol ratio of titanium elements and tin element is 1 ︰ 1, by the TiO of preparation
2-SnO
2carrier is for subsequent use after drying, grinding, calcining successively, dries as 110 DEG C of dry 12h in an oven, gets dried solid, pulverize and sieve, get 60 object solids after sieving, calcine 3.5h and namely obtain titanium tin solid solution, i.e. TiO in Muffle furnace at 450 DEG C
2-SnO
2, wherein, n (Ti)/n (Sn)=1, n is molal quantity.
(2) WO
3/ TiO
2-SnO
2preparation: load ammonium tungstate, calcining obtain WO
3/ TiO
2-SnO
2.
Get TiO prepared by step (1)
2-SnO
2carrier 5g, put into beaker, add in the oxalic acid deionized water solution that volume is 10ml, concentration is 0.5g/ml, then ammonium tungstate is added, oxalic acid only plays the effect promoting that ammonium tungstate dissolves, 5g oxalic acid is enough relative to the load capacity being at every turn no more than 2g, and oxalic acid can be decomposed into CO by follow-up oil bath link
2and H
2o, therefore the concentration of oxalic acid is on reaction not impact, chooses according to actual needs, the ammonium tungstate added and TiO
2-SnO
2the mass ratio of carrier is 10.82 ︰ 100, thus makes the quality of the oxide of tungsten account for oxide and the TiO of tungsten
2-SnO
29% of the gross mass of carrier, by beaker oil bath 4h at 90 DEG C of temperature, stir evaporate to dryness, take out the solid after evaporate to dryness, 110 DEG C of dry 12h, pulverize and sieve in an oven, get 60 object solids after sieving; Calcine 3.5h at 450 DEG C in Muffle furnace, namely obtain: 9%W/Ti-Sn (i.e. 9%WO
3/ TiO
2-SnO
2), wherein, the WO prepared by 9% representative
3/ TiO
2-SnO
2wO in catalyst
3quality account for WO
3/ TiO
2-SnO
2gross mass percentage by weight be 9%.
In above-mentioned steps (2), by beaker oil bath 5h at 80 DEG C of temperature, also can replace with and first under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, be then warming up to 80 ~ 90 DEG C and continue to stir dipping 4 ~ 5h, reaching same evaporate to dryness effect.
(3) V
2o
5-WO
3/ TiO
2-SnO
2the preparation of catalyst: load ammonium metavanadate, gets the 6%WO prepared
3/ TiO
2-SnO
22g, put into 25ml beaker, add in the oxalic acid deionized water solution that volume is 10ml, concentration is 0.5g/ml, then the ammonium metavanadate of 0.026g is added, oxalic acid only plays the effect promoting that ammonium tungstate dissolves, 5g oxalic acid is enough relative to the load capacity being at every turn no more than 2g, and oxalic acid can be decomposed into CO by follow-up oil bath link
2and H
2o, therefore the concentration of oxalic acid is on reaction not impact, chooses according to actual needs, the ammonium metavanadate added and WO
3/ TiO
2-SnO
2mass ratio be 1.29 ︰ 100, thus make V
2o
5-WO
3/ TiO
2-SnO
2in, the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst, and by beaker oil bath 4h at 90 DEG C of temperature, stir evaporate to dryness, take out the solid after evaporate to dryness, 110 DEG C of dry 12h, pulverize and sieve in an oven, get 60 object solids after sieving; Calcine 3.5h at 450 DEG C in Muffle furnace, namely obtain V
2o
5-WO
3/ TiO
2-SnO
2catalyst, in this catalyst, the mol ratio of titanium elements and tin element is 1 ︰ 1, and the quality of the oxide of tungsten accounts for 9% of the oxide of tungsten and the gross mass of titanium tin-oxide, and the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
In above-mentioned steps (3), by beaker oil bath 5h at 80 DEG C of temperature, also can replace with and first under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, be then warming up to 80 ~ 90 DEG C and continue to stir dipping 4 ~ 5h, reaching same evaporate to dryness effect.
Embodiment 3
High temperature SCR denitration in the wide window of a kind of vanadium system, this catalyst is with titanium tin-oxide for carrier, and with the oxide of vanadium for active component, with the oxide of tungsten for co-catalyst, titanium tin-oxide is TiO
2-SnO
2, the oxide of vanadium is V
2o
5, the oxide of tungsten is WO
3, catalyst is V
2o
5-WO
3/ TiO
2-SnO
2, wherein, in catalyst, the mol ratio of titanium elements and tin element is 1 ︰ 1, and the quality of the oxide of tungsten accounts for 12% of the oxide of tungsten and the gross mass of titanium tin-oxide, and the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
The preparation method of above-mentioned catalyst, comprises the steps:
(1) TiO
2-SnO
2the preparation of carrier: use Co deposited synthesis TiO
2-SnO
2solid solution (titanium tin solid solution, Ti-Sn).
With titanium tetrachloride (TiCl
4, density 1.726g/ml) and stannic chloride pentahydrate (SnCl
45H
2o) be raw material, first in fume hood, place 2L large beaker, moved in frozen water by 2L large beaker, insert magnetic stirring apparatus in large beaker, open and stir, mixing speed is 30r/s.30.5677g stannic chloride pentahydrate dissolves by the experimental bench outside fume hood in 25ml beaker, and lysate is proceeded in the large beaker of 2L, add deionized water, add the stannic chloride pentahydrate deionized water solution that rear formation volume is 200ml, concentration is 0.1528g/ml, stir with back and just dropwise instill 9.56ml titanium tetrachloride, often drip interval 10s, to guarantee that titanium tetrachloride solution thoroughly can be hydrolyzed in the solution of stannic chloride pentahydrate.Then NH is dripped
3content be the ammoniacal liquor of 25%, regulate the pH value to 10 of solution in large beaker, in dropping process, should stagger in the two dropping positions of ammoniacal liquor in large beaker solution, front and back, dropwise drip until produce white " milky " precipitation in solution, continuous glass bar dips the solution in large beaker in the process, surveys the pH value of solution with pH test paper, when pH value is 10, stop dripping.By precipitation leave standstill 12 hours, deionized water washing, suction filtration, repeated washing until in filtrate inspection do not measure Cl
-till, obtain TiO
2-SnO
2carrier, the TiO of preparation
2-SnO
2in carrier, the mol ratio of titanium elements and tin element is 1 ︰ 1, by the TiO of preparation
2-SnO
2carrier is for subsequent use after drying, grinding, calcining successively, dries as 120 DEG C of dry 11h in an oven, gets dried solid, pulverize and sieve, get 60 object solids after sieving, calcine 3h and namely obtain titanium tin solid solution, i.e. TiO in Muffle furnace at 500 DEG C
2-SnO
2, wherein, n (Ti)/n (Sn)=1, n is molal quantity.
(2) WO
3/ TiO
2-SnO
2preparation: load ammonium tungstate, calcining obtain WO
3/ TiO
2-SnO
2.
Get TiO prepared by step (1)
2-SnO
2carrier 5g, put into beaker, add in the oxalic acid deionized water solution that volume is 10ml, concentration is 0.5g/ml, then ammonium tungstate is added, oxalic acid only plays the effect promoting that ammonium tungstate dissolves, 5g oxalic acid is enough relative to the load capacity being at every turn no more than 2g, and oxalic acid can be decomposed into CO by follow-up oil bath link
2and H
2o, therefore the concentration of oxalic acid is on reaction not impact, chooses according to actual needs, the ammonium tungstate added and TiO
2-SnO
2the mass ratio of carrier is 14.9 ︰ 100, thus makes the quality of the oxide of tungsten account for oxide and the TiO of tungsten
2-SnO
212% of the gross mass of carrier, by beaker oil bath 5h at 80 DEG C of temperature, stir evaporate to dryness, take out the solid after evaporate to dryness, 120 DEG C of dry 11h, pulverize and sieve in an oven, get 60 object solids after sieving; Calcine 3h at 500 DEG C in Muffle furnace, namely obtain: 12%W/Ti-Sn (i.e. 6%WO
3/ TiO
2-SnO
2), wherein, the WO prepared by 12% representative
3/ TiO
2-SnO
2wO in catalyst
3quality account for WO
3/ TiO
2-SnO
2gross mass percentage by weight be 12%.
In above-mentioned steps (2), by beaker oil bath 5h at 80 DEG C of temperature, also can replace with and first under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, be then warming up to 80 ~ 90 DEG C and continue to stir dipping 4 ~ 5h, reaching same evaporate to dryness effect.
(3) V
2o
5-WO
3/ TiO
2-SnO
2the preparation of catalyst: load ammonium metavanadate, gets the 6%WO prepared
3/ TiO
2-SnO
22g, put into 25ml beaker, add in the oxalic acid deionized water solution that volume is 10ml, concentration is 0.5g/ml, then the ammonium metavanadate of 0.026g is added, oxalic acid only plays the effect promoting that ammonium tungstate dissolves, 5g oxalic acid is enough relative to the load capacity being at every turn no more than 2g, and oxalic acid can be decomposed into CO by follow-up oil bath link
2and H
2o, therefore the concentration of oxalic acid is on reaction not impact, chooses according to actual needs, the ammonium metavanadate added and WO
3/ TiO
2-SnO
2mass ratio be 1.29 ︰ 100, thus make V
2o
5-WO
3/ TiO
2-SnO
2in, the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst, and by beaker oil bath 5h at 80 DEG C of temperature, stir evaporate to dryness, take out the solid after evaporate to dryness, 130 DEG C of dry 11h, pulverize and sieve in an oven, get 60 object solids after sieving; Calcine 3h at 500 DEG C in Muffle furnace, namely obtain V
2o
5-WO
3/ TiO
2-SnO
2catalyst, in this catalyst, the mol ratio of titanium elements and tin element is 1 ︰ 1, and the quality of the oxide of tungsten accounts for 12% of the oxide of tungsten and the gross mass of titanium tin-oxide, and the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
In above-mentioned steps (3), by beaker oil bath 5h at 80 DEG C of temperature, also can replace with and first under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, be then warming up to 80 ~ 90 DEG C and continue to stir dipping 4 ~ 5h, reaching same evaporate to dryness effect.
Following analysis is done to the catalyst that above-mentioned 3 embodiments obtain
(1) NH
3-TPD analyzes
NH
3-TPD analyzes full auto-programs intensification chemical adsorption instrument (FINESORB-3010) pretreatment temperature 150 DEG C adopting Zhejiang Fan Tai instrument company, heating rate 10 DEG C/min, desorption temperature 25 DEG C ~ 800 DEG C, nitrogen purges 10min, and data acquisition TCD thermal conductivity detector (TCD) detects.Fig. 2 is V
2o
5(1%)-WO
3(x%)/TiO
2-SnO
2the NH of catalyst series
3-TPD result, x% is respectively 0%, 6%, 9% and 12%, 6%W/Ti-Sn (6%WO
3/ TiO
2-SnO
2), 9%W/Ti-Sn (9%WO
3/ TiO
2-SnO
2), 12%W/Ti-Sn (12%WO
3/ TiO
2-SnO
2) (wherein, 6%, 9% and 12% represent prepared WO respectively
3/ TiO
2-SnO
2wO in catalyst
3account for WO
3/ TiO
2-SnO
2the percentage by weight of catalyst is 6%, 9% and 12%).WO
3after load, the quantity in catalyst surface acid site and acid amount obviously increase, especially at the strong acid center of about 375 DEG C appearance, within the denitration temperature window being just positioned at catalyst, and the NH in this acid site
3adsorbance is all greater than V
2o
5/ TiO
2-SnO
2catalyst this may be cause WO
3after load, the reason that catalyst efficiency improves, for along with WO
3load capacity increases, and the efficiency of catalyst increases gradually, and in conjunction with infrared analysis, this may be due to WO
3load capacity increases, and causes the Surface acidity of catalyst to increase gradually and then causes the efficiency of catalyst to improve gradually.
(2) FT-IR analyzes
FT-IR analyzes and adopts U.S. Buddhist nun high-tensile strength 6700 type Fourier transform infrared analyzer, pretreatment temperature 400 DEG C, heating rate 10 DEG C/min, adsorption temp 25 DEG C (normal temperature absorption), adsorption time 1h, nitrogen purges 15min, DTGS detector and detection record response data.Fig. 4 to Fig. 7 is (1%) V
2o
5-(x%) WO
3/ TiO
2-SnO
2catalyst series FT-IR spectrogram.X% is respectively 0%, 6%, 9% and 12%, wherein, 6%, 9% and 12% represents prepared WO respectively
3/ TiO
2-SnO
2wO in catalyst
3account for WO
3/ TiO
2-SnO
2the percentage by weight of catalyst is 6%, 9% and 12%.Result shows: can find out, NH
3after acidic catalyst adsorption, both there is NH
3in the adsorption peak in Louis Lewis acid site, there is NH again
3?
the adsorption peak in acid site, but the adsorption peak of four kinds of catalyst is roughly the same.25 DEG C of NH
3at V
2o
5/ TiO
2-SnO
2after upper absorption, at 1450cm
-1there is stronger absworption peak in place, catalyst surface
the NH of the absorption in acid site
4 +the symmetrical deformation vibration of middle N-H key, 1657cm
-1the weak absworption peak that place occurs, belongs to catalyst surface
the NH of the absorption in acid site
4 +the asymmetrical deformation vibration of middle N-H key, and 1160 and 1214,1600cm
-1place's absorption peak strength belongs to NH
3asymmetrical deformation vibration and symmetrical deformation vibration.
And for modified V
2o
5-(x%) WO
3/ TiO
2-SnO
2catalyst, position and quantity too large change of nothing compared with before unmodified of the absworption peak that FT-IR collection of illustrative plates occurs, but along with WO
3the increase of content, at 1450cm
-1the intensity of place's absworption peak obviously strengthens, NH
3the active sites showed increased of absorption, and 1160cm
-1, 1214cm
-1, 1600cm
-1, 1657cm
-1, 1680cm
-1, place absorption peak strength do not have too large change, therefore can initial guess through WO
3modified catalyst is to NH
3adsorption capacity increases, wherein
acid position plays Main Function, this and WO
3have stronger
acidity matches, and also can find out in conjunction with denitration rate figure,
increasing of acid position, the raising being conducive to denitration efficiency (works as WO
3account for WO
3/ TiO
2-SnO
2when the percentage by weight of catalyst is 6% ~ 12%).
(3) X-ray diffraction analysis
Adopt XRD-2 type X-ray diffraction analyzer, tube voltage 35kV, tube current 20mA, step-length 0.02 °/s, X-ray wavelength is 1.5406A, Cu target, 2 θ/θ coupling continuous sweeps, scanning angle is 10 ° ~ 70 °, and catalyst sample needs abundant grinding before testing, get and powder filledly in right amount to flatten on glass carrier, sample powder thickness is about 1mm.Fig. 3 shows: TiO
2and TiSnO
4diffraction maximum clearly, this is because along with WO
3the increase TiO of load capacity
2and TiSnO
4heat endurance better; Along with WO
3the increase of load capacity, V
2o
5diffraction maximum all not obvious, diffraction maximum height and area are all without too large change, and this shows WO
3add and improve V
2o
5crystalline phase conversion temperature, i.e. V
2o
5in amorphous state, decrease V
2o
5sintering temperature, enhance V
2o
5heat endurance, thus improve the heat endurance of catalyst, facilitate the raising of catalyst efficiency.
(4) catalyst denitration reaction
Test condition:
Described catalyst carries out denitration test under fixed bed simulated flue gas condition: get described modified denitrating catalyst, be placed in reaction tube isothermal region, flue gas enters reaction tube, and in reaction tube, (internal diameter 6mm, sample size: 300mg) carries out selective-catalytic-reduction denitrified reaction.
Carry out simulated flue gas composition flue gas with steel gas cylinder and comprise NO, O
2, N
2, NH
3, flue gas consists of volume fraction Φ (NO)=Φ (NH3)=0.08%, Φ (O
2)=5%, with N
2for Balance Air.Air speed is=2.0 × 10
4h
-1, total flue gas flow is 100ml/min.Each pipeline gas enters reactor again after mass flowmenter (all flowmeters are all through soap-foam flowmeter calibration) enters gas mixer mixed equilibrium.German Testo330-2LL flue gas analyzer is adopted to measure NO, NO
2, O
2concentration.Calculate NOx removal efficiency accordingly.
Test result:
Catalyst provided by the invention adopts coprecipitation to prepare carrier, infusion process carrying active substance.Fig. 1 shows: the denitration efficiency of three kinds of catalyst all presents the trend first raising and reduce afterwards, and all 300 DEG C time, the denitration efficiency of catalyst reaches maximum, especially V
2o
5(1%)-WO
3(12%)/TiO
2-SnO
2, within the scope of 250 DEG C-400 DEG C, it is more than 97% that NOx removal efficiency reaches mean value, and temperature window is wide, and stability is high, and this may be because WO
3content when being 12%, WO
3add and greatly improve catalyst surface
the NH of acid position
3adsorbance, and then V
2o
5(1%)-WO
3(9%)/TiO
2-SnO
2the denitration efficiency of catalyst is the highest relative to homologous series catalyst efficiency.
Claims (10)
1. a high temperature SCR denitration in the wide window of vanadium system, is characterized in that: described catalyst is with titanium tin-oxide for carrier, and with the oxide of vanadium for active component, with the oxide of tungsten for co-catalyst, described titanium tin-oxide is TiO
2-SnO
2, the oxide of described vanadium is V
2o
5, the oxide of described tungsten is WO
3, described catalyst is V
2o
5-WO
3/ TiO
2-SnO
2, wherein, in described catalyst, the mol ratio of titanium elements and tin element is 1 ︰ 1, and the quality of the oxide of described tungsten accounts for 6 ~ 12% of the oxide of tungsten and the gross mass of titanium tin-oxide, and the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
2. the preparation method of high temperature SCR denitration in the wide window of vanadium system as claimed in claim 1, it is characterized in that, the method comprises the steps:
(1) TiO
2-SnO
2the preparation of carrier: utilize coprecipitation to prepare TiO
2-SnO
2carrier, the TiO of preparation
2-SnO
2in carrier, the mol ratio of titanium elements and tin element is 1 ︰ 1, by the TiO of preparation
2-SnO
2carrier is for subsequent use after drying, grinding, calcining successively;
(2) WO
3/ TiO
2-SnO
2preparation: the TiO that step (1) is obtained
2-SnO
2carrier joins in oxalic acid deionized water solution, then adds ammonium tungstate, under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, is warming up to 80 ~ 90 DEG C and continues to stir dipping 4 ~ 5h, after band moisture evaporate to dryness, then obtains WO after drying, grinding, calcining successively
3/ TiO
2-SnO
2catalyst, the ammonium tungstate wherein added and TiO
2-SnO
2the mass ratio of carrier is 6.98 ~ 14.9 ︰ 100, thus makes the quality of the oxide of tungsten account for oxide and the TiO of tungsten
2-SnO
26 ~ 12% of the gross mass of carrier;
(3) V
2o
5-WO
3/ TiO
2-SnO
2the preparation of catalyst: the WO that step (2) is obtained
3/ TiO
2-SnO
2join in oxalic acid deionized water solution, then add ammonium metavanadate, under 30 ~ 40 DEG C of oil baths, stir 2 ~ 3h, be warming up to 80 ~ 90 DEG C and continue to stir dipping 4 ~ 5h, after moisture evaporate to dryness, obtaining V after drying, grinding, calcining successively
2o
5-WO
3/ TiO
2-SnO
2catalyst, wherein, the ammonium metavanadate added and WO
3/ TiO
2-SnO
2mass ratio be 1.29 ︰ 100, thus make V
2o
5-WO
3/ TiO
2-SnO
2in, the quality of the oxide of vanadium accounts for 1% of the quality of total catalyst.
3. preparation method according to claim 2, is characterized in that: in described step (1), coprecipitation prepares TiO
2-SnO
2the concrete steps of carrier are: under the condition of ice-water bath, stirring, to volume be 200ml, concentration is drip the TiCl of 9.56ml with the speed of 0.8 ~ 1ml/min while stirring in the stannic chloride pentahydrate deionized water solution of 0.1528g/ml
4, drip NH with the speed of 3 ~ 5ml/min simultaneously
3mass content is that the ammoniacal liquor of 25% ~ 28% is in reactor, until be 9 ~ 10 with the pH that pH test paper records solution in reactor, then leave standstill 12 ~ 14h hypsokinesis and go supernatant liquor to be precipitated thing, spend sediment described in deionized water, and suction filtration, repeated washing until in filtrate inspection do not measure Cl
-till, obtain TiO
2-SnO
2carrier.
4. preparation method according to claim 2, is characterized in that: the concentration of described step (2) mesoxalic acid deionized water solution is 0.5g/ml, the quality of oxalic acid and TiO
2-SnO
2the quality of carrier is 1 ︰ 1; The concentration of described step (3) mesoxalic acid deionized water solution is 0.5g/ml, the quality of oxalic acid and TiO
2-SnO
2the mass ratio of carrier is 2.5 ︰ 1.
5. preparation method according to claim 3, is characterized in that: the stirring in described step (1), (2) and (3) is magnetic agitation or mechanical agitation, and stir speed (S.S.) is 20 ~ 30r/s.
6. the preparation method according to Claims 2 or 3, is characterized in that: the drying condition in described step (1), (2) and (3) is dry 11 ~ 13h at 100 ~ 120 DEG C of temperature.
7. the preparation method according to Claims 2 or 3, is characterized in that: the calcination condition in described step (1), (2) and (3) is 400 ~ 500 DEG C of temperature lower calcination 3 ~ 4h.
8. the preparation method according to Claims 2 or 3, is characterized in that: the grinding condition in described step (1), (2) and (3) is for being ground to 60 orders.
9. the application of high temperature SCR denitration in thermal power plant in high temperature SCR denitration in the wide window of vanadium system as claimed in claim 1.
10. application according to claim 9, is characterized in that: the temperature range of described middle high temperature is 250 ~ 400 DEG C.
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| CN106732545A (en) * | 2016-12-28 | 2017-05-31 | 河北省沙河玻璃技术研究院 | A kind of SCR denitration suitable for flue gas of glass melting furnace and preparation method thereof |
| CN108905602A (en) * | 2018-05-29 | 2018-11-30 | 清华大学盐城环境工程技术研发中心 | A kind of tin dope composite vanadium-titanium oxides catalyst and preparation method and application |
| CN110586073A (en) * | 2019-10-23 | 2019-12-20 | 中国科学院兰州化学物理研究所 | Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof |
| CN112827499A (en) * | 2020-12-31 | 2021-05-25 | 江苏中研创星材料科技有限公司 | Nano titanium dioxide composite powder and preparation method thereof |
| CN113908826A (en) * | 2021-10-15 | 2022-01-11 | 中国科学院生态环境研究中心 | Denitration catalyst suitable for high temperature and preparation method and application thereof |
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