CN104209116A - Vanadium-series middle-temperature and high-temperature SCR catalyst and preparation method thereof - Google Patents

Vanadium-series middle-temperature and high-temperature SCR catalyst and preparation method thereof Download PDF

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CN104209116A
CN104209116A CN201410441977.7A CN201410441977A CN104209116A CN 104209116 A CN104209116 A CN 104209116A CN 201410441977 A CN201410441977 A CN 201410441977A CN 104209116 A CN104209116 A CN 104209116A
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catalyst
tio
zro
oxide
vanadium
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张亚平
王龙飞
郭婉秋
沈凯
徐海涛
周长城
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Southeast University
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Abstract

The invention discloses a vanadium-series middle-temperature and high-temperature catalyst. The catalyst takes a titanium zirconium oxide as a carrier, takes an oxide of vanadium as an active component and takes an oxide of tungsten as a cocatalyst, wherein the mol ratio of titanium to zirconium in the catalyst is 1 to 1; the mass of the oxide of the tungsten accounts for 6%-12% of the total mass of the oxide of tungsten and the titanium zirconium oxide; and the mass of the oxide of the vanadium accounts for 1% of the total mass of the catalyst. The invention further provides a preparation method of the catalyst; tungsten trioxide is added so that the heat stability and the reduction capability of V2O5 are enhanced; the pore diameter and the pore volume of the catalyst are increased; and the staying time of NH3 on the surface of the catalyst is prolonged and the amount of br.nsted acid on the surface of the catalyst is increased, so that the denitration efficiency of the catalyst is improved.

Description

High temperature SCR Catalysts and its preparation method in one vanadium system
Technical field
The invention belongs to Flue Gas Denitration Technology of Coal-buming Power Plant field, particularly the preparation method of high temperature SCR catalyst in a kind of vanadium system.
Background technology
Selective catalytic reduction (SCR) is current most widely used general, denitration technology that treatment effeciency is the highest, has much at present V for SCR denitration reaction catalyst type 2o 5/ WO 3(MoO 3)/TiO 2the advantages such as (Detitanium-ore-type) catalyst series is high, high temperature resistant with its denitration efficiency, active high and anti-poisoning performance is good, become most widely used SCR industrial catalyst at present.But it is temperature required higher, and General Requirements is controlled at 573～673K, higher flue-gas temperature is that catalyst exists the problems such as sintering, and these have all caused the inactivation of catalyst.
It is generally acknowledged V 2o 5there is the performance of good Reduction of NO, WO 3there is certain effect as auxiliary agent at aspects such as rugged catalyst structure and change catalyst texture, and TiO 2there is good sulfur tolerance.Select TiO 2as carrier, be because at SO 2with TiO under oxygen effect 2be micro-weakly invertible curing, TiO in addition 2also can with V 2o 5there is good electronic action, make catalyst there is good activity.Correlative study shows, on the surface of new catalyst, and the V of catalyst surface 2o 5exist with polymeric form as main taking individual layer, along with the increase of catalyst reaction time, the V of Monolayer Dispersion 2o 5reduce gradually crystalline state V 2o 5increase gradually, after aging 24h, the V of dispersion 2o 5basic disappearance, crystalline state V 2o 5directly cause NH 3oxidation, cause NO conversion ratio reduce.It should be noted that V simultaneously 2o 5/ TiO 2(anatase) 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 while being heated, very easily shrink on surface, is easily converted into the more stable rutile of thermodynamic state under uniform temperature and pressure condition, and WO 3add the conversion that contributes to stop anatase form, stable crystal structure, improves crystal phase transition temperature, simultaneously WO 3also can suppress V 2o 5the formation of crystalline state species.Therefore Chang Zuowei WO 3co-catalyst is used for improving the heat endurance of catalyst.
Summary of the invention
Technical problem to be solved by this invention is to provide high temperature SCR catalyst in a kind of vanadium system, and in this vanadium system, high temperature SCR catalyst not only possesses stronger high-temperature catalytic activity, and temperature window is wider, has stronger anti-caking power.
The technical problem that the present invention also will solve is to provide the preparation method of high temperature SCR catalyst in above-mentioned vanadium system.
For solving the problems of the technologies described above, the invention provides high temperature SCR catalyst in a kind of vanadium system, described catalyst is taking titanium Zirconium oxide as carrier, taking the oxide of vanadium as active component, taking the oxide of tungsten as co-catalyst, wherein, in described catalyst, the mol ratio of titanium elements and zr 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 Zirconium oxide; The quality of the oxide of vanadium account for total catalyst quality 1%.
Particularly, described titanium Zirconium oxide is TiO 2-ZrO 2, the oxide of described vanadium is V 2o 5, the oxide of described tungsten is WO 3.
The preparation method who the invention allows for high temperature SCR catalyst in above-mentioned vanadium system, comprises the steps:
(1) TiO 2-ZrO 2the preparation of carrier: utilize coprecipitation to prepare TiO 2-ZrO 2carrier, for subsequent use through being first dried after calcining afterwards, wherein, TiO 2-ZrO 2tiO in carrier 2and ZrO 2mol ratio be 1: 1;
(2) WO 3/ TiO 2-ZrO 2the preparation of catalyst: get TiO prepared by step (1) 2-ZrO 2carrier joins in the oxalic acid solution of ammonium tungstate, under 30～40 DEG C of oil baths, stirs 2～3h, is warming up to 80～90 DEG C and continuation stirring dipping 4～5h, after band moisture evaporate to dryness, then after drying, grinding, calcining, obtains WO successively 3/ TiO 2-ZrO 2catalyst, oxalic acid only plays the effect that promotes that ammonium tungstate dissolves, and 5g oxalic acid is enough with respect to the load capacity that is no more than 2g at every turn, and follow-up oil bath link can be decomposed into CO by unnecessary oxalic acid 2and H 2o.Wherein ammonium tungstate and TiO 2-ZrO 2the mass ratio of carrier is 6.97%～13.54%, thereby makes the quality of the oxide of tungsten account for oxide and the TiO of tungsten 2-ZrO 26～12% of the gross mass of carrier;
(3) 1%V 2o 5-WO 3/ TiO 2-ZrO 2the preparation of catalyst: WO prepared by step (2) 3/ TiO 2-ZrO 2join in oxalic acid solution, then continue to add ammonium metavanadate, under 30～40 DEG C of oil baths, stir 2～3h, be warming up to 80～90 DEG C and continuation stirring dipping 4～5h, after moisture evaporate to dryness, after drying, grinding, calcining, obtain V successively 2o 5-WO 3/ TiO 2-ZrO 2catalyst, oxalic acid only plays the effect that promotes that ammonium metavanadate dissolves, and 5g oxalic acid is enough with respect to the load capacity that is no more than 2g at every turn, and follow-up oil bath link can be decomposed into CO by unnecessary oxalic acid 2and H 2o.Wherein, ammonium metavanadate and WO 3/ TiO 2-ZrO 2the mass ratio of catalyst is 1.29%, thereby makes V in described catalyst 2o 5quality account for V 2o 5-WO 3/ TiO 2-ZrO 21% of catalyst gross mass.
Particularly, in step (1), the step of co-precipitation is: under the condition of ice-water bath, magnetic agitation, in the aqueous solution of eight water zirconium oxychlorides, drip TiCl while stirring with the speed of 0.8～1ml/min 4drip ammoniacal liquor to reactor with the speed of 3～5ml/min simultaneously, be 9～10 until pH test paper records the pH of solution, then under dark condition, leaving standstill 12～14h hypsokinesis goes supernatant liquor to be precipitated, wash described precipitation by deionized water, and decompress filter, repeated washing is until the Cl that in filtrate, inspection does not measure -till, obtain TiO 2-ZrO 2precipitation.To TiCl 4with in the solution of eight water zirconium oxychlorides, dropwise drip ammoniacal liquor (NH 3content is 25%～28%) regulate pH value to 9～10, while dripping ammoniacal liquor with glue head dropper, TiCl 4with in the solution of eight water zirconium oxychlorides, can produce white creaming, while splashing into next ammoniacal liquor, observe the position that an ammoniacal liquor drips in solution, next drip ammoniacal liquor drip position want and upper one stagger, can ensure that like this diverse location all can form precipitation in solution; Dripping in ammoniacal liquor process, dip the solution in large beaker with glass bar continuously, the pH value of surveying solution with pH test paper until 9～10, now stops dripping ammoniacal liquor, obtains white creaming, leaves standstill 12～14h, washs, suction filtration.Particularly, wash by deionized water, collect the waste liquid of washing precipitation, waste liquid is placed in to beaker, among liquor argenti nitratis ophthalmicus inspection waste liquid with 0.1mol/L, have or not chlorion, if also have chlorion to continue washing, until in silver nitrate inspection waste liquid without chlorion, the object of this method is to prevent raw material TiCl 4in precipitation, form the metal complex of chloride ion-containing with the chlorion symbiosis in eight water zirconium oxychlorides, and then affect the quality of precipitation.
Preferably, in above-mentioned steps, magnetic agitation or churned mechanically mixing speed are 20～30r/s.
As preferably, the drying condition in step (1), (2) and (3) is 100～120 DEG C of dry 11～13h.
Calcination condition in step (1), (2) and (3) is to calcine 3～4h at 400～500 DEG C, the calcining heat of whole preparation process can not be higher than 500 DEG C, when calcining heat is during higher than 500 DEG C, titanium dioxide starts to have anatase crystal to change to rutile crystal type, to reacting unfavorable.Preferably, the condition of described calcining is to calcine 4h at 450 DEG C.
In order further to improve the performance of catalyst, it is characterized in that, in step (2) and step (3), described TiO 2-ZrO 2carrier and WO 3/ TiO 2-ZrO 2catalyst ground after 60 mesh sieves, and then be dissolved in deionized water or the oxalic acid solution of ammonium tungstate in.
The present invention has further proposed the application of the system supported Medium temperature SCR catalyst of above-mentioned vanadium in middle high temperature SCR denitration.
Preferably, the temperature range of described middle temperature is 300～400 DEG C.
Beneficial effect: compared with prior art, in vanadium of the present invention system, high temperature SCR denitrating catalyst is by adding WO 3, strengthened V 2o 5heat endurance and reducing power, improved aperture and the pore volume of catalyst, strengthened NH 3at time of staying of catalyst surface and catalyst surface acid is measured, and then has improved the denitration efficiency of catalyst.
Brief description of the drawings
The denitration performance comparison diagram of Fig. 1 catalyst series of the present invention;
The sulfur resistance figure of Fig. 2 catalyst series of the present invention;
The NH of Fig. 3 catalyst series of the present invention 3-TPD spectrogram;
The FT-IR spectrogram of Fig. 4 catalyst series of the present invention;
The XRD spectra of Fig. 5 catalyst series of the present invention.
Detailed description of the invention
According to following embodiment, the present invention may be better understood.But, those skilled in the art will readily understand, the described concrete material proportion of embodiment, process conditions and result thereof be only for the present invention is described, and should also can not limit the present invention described in detail in claims.
Embodiment 1:
(1) with the synthetic TiO of coprecipitation 2-ZrO 2solid solution (titanium zirconium solid solution, Ti-Zr).
With titanium tetrachloride (TiCl 4, density 1.726g/ml) and eight water zirconium oxychloride (ZrOCl 28H 2o) be raw material, first in fume hood, 2L large beaker adds 200ml deionized water, and 2L large beaker is moved in frozen water, inserts magnetic stirring apparatus in large beaker, opens and stirs, and mixing speed is 20～30r/s.On the experimental bench of fume hood outside, 31.7346g eight water zirconium oxychlorides are dissolved in 25ml beaker, and lysate is proceeded in the large beaker of 2L, stir and just dropwise splash into 10.8ml titanium tetrachloride solution with back, every interval 10s, to guarantee that titanium tetrachloride solution can thoroughly hydrolysis in the solution of eight water zirconium oxychlorides.Then drip ammoniacal liquor (NH 3content is 25%～28%) regulate pH value to 9～10 of solution in large beaker, in dropping process, should stagger in the dropping position of two of front and back ammoniacal liquor in large beaker solution, dropwise drip until produce white creaming in solution, in this process, dip the solution in large beaker with glass bar continuously, survey the pH value of solution with pH test paper, in the time that pH value is 9～10, stop dripping.To precipitate leave standstill 12 hours, in deionized water washing, suction filtration, baking oven, 110 DEG C of dry 12h, get dried solid, pulverize and sieve, get sieve after 60 object solids, in Muffle furnace, at 450 DEG C, calcine 3h and obtain titanium zirconium solid solution (TiO 2-ZrO 2, n (Ti)/n (Zr)=1, n is molal quantity).The characterization result of titanium zirconium solid solution is as Fig. 4.
(2) load ammonium tungstate, calcining obtains WO 3/ TiO 2-ZrO 2(W/Ti-Zr) catalyst.
Get titanium zirconium solid solution prepared by three parts of steps (1), every part of 5g, get three 25ml beakers, (oxalic acid only plays the effect that promotes that ammonium tungstate dissolves, and follow-up oil bath link can be decomposed into CO by oxalic acid in three beakers, to add respectively 10ml deionized water, 5g oxalic acid 2and H 2o), add respectively subsequently 5g titanium zirconium solid solution, then get respectively ammonium tungstate 0.349g, 0.541g, 0.745g, join respectively in three beakers, 1. 2. 3. beaker numbers, 80 DEG C of oil baths, stir evaporate to dryness, take out the solid after evaporate to dryness, 110 DEG C of dry 12h in baking oven, pulverize and sieve, get sieve after 60 object solids; In Muffle furnace, at 450 DEG C, calcine 3h, obtain: 6%W/Ti-Zr (6%WO 3/ TiO 2-ZrO 2), 9%W/Ti-Zr (9%WO 3/ TiO 2-ZrO 2), 12%W/Ti-Zr (12%WO 3/ TiO 2-ZrO 2) (wherein, 6%, 9% and 12% represent respectively prepared WO 3/ TiO 2-ZrO 2wO in catalyst 3account for WO 3/ TiO 2-ZrO 2the percentage by weight of catalyst is 6%, 9% and 12%).
(3) load ammonium metavanadate, calcining obtains 1%V 2o 5-(X%) WO 3/ TiO 2-ZrO 2(brief note is V-X%W/Ti-Zr or V-(X%) W/Ti-Zr) catalyst.Wherein, X% represents WO 3with tungsten oxide and WO 3/ TiO 2-ZrO 2the mass ratio of carrier is X%.
Get respectively each 3 grams of three kinds of W/Ti-Zr catalyst that step (2) makes, get three 25ml beakers, in each beaker, add 10ml deionized water, (oxalic acid only plays the object that promotes that ammonium metavanadate dissolves to add 5g oxalic acid, even if what add is many, follow-up in oil bath process, unnecessary oxalic acid also can be decomposed into CO 2and H 2o), add subsequently 3gW/Ti-Zr catalyst, get respectively 0.0389g ammonium metavanadate, and add respectively in three beakers, 80 DEG C of oil baths, evaporation, gets solid after oil bath, in baking oven, 110 DEG C of dry 12h, pulverize and sieve, get sieve after 60 object solids; In Muffle furnace, at 450 DEG C, calcine 3h, to obtain final product: 1%V 2o 5-6%WO 3/ TiO 2-ZrO 2(1%V-6%W/Ti-Zr), 1%V 2o 5-9%WO 3/ TiO 2-ZrO 2(1%V-9%W/Ti-Zr) and 1%V 2o 5-12%WO 3/ TiO 2-ZrO 2(1%V-12%W/Ti-Zr), wherein, 1% represents V 2o 5account for V 2o 5-WO 3/ TiO 2-ZrO 2the percentage of the gross weight of catalyst is 1%; 6%, 9% and 12% represent respectively WO 3account for WO 3/ TiO 2-ZrO 2the percentage by weight of catalyst is 6%, 9% and 12%.
Embodiment 21%V 2o 5-(X%) WO 3/ TiO 2-ZrO 2the sign of catalyst.
(1) BET characterization result
Specific surface area of catalyst BET is measured by the Full-automatic gas adsorption system ASAP of Mike Mo Rui company of the U.S. 2020, and sample vacuumizes pretreatment 2h at 200 DEG C, with N 2adsorbate is measured at-196 DEG C.
Table 1 1%V 2o 5-(X%) WO 3/ TiO 2-ZrO 2the specific area of catalyst series
As can be seen from Table 1, along with WO 3the increase of load capacity, the specific area of catalyst reduces gradually, this be possible because the obstruction of load the duct of catalyst, make the specific area of catalyst along with WO 3the increase of load capacity and reducing.From table 1, also can find out, work as WO 3when load capacity is 9%, it is maximum that the accumulation pore volume of catalyst and average pore diameter reach.Because the catalytic reaction of catalyst is to carry out in the duct at catalyst surface, first the nitrogen oxide in flue gas is adsorbed on the surface of catalyst, then could react on the one hand; On the other hand, the denitration efficiency of catalyst has more than relevant with the specific area of catalyst, because specific area is used nitrogen to measure, what its reacted is total specific area of catalyst, can not reflect the specific activity surface area of catalyst surface; Although work as WO 3when load capacity is 9%, the specific area of catalyst is not maximum, but because the increase of catalyst aperture and pore volume truly has the catalytic reaction that is beneficial to catalyst, this illustrates for the catalyst for V-X%W/Ti-Zr series, the volume in the hole of catalyst has played important function in denitration reaction, and in this and performance test, the denitration efficiency of catalyst has formed well and shone upon.
(2) NH 3-TPD analyzes
NH 3150 DEG C of full-automatic temperature programming chemical adsorption instrument (FINESORB-3010) pretreatment temperatures of-TPD analysis employing Zhejiang Fan Tai instrument company, 10 DEG C/min of heating rate, 25 DEG C～800 DEG C of desorption temperatures, nitrogen blowing 10min, data acquisition detects with TCD thermal conductivity detector (TCD).Fig. 3 is V 2o 5(1%)-WO 3(X%)/TiO 2-ZrO 2the NH of catalyst series 3-TPD figure, table 2 is V 2o 5(1%)-WO 3(X%)/TiO 2-ZrO 2the NH of catalyst series 3adsorbance and desorption temperature.Result shows: the comparing result of three kinds of catalyst shows: three kinds of catalyst all exist a desorption peaks at 100 DEG C～160 DEG C, prove that three kinds of catalyst all exist weak acid center (100 DEG C～160 DEG C), and table 2 shows: V 2o 5-9%WO 3/ TiO 2-ZrO 2acid amount minimum, but the required activation energy higher (being that desorption temperature is higher) of its desorption, compared with other two kinds of catalyst, is adsorbed on the NH of catalyst surface 3be difficult for desorption, strengthened NH 3in the time of staying of catalyst surface, promote NO xremove.Contrast V 2o 5-6%WO 3/ TiO 2-ZrO 2and V 2o 5-12%WO 3/ TiO 2-ZrO 2two kinds of catalyst, in the case of the activation energy of desorption is identical, NH 3the time of staying at catalyst surface is identical, now, the catalyst that adsorption ammonia amount is more, its denitration efficiency is higher, and this is corresponding with the result of catalyst activity test; And V 2o 5/ TiO 2-ZrO 2although catalyst has presented higher acid amount and desorption temperature, its efficiency is minimum on the contrary, and this may be because owing to lacking WO 3, V 2o 5/ TiO 2-ZrO 2v in catalyst 2o 5heat endurance variation causes, this is also consistent with the performance test of catalyst.
Table 2 V 2o 5(1%)-WO 3(X%)/TiO 2-ZrO 2the Surface acidity of catalyst series and desorption temperature
Sample Surface acidity (ml/g) Desorption temperature (DEG C)
V-6％W/Ti-Zr 30.7344 111
V-9％W/Ti-Zr 23.6610 127
V-12％W/Ti-Zr 37.2289 111
V/Ti-Zr 45.3169 151
(3) FT-IR analyzes
FT-IR analyzes and adopts U.S. Buddhist nun high-tensile strength 6700 type Fourier transform infrared analyzers, 400 DEG C of pretreatment temperatures, 10 DEG C/min of heating rate, 25 DEG C of adsorption temps (normal temperature absorption), adsorption time 1h, nitrogen blowing 15min, DTGS detector detection record response data.Fig. 4 is (1%) V 2o 5-(X%) WO 3/ TiO 2-ZrO 2catalyst series FT-IR spectrogram.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 again NH 3? the adsorption peak in acid site, the adsorption peak of two kinds of catalyst is roughly the same.25 DEG C of NH 3at V 2o 5/ TiO 2-ZrO 2after upper absorption, 1454, weak absworption peak, 1168cm appear in 1168cm-1 place -1the peak at place belongs to the NH of Lewis acid site absorption 3the degeneracy stretching vibration of middle N-H key, 1454cm -1the absworption peak at place is catalyst surface the NH of the absorption in acid site 4 +the deformation vibration of middle N-H key, 1680cm -1place's absworption peak belongs to the NH of acid site absorption 4 +the symmetrical stretching vibration of middle N-H key.For the WO after modification 3v after modification 2o 5/ TiO 2-ZrO 2catalyst, the absworption peak position occurring on FT-IR collection of illustrative plates is with unmodified front mostly identical, but along with the increase of content, 1454cm -1the intensity of place's absworption peak obviously strengthens, NH 3the active sites showed increased of absorption, and 1168cm -1place's absorption peak strength does not have too large variation, therefore can tentatively infer through WO 3catalyst after modification is to NH 3adsorption activity site increase, NH 3adsorption capacity increases, wherein acid position performance Main Function, this and WO 3have stronger acidity matches, and in conjunction with denitration rate, figure also can find out, increasing of acid position, the raising that is conducive to denitration efficiency (is worked as WO 3account for WO 3/ TiO 2-ZrO 2when the percentage by weight of catalyst is 6%～12%).
(4) X-ray diffraction analysis
Adopt XRD-2 type X-ray diffraction analyzer, tube voltage 35kV, tube current 20mA, 0.02 °/s of step-length, X ray wavelength is 1.5406A, Cu target, 2 θ/θ coupling continuous sweep, scanning angle is 10 °～70 °, catalyst sample needs abundant grinding before test, get appropriate powder filled also pressing on glass carrier, the about 1mm of sample powder thickness.Fig. 5 shows: ZrO 2and ZrTiO 4diffraction maximum clearly, this is because along with WO 3the increase ZrO of load capacity 2and ZrTiO 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 variation, this shows WO 3add and improved V 2o 5crystalline phase conversion temperature, i.e. V 2o 5be amorphous state, increased the quantity of catalyst surface acid centre, reduced V 2o 5sintering temperature, strengthened V 2o 5heat endurance, thereby improved the heat endurance of catalyst, promoted the raising of catalyst efficiency.
(5) catalyst denitration reaction
Test condition:
Described catalyst carries out denitration test under fixed bed simulated flue gas condition: get the denitrating catalyst after described modification, 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 composition is volume fraction Φ (NO)=Φ (NH3)=0.08%, Φ (0 2)=5%, with N 2for Balance Air.Air speed is=3.0 × 10 4h -1, total flue gas flow is 100ml/min.Each pipeline gas enters reactor after mass flowmenter (all flowmeters are all through soap-foam flowmeter calibration) enters gas mixer mixed equilibrium again.Adopt German Testo 330-2LL flue gas analyzer to measure NO, NO 2, O 2concentration.Calculate accordingly NO removal efficiency.In order to ensure stability and the accuracy of data, each operating mode is at least stablized 30 minutes.
Test result:
High temperature catalyst in vanadium provided by the invention system is to adopt coprecipitation to prepare carrier, infusion process carrying active substance.Fig. 1 shows: the denitration efficiency of three kinds of catalyst all presents the trend that first raises and reduce afterwards, and all in the time of 300 DEG C, the denitration efficiency of catalyst reaches maximum, especially V 2o 5(1%)-WO 3(9%)/TiO 2-ZrO 2, within the scope of 300 DEG C-400 DEG C, it is more than 91% that NO removal efficiency reaches mean value, and temperature window is wide, and stability is high, and this may be because WO 3content while being 9%, WO 3add and improved V 2o 5crystallization temperature, make to be amorphous state, strengthened V 2o 5heat endurance, and then the denitration efficiency of catalyst is the highest with respect to homologous series catalyst efficiency.
(6) sulfur resistance of catalyst test.
Test condition:
Described catalyst carries out denitration test under fixed bed simulated flue gas condition: get the denitrating catalyst after described modification, be placed in reaction tube isothermal region, flue gas enters reaction tube, in reaction tube, carries out selective-catalytic-reduction denitrified reaction through catalyst action.
Carry out simulated flue gas composition flue gas with steel gas cylinder and comprise NO, O 2, N 2, NH 3, flue gas composition is volume fraction Φ (NO)=Φ (NH 3)=0.08%, Φ (O 2)=5%, Φ (SO 2)=1% (being roughly equal to 150ppm), with N 2for Balance Air.Air speed is=3.0 × 10 4h -1, total flue gas flow is 100ml/min, probe temperature is 300 DEG C.Each pipeline gas enters reactor after mass flowmenter (all flowmeters are all through soap-foam flowmeter calibration) enters gas mixer mixed equilibrium again.Adopt German Testo 330-2LL flue gas analyzer to measure NO, NO 2concentration, in order to ensure stability and the accuracy of data, each operating mode is at least stablized 30 minutes.Reactions steps brief introduction: obstructed SO in front 160min 2, adopt a sample every 40min, start to gather 5 samples from 0min; In middle 160-360min, pass into SO 2, also gather 5 samples; 360-560mm stops passing into SO 2also gather 5 samples; Measure the content of NOx in each sample, and calculate denitration efficiency, then graphing, as Fig. 2:
Experimental result shows: V 2o 5(1%)-WO 3(9%)/TiO 2-ZrO 2and V 2o 5(1%)-WO 3(12%)/TiO 2-ZrO 2these two kinds of catalyst all have good sulfur resistance at 300 DEG C, simultaneously for V 2o 5(1%)-WO 3(12%)/TiO 2-ZrO 2, when stopping passing into SO 2time catalyst performance have a small amount of lifting and be promoted to 94% from 92%, this may be because work as SO 2during for 150ppm, the Zr (SO that catalyst surface generates 4) 2species have strengthened the acidity of catalyst surface, and test result also shows to work as WO again simultaneously 3at WO 3/ TiO 2-ZrO 2in content while being 9% and 12%, the heat endurance of catalyst obviously strengthens, and makes ZrO 2in amorphous state, therefore ZrO 2just can and SO 2reaction generates Zr (SO 4) 2, and then the sulfur resistance of enhancing catalyst.

Claims (10)

1. high temperature SCR catalyst in a vanadium system, it is characterized in that, described catalyst is taking titanium Zirconium oxide as carrier, taking the oxide of vanadium as active component, taking the oxide of tungsten as co-catalyst, wherein, in described catalyst, the mol ratio of titanium elements and zr 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 Zirconium oxide; The quality of the oxide of vanadium account for total catalyst quality 1%.
2. high temperature SCR catalyst in vanadium according to claim 1 system, is characterized in that, described titanium Zirconium oxide is TiO 2-ZrO 2, the oxide of described vanadium is V 2o 5, the oxide of described tungsten is WO 3.
3. the preparation method of high temperature SCR catalyst in vanadium claimed in claim 1 system, is characterized in that, comprises the steps:
(1) TiO 2-ZrO 2the preparation of carrier: utilize coprecipitation to prepare TiO 2-ZrO 2carrier, then for subsequent use after drying, grinding, calcining successively;
(2) WO 3/ TiO 2-ZrO 2the preparation of catalyst: get TiO prepared by step (1) 2-zrO 2carrier joins in the oxalic acid solution of ammonium tungstate, under 30～40 DEG C of oil baths, stirs 2～3h, is warming up to 80～90 DEG C and continuation stirring dipping 4～5h, after band moisture evaporate to dryness, then after drying, grinding, calcining, obtains WO successively 3/ TiO 2-ZrO 2catalyst;
(3) 1%V 2o 5-WO 3/ TiO 2-ZrO 2the preparation of catalyst: WO prepared by step (2) 3/ TiO 2-ZrO 2catalyst joins in oxalic acid solution, then adds ammonium metavanadate, under 30～40 DEG C of oil baths, stirs 2～3h, is warming up to 80～90 DEG C and continuation stirring dipping 4～5h, after moisture evaporate to dryness, obtains V successively after drying, grinding, calcining 2o 5-WO 3/ TiO 2-ZrO 2catalyst.
4. preparation method according to claim 3, it is characterized in that, in step (1), the step of co-precipitation is: under the condition of ice-water bath, magnetic agitation, in the aqueous solution of eight water zirconium oxychlorides, drip TiCl while stirring with the speed of 0.8～1ml/min 4drip ammoniacal liquor to reactor with the speed of 3～5ml/min simultaneously, be 9～10 until pH test paper records the pH of solution, then under dark condition, leaving standstill 12～14h hypsokinesis goes supernatant liquor to be precipitated, wash described precipitation by deionized water, and decompress filter, repeated washing is until the Cl that in filtrate, inspection does not measure -till, obtain TiO 2-ZrO 2precipitation.
5. according to the preparation method described in claim 3 or 4, it is characterized in that, described magnetic agitation or churned mechanically mixing speed are 20～30r/s.
6. preparation method according to claim 3, is characterized in that, the drying condition in step (1), (2) and (3) is 100～120 DEG C of dry 11～13h.
7. preparation method according to claim 3, is characterized in that, the calcination condition in step (1), (2) and (3) is to calcine 3～4h at 400～500 DEG C.
8. preparation method according to claim 3, is characterized in that, in step (2) and step (3), and described TiO 2-ZrO 2carrier and WO 3/ TiO 2-ZrO 2catalyst ground after 60 mesh sieves, and then be dissolved in deionized water or the oxalic acid solution of ammonium tungstate in.
9. the application of the system supported Medium temperature SCR catalyst of vanadium claimed in claim 1 in middle high temperature SCR denitration.
10. application according to claim 9, is characterized in that, the temperature range of described middle high temperature is 300～400 DEG C.
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