CN103170346A - Tungsten oxide surface modified Fe2O3 catalyst as well as preparation method and application thereof - Google Patents

Tungsten oxide surface modified Fe2O3 catalyst as well as preparation method and application thereof Download PDF

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CN103170346A
CN103170346A CN2013101238135A CN201310123813A CN103170346A CN 103170346 A CN103170346 A CN 103170346A CN 2013101238135 A CN2013101238135 A CN 2013101238135A CN 201310123813 A CN201310123813 A CN 201310123813A CN 103170346 A CN103170346 A CN 103170346A
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catalyst
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tungsten oxide
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CN103170346B (en
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贺泓
刘福东
连志华
谢利娟
石晓燕
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Research Center for Eco Environmental Sciences of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

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Abstract

The invention relates to a tungsten oxide surface modified Fe2O3 catalyst comprising the following chemical compositions: WOx/Fe2O3(x=2-3), wherein the mass percent of WOx in the catalyst is 1-10 wt.%. The invention further discloses a method for preparing the catalyst. The NH3 selective catalytic reduction activity of surface non-modified Fe2O3 material into NOx (NH3-SCR) is extremely low, the operation temperature window is extremely narrow, and a large amount of N2O side product is generated, but the NH3-SCR catalyst activity and the N2 generation selectivity are remarkably improved after WOx surface modification. The tungsten oxide surface modified Fe2O3 catalyst as well the preparation method and the application thereof are suitable for catalytic elimination of stationary source and mobile source NOx.

Description

A kind of Fe of tungsten oxide finishing 2O 3Catalyst, preparation method and its usage
Technical field
The present invention relates to a kind of Fe of tungsten oxide finishing 2O 3Catalyst, preparation method and its usage, described catalyst is used for NH 3Selective Catalytic Reduction of NO x
Background technology
Ferriferous oxide can be used for multiple catalytic reaction as eco-friendly catalysis material.Due to F e 3+And F e 2+Between exist good redox cycle ability, Fe is catalyst based also has good catalyzing N H 3Selective reduction NO xAbility (NH 3-SCR), can be used for stationary source and moving source NO xCatalysis eliminate, to replace traditional vanadium base (V 2O 5-WO 3(MoO 3)/TiO 2) catalyst system.
Main concern in researchers' early stage Fe 2O 3The pattern controlledly synthesis of material (X.Mou, B.Zhang, Y.Li, L.Yao, X.Wei, D.S.Su, W.Shen, Angew.Chem.Int.Ed., 2012,51:2989), Fe 2O 3High-dispersion load (N.Apostolescu, B.Geiger, the K.Hizbullah of material on carrier material, M.T.Jan, S.Kureti, D.Reichert, F.Schott, W.Weisweiler, Appl.Catal.B:Environ., 2006,62:104) and synthetic (F.Liu, the H.He that contain the Fe composite oxides, C.Zhang, Chem.Commun., 2008,2043) etc.CN101380578A, the applicant in first to file but undocumented patent CN201310007168.0, the applicant in first to file but undocumented patent CN201310034144.4 has all related to preparation ferrotitanium composite oxides thing, ferrotungsten titanium composite oxide, iron cerium-titanium composite oxide material with catalyst based denitration performance and the anti-H of effective raising Fe 2O/SO 2The method of poisoning capability.
Tungsten oxide (WO 3) can effectively improve NH as a kind of catalyst promoter commonly used 3The heat endurance of-SCR catalyst, surface acidity and SCR active (W.Shan, F.Liu, H.He, X.Shi, C.Zhang, Chem.Commun., 2011,47,8046; PCT/CN2011/081962; CN102302930A; CN102000560A; L.Chen, J.Li, W.Ablikim, J.Wang, H.Chang, L.Ma, J.Xu, M.Ge, H.Arandiyan, Catal.Lett., 2011,141,1859), successfully be used for CeO 2The finishing of material is to improve denitration performance (Z.Ma, D.Weng, X.Wu, Z.Si, J.Environ.Sci., 2012,24,1305).
But in prior art, rarely researcher's report is to Fe 2O 3Material carries out finishing significantly to improve its NH 3-SCR reactivity worth.
Summary of the invention
One of purpose of the present invention is to provide a kind of Fe of tungsten oxide finishing 2O 3Catalyst, Fe can be effectively regulated in the tungsten oxide finishing 2O 3The surface acidity of material and redox ability, thus it significantly improved at the NH of middle high temperature section 3-SCR reactivity.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of Fe of tungsten oxide finishing 2O 3Catalyst, described catalyst has following chemical composition: WO x/ Fe 2O 3, x=2～3, described WO xThe mass percent that accounts for described catalyst is 1～10wt.%.
Preferably, described WO xThe mass percent that accounts for described catalyst is 1.5～8.5wt.%, preferred 3～6wt.%, further preferred 5wt.%.WO xThe NH when mass percent that accounts for described catalyst is 1～10wt.% 3-SCR activity can obviously improve, but WO xActive can decline during too high levels, and cost can improve when increasing tungsten oxide, and optimum is 5wt.%.
Described WO xThe mass percent that accounts for described catalyst for example is 1.8wt.%, 2.5wt.%, 3.5wt.%, 4wt.%, 4.5wt.%, 5wt.%, 5.5wt.%, 6wt.%, 6.5wt.%, 7wt.%, 7.5wt.%, 8wt.%, 9wt.%, 9.5wt.%.
Two of purpose of the present invention is to provide a kind of Fe of tungsten oxide finishing as above 2O 3The preparation method of catalyst adopts catalyst that sluggish precipitation of the present invention and infusion process obtain at the NH of middle high temperature section 3-SCR reactivity is high, has very excellent anti-SO 2Poisoning performance, high high-temp stability is excellent, and the operating temperature window is wide.
A kind of Fe of tungsten oxide finishing 2O 3The preparation method of catalyst, described method comprises the steps:
(1) preparation source of iron solution, add excessive urea precipitating reagent in solution, makes precipitation of iron ions complete, with the precipitated product suction filtration that obtains, and washing, drying, roasting obtains Fe 2O 3
(2) under the oxalic acid existence condition, preparation tungsten source solution adds Fe in the solution of tungsten source 2O 3Powder stirs by rotary evaporation the solution evaporate to dryness, drying, and roasting obtains the Fe of tungsten oxide finishing 2O 3Catalyst.
Described source of iron is selected from the mixture of any one or at least two kinds in ferric nitrate, ferric sulfate, ferric phosphate or iron chloride, preferred ferric nitrate.Described source of iron is the mixture of iron chloride and ferric phosphate for example, the mixture of ferric phosphate and ferric sulfate, the mixture of ferric sulfate and ferric nitrate, the mixture of iron chloride and ferric sulfate, the mixture of ferric phosphate and ferric nitrate, the mixture of iron chloride, ferric phosphate and ferric sulfate, the mixture of iron chloride, ferric phosphate, ferric sulfate and ferric nitrate.
In sluggish precipitation, make precipitating reagent with urea, the precipitation source of iron can precipitate when the molar ratio of urea and source of iron is 1.5:1 in theory fully, might have the problem of incomplete hydrolysis due to urea, therefore need to add excessive urea.Urea is hydrolyzed, it is a process that slowly discharges hydroxide ion and carbanion, the slow hydrolysis of urea makes the reactant concentration around iron ion in solution too large variation can not occur, with respect to other precipitating reagents such as ammoniacal liquor and carbonic hydroammonium etc., precipitate with more being conducive to the oxide precursor uniform particles.
Urea/source of iron mol ratio is 8～12:1, for example 8.2:1,8.4:1,8.6:1,8.8:1,9:1,9.2:1,9.4:1,9.6:1,9.8:1,10.2:1,10.6:1,10.8:1,11:1,11.4:1,11.8:1, preferably 10:1.
Urea/source of iron mol ratio is larger, hydrolysis of urea and corresponding the increasing of ammonia amount that discharge, and solution alkalescence strengthens, and sedimentary growing amount also increases thereupon, precipitate more fully, and productive rate is increase gradually also.Simultaneously, the degree of supersaturation of precipitation increases, and is theoretical according to Chemical Kinetics, and degree of supersaturation increases, and the generating rate of crystal grain is faster, makes nucleation rate apparently higher than the speed of growth of nucleus, is conducive to generate small size particle.Excessive when urea/source of iron mol ratio, sedimentary recruitment is not remarkable, and precipitation is close to fully, and excessive concentration, wastes raw material, and increases cost.
Described precipitation temperature is 80～100 ℃, for example 81 ℃, 83 ℃, 85 ℃, 87 ℃, 89 ℃, 91 ℃, 91.5 ℃, 92 ℃, 92.5 ℃, 93 ℃, 93.5 ℃, 94 ℃, 94.5 ℃, 95 ℃, 95.5 ℃, 96 ℃, 96.5 ℃, 97 ℃, 97.5 ℃, 98 ℃, 98.5 ℃, 99 ℃, 99.5 ℃, preferred 90 ℃.
The time of described precipitation is 8～15h, for example 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, preferred 9～13h, further preferred 12h.
The temperature of the described drying of step (1) is 90～110 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, preferred 95～105 ℃, further preferred 100 ℃.
The time of the described drying of step (1) is 3～8h, for example 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, preferred 3.5～6.5h, further preferred 5h.
The described roasting of step (1) is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and for example 430 ℃, 460 ℃, 510 ℃, 540 ℃, 570 ℃, 580 ℃, 590 ℃, preferred 500～600 ℃, further preferred 500 ℃.
The described roasting time of step (1) is 2～5h, for example 2.4h, 2.7h, 3.1h, 3.4h, 3.6h, 3.9h, 4.2h, 4.5h, 4.8h, preferably 3h.
Preparation tungsten source solution, and take Fe 2O 3Powder impregnated in solution, controls WO xThe mass percent that accounts for described catalyst is 1～10wt.%.
Described tungsten source is selected from tungstates or/and tungsten phosphate, and preferred ammonium tungstate is or/and sodium tungstate, further preferred ammonium tungstate.
The time of the described stirring of step (2) is 0.5～1.5 hour, for example 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, and preferred 1 hour.
The temperature of described rotary evaporation evaporate to dryness is 70～90 ℃, for example 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, and preferred 73～87 ℃, further preferred 80 ℃.
The temperature of the described drying of step (2) is 90～110 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, preferred 95～105 ℃, further preferred 100 ℃.
The time of the described drying of step (2) is 3～8h, for example 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, preferred 3.5～6.5h, further preferred 5h.
The described roasting of step (2) is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and for example 430 ℃, 460 ℃, 510 ℃, 540 ℃, 570 ℃, 580 ℃, 590 ℃, preferred 500～600 ℃, further preferred 500 ℃.
The described roasting time of step (2) is 2～5h, for example 2.4h, 2.7h, 3.1h, 3.4h, 3.6h, 3.9h, 4.2h, 4.5h, 4.8h, preferably 3h.
20～80 orders that preferably step (2) product of roasting compressing tablet sieved, preferred 40～60 orders.
A kind of Fe of tungsten oxide finishing 2O 3The preparation method of catalyst, described method comprises the steps:
(1 ') preparation iron nitrate solution, add excessive urea precipitating reagent in solution, urea/source of iron mol ratio is 10:1, continuous stirring 12h under 90 ℃ of water bath condition, make precipitation of iron ions complete, sediment is carried out suction filtration and washing, afterwards filter cake is put in 100 ℃ of oven drying 5h, at last in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h, obtain Fe 2O 3
(2 '), the preparation ammonium tungstate solution added Fe in ammonium tungstate solution under the oxalic acid existence condition 2O 3Powder, after stirring 1h, through rotary evaporation at 80 ℃ with the solution evaporate to dryness, 100 ℃ of dry 5h, at last under air atmosphere in 500 ℃ of roasting 3h, compressing tablet sieves into 40～60 orders, obtains the Fe of tungsten oxide finishing 2O 3Catalyst.
Three of purpose of the present invention is to provide a kind of Fe of tungsten oxide finishing as above 2O 3The purposes of catalyst, described catalyst is used for NH 3Selective Catalytic Reduction of NO x
Compared with prior art, the present invention has following beneficial effect:
(1) Fe of surperficial unmodified 2O 3Material NH 3-SCR catalytic activity is extremely low, and the operating temperature window is extremely narrow, and a large amount of N are arranged 2The O accessory substance generates, and passes through WO xAfter finishing, NH 3-SCR catalytic activity and N 2Generate selectively all to have very significantly and improve;
(2) the present invention adopts the simple precipitation method and infusion process to synthesize first tungsten oxide WO xThe Fe of finishing 2O 3Catalyst, preferred WO xLoad capacity is the WO of 5wt.% x/ Fe 2O 3Catalyst n H 3-SCR operating temperature window is significantly widened, and has good NO in middle high temperature range xPurification efficiency, N 2Generate selective and anti-SO 2Poisoning performance is applicable to stationary source and moving source NO xCatalysis eliminate;
(3) tungsten oxide WO xFinishing has effectively improved Fe 2O 3The surface acidity of catalyst has promoted reducing agent NH 3In the absorption of catalyst surface, can effectively improve NO xCatalytic reduction efficiency;
(4) tungsten oxide WO xFe has significantly been regulated in finishing 2O 3The redox ability of catalyst has suppressed reducing agent NH 3Non-selective oxidation reaction, make more reducing agent NH 3Can participate in the SCR reaction and go, improve simultaneously NO xPurification efficiency and N 2Generate selective.
The specific embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
A kind of Fe of tungsten oxide finishing 2O 3Catalyst, described catalyst has following chemical composition: WO x/ Fe 2O 3, x=2～3, described WO xThe mass percent that accounts for described catalyst is 1wt.%.
A kind of Fe of tungsten oxide finishing 2O 3The preparation method of catalyst, described method comprises the steps:
(1) preparation iron nitrate solution, add excessive urea precipitating reagent in solution, urea/source of iron mol ratio is 10:1, continuous stirring 12h under 90 ℃ of water bath condition, make precipitation of iron ions complete, sediment is carried out suction filtration and washing, afterwards filter cake is put in 100 ℃ of oven drying 5h, at last in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h, obtain Fe 2O 3
(2) under the oxalic acid existence condition, the preparation ammonium tungstate solution is controlled WO xThe mass percent that accounts for described catalyst is 1wt.%, adds Fe in ammonium tungstate solution 2O 3Powder, after stirring 1h, through rotary evaporation at 80 ℃ with the solution evaporate to dryness, 100 ℃ of dry 5h, at last in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h, compressing tablet sieves into the 40-60 order, obtains tungsten oxide WO xThe Fe of finishing 2O 3Catalyst.
Embodiment 2
A kind of Fe of tungsten oxide finishing 2O 3Catalyst, described catalyst has following chemical composition: WO x/ Fe 2O 3, x=2～3, described WO xThe mass percent that accounts for described catalyst is 5wt.%.
A kind of Fe of tungsten oxide finishing 2O 3The preparation method of catalyst, described method comprises the steps:
(1) preparation iron nitrate solution, add excessive urea precipitating reagent in solution, urea/source of iron mol ratio is 10:1, continuous stirring 12h under 90 ℃ of water bath condition, make precipitation of iron ions complete, sediment is carried out suction filtration and washing, afterwards filter cake is put in 100 ℃ of oven drying 5h, at last in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h, obtain Fe 2O 3
(2) under the oxalic acid existence condition, the preparation ammonium tungstate solution is controlled WO xThe mass percent that accounts for described catalyst is 5wt.%, adds Fe in ammonium tungstate solution 2O 3Powder, after stirring 1h, through rotary evaporation at 80 ℃ with the solution evaporate to dryness, 100 ℃ of dry 5h, at last in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h, compressing tablet sieves into the 40-60 order, obtains tungsten oxide WO xThe Fe of finishing 2O 3Catalyst.
Embodiment 3
A kind of Fe of tungsten oxide finishing 2O 3Catalyst, described catalyst has following chemical composition: WO x/ Fe 2O 3, x=2～3, described WO xThe mass percent that accounts for described catalyst is 10wt.%.
A kind of Fe of tungsten oxide finishing 2O 3The preparation method of catalyst, described method comprises the steps:
(1) preparation iron nitrate solution, add excessive urea precipitating reagent in solution, urea/source of iron mol ratio is 10:1, continuous stirring 12h under 90 ℃ of water bath condition, make precipitation of iron ions complete, sediment is carried out suction filtration and washing, afterwards filter cake is put in 100 ℃ of oven drying 5h, at last in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h, obtain Fe 2O 3
(2) under the oxalic acid existence condition, the preparation ammonium tungstate solution is controlled WO xThe mass percent that accounts for described catalyst is 10wt.%, adds Fe in ammonium tungstate solution 2O 3Powder, after stirring 1h, through rotary evaporation at 80 ℃ with the solution evaporate to dryness, 100 ℃ of dry 5h, at last in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h, compressing tablet sieves into the 40-60 order, obtains tungsten oxide WO xThe Fe of finishing 2O 3Catalyst.
Embodiment 4
A kind of Fe of tungsten oxide finishing 2O 3Catalyst, described catalyst has following chemical composition: WO x/ Fe 2O 3, x=2～3, described WO xThe mass percent that accounts for described catalyst is 2wt.%.
A kind of Fe of tungsten oxide finishing 2O 3The preparation method of catalyst, described method comprises the steps:
(1) preparation iron nitrate solution, add excessive urea precipitating reagent in solution, urea/source of iron mol ratio is 8:1, continuous stirring 15h under 80 ℃ of water bath condition, make precipitation of iron ions complete, sediment is carried out suction filtration and washing, afterwards filter cake is put in 90 ℃ of oven drying 8h, at last in Muffle furnace, under air atmosphere in 400 ℃ of roasting 5h, obtain Fe 2O 3
(2) under the oxalic acid existence condition, the preparation ammonium tungstate solution is controlled WO xThe mass percent that accounts for described catalyst is 2wt.%, adds Fe in ammonium tungstate solution 2O 3Powder, after stirring 0.5h, through rotary evaporation at 70 ℃ with the solution evaporate to dryness, 90 ℃ of dry 8h, at last in Muffle furnace, under air atmosphere in 400 ℃ of roasting 5h, compressing tablet sieves into the 40-60 order, obtains tungsten oxide WO xThe Fe of finishing 2O 3Catalyst.
Embodiment 5
A kind of Fe of tungsten oxide finishing 2O 3Catalyst, described catalyst has following chemical composition: WO x/ Fe 2O 3, x=2～3,, described WO xThe mass percent that accounts for described catalyst is 6wt.%.
A kind of Fe of tungsten oxide finishing 2O 3The preparation method of catalyst, described method comprises the steps:
(1) preparation iron nitrate solution, add excessive urea precipitating reagent in solution, urea/source of iron mol ratio is 12:1, continuous stirring 8h under 100 ℃ of water bath condition, make precipitation of iron ions complete, sediment is carried out suction filtration and washing, afterwards filter cake is put in 110 ℃ of oven drying 3h, at last in Muffle furnace, under air atmosphere in 600 ℃ of roasting 2h, obtain Fe 2O 3
(2) under the oxalic acid existence condition, the preparation ammonium tungstate solution is controlled WO xThe mass percent that accounts for described catalyst is 6wt.%, adds Fe in ammonium tungstate solution 2O 3Powder, after stirring 1.5h, through rotary evaporation at 90 ℃ with the solution evaporate to dryness, 110 ℃ of dry 3h, at last in Muffle furnace, under air atmosphere in 600 ℃ of roasting 2h, compressing tablet sieves into the 40-60 order, obtains tungsten oxide WO xThe Fe of finishing 2O 3Catalyst.
Get the Fe of surperficial unmodified 2O 3Material and different WO xThe WO of load capacity x/ Fe 2O 3Catalyst series (embodiment 1～3), catalyst volume 0.6mL, the 40-60 order is put into the catalyst activity evaluating apparatus, and activity rating carries out in fixed bed reactors.Simulated flue gas consists of (500ppm NH 3, 500ppm NO, 5%O 2), N 2Be Balance Air, total flow is 500mL/min, and reaction velocity is 50000h -1Test result is as shown in the table:
Figure BDA00003033490600091
Can be obtained by upper table:
The Fe of surface unmodified 2O 3Material NH 3-SCR catalytic activity is extremely low, and the operating temperature window is extremely narrow, and a large amount of N are arranged 2The O accessory substance generates, and passes through WO xAfter finishing, NH 3-SCR catalytic activity and N 2Generate selectively all to have very significantly and improve.Described optimal catalyst (5wt.%WO x/ Fe 2O 3) have a NO more than 80% in the middle high temperature range of 300-450 ℃ xPurification efficiency, and have very excellent anti-SO 2Poisoning performance, SO 2The SCR activity of this catalyst of poisoning front and back in whole temperature section all do not have significant change.
Should be noted that and understand, in the situation that do not break away from the desired the spirit and scope of the present invention of accompanying claim, can make to the present invention of foregoing detailed description various modifications and improvement.Therefore, the scope of claimed technical scheme is not subjected to the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not mean that namely the present invention must rely on above-mentioned method detailed and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention is to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims (10)

1. the Fe of a tungsten oxide finishing 2O 3Catalyst is characterized in that, described catalyst has following chemical composition: WO x/ Fe 2O 3, x=2～3, described WO xThe mass percent that accounts for described catalyst is 1～10wt.%.
2. catalyst as claimed in claim 1, is characterized in that, described WO xThe mass percent that accounts for described catalyst is 1.5～8.5wt.%, preferred 3～6wt.%, further preferred 5wt.%.
3. the Fe of a tungsten oxide finishing as claimed in claim 1 or 2 2O 3The preparation method of catalyst is characterized in that, described method comprises the steps:
(1) preparation source of iron solution, add excessive urea precipitating reagent in solution, makes precipitation of iron ions complete, with the precipitated product suction filtration that obtains, and washing, drying, roasting obtains Fe 2O 3
(2) under the oxalic acid existence condition, preparation tungsten source solution adds Fe in the solution of tungsten source 2O 3Powder stirs by rotary evaporation the solution evaporate to dryness, drying, and roasting obtains the Fe of tungsten oxide finishing 2O 3Catalyst.
4. method as claimed in claim 3, is characterized in that, described source of iron is selected from the mixture of any one or at least two kinds in ferric nitrate, ferric sulfate, ferric phosphate or iron chloride, preferred ferric nitrate;
Preferably, urea/source of iron mol ratio is 8～12:1, preferred 10:1.
5. method as described in claim 3 or 4, is characterized in that, described precipitation temperature is 80～100 ℃, preferred 90 ℃;
Preferably, the time of described precipitation is 8～15h, preferred 9～13h, further preferred 12h;
Preferably, the temperature of the described drying of step (1) is 90～110 ℃, preferred 95～105 ℃, and further preferred 100 ℃;
Preferably, the time of the described drying of step (1) is 3～8h, preferred 3.5～6.5h, further preferred 5h.
6. method as described in one of claim 3-5, is characterized in that, the described roasting of step (1) is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, preferred 500～600 ℃, and further preferred 500 ℃;
Preferably, the described roasting time of step (1) is 2～5h, preferred 3h;
Preferably, described tungsten source is selected from tungstates or/and tungsten phosphate, and preferred ammonium tungstate is or/and sodium tungstate, further preferred ammonium tungstate.
7. method as described in one of claim 3-6, is characterized in that, the time of the described stirring of step (2) is 0.5～1.5 hour, preferred 1 hour;
Preferably, the temperature of described rotary evaporation evaporate to dryness is 70～90 ℃, preferred 73～87 ℃, and further preferred 80 ℃;
Preferably, the temperature of the described drying of step (2) is 90～110 ℃, preferred 95～105 ℃, and further preferred 100 ℃;
Preferably, the time of the described drying of step (2) is 3～8h, preferred 3.5～6.5h, further preferred 5h.
8. method as described in one of claim 3-7, is characterized in that, the described roasting of step (2) is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, preferred 500～600 ℃, and further preferred 500 ℃;
Preferably, the described roasting time of step (2) is 2～5h, preferred 3h;
Preferably, with step (2) product of roasting compressing tablet 20～80 orders that sieve, preferred 40～60 orders.
9. method as described in one of claim 3-8, is characterized in that, described method comprises the steps:
(1 ') preparation iron nitrate solution, add excessive urea precipitating reagent in solution, urea/source of iron mol ratio is 10:1, continuous stirring 12h under 90 ℃ of water bath condition, make precipitation of iron ions complete, sediment is carried out suction filtration and washing, afterwards filter cake is put in 100 ℃ of oven drying 5h, at last in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h, obtain Fe 2O 3
(2 '), the preparation ammonium tungstate solution added Fe in ammonium tungstate solution under the oxalic acid existence condition 2O 3Powder, after stirring 1h, through rotary evaporation at 80 ℃ with the solution evaporate to dryness, 100 ℃ of dry 5h, at last under air atmosphere in 500 ℃ of roasting 3h, compressing tablet sieves into the 40-60 order, obtains the Fe of tungsten oxide finishing 2O 3Catalyst.
10. the Fe of a tungsten oxide finishing as claimed in claim 1 or 2 2O 3The purposes of catalyst is characterized in that, described catalyst is used for NH 3Selective Catalytic Reduction of NO x
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CN112593248A (en) * 2020-12-15 2021-04-02 苏州大学张家港工业技术研究院 Ruthenium and iron co-doped tungsten oxide and preparation method and application thereof

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CN103877986A (en) * 2014-01-27 2014-06-25 济南大学 Ferro-tungsten composite oxide denitrification catalyst with flower petal structure and preparation method and application of ferro-tungsten composite oxide denitrification catalyst with flower petal structure
CN103877986B (en) * 2014-01-27 2016-01-20 济南大学 A kind of ferrotungsten composite oxides denitrating catalyst with sheet flower-like structure and preparation method thereof and application
CN103785420A (en) * 2014-02-17 2014-05-14 中国科学院生态环境研究中心 Catalyst for surface sulfation of ferric oxide, as well as preparation method and application thereof
CN104941655A (en) * 2015-06-02 2015-09-30 清华大学 Novel iron-tungsten composite oxide denitration catalyst and preparation and application thereof
CN104941655B (en) * 2015-06-02 2017-10-17 清华大学 A kind of new ferrotungsten composite oxides denitrating catalyst and its preparation and application
CN109158109A (en) * 2018-09-15 2019-01-08 天津大学 A kind of application of the preparation method and middle low temperature sulfur resistive SCR catalyst of environmental-friendly middle low temperature sulfur resistive SCR catalyst
CN109331835A (en) * 2018-12-05 2019-02-15 黑龙江大学 A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its preparation method and application
CN110586118A (en) * 2019-10-11 2019-12-20 上海理工大学 Magnetic iron-based catalyst for selective catalytic reduction denitration and preparation method thereof
CN112593248A (en) * 2020-12-15 2021-04-02 苏州大学张家港工业技术研究院 Ruthenium and iron co-doped tungsten oxide and preparation method and application thereof
CN112593248B (en) * 2020-12-15 2021-09-03 苏州大学张家港工业技术研究院 Ruthenium and iron co-doped tungsten oxide and preparation method and application thereof

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