CN103785420A - Catalyst for surface sulfation of ferric oxide, as well as preparation method and application thereof - Google Patents
Catalyst for surface sulfation of ferric oxide, as well as preparation method and application thereof Download PDFInfo
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- CN103785420A CN103785420A CN201410052359.3A CN201410052359A CN103785420A CN 103785420 A CN103785420 A CN 103785420A CN 201410052359 A CN201410052359 A CN 201410052359A CN 103785420 A CN103785420 A CN 103785420A
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- ferric oxide
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Abstract
The invention discloses a preparation method of a catalyst for surface sulfation of ferric oxide. The method comprises the following steps: (1) preparing ferric oxide; (2) performing sulfation treatment on the surface of the ferric oxide to obtain a ferric oxide catalyst of which the surface is sulfated. The ferric oxide catalyst with the enhanced surface acidity and the proper oxidation-reduction capacity is synthesized for the first time through performing sulfating process on the surface of the ferric oxide, so that the NOx purification activity of middle and high temperature sections in NH3 selectively reducing NOx (namely NH3-SCR) reaction is obviously improved, an operation temperature window is obviously broadened, and the catalyst has the extremely excellent SO2 poisoning resistance performance and is very applicable for catalytic elimination of a stationary source and a mobile source NOX.
Description
Technical field
The present invention relates to a kind of surperficial Sulfated ferric oxide catalyst, preparation method and its usage, this catalyst is for the SCR purification process of nitrogen oxide.
Background technology
Iron oxide (Fe
2o
3) the cheap and environmental friendliness as a kind of catalysis material, Fe
3+and Fe
2+between efficient oxidation reduction circulation (redox) ability of existing make it at NH
3selective reduction NO
x(NH
3-SCR) reaction in there is high activity and N
2generate selective.For example researcher had once developed the Fe of support type
2o
3/ TiO
2(A.Kato, S.Matsuda, F.Nakajima, M.Imanari and Y.Watanabe, J.Phys.Chem., 1981,85,1710.), Fe
2o
3-pillared layered clay (J.P.Chen, M.C.Hausladen and R.T.Yang, J.Catal., 1995,151,135.), Fe
2o
3/ SiO
2(P.Fabrizioli, T.
and A.Baiker, J.Catal., 2002,206,143.) and Fe
2o
3/ WO
3/ ZrO
2catalyst such as (N.Apostolescu, B.Geiger, K.Hizbullah, M.T.Jan, S.Kureti, D.Reichert, F.Schott, W.Weisweiler, Appl.Catal.B:Environ., 2006,62,104.), all at NH
3in-SCR reaction, there is comparatively excellent middle high temperature section NO
xpurify active.Containing the composite oxides class catalyst of Fe, as FeTiO
x(F.Liu, H.He, C.Zhang, Chem.Commun., 2008,2043; The disclosed a kind of ferrotitanium composite oxides thing catalyst for ammonia selective reducing nitrogen oxide of CN101380578) and Fe-Ti spinelle (S.Yang, J.Li, C.Wang, J.Chen, L.Ma, H.Chang, L.Chen, Y.peng and N.Yan, Appl.Catal.B:Environ., 2012,117-118,73.), above-mentioned prior art disclosed containing Fe composite oxides class catalyst owing to thering is stronger interaction with other oxide components, and make its low temperature NO
xpurify activity and water resistant, SO
2poisoning performance significantly improves.In addition, also have part Study person to utilize the synthetic method of pattern control to prepare pure Fe
2o
3material (X.-Y.Yang, L.Sun, Z.-W.Huang, X.-M.Cheng, T.-W.Zhang, B.Li and X.-F.Tang, Acta Phys.-Chim.Sin., 2012,28,184. and X.Mou, B.Zhang, Y.Li, L.Yao, X.Wei, D.S.Su and W.Shen, Angew.Chem.Int.Ed., 2012,51,2989.), also in SCR reaction, there is good catalytic performance, but these preparation methods are generally comparatively loaded down with trivial details, are unfavorable for industrial applications.
(Lu Yuhui pays fame and gain, Ye Daiqi, sulphation NO to Lu Yuhui
xthe investigation progress of denitrifying catalyst with selective catalytic reduction, Industrial Catalysis, 2007,20～23) etc. 15(3): people discloses sulphation SCR catalyst and can improve the activity and selectivity of catalyst in high temperature application aspect, but middle gentle cryogenic applications aspect cannot be improved significantly, and its also Sulfated concrete technology in unexposed iron oxide material surface.
Summary of the invention
For the problem of prior art, one of object of the present invention is to provide the preparation method of the Sulfated ferric oxide catalyst in a kind of surface, described method is by carrying out surperficial sulphation processing to iron oxide, the iron oxide surface acidity and the redox ability that obtain have all obtained effective adjusting, and then have significantly improved its NH in middle high temperature section
3-SCR reactivity.
In order to achieve the above object, the present invention has adopted following technical scheme:
A preparation method for the Sulfated ferric oxide catalyst in surface, described method comprises the steps:
(1) prepare iron oxide;
(2) iron oxide surface is carried out to sulphation processing, obtain surperficial Sulfated ferric oxide catalyst.
First the present invention prepares pure iron oxide, then iron oxide surface is carried out to sulphation processing, and the iron oxide material surface acidity and the redox ability that obtain have all obtained effective adjusting, and then has significantly improved its NH in middle high temperature section
3-SCR reactivity.In addition, iron oxide material environmental friendliness, cheap, and exist efficient oxidation-reduction process between trivalent Fe and divalence Fe, be conducive to promote the generation of SCR reaction.
Preferably, step (1), using ammoniacal liquor as precipitating reagent, is prepared iron oxide by the precipitation method, comprises the steps:
(1 ') preparation source of iron solution then drips ammoniacal liquor in solution, and regulator solution pH value to 8～10, make Fe ion precipitation complete;
The sediment that (2 ') obtained (1 ') carries out suction filtration and washing, and then by filtration cakes torrefaction, roasting under air atmosphere, obtains iron oxide.
Preferably, the described source of iron of step (1) is selected from the mixture of any one or at least two kinds in ferric nitrate, ferric sulfate, ferric phosphate or iron chloride.
Preferably, the concentration of described ammoniacal liquor is 10～25wt%, for example 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt% or 24wt%, preferably 12～22wt%.
Preferably, drip ammoniacal liquor by base buret, rate of addition is controlled at 1～3 drop/sec.
Step (1 ') regulator solution pH value to 8～10, for example 8.2,8.4,8.6,8.8,9,9.2,9.4,9.6 or 9.8.
Preferably, described baking temperature is 90～120 ℃, and be 10～15h drying time.
Described baking temperature is for example 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃ or 118 ℃.
Be for example 10.3h, 10.6h, 10.9h, 11.2h, 11.5h, 11.8h, 12h, 12.3h, 12.6h, 12.9h, 13.2h, 13.5h, 13.8h, 14h, 14.3h, 14.6h or 14.9h described drying time.
Preferably, described sintering temperature is 400～600 ℃, and roasting time is 2～5h.
Described sintering temperature is for example 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃ or 580 ℃.
Described roasting time is for example 2.3h, 2.6h, 2.9h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h or 4.8h.
Preferably, in roasting process, be warming up to 400～600 ℃ with the heating rate of 3～8 ℃/min, described heating rate is for example 3.3 ℃/min, 3.6 ℃/min, 3.9 ℃/min, 4.2 ℃/min, 4.5 ℃/min, 4.8 ℃/min, 5.1 ℃/min, 5.4 ℃/min, 5.7 ℃/min, 6 ℃/min, 6.3 ℃/min, 6.6 ℃/min, 6.9 ℃/min, 7.2 ℃/min, 7.5 ℃/min or 7.8 ℃/min, preferably 3.5～7 ℃/min.
Preferably, the iron oxide after roasting is ground and sieved, choose 20～60 object particles for subsequent use to carry out step (2).
Preferably, the preparation method of step (1) iron oxide comprises the steps:
Preparation Fe (NO
3)
3solution, take the ammoniacal liquor of 10～25wt% as precipitating reagent, uses base buret to drip ammoniacal liquor in solution, and rate of addition is controlled at 1～3 drop/sec, and regulator solution pH value to 8～10 make Fe ion precipitation complete; Sediment is carried out to suction filtration and washing, afterwards filter cake is placed in to baking oven, 90～120 ℃ of dry 10～15h; Then be placed in Muffle furnace, heating rate is controlled at 3～8 ℃/min, and under air atmosphere, 400～600 ℃ of roasting 2～5h, obtain iron oxide.
Preferably, step (2) adopts gas phase sulfur acidifying method or liquid phase sulphation method to carry out sulphation processing to iron oxide surface.
Preferably, adopt and contain SO
2and O
2gas iron oxide surface is carried out to sulphation processing.Described gas is except containing SO
2and O
2also can contain inert gas outward.
Preferably, SO in described gas
2concentration be 400～600ppm.
Preferably, O in described gas
2concentration be 4～6%.
Preferably, SO
2concentration and pending iron oxide ratio are 100～300ppm/g.Can realize catalyst surface sulphur atom concentration by the setting of this ratio controlled in 0.5～5% scope.
Preferably, the flow of described gas is 400～600ml/min.
Preferably, the temperature of described sulphation processing is 200～500 ℃, and the time of sulphation processing is 0.5～24h.
The temperature of described sulphation processing is for example 230 ℃, 260 ℃, 290 ℃, 320 ℃, 350 ℃, 380 ℃, 410 ℃, 440 ℃, 470 ℃ or 490 ℃.
The time of described sulphation processing is 1h, 3h, 5h, 7h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h.
The present invention is by selecting the SO of above-mentioned technological parameter
2in-situ surface process of sulfating carries out sulphation processing to iron oxide surface, can prepare the sulphation ferric oxide catalyst that order number is adjustable, quality is adjustable and sulfur content is adjustable with very simple method, and then significantly improve its NH in middle high temperature section
3-SCR reactivity.Through XPS detecting catalyst surface, sulphur atom concentration is controlled in 0.5～5% scope, has realized middle high temperature NH
3-SCR activity is adjustable.
Preferably, iron oxide is flooded to sulfate, and then carry out roasting, realize the sulphation processing to iron oxide surface.
Preferably, described sulfate is selected from ammonium sulfate or/and ammonium hydrogen sulfate.
Preferably, iron oxide be impregnated in to ammonium sulfate or/and in ammonium hydrogen sulfate solution, stir, then evaporate to dryness, dry, roasting under air atmosphere, so that ammonium sulfate is or/and ammonium hydrogen sulfate decomposes completely, obtains surperficial Sulfated ferric oxide catalyst.
Preferably, described ammonium sulfate or/and the concentration of ammonium hydrogen sulfate solution determine according to the concentration of the sulphur atom of iron oxide surface load, determine according to the load capacity 0.5～5% of sulphur atom.
Preferably, described mixing time is 0.5～3h, for example 0.7h, 0.9h, 1.1h, 1.3h, 1.5h, 1.7h, 1.9h, 2.1h, 2.3h, 2.5h, 2.7h or 2.9h, preferably 0.8～2.5h.
Preferably, adopt the method for rotary evaporation to carry out evaporate to dryness, described evaporate to dryness temperature is 60～90 ℃, for example 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃ or 88 ℃, and preferably 65～85 ℃.
Described dry temperature is 90～120 ℃, and the dry time is 10～15h.
Described dry temperature is for example 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃ or 118 ℃.
The described dry time is for example 10.3h, 10.6h, 10.9h, 11.2h, 11.5h, 11.8h, 12.1h, 12.4h, 12.7h, 13h, 13.3h, 13.6h, 13.9h, 14.2h, 14.5h or 14.8h.
Described sintering temperature is 400～600 ℃, and roasting time is 2～5h.
Described sintering temperature is for example 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃ or 580 ℃.
Described roasting time is for example 2.3h, 2.6h, 2.9h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h or 4.8h.
Preferably, in roasting process, be warming up to 400～600 ℃ with the heating rate of 3～8 ℃/min, described heating rate is for example 3.3 ℃/min, 3.6 ℃/min, 3.9 ℃/min, 4.2 ℃/min, 4.5 ℃/min, 4.8 ℃/min, 5.1 ℃/min, 5.4 ℃/min, 5.7 ℃/min, 6 ℃/min, 6.3 ℃/min, 6.6 ℃/min, 6.9 ℃/min, 7.2 ℃/min, 7.5 ℃/min or 7.8 ℃/min, preferably 3.5～7 ℃/min.
The present invention carries out sulphation processing by the sulfate surface impregnation method of selecting above-mentioned technological parameter to iron oxide surface, can prepare the sulphation ferric oxide catalyst that order number is adjustable, quality is adjustable and sulfur content is adjustable with very simple method, and then significantly improve its NH in middle high temperature section
3-SCR reactivity.Through XPS detecting catalyst surface, sulphur atom concentration is controlled in 0.5～5% scope, has realized middle high temperature NH
3-SCR activity is adjustable.
Two of object of the present invention is to provide a kind of surperficial Sulfated ferric oxide catalyst, and it is prepared by method as above.Adopt method of the present invention can obtain the sulphation ferric oxide catalyst that order number is adjustable, quality is adjustable and sulfur content is adjustable, and then significantly improved its NH in middle high temperature section
3-SCR reactivity.Described method has given the catalyst obtaining more excellent catalytic performance.Through XPS detecting catalyst surface, sulphur atom concentration is controlled in 0.5～5% scope, has realized middle high temperature NH
3-SCR activity is adjustable.
Three of object of the present invention is to provide the purposes of the Sulfated ferric oxide catalyst in a kind of surface as above, and described catalyst is for the SCR purification process of nitrogen oxide.
Compared with the prior art, the present invention has following beneficial effect:
(1) the present invention adopts the extremely simple precipitation method and SO
2the liquid phase sulphation method of in-situ surface sulphation method and sulfate dipping has been synthesized surperficial Sulfated ferric oxide catalyst first, makes it at NH
3middle high temperature section NO in-SCR reaction
xpurify active obviously raising, operating temperature window is significantly widened, and has very excellent anti-SO
2poisoning performance, is highly suitable for stationary source and moving source NO
xcatalysis eliminate.And sulphation modification of the present invention has effectively improved Fe
2o
3the surface acid intensity of material and acidic site quantity, as abundant NH
3storage site, has significantly improved reducing agent NH
3in absorption and the activation of catalyst surface, can effectively improve NH
3-SCR reactivity worth.In addition, process of sulfating of the present invention has also significantly regulated Fe
2o
3the redox cycle ability of catalyst, by suppressing NH
3non-selective oxidation reaction, avoided the undue oxidation of reducing agent at high-temperature area, make more reducing agent NH
3can participate in NH
3in-SCR reaction, go, improved NO simultaneously
xpurification efficiency and N
2generate selective.
The specific embodiment
Further illustrate technical scheme of the present invention below by the specific embodiment.
Embodiment 1
A preparation method for the Sulfated ferric oxide catalyst in surface, described method comprises the steps:
(1), using ferric nitrate as Fe source, ammoniacal liquor, as precipitating reagent, is prepared Fe by the precipitation method
2o
3: prepare certain density Fe (NO
3)
3solution, take the ammoniacal liquor of 25wt% as precipitating reagent, uses base buret to mixed solution and dripping ammoniacal liquor, and rate of addition is controlled at about 1 drop/sec, and regulator solution pH value to 9 makes Fe ion precipitation complete; Sediment is carried out to suction filtration and washing, afterwards the good filter cake of suction filtration is placed in to baking oven, 100 ℃ of dry 12h; Dried sample is placed in to Muffle furnace, and heating rate is controlled at 5 ℃/min, 500 ℃ of roasting 3h under air atmosphere.By cooled roasting Fe
2o
3sample grinds and sieves, and chooses 20-60 object particle for subsequent use.
(2) adopt SO
2original position sulphation is processed Fe
2o
3obtain surperficial Sulfated Fe
2o
3catalyst: 20-60 order Fe
2o
3, each quantity of sample handling is 3g, SO
2=500ppm, O
2=5%, total flow 500ml/min, 300 ℃ for the treatment of temperatures, processing time 1h, obtains surperficial Sulfated ferric oxide catalyst.
Embodiment 2
Adopt the method identical with embodiment 1, except step (2) processing time is 8h.
Embodiment 3
Adopt the method identical with embodiment 1, except step (2) processing time is 24h.
Get pure Fe
2o
3material SOs different from embodiment 1～3
2the Sulfated ferric oxide catalyst in surface that processing time obtains, catalyst volume 0.6mL, 40～60 orders, put into 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
2for Balance Air, total flow is 500mL/min, and reaction velocity is 50000h
-1.Test result as shown in Table 1 and Table 2.
Table 1 different catalysts is at NH
3nO in-SCR reaction
xconversion ratio
Table 2 different catalysts is at NH
3n in-SCR reaction
2selectively
Pure Fe
2o
3material NH
3-SCR catalytic activity is extremely low, the highest NO
xconversion ratio only has 50% left and right, and operating temperature window is extremely narrow, and has a large amount of N
2o accessory substance generates.Pass through SO
2carry out after in-situ surface sulphation modification, wherein high temperature section NH
3-SCR catalytic activity and N
2generate selectively all to have very significantly and improve.SO in embodiment 1
2the catalyst that processing time 1h obtains can reach more than 90% NO in the temperature range of 300～400 ℃
xpurification efficiency, and along with SO
2the growth in processing time, the NH of its low-temperature zone
3-SCR activity also can further improve.The Sulfated Fe in this surface
2o
3catalyst has 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.
Embodiment 4
A preparation method for the Sulfated ferric oxide catalyst in surface, described method comprises the steps:
(1), using ferric sulfate as Fe source, ammoniacal liquor, as precipitating reagent, is prepared Fe by the precipitation method
2o
3: prepare certain density Fe (NO
3)
3solution, take the ammoniacal liquor of 10wt% as precipitating reagent, uses base buret to drip ammoniacal liquor in solution, and rate of addition is controlled at about 3 drops/sec, and regulator solution pH value to 8 makes Fe ion precipitation complete; Sediment is carried out to suction filtration and washing, afterwards filter cake is placed in to baking oven, 90 ℃ of dry 15h; Dried sample is placed in to Muffle furnace, and heating rate is controlled at 3 ℃/min, 400 ℃ of roasting 5h under air atmosphere.By cooled roasting Fe
2o
3sample grinds and sieves, and chooses 20-60 object particle for subsequent use.
(2) adopt SO
2original position sulphation is processed Fe
2o
3obtain surperficial Sulfated Fe
2o
3catalyst: 20-60 order Fe
2o
3, each quantity of sample handling is 4g, SO
2=400ppm, O
2=4%, total flow 400ml/min, 200 ℃ for the treatment of temperatures, processing time 24h, obtains surperficial Sulfated ferric oxide catalyst.
Embodiment 5
A preparation method for the Sulfated ferric oxide catalyst in surface, described method comprises the steps:
(1), using iron chloride as Fe source, ammoniacal liquor, as precipitating reagent, is prepared Fe by the precipitation method
2o
3: prepare certain density Fe (NO
3)
3solution, take the ammoniacal liquor of 18wt% as precipitating reagent, uses base buret to drip ammoniacal liquor in solution, and rate of addition is controlled at about 2 drops/sec, and regulator solution pH value to 10 makes Fe ion precipitation complete; Sediment is carried out to suction filtration and washing, afterwards filter cake is placed in to baking oven, 120 ℃ of dry 10h; Dried sample is placed in to Muffle furnace, and heating rate is controlled at 8 ℃/min, 500 ℃ of roasting 2h under air atmosphere.By cooled roasting Fe
2o
3sample grinds and sieves, and chooses 20-60 object particle for subsequent use.
(2) adopt SO
2original position sulphation is processed Fe
2o
3obtain surperficial Sulfated Fe
2o
3catalyst: 20-60 order Fe
2o
3, each quantity of sample handling is 4g, SO
2=600ppm, O
2=6%, total flow 600ml/min, 500 ℃ for the treatment of temperatures, processing time 0.5h, obtains surperficial Sulfated ferric oxide catalyst.
Embodiment 6
A preparation method for the Sulfated ferric oxide catalyst in surface, described method comprises the steps:
(1), using ferric sulfate as Fe source, ammoniacal liquor, as precipitating reagent, is prepared Fe by the precipitation method
2o
3: prepare certain density Fe (NO
3)
3solution, take the ammoniacal liquor of 10wt% as precipitating reagent, uses base buret to drip ammoniacal liquor in solution, and rate of addition is controlled at about 3 drops/sec, and regulator solution pH value to 8 makes Fe ion precipitation complete; Sediment is carried out to suction filtration and washing, afterwards filter cake is placed in to baking oven, 90 ℃ of dry 15h; Dried sample is placed in to Muffle furnace, and heating rate is controlled at 3 ℃/min, 400 ℃ of roasting 5h under air atmosphere.By cooled roasting Fe
2o
3sample grinds and sieves, and chooses 20-60 object particle for subsequent use.
(2) by 20-60 order Fe
2o
3particle or powder sample, impregnated in certain density ammonium sulfate or ammonium hydrogen sulfate solution, stirs 0.5h, then adopted the method for rotary evaporation in 60 ℃ of evaporates to dryness, and be positioned in baking oven in 90 ℃ of dry 15h; Dried sample is placed in to Muffle furnace, and heating rate is controlled at 3 ℃/min, and 400 ℃ of roasting 5h under air atmosphere decompose completely ammonium sulfate or ammonium hydrogen sulfate, obtain surperficial Sulfated ferric oxide catalyst.
Embodiment 7
A preparation method for the Sulfated ferric oxide catalyst in surface, described method comprises the steps:
(1), using iron chloride as Fe source, ammoniacal liquor, as precipitating reagent, is prepared Fe by the precipitation method
2o
3: prepare certain density Fe (NO
3)
3solution, take the ammoniacal liquor of 18wt% as precipitating reagent, uses base buret to drip ammoniacal liquor in solution, and rate of addition is controlled at about 2 drops/sec, and regulator solution pH value to 10 makes Fe ion precipitation complete; Sediment is carried out to suction filtration and washing, afterwards filter cake is placed in to baking oven, 120 ℃ of dry 10h; Dried sample is placed in to Muffle furnace, and heating rate is controlled at 8 ℃/min, 500 ℃ of roasting 2h under air atmosphere.By cooled roasting Fe
2o
3sample grinds and sieves, and chooses 20-60 object particle for subsequent use.
(2) by 20-60 order Fe
2o
3particle or powder sample, impregnated in certain density ammonium sulfate or ammonium hydrogen sulfate solution, stirs 3h, then adopted the method for rotary evaporation in 90 ℃ of evaporates to dryness, and be positioned in baking oven in 120 ℃ of dry 10h; Dried sample is placed in to Muffle furnace, and heating rate is controlled at 8 ℃/min, and 600 ℃ of roasting 2h under air atmosphere decompose completely ammonium sulfate or ammonium hydrogen sulfate, obtain surperficial Sulfated ferric oxide catalyst.
Embodiment 8
A preparation method for the Sulfated ferric oxide catalyst in surface, described method comprises the steps:
(1), using ferric nitrate as Fe source, ammoniacal liquor, as precipitating reagent, is prepared Fe by the precipitation method
2o
3: prepare certain density Fe (NO
3)
3solution, take the ammoniacal liquor of 18wt% as precipitating reagent, uses base buret to drip ammoniacal liquor in solution, and rate of addition is controlled at about 2 drops/sec, and regulator solution pH value to 10 makes Fe ion precipitation complete; Sediment is carried out to suction filtration and washing, afterwards filter cake is placed in to baking oven, 120 ℃ of dry 10h; Dried sample is placed in to Muffle furnace, and heating rate is controlled at 8 ℃/min, 500 ℃ of roasting 2h under air atmosphere.By cooled roasting Fe
2o
3sample grinds and sieves, and chooses 20-60 object particle for subsequent use.
(2) by 20-60 order Fe
2o
3particle or powder sample, impregnated in certain density ammonium sulfate or ammonium hydrogen sulfate solution, stirs 2h, then adopted the method for rotary evaporation in 80 ℃ of evaporates to dryness, and be positioned in baking oven in 100 ℃ of dry 12h; Dried sample is placed in to Muffle furnace, and heating rate is controlled at 5 ℃/min, and 500 ℃ of roasting 3h under air atmosphere decompose completely ammonium sulfate or ammonium hydrogen sulfate, obtain surperficial Sulfated ferric oxide catalyst.
Applicant's statement, the present invention illustrates detailed method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed method, does not mean that the present invention must rely on above-mentioned detailed method and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for the Sulfated ferric oxide catalyst in surface, is characterized in that, described method comprises the steps:
(1) prepare iron oxide;
(2) iron oxide surface is carried out to sulphation processing, obtain surperficial Sulfated ferric oxide catalyst.
2. the method for claim 1, is characterized in that, step (1), using ammoniacal liquor as precipitating reagent, is prepared iron oxide by the precipitation method, comprises the steps:
(1 ') preparation source of iron solution then drips ammoniacal liquor in solution, and regulator solution pH value to 8～10, make Fe ion precipitation complete;
The sediment that (2 ') obtained (1 ') carries out suction filtration and washing, and then by filtration cakes torrefaction, roasting under air atmosphere, obtains iron oxide.
3. method as claimed in claim 2, is characterized in that, the described source of iron of step (1) is selected from the mixture of any one or at least two kinds in ferric nitrate, ferric sulfate, ferric phosphate or iron chloride;
Preferably, the concentration of described ammoniacal liquor is 10～25wt%, preferably 12～22wt%;
Preferably, drip ammoniacal liquor by base buret, rate of addition is controlled at 1～3 drop/sec;
Preferably, described baking temperature is 90～120 ℃, and be 10～15h drying time.
Preferably, described sintering temperature is 400～600 ℃, and roasting time is 2～5h.
4. method as claimed in claim 3, is characterized in that, in roasting process, is warming up to 400～600 ℃ with the heating rate of 3～8 ℃/min, and heating rate is 3.5～7 ℃/min preferably;
Preferably, the preparation method of step (1) iron oxide comprises the steps:
Preparation Fe (NO
3)
3solution, take the ammoniacal liquor of 10～25wt% as precipitating reagent, uses base buret to drip ammoniacal liquor in solution, and rate of addition is controlled at 1～3 drop/sec, and regulator solution pH value to 8～10 make Fe ion precipitation complete; Sediment is carried out to suction filtration and washing, afterwards filter cake is placed in to baking oven, 90～120 ℃ of dry 10～15h; Then be placed in Muffle furnace, heating rate is controlled at 3～8 ℃/min, and under air atmosphere, 400～600 ℃ of roasting 2～5h, obtain iron oxide.
5. the method as described in one of claim 1-4, is characterized in that, step (2) adopts gas phase sulfur acidifying method or liquid phase sulphation method to carry out sulphation processing to iron oxide surface.
6. the method as described in one of claim 1-5, is characterized in that, adopts and contains SO
2and O
2gas iron oxide surface is carried out to sulphation processing;
Preferably, SO in described gas
2concentration be 400～600ppm;
Preferably, O in described gas
2concentration be 4～6%;
Preferably, SO
2concentration and pending iron oxide ratio are 100～300ppm/g;
Preferably, the flow of described gas is 400～600ml/min;
Preferably, the temperature of described sulphation processing is 200～500 ℃, and the time of sulphation processing is 0.5～24h.
7. the method as described in one of claim 1-5, is characterized in that, iron oxide is flooded to sulfate, and then carries out roasting, realizes the sulphation processing to iron oxide surface;
Preferably, described sulfate is selected from ammonium sulfate or/and ammonium hydrogen sulfate;
Preferably, described ammonium sulfate or/and the concentration of ammonium hydrogen sulfate solution determine according to the concentration 0.5～5% of the sulphur atom of iron oxide surface load;
Preferably, iron oxide be impregnated in to ammonium sulfate or/and in ammonium hydrogen sulfate solution, stir, then evaporate to dryness, dry, roasting under air atmosphere, obtains surperficial Sulfated ferric oxide catalyst.
8. method as claimed in claim 7, is characterized in that, described mixing time is 0.5～3h, preferably 0.8～2.5h;
Preferably, adopt the method for rotary evaporation to carry out evaporate to dryness, described evaporate to dryness temperature is 60～90 ℃, preferably 65～85 ℃;
Preferably, described dry temperature is 90～120 ℃, and the dry time is 10～15h;
Preferably, described sintering temperature is 400～600 ℃, and roasting time is 2～5h.
Preferably, in roasting process, be warming up to 400～600 ℃ with the heating rate of 3～8 ℃/min, heating rate is 3.5～7 ℃/min preferably.
9. the Sulfated ferric oxide catalyst in surface, is characterized in that, described catalyst is prepared by the method one of claim 1-8 Suo Shu.
10. a purposes for the Sulfated ferric oxide catalyst in surface as claimed in claim 9, is characterized in that, described catalyst is for the SCR purification process of nitrogen oxide.
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| CN107597177A (en) * | 2017-09-18 | 2018-01-19 | 中节能万润股份有限公司 | A kind of iron Cu oxide and molecular sieve composite honeycomb formula denitrating catalyst and preparation method thereof |
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| CN114797893A (en) * | 2022-04-25 | 2022-07-29 | 昆明理工大学 | Ammonia oxidation catalyst and preparation method and application thereof |
| CN114797893B (en) * | 2022-04-25 | 2023-08-11 | 昆明理工大学 | Ammonia oxidation catalyst, preparation method and application thereof |
| CN115090302A (en) * | 2022-06-27 | 2022-09-23 | 重庆三峡学院 | Modified sulfated load-type cerium-aluminum denitration catalyst and preparation method thereof |
| CN115090302B (en) * | 2022-06-27 | 2023-09-15 | 重庆三峡学院 | Modified sulfated supported cerium-aluminum denitration catalyst and preparation method thereof |
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