CN104226296A - Vanadium-loaded middle-temperature SCR catalyst and preparation method thereof - Google Patents

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

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CN104226296A
CN104226296A CN201410441962.0A CN201410441962A CN104226296A CN 104226296 A CN104226296 A CN 104226296A CN 201410441962 A CN201410441962 A CN 201410441962A CN 104226296 A CN104226296 A CN 104226296A
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vanadium
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张亚平
郭婉秋
王龙飞
沈凯
徐海涛
周长城
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Southeast University
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Abstract

The invention discloses a vanadium-loaded middle-temperature SCR catalyst. A titanium-zirconium oxide is used as a carrier, a vanadium oxide is used as an active component, and a cerium oxide is used as a catalyst promoter, wherein the mole ratio of a cerium element to a titanium element to a zirconium element in the catalyst is (0.1-0.3) to 1 to 1; the mass of vanadium oxide accounts for 1 percent of the mass of the whole catalyst. The invention also discloses a preparation method of the vanadium-loaded middle-temperature SCR catalyst. Compared with a single vanadium-based catalyst, the vanadium-loaded middle-temperature SCR catalyst disclosed by the invention has the advantages that by the adding of a proper amount of 0.2CeO2, the heat resistance of the catalyst is improved, the reducing temperature of the catalyst is reduced, the denitration efficiency is improved, and a selective catalytic reduction denitration active temperature window is expanded; an extremely good modification effect on a V2O5/TiO2-ZrO2 catalyst is achieved.

Description

The system supported Medium temperature SCR Catalysts and its preparation method of a kind of vanadium
Technical field
The invention belongs to catalyst technical field, relate to the system supported Medium temperature SCR Catalysts and its preparation method of a kind of vanadium being applied to coal steam-electric plant smoke particularly.
Background technology
Nitrogen oxide is the important composition of atmosphere pollution, and the acid rain caused by it, photochemical fog, surface ozone concentration increase and haze weather, causes very large harm to the health of the mankind and vegeto-animal growth.Within 2012, China has revised " ambient air quality " third time, it is 100mg/m3 (key area) that standard clearly proposes nitrous oxides concentration limit value, " key area prevention and control of air pollution " the 12 " planning " of State Council approved clearly proposed the Con trolling index of NOx by 2015, key area discharge capacity declines 13%, air quality makes moderate progress, NO 2mean annual concentration 7%.
Selective catalytic reduction (SCR) is current most widely used general, denitration technology that treatment effeciency is the highest, and what its catalyst application was maximum is V-W (Mo)-Ti series, used carrier TiO 2carrier specific area is smaller, TiO 2and ZrO 2character due to its uniqueness causes the broad interest of catalytic field, composite oxides TiO 2-ZrO 2generally there is larger specific area and stronger acidity, thus can be better than single oxide as carrier.The reaction temperature of SCR catalyst must more than 350 DEG C.Reach this temperature, after flue gas denitration reactor must be placed in boiler economizer, before air preheater.Cause catalyst to be subject to the washing away of high concentration flue dust, wear and tear and the pollution of impurity in flying dust, cigarette temperature is too high also can make sintering of catalyst, inactivation, or NH occurs 3be oxidized to the side reaction etc. of NO; And for the existing most of boiler of China, economizer, air preheater and boiler are assembled into one, this technology is mated with China existing boiler certain difficulty.For these problems, the research of middle temperature high activity denitrating flue gas SCR catalyst becomes focus.
CeO in recent years 2because of its outstanding oxygen storage capacity, redox ability, make it receive very big concern in catalyst field, researchers develop some and are applied to NH 3what-SCR reacted contains cerium catalyst, compares CeO 2/ TiO 2catalyst, CeO 2-WO 3/ TiO 2catalyst CeO 2-Fe 2o 3/ TiO 2catalyst, CeO 2/ TCNTs catalyst etc., all have higher catalytic activity in 200 ~ 450 DEG C.Therefore study at V 2o 5/ TiO 2-ZrO 2load C eO on basis 2catalyst to reducing denitration reaction temperature, improve the heat resistanceheat resistant performance of denitration efficiency and catalyst, widen denitration temperature window.
Summary of the invention
Goal of the invention: for solving problems of the prior art, the invention provides the system supported Medium temperature SCR catalyst of a kind of vanadium, this catalyst is by adding CeO 2improve the heat resistance of catalyst, reduce the reduction temperature of catalyst, improve denitration efficiency, widen its selective-catalytic-reduction denitrified active temperature windows, to V 2o 5/ TiO 2-ZrO 2catalyst has good modifying function.
The technical problem that the present invention also will solve is to provide the preparation method of the system supported Medium temperature SCR catalyst of above-mentioned vanadium.
Technical scheme: for solving the problems of the technologies described above, the present invention proposes the system supported Medium temperature SCR catalyst of a kind of vanadium, with titanium Zirconium oxide for carrier, with the oxide of vanadium for active component, with the oxide of cerium for co-catalyst, wherein, the mol ratio of described Cerium in Catalysts element, titanium elements and zr element is (0.1 ~ 0.3): 1: 1, and the quality of the oxide of vanadium accounts for 1% of whole catalyst quality.
Particularly, described titanium Zirconium oxide is TiO 2-ZrO 2, the oxide of described vanadium is V 2o 5, the oxide of cerium is CeO 2.
The invention allows for the preparation method of the system supported Medium temperature SCR catalyst of above-mentioned vanadium, comprise the steps:
(1) TiO 2-ZrO 2the preparation of carrier: utilize Co deposited synthesis TiO 2-ZrO 2carrier, for subsequent use after first drying and grinding calcining more again, wherein, TiO 2with ZrO 2mol ratio 1: 1;
(2) CeO 2/ TiO 2-ZrO 2the preparation of catalyst: the TiO obtained by step (1) 2-ZrO 2carrier is dissolved in deionized water, adds Ce (NO 3) 36H 2o, stirs 2 ~ 2.5h under 20 ~ 25 DEG C of oil baths, magnetic agitation, is then warming up to 80 ~ 90 DEG C and continues to stir dipping 4 ~ 5h, after moisture evaporate to dryness, obtain CeO successively after drying, grinding, calcining 2/ TiO 2-ZrO 2catalyst, wherein, the Ce (NO added 3) 36H 2o and TiO 2-ZrO 2mol ratio be (0.1 ~ 0.3): 1;
(3) by CeO that step (2) obtains 2/ TiO 2-ZrO 2catalyst joins in the aqueous solution of metavanadic acid ammonia, add simultaneously 1 ~ 2g oxalic acid promote metavanadic acid ammonia dissolving, 2 ~ 2.5h is stirred under 20 ~ 25 DEG C of oil baths, magnetic agitation, then be warming up to 80 ~ 90 DEG C to continue to stir dipping 4 ~ 5h, after moisture evaporate to dryness, obtain V after drying, grinding, calcining successively 2o 5-C eo 2/ TiO 2-ZrO 2catalyst, wherein, V 2o 5quality account for 1% of whole catalyst quality, particularly, the quality of metavanadic acid ammonia is 1.28% of the product quality after step (2) calcining, makes the mass percentage of the oxide of vanadium in the catalyst finally prepared be 1%.
Wherein, particularly, the co-precipitation step in step (1) comprises: in step (1), the step of co-precipitation is: by TiCl under ice-water bath, churned mechanically condition 4dropping to the speed of 0.8 ~ 1ml/min is equipped with in the reactor of deionized water, then by ZrOCl 28H 2o joins in reactor, continues stirring and makes ZrOCl 28H 2o dissolves completely, drip ammoniacal liquor in reactor with the speed of 3 ~ 5ml/min simultaneously, until the pH that pH test paper records solution is 9 ~ 10, then under dark condition, leave standstill 12 ~ 14h hypsokinesis goes supernatant liquor to be precipitated, then deionized water precipitation is spent, and decompress filter, repeated washing is until examine the Cl do not measured in filtrate with liquor argenti nitratis ophthalmicus -till, obtain TiO 2-ZrO 2precipitation, wherein, the concentration of ammoniacal liquor is 25 ~ 28wt%.
Wherein, preferably, the mechanical agitation in above-mentioned steps or the speed of agitator of magnetic agitation are 40 ~ 50r/s.
As preferably, in step (1), step (2) and step (3), the condition of oven dry is in baking oven, dry 11 ~ 13h at 100 ~ 120 DEG C.
In step (1), step (2) and step (3), the condition of calcining is calcine 3 ~ 4h at 400 ~ 500 DEG C, the calcining heat of whole preparation process can not higher than 500 DEG C, when calcining heat is higher than 500 DEG C, titanium dioxide starts have anatase crystal to change to rutile crystal type, unfavorable to reaction.Preferably, the condition of described calcining is calcine 4h at 450 DEG C.
In order to improve the performance of catalyst further, in step (2) and step (3), described TiO 2-ZrO 2carrier and CeO 2/ TiO 2-ZrO 2first catalyst is polished and after crossing 60 mesh sieves, and then is dissolved in deionized water.
Present invention further proposes the application of the system supported Medium temperature SCR catalyst of above-mentioned vanadium in middling temperature DeNOx.
Preferably, the temperature range of described middle temperature is 200 ~ 300 DEG C.
Beneficial effect: vanadium of the present invention system supported Medium temperature SCR catalyst, relative to single catalytic component based on vanadium, adds appropriate CeO 2improve the heat resistance of catalyst, reduce the reduction temperature of catalyst, improve denitration efficiency, widen its selective-catalytic-reduction denitrified active temperature windows, to V 2o 5/ TiO 2-ZrO 2catalyst has good modifying function.Gained catalyst, by carrying out denitration test under simulated flue gas condition in fixing tube furnace, finds that this catalyst has lower light-off temperature, higher catalytic efficiency and wider temperature window.
Accompanying drawing explanation
The X-ray diffractogram of Fig. 1 catalyst of the present invention and carrier;
The H of Fig. 2 catalyst of the present invention and carrier 2-TPR schemes;
Fig. 3 is CeO 2to TiO 2-ZrO 2the impact of the catalytic performance of catalyst.
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, concrete material proportion, process conditions and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1:TiO 2-ZrO 2prepared by carrier (Ti-Zr).
TiO 2-ZrO 2prepared by carrier (Ti-Zr): adopt coprecipitation to prepare the TiO that mol ratio is 1: 1 2-ZrO 2composite oxides: with eight water zirconium oxychloride ZrOCl 28H 2o (AR, Chemical Reagent Co., Ltd., Sinopharm Group produces), titanium tetrachloride (TiCl 4) solution (density is 1.73g/ml, AR, and Shanghai Ling Feng chemical reagent Co., Ltd produces), ammoniacal liquor (AR, pilot scale chemical corp, Shanghai produces) and deionized water are raw material.The TiCl of 5.3995ml is first measured with clean graduated cylinder 4, the beaker that 300 ~ 400ml deionized water is housed is put into ice-water bath, then the speed with 1ml/min in beaker adds TiCl 4.Adition process carries out mechanical agitation to beaker, and mixing speed is 45r/s, then adds the ZrOCl of 15.8673g 28H 2o is until solution clarification.Then in solution, drip the ammoniacal liquor of 28wt% with the speed of 3 ~ 5ml/min, control the pH of solution with pH test paper, until the pH of solution is 10, obtain white precipitate.Under dark condition, room temperature leaves standstill 12h, then washes away Cl by deionized water -1, and decompress filter, repeated washing is until examine the Cl do not measured in filtrate with liquor argenti nitratis ophthalmicus -till, be placed in the dry 12h of baking oven of 110 DEG C, grind and cross 60 mesh sieves after dry, then proceed to 450 DEG C of calcining 4h in Muffle furnace, obtain titanium zirconium solid solution (TiO 2-ZrO 2carrier), be ground to that to be more than or equal to 60 orders for subsequent use.
Embodiment 2:1.00%V 2o 5/ TiO 2-ZrO 2(V/Ti-Zr) preparation of catalyst.
Vehicle element: get titanium zirconium solid solution prepared by 2g embodiment 1, join in 50ml deionized water, obtain the aqueous solution of titanium zirconium solid solution.
Mass percent is the load of the barium oxide of 1.00%: in the aqueous solution of above-mentioned titanium zirconium solid solution, add 0.0260gNH 4vO 3, 40 ~ 50r/s uniform stirring 2h at 20 DEG C, is then stirred to the basic evaporate to dryness of moisture (usually need 4 hours) at 85 DEG C, need in preparation process to add 1 ~ 2g oxalic acid promote metavanadic acid ammonia dissolving; Take out after the basic evaporate to dryness of moisture, put into baking oven taking-up in dry 12 hours at 110 DEG C and grind and cross 60 mesh sieves; Put into Muffle furnace and calcine 4h at 450 DEG C, obtain 1.00%V 2o 5/ TiO 2-ZrO 2catalyst, wherein, in the catalyst of 1% representative synthesis, V 2o 5quality account for 1% of total catalyst quality.
Embodiment 3:1.00%V 2o 5-0.1CeO 2/ TiO 2-ZrO 2(V-0.1Ce/Ti-Zr) preparation of catalyst.
Vehicle element: get titanium zirconium solid solution prepared by 2g embodiment 1, join in 50ml deionized water, obtain the aqueous solution of titanium zirconium solid solution.
Mol ratio is the load of the cerium oxide of 0.1: in the aqueous solution of above-mentioned titanium zirconium solid solution, add 0.4275gCe (NO 3) 36H 2o, 40 ~ 50r/s uniform stirring, 2 ~ 2.5h at 20 DEG C, be then stirred to moisture evaporate to dryness (usually needing 4 hours) at 80 ~ 90 DEG C, puts into baking oven taking-up in dry 12 hours at 110 DEG C and grind and cross 60 mesh sieves; Finally put into Muffle furnace and calcine 4h at 450 DEG C, obtain 0.1CeO 2/ TiO 2-ZrO 2catalyst, grinds and to cross 60 mesh sieves for subsequent use, wherein n (Ce): n (Ti): n (Zr)=0.1: 1: 1.
Mass percent is the load of the barium oxide of 1.00%: in 50ml deionized water, add the above-mentioned ground 0.1CeO of 2g 2/ TiO 2-ZrO 2catalyst, adds 0.0260g NH 4vO 3, 40 ~ 50r/s uniform stirring 2h at 20 DEG C, is then stirred to the basic evaporate to dryness of moisture (usually need 4 hours) at 85 DEG C, need in preparation process to add 1 ~ 2g oxalic acid promote metavanadic acid ammonia dissolving; Take out after the basic evaporate to dryness of moisture, put into baking oven taking-up in dry 12 hours at 110 DEG C and grind and cross 60 mesh sieves; Put into Muffle furnace and calcine 4h at 450 DEG C, obtain 1.00%V 2o 5-0.1CeO 2/ TiO 2-ZrO 2catalyst, wherein, in the catalyst of 1% representative synthesis, V 2o 5quality account for 1% of total catalyst quality; In the catalyst of 0.1 representative preparation, CeO 2with TiO 2-ZrO 2mol ratio be 0.1.
Embodiment 4:1.00%V 2o 5-0.2CeO 2/ TiO 2-ZrO 2(V-0.2Ce/Ti-Zr) preparation of catalyst.
Vehicle element: the titanium zirconium solid solution carrier getting 2g embodiment 1 preparation is fully ground to granularity and is greater than 60 orders, adds in 50ml deionized water, obtains the aqueous solution of titanium zirconium solid solution.
Mol ratio is the load of the cerium oxide of 0.2: in the aqueous solution of above-mentioned titanium zirconium solid solution, add 0.8550g Ce (NO 3) 36H 2o, 40 ~ 50r/s uniform stirring, 2 ~ 2.5h at 20 DEG C, be then stirred to moisture evaporate to dryness (usually needing 4 hours) at 80 ~ 90 DEG C, puts into baking oven taking-up in dry 12 hours at 110 DEG C and grind and cross 60 mesh sieves; Put into Muffle furnace and calcine 4h at 450 DEG C, obtain 0.2CeO 2/ TiO 2-ZrO 2catalyst, grinds and to cross 60 mesh sieves for subsequent use, wherein n (Ce): n (Ti): n (Zr)=0.2: 1: 1.
Mass percent is the load of the barium oxide of 1.00%: in 50ml deionized water, add the above-mentioned ground 0.2CeO of 2g 2/ TiO 2-ZrO 2catalyst, adds 0.0260g NH 4vO 3, 40 ~ 50r/s uniform stirring 2h at 20 DEG C, is then stirred to the basic evaporate to dryness of moisture (usually need 4 hours) at 85 DEG C, need in preparation process to add 1 ~ 2g oxalic acid promote metavanadic acid ammonia dissolving; Take out after the basic evaporate to dryness of moisture, put into baking oven taking-up in dry 12 hours at 110 DEG C and grind and cross 60 mesh sieves; Put into Muffle furnace and calcine 4h at 450 DEG C, obtain 1.00%V 2o 5-0.2CeO 2/ TiO 2-ZrO 2catalyst, wherein, in the catalyst of 1% representative synthesis, V 2o 5quality account for 1% of total catalyst quality; In the catalyst of 0.2 representative preparation, CeO 2with TiO 2-ZrO 2mol ratio be 0.2.
Embodiment 5:1.00%V 2o 5-0.3CeO 2/ TiO 2-ZrO 2(V-0.3Ce/Ti-Zr) preparation of catalyst.
Vehicle element: 2g titanium zirconium solid solution carrier fully grinds, and adds in 50ml deionized water, obtains the aqueous solution of titanium zirconium solid solution.
Mol ratio is the load of the cerium oxide of 0.3: in the aqueous solution of above-mentioned titanium zirconium solid solution, add 1.2825g Ce (NO 3) 36H 2o, 40 ~ 50r/s uniform stirring, 2 ~ 2.5h at 20 DEG C, be then stirred to moisture evaporate to dryness (usually needing 4 hours) at 80 ~ 90 DEG C, puts into baking oven taking-up in dry 12 hours at 110 DEG C and grind and cross 60 mesh sieves; Put into Muffle furnace and calcine 4h at 450 DEG C, obtain 0.3CeO 2/ TiO 2-ZrO 2catalyst, grinds and crosses 60 mesh sieves, wherein n (Ce): n (Ti): n (Zr)=0.3: 1: 1.
Mass percent is the load of the barium oxide of 1.00%: in 50ml deionized water, add the above-mentioned ground 0.3CeO of 2g 2/ TiO 2-ZrO 2catalyst, adds 0.0260g NH 4vO 3, 40 ~ 50r/s uniform stirring 2h at 20 DEG C, is then stirred to the basic evaporate to dryness of moisture (usually need 4 hours) at 85 DEG C, need in preparation process to add 1 ~ 2g oxalic acid promote metavanadic acid ammonia dissolving; Take out after the basic evaporate to dryness of moisture, put into baking oven taking-up in dry 12 hours at 110 DEG C and grind and cross 60 mesh sieves; Put into Muffle furnace and calcine 4h at 450 DEG C, obtain 1.00%V 2o 5-0.3CeO 2/ TiO 2-ZrO 2catalyst, wherein, in the catalyst of 1% representative synthesis, V 2o 5quality account for 1% of total catalyst quality; In the catalyst of 0.3 representative preparation, CeO 2with TiO 2-ZrO 2mol ratio be 0.3.
Embodiment 6: the sign of catalyst and carrier.
(1) BET characterization result.
Specific area that company of Merck & Co., Inc of the U.S. produces that what the measurement of BET adopted is and Porosimetry ASAP2020.Sample vacuumizes pretreatment 2h at 200 DEG C, with N 2adsorbate, measures at-196 DEG C.
TiO 2-ZrO 2specific area be 255.7267m 2g -1, V 2o 5/ TiO 2-ZrO 2specific area is 1243.7703m 2g -1.Add V 2o 5and CeO 2rear catalyst specific area reduces, and this is because active component enters carrier duct, and duct diminishes even to block and causes, particularly V 2o 5-CeO 2/ TiO 2-ZrO 2the specific area of series reduces amplitude very greatly, but knows in conjunction with denitration performance: V 2o 5-CeO 2/ TiO 2-ZrO 2although catalyst series specific area is very little, its denitration efficiency is far longer than V 2o 5/ TiO 2-ZrO 2and TiO 2-ZrO 2.Composed from XRD: catalyst surface exists barium oxide and cerium oxide, and in amorphous state covering, active component occupies original duct makes its specific area and pore volume reduce.
When catalyst has higher specific area, the decentralization of active component is higher, and the area contacted with reacting gas is also larger, is conducive to the carrying out of NO subtractive process.NO removal effect is simultaneously also relevant with pore structure, because first reacting gas must spread arrival catalyst, micropore surface reacts, and generates product and leaves catalyst surface by diffusion again.Pore volume is larger, and in catalytic process, the inside diffusional resistance of reaction gas reduces relatively, and catalytic efficiency is also higher.
By table, we can draw, 1.00%V 2o 5-0.2CeO 2/ TiO 2-ZrO 2the specific area of catalyst, pore volume is maximum, and catalytic activity should be the highest, and denitration performance test result also shows that its performance is best, and namely reaches most high activity at 250 DEG C.
Table 1 carrier and specific surface area of catalyst
(2) XRD characterizes.
XRD characterizes and adopts D max/RB type diffractometer (company of Rigaku company) to carry out material phase analysis, tube voltage 35kV, tube current 20mA, Cu target, 2 θ coupling continuous sweeps, scanning angle 5 ° ~ 80 °, X-ray wavelength is 1.5406A, all catalyst samples all need abundant grinding before testing, gets powder filledly in right amount to flatten on glass carrier, sample powder thickness is about 1mm, and result as shown in Figure 1.
TiO in figure 2-ZrO 2compound diffraction maximum is according to obviously existing, and now composite oxides become amorphous state, and this dispersed is thermodynamically stable.TiO 2-ZrO 2impalpable structure, be because Ti and Zr has different oxygen ligancy (the oxygen ligancy of Ti is the ligancy of 6, Zr is 8), titanium zirconium boundary in composite oxides formed a large amount of " hetero-junctions ", prevents the reunion crystallization of one-component.So titanium zirconium mixed oxide still keeps a kind of noncrystalline, porous open structure after calcining.
But its diffraction maximum divides ZrO on the right 2diffraction maximum, in the diffraction maximum of its left side to anatase phase, can observe V simultaneously 2o 5diffraction maximum, but and not obvious.2 θ are greater than after 40, can obviously see many anatases, CeO 2and ZrO 2the existence of diffraction maximum, shows that now catalyst cupport composition is scattered among carrier.1.00%V can be found out from XRD figure 2o 5-0.2CeO 2/ TiO 2-ZrO 2catalyst diffraction maximum is more weak, and degree of crystallinity is the poorest, good dispersion, active high, conforms to performance test and BET result.
(3) H 2-TPR characterizes.
H 2-TPR is used to investigate load type metal catalyst interactional information between metal oxide or between metal oxide and carrier in reduction process.The H of catalyst prepared by the present invention 2as shown in Figure 2, the qualitative reaction reducing property of mixed oxide, the content of different collection of illustrative plates and the oxide content of cerium has relation to-TPR spectrum.Pure V 2o 5reduction be divided into 4 consecutive steps: V 2o 5-V 6o 13-V no 2n-1-V 2o 3(4 < n < 8), its reduction peak is also more than 700 DEG C.TiO 2-ZrO 2carrier heat endurance is very high, just there will be reduction peak after 700 DEG C.CeO 2there is oxidizable reproducibility, Ce can be reached very soon 4+/ Ce 3+balance, therefore it can store oxygen under excess oxygen, and discharges oxygen under oxygen lean conditions.CeO 2the usual available H of oxygen storage capacity 2-TPR characterizes, its H 2-TPR has two reduction peak, with surface C e 4+the Surface Oxygen anion that ion combines with octahedral coordination form reduces at 500 DEG C, with body two Ce mutually 4+the body phase negative oxygen ion that Ion Phase combines reduces at 750 DEG C.CeO 2reduction and its grain size have close relationship, specific area is large and CeO that crystallite dimension is little 2have low temperature (497 DEG C) and high temperature (827 DEG C) two reduction peak, specific area is little and the CeO that crystallite dimension is large 2only has the high temperature reduction peak (827 DEG C) of body phase oxonium ion.The reproducibility of catalyst is arranged by crystal grain and size of microcrystal determines jointly, and CeO 2with V 2o 5/ TiO 2-ZrO 2composite oxides interact, the oriented making the crystal of original arbitrary arrangement become more excellent, show better reproducibility, thus impel reduction peak to offset to low temperature direction.
In figure all there is a larger reduction peak in curve between 500 ~ 600 DEG C, and reduction temperature occurs because the content of cerium oxide increases first reducing the trend raised again.In conjunction with denitration activity test result deducibility CeO 2interpolation impel the interphase interaction of metal oxide, character is sent out in change, thus has better catalytic activity.CeO 2when mole load capacity is 0.2,0.3, reduction temperature is lower and the area at peak is comparatively large, comparatively speaking CeO 2during load capacity 0.2, reduction temperature is minimum, conforms to denitration performance result.
(4) CeO 2to V 2o 5/ TiO 2-ZrO 2the impact of catalyst catalytic performance.
TiO 2-ZrO 2carrier loaded CeO 2and V 2o 5after catalyst S CR denitration performance, probe temperature is 200 ~ 450 DEG C.Result as shown in Figure 3.Can see, the denitration performance of 4 kinds of catalyst all along with the rising of temperature, and presents the trend of first increases and then decreases.Because V 2o 5high temperature catalyst, therefore supported V 2o 5rear catalyst is except 1.00%V 2o 5-0.2CeO 2/ TiO 2-ZrO 2all 300 DEG C time, reach the highest denitration activity outward.Compared with the oxide of cerium-carrying, the denitration activity of V/Ti-Zr is obviously lower in whole temperature range, 1.00%V 2o 5-0.2CeO 2/ TiO 2-ZrO 2that activity is the highest at 250 DEG C, itself and 1.00%V after 300 DEG C 2o 5-0.3CeO 2/ TiO 2-ZrO 2equally active in V/Ti-Zr, and 1.00%V 2o 5-0.3CeO 2/ TiO 2-ZrO 2active obviously very low, visible in whole temperature range, the oxide carried amount of cerium increases can not improve catalyst light-off temperature and denitration activity.At low-temperature region 1.00%V 2o 5-0.2CeO 2/ TiO 2-ZrO 2rising lives can reach more than 90% denitration efficiency soon and at a lower temperature, therefore selects its optimal catalyst.

Claims (10)

1. the system supported Medium temperature SCR catalyst of vanadium, it is characterized in that, with titanium Zirconium oxide for carrier, with the oxide of vanadium for active component, with the oxide of cerium for co-catalyst, wherein, the mol ratio of described Cerium in Catalysts element, titanium elements and zr element is (0.1 ~ 0.3): 1: 1, and the quality of the oxide of vanadium accounts for 1% of whole catalyst quality.
2. the system supported Medium temperature SCR catalyst of vanadium according to claim 1, wherein, described titanium Zirconium oxide is TiO 2-ZrO 2, the oxide of described vanadium is V 2o 5, the oxide of cerium is CeO 2.
3. a preparation method for the system supported Medium temperature SCR catalyst of vanadium, it is characterized in that, the method comprises the steps:
(1) TiO 2-ZrO 2the preparation of carrier: utilize Co deposited synthesis TiO 2-ZrO 2carrier, for subsequent use after drying, grinding, calcining successively;
(2) CeO 2/ TiO 2-ZrO 2the preparation of catalyst: the TiO obtained by step (1) 2-ZrO 2carrier is dissolved in deionized water, adds Ce (NO 3) 36H 2o, stirs 2 ~ 2.5h under 20 ~ 25 DEG C of oil baths, magnetic agitation, is then warming up to 80 ~ 90 DEG C and continues to stir dipping 4 ~ 5h, after moisture evaporate to dryness, obtain CeO successively after drying, grinding, calcining 2/ TiO 2-ZrO 2catalyst;
(3) V 2o 5-CeO 2/ TiO 2-ZrO 2the preparation of catalyst: the CeO that step (2) is obtained 2/ TiO 2-ZrO 2catalyst joins in the aqueous solution of metavanadic acid ammonia, under 20 ~ 25 DEG C of oil baths, magnetic agitation, stir 2 ~ 2.5h, is then warming up to 80 ~ 90 DEG C and continues to stir dipping 4 ~ 5h, after moisture evaporate to dryness, obtain V successively after drying, grinding, calcining 2o 5-CeO 2/ TiO 2-ZrO 2catalyst.
4. preparation method according to claim 3, is characterized in that, the co-precipitation step in step (1) comprises: by TiCl under ice-water bath, churned mechanically condition 4dropping to the speed of 0.8 ~ 1ml/min is equipped with in the reactor of deionized water, then by ZrOCl 28H 2o joins in reactor, continues stirring and makes ZrOCl 28H 2o dissolves completely, drip ammoniacal liquor in reactor with the speed of 3 ~ 5ml/min simultaneously, until the pH that pH test paper records solution is 9 ~ 10, then under dark condition, leave standstill 12 ~ 14h hypsokinesis goes supernatant liquor to be precipitated, then deionized water precipitation is spent, and decompress filter, repeated washing until in filtrate inspection do not measure Cl -till, obtain TiO 2-ZrO 2precipitation.
5. the preparation method according to claim 3 or 4, is characterized in that, the speed of agitator of mechanical agitation or magnetic agitation is 40 ~ 50r/s.
6. preparation method according to claim 3, is characterized in that, in step (1), step (2) and step (3), the condition of oven dry is dry 11 ~ 13h at 100 ~ 120 DEG C.
7. preparation method according to claim 3, is characterized in that, in step (1), step (2) and step (3), calcination condition is 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 CeO 2/ TiO 2-ZrO 2after ground 60 mesh sieves of catalyst, and then be dissolved in deionized water.
9. the application of the system supported Medium temperature SCR catalyst of vanadium according to claim 1 in middling temperature DeNOx.
10. application according to claim 9, is characterized in that, the temperature range of described middle temperature is 200 ~ 300 DEG C.
CN201410441962.0A 2014-09-01 2014-09-01 Vanadium-loaded middle-temperature SCR catalyst and preparation method thereof Pending CN104226296A (en)

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CN105032395A (en) * 2015-05-29 2015-11-11 上海大学 Zirconium doped cerium vanadate denitration catalyst, preparation method and application
CN105363430A (en) * 2015-09-10 2016-03-02 上海大学 TiO2 cerium-zirconium-vanadate-loaded denitration catalyst, preparing method and application
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Application publication date: 20141224