CN103623808A - Selective catalytic reduction (SCR) catalyst and preparation method thereof - Google Patents
Selective catalytic reduction (SCR) catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a selective catalytic reduction (SCR) catalyst and a preparation method thereof. The SCR catalyst comprises a TiO2-SiO2 composite oxide carrier, a metal oxide solid acid, V2O5 and CeO2. Compared with the existing SCR catalyst, the SCR catalyst has the advantages that SiO2 is added, so phase change of TiO2 at high temperature can be inhibited and the heat stability of the catalyst is enhanced; the SiO2 has more specific surface area than that of the TiO2, so the specific surface area of the catalyst can be increased, active components are dispersed well, and the activity of the catalyst is further improved through the interaction of the metal and the carrier; the SiO2 has excellent heat stability, so the using temperature window of the SCR catalyst can be widened by inhibiting the phase change of the carrier at high temperature and inhibiting reduction of the specific surface area; and the active components such as the CeO2 are added, so the catalytic activity of the catalyst at a lower temperature can be improved by enhancing the oxidizing capacity at a low temperature.
Description
Technical field
The invention belongs to catalyst preparation and environmental catalysis technical field, relate in particular to a kind of SCR Catalysts and its preparation method.
Background technology
For the consideration of fuel economy, diesel engine obtains applying more and more widely with the feature of its low oil consumption, high power ratio.But the nitrogen oxide NO that the high pressure-temperature in cylinder of diesel engine produces
xbring serious environmental problem, aggravated the deterioration of air quality.At present in the main pollutant component of ， China atmosphere, the NO of motor vehicle exhaust emission
xbecome one of most important source, so China to being installed, the road vehicle of Diesel engine has also improved constantly corresponding discharge standard.
At present, at purifying tail gas of diesel vehicles NO
xaspect, SCR (SCR) technology is mainstream technology, SCR is with additional reducing agent reductive NO
xchanged into N
2and O
2smoke treating method.NH
3to adsorb the strongest reducing agent, NH
3and NO
xkey reaction process on catalyst is gaseous state NH
3from catalyst surface, be diffused in catalyst pores, be then adsorbed on the NO of activated centre and gaseous state
xreaction generates N
2and H
2o.In whole course of reaction, catalyst is core.
And apply maximum in SCR technology, be urea-SCR system, its principle is by spray a certain proportion of urea liquid before SCR catalyst, and the ammonia producing by hydrolysis of urea or pyrolysis carrys out selective reduction NO as reducing agent at catalyst surface
x.
But now, core component-SCR catalyst of this system still comes with some shortcomings and problem: under vehicle idling or low speed operating mode, exhaust temperature is mostly lower than 200 ℃, and the temperature window of traditional vanadium titanium tungsten type SCR is 280 ℃～400 ℃, so this catalyst can not meet NO under low temperature
xpurify; And the carrier of most of SCR catalyst adopts TiO
2or the loose structure such as zeolite, also studies have reported that and use Al
2o
3, active carbon and activated coke be as the carrier of SCR catalyst, although it is active to have good adaptation through these carriers of Practical Project testing identity, simple owing to forming, responsive to sulphur and steam, and catalyst can be worn and torn by the dust in flue gas, affects service life.Therefore, existing SCR catalyst is improved to improve its denitration efficiency and becomes problem in the urgent need to address service life.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of SCR Catalysts and its preparation method, and this catalyst activity is higher.
The invention provides a kind of SCR catalyst, comprise TiO
2-SiO
2composite oxide carrier, metal oxide solid, V
2o
5with CeO
2; Described TiO
2-SiO
2composite oxide carrier is prepared by sol-gal process; The load capacity of described metal oxide solid is 1～10wt%; Described V
2o
5load capacity be 0～5wt%; Described CeO
2load capacity be 0～10wt%; And described V
2o
5load capacity and CeO
2load capacity be 0 when different.
Preferably, described TiO
2-SiO
2siO in composite oxide carrier
2mass fraction be 0.1～40wt%.
Preferably, described TiO
2-SiO
2composite oxide carrier also comprises silicate, mica sheet, Al
2o
3with ZrO
2in one or more.
Preferably, described metal oxide solid is selected from WO
3, Nb
2o
5with MoO
3in one or more.
The present invention also provides a kind of preparation method of SCR catalyst, comprises the following steps:
S1) soluble silicon source is mixed in alcoholic solvent with soluble titanium source, add water, stirring, standing, obtains gel;
S2) described gel is dried, roasting, obtains TiO
2-SiO
2composite oxide carrier;
S3) soluble metallic salt, solubility cerium salt is soluble in water, then add described TiO
2-SiO
2composite oxide carrier, is stirred to and obtains powder solid, and dry, roasting, obtains intermediate product; The corresponding metal oxide of metal in described soluble metallic salt is solid acid; The quality of the respective metal oxide of described soluble metallic salt is TiO
2-SiO
21～10% of composite oxide carrier quality; The corresponding CeO of described solubility cerium salt
2quality is TiO
2-SiO
20～10% of composite oxide carrier quality;
S4) described intermediate product is added in the solution that contains solubility vanadic salts, stir, dry, roasting, obtains SCR catalyst; The corresponding V of described solubility vanadic salts
2o
5quality is TiO
2-SiO
20～5% of composite oxide carrier quality; When the quality of described solubility cerium salt and solubility vanadic salts is different, be 0.
Preferably, described soluble metallic salt is selected from one or more in niobium oxalate, ammonium molybdate, ammonium metatungstate, ammonium paratungstate and ammonium tungstate.
Preferably, described solubility cerium salt is selected from one or more in cerous nitrate, ammonium ceric nitrate and cerous nitrate.
Preferably, described solubility vanadic salts is selected from sodium metavanadate and/or vanadium oxalate.
Preferably, described step S3) dry and step S4 in) in dry temperature be 80 ℃～150 ℃ independently of one another, the time is 8～14h independently of one another.
Preferably, described step S3) roasting and step S4 in) temperature of middle roasting is 300 ℃～700 ℃ independently of one another, the time is 2～10h independently of one another.
The invention provides a kind of SCR Catalysts and its preparation method, this SCR catalyst comprises TiO
2-SiO
2composite oxide carrier, metal oxide solid, V
2o
5with CeO
2; Described TiO
2-SiO
2composite oxide carrier is prepared by sol-gal process; The load capacity of described metal oxide solid is 1～10wt%; Described V
2o
5load capacity be 0～5wt%; Described CeO
2load capacity be 0～10wt%; And described V
2o
5load capacity and CeO
2load capacity be 0 when different.Compare with existing SCR catalyst, first, the present invention is with TiO
2-SiO
2composite oxides are carrier, SiO
2interpolation can suppress TiO
2phase transformation under high temperature, the heat endurance of enhancing catalyst; Secondly, due to SiO
2compare TiO
2there is higher specific area, therefore can play the effect that increases specific surface area of catalyst, and then can make active component better be disperseed, simultaneously by the interaction between metal and carrier, further improve the activity of catalyst; Again, SiO
2excellent heat stability, can decline and make the serviceability temperature window broadening of SCR catalyst by carrier phase-change and specific area under inhibition high temperature, and the oxidability by strengthening under low temperature that adds of active component CeO2 etc. improves catalyst catalytic activity at a lower temperature.
The specific embodiment
The invention provides a kind of SCR catalyst, comprise TiO
2-SiO
2composite oxide carrier, metal oxide solid, V
2o
5with CeO
2; Described TiO
2-SiO
2composite oxide carrier is prepared by sol-gal process; The load capacity of described metal oxide solid is 1～10wt%; Described V
2o
5load capacity be 0～5wt%; Described CeO
2load capacity be 0～10wt%; And described V
2o
5load capacity and CeO
2load capacity be 0 when different.
SCR catalyst of the present invention is with TiO
2-SiO
2composite oxides are carrier, wherein SiO
2mass fraction be preferably 0.1～40wt%, 1～40wt% more preferably, then be preferably 5～30wt%, most preferably is 10～30wt%.
According to the present invention, described TiO
2-SiO
2composite oxides preferably also can comprise silicate, mica sheet, Al
2o
3with ZrO
2in one or more.Metal oxide solid is co-catalyst, and its Main Function is the acidity of Enhanced SC R catalyst, is convenient to NH
3absorption to improve catalytic activity, in addition, metal oxide solid also has the effects such as specific area, heat endurance that improve carrier.In the present invention, the load capacity of described metal oxide solid is preferably 1～10wt%, 2～8wt% more preferably, then be preferably 2～6wt%; The kind of described metal oxide solid is the metal oxide that can be used as solid acid well known to those skilled in the art, there is no special restriction, is preferably WO in the present invention
3, Nb
2o
5with MoO
3in one or more, WO more preferably
3.
V
2o
5with CeO
2for the active component of catalyst, wherein, described V
2o
5load capacity be preferably 0.5～5wt%, 1～5wt% more preferably, then be preferably 2～5wt%; Described CeO
2load capacity be preferably 0.5～10wt%, 2～10wt% more preferably, then be preferably 5～8wt%.
The present invention is with TiO
2-SiO
2composite oxides are carrier, SiO
2interpolation can suppress TiO
2phase transformation under high temperature, the heat endurance of enhancing catalyst; Due to SiO
2compare TiO
2there is higher specific area, therefore can play the effect that increases specific surface area of catalyst, and then can make active component better be disperseed, simultaneously by the interaction between metal and carrier, further improve the activity of catalyst; In addition, SiO
2serviceability temperature window wider, thereby also make the serviceability temperature window broadening of SCR catalyst, make it at lower temperature, also there is catalytic activity.
The present invention also provides a kind of preparation method of above-mentioned SCR catalyst, comprises the following steps: S1) soluble silicon source is mixed in alcoholic solvent with soluble titanium source, add water, stirring, standing, obtains gel; S2) described gel is dried, roasting, obtains TiO
2-SiO
2composite oxide carrier; S3) soluble metallic salt, solubility cerium salt is soluble in water, then add TiO
2-SiO
2composite oxide carrier, is stirred to and obtains powder solid, and dry, roasting, obtains intermediate product; The corresponding metal oxide of metal in described soluble metallic salt is solid acid; The quality of the respective metal oxide of described soluble metallic salt is TiO
2-SiO
21～10% of composite oxide carrier quality; The corresponding CeO of described solubility cerium salt
2quality is TiO
2-SiO
20～10% of composite oxide carrier quality; S4) intermediate product is added in the solution that contains solubility vanadic salts, stir, dry, roasting, obtains SCR catalyst; The corresponding V of described solubility vanadic salts
2o
5quality is TiO
2-SiO
20～10% of composite oxide carrier quality; When the quality of described solubility cerium salt and solubility vanadic salts is different, be 0.
The present invention does not have special restriction to the source of all raw materials, for commercially available.
Wherein, described soluble metallic salt is the corresponding soluble metallic salt of metal oxide solid well known to those skilled in the art, there is no special restriction, in the present invention, be preferably one or more in niobium oxalate, ammonium molybdate, ammonium metatungstate, ammonium paratungstate and ammonium tungstate, more preferably one or more in ammonium metatungstate, ammonium paratungstate and ammonium tungstate.
Described solubility cerium salt is solubility cerium salt well known to those skilled in the art, there is no special restriction, in the present invention, be preferably one or more in cerous nitrate, ammonium ceric nitrate and cerous nitrate, more preferably a kind of in cerous nitrate, ammonium ceric nitrate and cerous nitrate.
Described TiO
2-SiO
2composite oxide carrier is prepared by sol-gal process
Soluble silicon source is mixed in alcoholic solvent with soluble titanium source, wherein, described soluble silicon source is soluble silicon well known to those skilled in the art source, there is no special restriction, in the present invention, be preferably one or more in waterglass, ethyl orthosilicate and Ludox, more preferably ethyl orthosilicate; Described soluble titanium source is soluble titanium well known to those skilled in the art source, there is no special restriction, is preferably butyl titanate and/or titanium tetrachloride, more preferably butyl titanate in the present invention; Described alcohols solvent is preferably the alcohols solvent of C1～C5, more preferably ethanol.
The alcoholic solution in soluble silicon source is mixed with the alcoholic solution in soluble titanium source, add water, wherein said soluble silicon source is preferably 1:(1～10 with the ratio of the amount of substance sum in soluble titanium source and the amount of substance of water), 1:(3～8 more preferably), 1:(4～6 more preferably).
Add after water, stir, the time of described stirring is preferably 2～10h, more preferably 4～8h; Then still aging, the described standing time is preferably 24～72h, 30～60h more preferably, then be preferably 30～50h.After standing, obtain gel.
By described gel oven dry, roasting, obtain TiO
2-SiO
2composite oxide carrier.Wherein, the temperature of described oven dry is preferably 80 ℃～150 ℃, and more preferably 80 ℃～120 ℃, then be preferably 90 ℃～110 ℃; The time of described oven dry is preferably 8～14h, more preferably 10～14h; The temperature of described roasting is preferably 300 ℃～700 ℃, more preferably 400 ℃～600 ℃; The time of described roasting is preferably 2～10h, more preferably 2～5h.
The TiO obtaining
2-SiO
2in composite oxide carrier, SiO
2mass fraction be preferably 0.1%～40%, be preferably 1%～40%, then be preferably 5%～30%, most preferably be 10%～30%.
Above-mentioned soluble metallic salt, solubility cerium salt is soluble in water, then add TiO
2-SiO
2composite oxide carrier, is stirred to and obtains powder solid, dry.In this step, described stirring is preferably carried out under the condition of heating, more preferably under the condition of 40 ℃～70 ℃, carries out; Described dry temperature is preferably 80 ℃～150 ℃, and more preferably 80 ℃～120 ℃, then be preferably 90 ℃～110 ℃; The described dry time is preferably 8～14h, more preferably 10～14h.
After dry, roasting, obtains intermediate product, and in this step, the temperature of roasting is preferably 300 ℃～700 ℃, more preferably 400 ℃～600 ℃; The time of described roasting is preferably 2～10h, more preferably 2～5h.
This step, the addition of soluble metallic salt and solubility cerium salt is preferably according to adding below: after described soluble metallic salt roasting, obtain corresponding metal oxide, the quality of this metal oxide is TiO
2-SiO
2composite oxide carrier quality be 1～10%, be preferably 2～8%, more preferably 2～6%; After the roasting of described solubility cerium salt, obtain CeO
2, described CeO
2quality be TiO
2-SiO
20～10% of composite oxide carrier quality, is preferably 1～10%, and more preferably 2～10%, then be preferably 5～8%.
Described intermediate product is added in the solution that contains solubility vanadic salts, stir, described stirring is preferably under the condition of 50 ℃～80 ℃ to be carried out, and the time of stirring is preferably 0.8～1.5h.
After stirring, dry, roasting, obtains SCR catalyst.In this step, described dry temperature is preferably 80 ℃～150 ℃, and more preferably 80 ℃～120 ℃, then be preferably 90 ℃～110 ℃; The described dry time is preferably 8～14h, more preferably 10～14h; The temperature of described roasting is preferably 300 ℃～700 ℃, more preferably 400 ℃～600 ℃; The time of described roasting is preferably 2～10h, more preferably 2～6h.
According to the present invention, described step B) in, the amount of solubility vanadic salts preferably adds in such a way: after the roasting of solubility vanadic salts, obtain V
2o
5, described V
2o
5quality be 0～10% of composite oxide carrier quality, be preferably 0.5～5wt%, 1～5wt% more preferably, then be preferably 2～5wt%.
In order to reduce the impurity of the SCR catalyst finally obtaining or in order to reduce other electrolytical impacts, water used in the present invention is all preferably deionized water.
After the preferred roasting of the present invention, grind, obtain SCR catalyst.
The present invention by stirring, the step such as dry, roasting can obtain SCR catalyst, preparation method is simple.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of SCR Catalysts and its preparation method provided by the invention is described in detail.
In following examples, reagent used is commercially available.
Embodiment 1
1.1 by 60ml absolute ethyl alcohol, 12ml butyl titanate and 12ml ethyl orthosilicate mixing and stirring, again according to the amount of substance of butyl titanate and ethyl orthosilicate and add deionized water with the ratio that the ratio of the amount of substance of water is 1:5, continue to stir 5h, still aging 48h, obtains gel; By resulting gel 80 ℃ of dry 14h in baking oven, and in Muffle furnace 300 ℃ of roasting 10h, obtain TiO
2-SiO
2composite oxide carrier.
1.2 add 3.04g ammonium metatungstate and 3.26g cerous nitrate in 50ml deionized water, stir 2h, then add the TiO obtaining in 20g1.1
2-SiO
2composite oxide carrier constantly stirs at 60 ℃, until stir dryly, obtains powder solid, by the powder solid of gained 80 ℃ of dry 14h in baking oven, and in Muffle furnace 300 ℃ of roasting 10h, after grinding, obtain SCR catalyst.
The SCR catalyst obtaining in 1.2 being carried out to performance test: the SCR catalyst obtaining in 1.2 is packed in catalytic reactor, pass into simulation exhaust gas from diesel vehicle, gas composition is 0.05%(intrinsic standoff ratio) NO(of left and right is wherein containing the NO of approximately 5% left and right
2), 0.05%(intrinsic standoff ratio) NH
3, O
2intrinsic standoff ratio is 5%, and all the other are balanced gas N
2, in air speed, be 12000h
-1, reaction temperature is that under 150 ℃～450 ℃ conditions, the extrusion rate of NO is 90%～98%.The catalytic activity of the SCR catalyst obtaining in embodiment 1 under different air speeds is as shown in table 1.And for this example TiO
2-SiO
2other conditions of carrier contrast are all identical with TiO
2the catalyst making for carrier catalytic activity is under the same conditions as shown in table 2.Can find out and adopt TiO
2-SiO
2carrier can obviously be widened about 30 ℃～40 ℃ of the temperature window of catalyst.
The catalytic activity of the SCR catalyst of table 1 embodiment 1 preparation
The TiO that table 2 is corresponding with embodiment 1
2the catalytic activity of carrier S CR catalyst
Embodiment 2
The 2.1 sodium silicate solution mixing and stirring that are 60% by 60ml absolute ethyl alcohol, 12ml butyl titanate and 20ml mass fraction, again according to the amount of substance of butyl titanate and ethyl orthosilicate and add deionized water with the ratio that the ratio of the amount of substance of water is 1:5, continue to stir 5h, still aging 48h, obtains gel; By resulting gel 150 ℃ of dry 8h in baking oven, and in Muffle furnace 700 ℃ of roasting 2h, obtain TiO
2-SiO
2composite oxide carrier.
2.2 add 3.04g niobium oxalate in 50ml deionized water, stir 2h, then add the TiO obtaining in 20g 2.1
2-SiO
2composite oxide carrier constantly stirs at 60 ℃, until stir dryly, obtains powder solid, by the powder solid of gained 150 ℃ of dry 8h in baking oven, and in Muffle furnace 700 ℃ of roasting 2h, obtain intermediate product.
2.3 by 1.05gV
2o
5powder is dissolved in 10ml oxalic acid solution, and the condition lower magnetic force of 70 ℃ stirs 30min, obtains vanadium oxalate solution, more progressively adds the intermediate product obtaining in 20g2.2 therein, and constant temperature stirs 1h, 150 ℃ of dry 8h, and 700 ℃ of roasting 2h, obtain SCR catalyst after grinding.
The SCR catalyst obtaining in 2.3 being carried out to performance test: the SCR catalyst obtaining in 2.3 is packed in catalytic reactor, pass into simulation exhaust gas from diesel vehicle, gas composition is 0.05%(intrinsic standoff ratio) NO(of left and right is wherein containing the NO of approximately 5% left and right
2), 0.05%(intrinsic standoff ratio) NH
3, O
2intrinsic standoff ratio is 5%, and all the other are balanced gas N
2, in air speed, be 12000h
-1, reaction temperature is that under 200 ℃～500 ℃ conditions, the extrusion rate of NO is 88%～98%.The catalytic activity of the SCR catalyst obtaining in embodiment 2 under different air speeds is as shown in table 3.And for this example TiO
2-SiO
2other conditions of carrier contrast are all identical with TiO
2the catalyst making for carrier catalytic activity is under the same conditions as shown in table 4.
The catalytic activity of the SCR catalyst of table 3 embodiment 2 preparations
The TiO that table 4 is corresponding with embodiment 2
2the catalytic activity of carrier S CR catalyst
Embodiment 3
3.1 by 60ml absolute ethyl alcohol, 12ml butyl titanate and 12ml ethyl orthosilicate mixing and stirring, again according to the amount of substance of butyl titanate and ethyl orthosilicate and add deionized water with the ratio that the ratio of the amount of substance of water is 1:5, continue to stir 5h, still aging 48h, obtains gel; By resulting gel 100 ℃ of dry 12h in baking oven, and in Muffle furnace 500 ℃ of roasting 3h, obtain TiO
2-SiO
2composite oxide carrier.
3.2 add 2.03g ammonium molybdate and 1.63g cerous nitrate in 50ml deionized water, stir 2h, then add the TiO obtaining in 20g3.1
2-SiO
2composite oxide carrier constantly stirs at 60 ℃, until stir dryly, obtains powder solid, by the powder solid of gained 100 ℃ of dry 12h in baking oven, and in Muffle furnace 500 ℃ of roasting 3h, obtain intermediate product.
3.3 by 0.91gV
2o
5powder is dissolved in 10ml oxalic acid solution, and the condition lower magnetic force of 70 ℃ stirs 30min, obtains vanadium oxalate solution, progressively add therein the intermediate product obtaining in 20g3.2, constant temperature stirs 1h, 100 ℃ of dry 12h again, 500 ℃ of roasting 3h, obtain SCR catalyst after grinding.
The SCR catalyst obtaining in 3.3 being carried out to performance test: the SCR catalyst obtaining in 3.3 is packed in catalytic reactor, pass into simulation exhaust gas from diesel vehicle, gas composition is 0.05%(intrinsic standoff ratio) NO(of left and right is wherein containing the NO of approximately 5% left and right
2), 0.05%(intrinsic standoff ratio) NH
3, O
2intrinsic standoff ratio is 5%, and all the other are balanced gas N
2, in air speed, be 12000h
-1, reaction temperature is that under 150 ℃～400 ℃ conditions, the extrusion rate of NO is 88%～98%.The catalytic activity of the SCR catalyst obtaining in embodiment 3 under different air speeds is as shown in table 5.
The catalytic activity of the SCR catalyst of table 5 embodiment 3 preparations
Embodiment 4
4.1 by 60ml absolute ethyl alcohol, 12ml butyl titanate and 12ml ethyl orthosilicate mixing and stirring, again according to the amount of substance of butyl titanate and ethyl orthosilicate and add deionized water with the ratio that the ratio of the amount of substance of water is 1:5, continue to stir 5h, still aging 48h, obtains gel; By resulting gel 100 ℃ of dry 12h in baking oven, and in Muffle furnace 500 ℃ of roasting 3h, obtain TiO
2-SiO
2composite oxide carrier.
4.2 add 3.04g ammonium metatungstate and 1.63g cerous nitrate in 50ml deionized water, stir 2h, then add the TiO obtaining in 20g4.1
2-SiO
2composite oxide carrier constantly stirs at 60 ℃, until stir dryly, obtains powder solid, by the powder solid of gained 100 ℃ of dry 12h in baking oven, and in Muffle furnace 500 ℃ of roasting 3h, obtain intermediate product.
4.3 by 0.91gV
2o
5powder is dissolved in 10ml oxalic acid solution, and the condition lower magnetic force of 70 ℃ stirs 30min, obtains vanadium oxalate solution, progressively add therein the intermediate product obtaining in 20g4.2, constant temperature stirs 1h, 100 ℃ of dry 12h again, 500 ℃ of roasting 3h, obtain SCR catalyst after grinding.
The SCR catalyst obtaining in 4.3 being carried out to performance test: the SCR catalyst obtaining in 4.3 is packed in catalytic reactor, pass into simulation exhaust gas from diesel vehicle, gas composition is 0.05%(intrinsic standoff ratio) NO(of left and right is wherein containing the NO of approximately 5% left and right
2), 0.05%(intrinsic standoff ratio) NH
3, O
2intrinsic standoff ratio is 5%, and all the other are balanced gas N
2, in air speed, be 12000h
-1, reaction temperature is that under 150 ℃～500 ℃ conditions, the extrusion rate of NO is 90%～98%.The catalytic activity of the SCR catalyst obtaining in embodiment 4 under different air speeds is as shown in table 6.
The catalytic activity of the SCR catalyst of table 6 embodiment 4 preparations
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a SCR catalyst, is characterized in that, comprises TiO
2-SiO
2composite oxide carrier, metal oxide solid, V
2o
5with CeO
2; Described TiO
2-SiO
2composite oxide carrier is prepared by sol-gal process; The load capacity of described metal oxide solid is 1～10wt%; Described V
2o
5load capacity be 0～5wt%; Described CeO
2load capacity be 0～10wt%; And described V
2o
5load capacity and CeO
2load capacity be 0 when different.
2. SCR catalyst according to claim 1, is characterized in that, described TiO
2-SiO
2siO in composite oxide carrier
2mass fraction be 0.1～40wt%.
3. SCR catalyst according to claim 1, is characterized in that, described TiO
2-SiO
2composite oxide carrier also comprises silicate, mica sheet, Al
2o
3with ZrO
2in one or more.
4. SCR catalyst according to claim 1, is characterized in that, described metal oxide solid is selected from WO
3, Nb
2o
5with MoO
3in one or more.
5. a preparation method for SCR catalyst, is characterized in that, comprises the following steps:
S1) soluble silicon source is mixed in alcoholic solvent with soluble titanium source, add water, stirring, standing, obtains gel;
S2) described gel is dried, roasting, obtains TiO
2-SiO
2composite oxide carrier;
S3) soluble metallic salt, solubility cerium salt is soluble in water, then add described TiO
2-SiO
2composite oxide carrier, is stirred to and obtains powder solid, and dry, roasting, obtains intermediate product; The corresponding metal oxide of metal in described soluble metallic salt is solid acid; The quality of the respective metal oxide of described soluble metallic salt is TiO
2-SiO
21～10% of composite oxide carrier quality; The corresponding CeO of described solubility cerium salt
2quality is TiO
2-SiO
20～10% of composite oxide carrier quality;
S4) described intermediate product is added in the solution that contains solubility vanadic salts, stir, dry, roasting, obtains SCR catalyst; The corresponding V of described solubility vanadic salts
2o
5quality is TiO
2-SiO
20～5% of composite oxide carrier quality; When the quality of described solubility cerium salt and solubility vanadic salts is different, be 0.
6. preparation method according to claim 5, is characterized in that, described soluble metallic salt is selected from one or more in niobium oxalate, ammonium molybdate, ammonium metatungstate, ammonium paratungstate and ammonium tungstate.
7. preparation method according to claim 5, is characterized in that, described solubility cerium salt is selected from one or more in cerous nitrate, ammonium ceric nitrate and cerous nitrate.
8. preparation method according to claim 5, is characterized in that, described solubility vanadic salts is selected from sodium metavanadate and/or vanadium oxalate.
9. preparation method according to claim 5, is characterized in that, described step S3) in dry and step S4) in dry temperature be 80 ℃～150 ℃ independently of one another, the time is 8～14h independently of one another.
10. preparation method according to claim 5, is characterized in that, described step S3) in roasting and step S4) temperature of middle roasting is 300 ℃～700 ℃ independently of one another, the time is 2～10h independently of one another.
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| CN104014324A (en) * | 2014-05-14 | 2014-09-03 | 华东理工大学 | Cerium oxide-based loaded smoke denitrification catalyst and preparation method thereof |
| CN104148052A (en) * | 2014-08-14 | 2014-11-19 | 浙江大学 | Cerium-vanadium-silicon-titanium composite oxide catalyst and preparation method thereof |
| CN104307473A (en) * | 2014-10-21 | 2015-01-28 | 同济大学 | Preparation method of adsorbing visible light catalytic material used for air pollution management |
| CN105642272A (en) * | 2016-01-29 | 2016-06-08 | 大唐南京环保科技有限责任公司 | SCR denitrification catalyst and preparing method thereof |
| CN106466598A (en) * | 2016-09-09 | 2017-03-01 | 清华大学 | A kind of active carrier for denitrating catalyst and preparation method thereof |
| CN106622348A (en) * | 2016-11-14 | 2017-05-10 | 天津大学 | Ferrous modified molecular sieve type diesel engine selective catalytic reduction catalyst |
| CN107335453A (en) * | 2017-07-07 | 2017-11-10 | 国电环境保护研究院 | A kind of board-like catalyst of denitration demercuration and preparation method thereof |
| CN108031466A (en) * | 2017-11-14 | 2018-05-15 | 浙江浙能催化剂技术有限公司 | Have the low SO of anti-arsenic poisoning and wide active temperature windows concurrently2Oxygenation efficiency SCR denitration and preparation method thereof |
| CN108212143A (en) * | 2017-12-29 | 2018-06-29 | 浙江德创环保科技股份有限公司 | It is a kind of for denitrating catalyst of porous wide temperature window and preparation method thereof |
| CN108816216A (en) * | 2018-06-29 | 2018-11-16 | 凯龙高科技股份有限公司 | A kind of high temperature modification SCR catalyst and its preparation method and application |
| CN110038554A (en) * | 2019-06-03 | 2019-07-23 | 运城学院 | A kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst |
| CN110721669A (en) * | 2019-11-06 | 2020-01-24 | 大唐南京环保科技有限责任公司 | Denitration catalyst with high sulfur resistance and alkali metal resistance and preparation method thereof |
| CN111530448A (en) * | 2020-04-08 | 2020-08-14 | 上海大学 | High-sulfur-resistance nonmetal-doped metal oxide denitration catalyst and preparation method thereof |
| CN115414923A (en) * | 2022-09-19 | 2022-12-02 | 常州大学 | Heterogeneous TiO for the synthesis of polycarbonate diols 2 /SiO 2 Catalyst and preparation method thereof |
| US20230038263A1 (en) * | 2017-11-14 | 2023-02-09 | Umicore Ag & Co. Kg | SCR Catalyst |
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| CN104014324A (en) * | 2014-05-14 | 2014-09-03 | 华东理工大学 | Cerium oxide-based loaded smoke denitrification catalyst and preparation method thereof |
| CN104014324B (en) * | 2014-05-14 | 2016-08-17 | 华东理工大学 | Cerium oxide base support type catalyst for denitrating flue gas and preparation method thereof |
| CN104148052A (en) * | 2014-08-14 | 2014-11-19 | 浙江大学 | Cerium-vanadium-silicon-titanium composite oxide catalyst and preparation method thereof |
| CN104307473A (en) * | 2014-10-21 | 2015-01-28 | 同济大学 | Preparation method of adsorbing visible light catalytic material used for air pollution management |
| CN105642272A (en) * | 2016-01-29 | 2016-06-08 | 大唐南京环保科技有限责任公司 | SCR denitrification catalyst and preparing method thereof |
| CN106466598A (en) * | 2016-09-09 | 2017-03-01 | 清华大学 | A kind of active carrier for denitrating catalyst and preparation method thereof |
| CN106622348B (en) * | 2016-11-14 | 2019-12-03 | 天津大学 | Ferrous modified molecular screen diesel engine selective catalytic reduction catalysts |
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| CN108031466A (en) * | 2017-11-14 | 2018-05-15 | 浙江浙能催化剂技术有限公司 | Have the low SO of anti-arsenic poisoning and wide active temperature windows concurrently2Oxygenation efficiency SCR denitration and preparation method thereof |
| US20230038263A1 (en) * | 2017-11-14 | 2023-02-09 | Umicore Ag & Co. Kg | SCR Catalyst |
| CN108212143A (en) * | 2017-12-29 | 2018-06-29 | 浙江德创环保科技股份有限公司 | It is a kind of for denitrating catalyst of porous wide temperature window and preparation method thereof |
| CN108816216A (en) * | 2018-06-29 | 2018-11-16 | 凯龙高科技股份有限公司 | A kind of high temperature modification SCR catalyst and its preparation method and application |
| CN110038554A (en) * | 2019-06-03 | 2019-07-23 | 运城学院 | A kind of V that mica supports2O5-WO3/TiO2The preparation method of catalyst |
| CN110721669A (en) * | 2019-11-06 | 2020-01-24 | 大唐南京环保科技有限责任公司 | Denitration catalyst with high sulfur resistance and alkali metal resistance and preparation method thereof |
| CN111530448A (en) * | 2020-04-08 | 2020-08-14 | 上海大学 | High-sulfur-resistance nonmetal-doped metal oxide denitration catalyst and preparation method thereof |
| CN111530448B (en) * | 2020-04-08 | 2023-07-18 | 上海大学 | Non-metal doped metal oxide denitration catalyst with strong sulfur resistance and preparation method thereof |
| CN115414923A (en) * | 2022-09-19 | 2022-12-02 | 常州大学 | Heterogeneous TiO for the synthesis of polycarbonate diols 2 /SiO 2 Catalyst and preparation method thereof |
| CN115414923B (en) * | 2022-09-19 | 2024-02-13 | 常州大学 | Heterogeneous TiO for synthesizing polycarbonate diol 2 /SiO 2 Catalyst and preparation method thereof |
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