CN101559363A - Catalyst for removing nitrogen oxide through selective catalytic reduction for Ce2O3 and V2O5 double active composition diesel truck - Google Patents

Catalyst for removing nitrogen oxide through selective catalytic reduction for Ce2O3 and V2O5 double active composition diesel truck Download PDF

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CN101559363A
CN101559363A CNA2009100690190A CN200910069019A CN101559363A CN 101559363 A CN101559363 A CN 101559363A CN A2009100690190 A CNA2009100690190 A CN A2009100690190A CN 200910069019 A CN200910069019 A CN 200910069019A CN 101559363 A CN101559363 A CN 101559363A
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tio
catalyst
ammonium
active component
coating
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CN101559363B (en
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宋崇林
吕刚
裴毅强
宾峰
张清茂
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Tianjin University
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Tianjin University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Abstract

The invention relates to a catalyst for removing nitrogen oxide through selective catalytic reduction for an automobile diesel engine adopting Ce2O3 and V2O5 double active compositions. The catalyst adopts scordierite honeycomb ceramics as a framework material, the Ce2O3 and the V2O5 as main active compositions, WO3 or MoO3 as an auxiliary catalyst composition, and TiO2 as a coating substrate, wherein the mass fraction of the main active compositions, namely the Ce2O3 and the V2O5, to the auxiliary catalyst composition WO3 or MoO3 to the coating substrate TiO2 is 1-3:6:12:85-93. The specific process comprises the following steps: preparing a TiO2 precursor solution; coating a TiO2 coating; coating an auxiliary catalyst; determining the loading of active compositions of oxides; and coating the main active compositions, namely the Ce2O3 and the V2O5. The catalyst replaces the V2O5 with high toxicity with the Ce2O3 with low toxicity, and reduces the environmental hazards of the catalyst, and the replaced catalyst has wider active temperature range, particularly greatly improves the low-temperature activity, and is particularly suitable for the traffic conditions of urban highways of China.

Description

Ce 2O 3And V 2O 5Dual-active component diesel vehicle removes nitrogen oxide catalyst with SCR
Technical field
The invention belongs to the diesel oil automotive catalyst, be specifically related to a kind of Ce of having 2O 3And V 2O 5The diesel vehicle of double activity component removes the Catalysts and its preparation method of nitrogen oxide with SCR.
Background technology
The diesel vehicle loading capacity is big, specific fuel consumption is low, in the large and medium-sized visitor of China, lorry, occupy dominant position, but because its nitrogen oxide (NOx) discharging is more, severe contamination atmospheric environment, the mankind healthy caused potential threat, therefore, many countries have all formulated the NOx discharging that more and more stricter Abgasgesetz limits diesel vehicle.And NH 3Or urea-SCR (Selective Catalytic Reduction-SCR) technology has high NOx detergent power, simultaneously by combining with the technical measures of optimizing in-cylinder combustion, can also reduce the fuel consume of diesel vehicle, be a kind of emission control technique that can realize environmental protection and energy conservation object simultaneously, large-scale application in the world.
Existing commercial SCR catalyst adopts with V more 2O 5Be the V of main active component 2O 5-WO 3(MoO 3)-TiO 2-supported catalyst, this catalyst generally have reactivity preferably when the diesel engine truck exhaust temperature is in 280 ℃～480 ℃, relatively be fit to the running conditions of vehicle of states such as Europe, the United States.But China's urban road is crowded, and vehicle loiters, and diesel vehicle row temperature is lower, and above-mentioned vanadium type SCR catalyst can not satisfy China's diesel vehicle to the active actual requirement of SCR catalyst low temperature (＜300 ℃).While V 2O 5Belong to highly toxic substance, bigger to human health damage.Therefore, the Novel SCR catalyst that adopts the low toxicity developing material to have the good low temperature serviceability becomes the developmental research focus of domestic and international association area.
Summary of the invention
The objective of the invention is to utilize the Ce of low toxicity 2O 3Part substitutes the V of high poison 2O 5As SCR catalyst master active component, invent a kind of Ce that has 2O 3And V 2O 5The diesel vehicle of double activity component removes nitrogen oxide catalyst and preparation method thereof with SCR, when reducing the harm of catalyst environment, and the serviceability temperature scope of expansion catalyst.
Ce 2O 3And V 2O 5Dual-active component diesel vehicle removes nitrogen oxide catalyst with SCR, and it is framework material that catalyst adopts cordierite honeycomb ceramic, and main active component is by Ce 2O 3(cerium sesquioxide) and V 2O 5(vanadic anhydride) is common to be constituted, and adopts WO 3(tungstic acid) or MoO 3(molybdenum trioxide) is cocatalyst component, adopts Detitanium-ore-type TiO 2(titanium dioxide) is coated substrate.Wherein main active component (comprises Ce 2O 3And V 2O 5) and cocatalyst component WO 3(or MoO 3) and coated substrate TiO 2Mass percent be respectively (1～3%): (6～12%): (85～93%), the mass percent sum is 100%; Main active component adds cocatalyst component and adds coated substrate TiO again 2Gross mass be (9.1～23.1%) and the ratio of the quality (90.9～76.9%) of cordierite honeycomb ceramic carrier, i.e. (9.1～23.1%): (90.9～76.9%) mass percent sum is 100%; Main active component Ce 2O 3And V 2O 5Mass ratio be (30～70%): (70～30%), the mass percent sum is 100%.
The present invention is at existing V 2O 5-WO 3(MoO 3)-TiO 2On the basis of-carrier model SCR catalyst, introduced low toxicity rare-earth oxide---Ce 2O 3Part replaces V 2O 5-WO 3(MoO 3)-TiO 2Primary catalyst component V in the-carrier model SCR catalyst 2O 5, reduced the bio-toxicity of SCR catalyst.Simultaneously, on catalytic performance since the valence electron of Ce elements can be between different valence state the phase co-conversion, thereby present Ce 2O 3, Ce 2O 5Etc. different oxide types, under the effect of reaction temperature and reactant composition, different oxides can transform mutually, and the free oxygen of generation or free electron can further promote the carrying out of catalytic reaction.Therefore, with the middle valence state oxide Ce of Ce elements 2O 3Part substitutes V 2O 5Ce 2O 3-V 2O 5-WO 3(MoO 3)-TiO 2-carrier model SCR catalyst has the V of ratio 2O 5-WO 3(MoO 3)-TiO 2Better low temperature active of-carrier model SCR catalyst and high-temperature selective promptly have wideer high activity temperature window.
The preparation method that the present invention proposes mainly comprises 5 steps:
(1) TiO 2The preparation of precursor liquid
At first add cocatalyst component and add coated substrate TiO according to main active component 2Gross mass and the mass ratio of ceramic monolith calculate TiO 2Load capacity produces 79.88g TiO according to every 340.35g butyl titanate again 2Proportional meter calculate the quality that need to add butyl titanate, again butyl titanate is joined volume and be in 2～3 times the absolute ethyl alcohol, drip the hydrochloric acid that concentration is not less than 10% (weight ratio) when stirring, a most back continues to stir becomes transparent, supernatant liquid up to mixture, as TiO 2Precursor liquid.
(2) TiO 2The coating of coating
After cordierite honeycomb ceramic carrier cleaning, drying, the TiO that is preparing 2Flood 1h in the precursor liquid under 60 ℃, blow residual liquid in the duct after the taking-up off, drying 6～24 under 80～110 ℃ is calcined 2h down at 500～600 ℃ again.Repeatedly repeated impregnations, drying and calcination process are up to described TiO 2Precursor liquid is used and is finished,
(3) capacity of oxide active ingredients determines
According to aforementioned Ce 2O 3And V 2O 5: WO 3Or MoO 3: TiO 2Mixing ratio and Ce 2O 3: V 2O 5Mixing ratio calculate the quality of required each component of Preparation of Catalyst respectively.Produce 328.23g Ce according to every 908.44g cerous nitrate 2O 3, every 234g ammonium metavanadate produces 182g V 2O 5And every 1602.4g ammonium tungstate produces 1391.1g WO 3Or every 1236g ammonium molybdate produces 1008gMoO 3Ratiometric conversion go out the quality of needed raw material cerous nitrate, ammonium metavanadate and ammonium tungstate or ammonium molybdate.
(4) coating of ammonium tungstate or ammonium molybdate co-catalyst
Be dissolved in the ratio of 2000～4000ml deionized water according to every 16.02g ammonium tungstate or every 12.36g ammonium molybdate, ammonium tungstate or ammonium molybdate are mixed with deionized water, the pH value that adds the oxalic acid regulator solution then is 2～6.To apply TiO 2Ceramic monolith put into the solution of ammonium tungstate (or ammonium molybdate), oxalic acid and water, in 60 ℃ of dipping 4～6h down, blow the residual liquid duct in after the taking-up off, at 80～110 ℃ of down dry 6～24h, calcine 2h down at 500～600 ℃ again.Repeatedly repeated impregnations, drying and calcination process, up to the solution of described ammonium tungstate (or ammonium molybdate), oxalic acid and water all with finishing.
(5) Ce 2O 3And V 2O 5The load of main active component
The ratio that is dissolved in 500～1000ml deionized water according to every 4.54g cerous nitrate and every 1.17g ammonium metavanadate respectively is mixed with mixed solution again, and the pH value that adds the oxalic acid regulator solution is 2～6.To apply TiO 2Put into the solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water with the ceramic monolith of co-catalyst,, blow the residual liquid duct in after the taking-up off,, calcine 2h down at 500～600 ℃ again at 80～110 ℃ of down dry 6～24h in 60 ℃ of dipping 6h down.Repeatedly repeated impregnations, drying and calcination process, up to the mixed solution of described cerous nitrate, ammonium metavanadate, oxalic acid and deionized water all with finishing.Then the ceramic monolith behind the described load master active component is calcined 4～6h down at 500～600 ℃.
Description of drawings
Fig. 1 SCR catalyst activity laboratory evaluation device schematic diagram:
Wherein: 1-single channel mass flow controller; 2-3 channel quality flow controller; The 3-spinner flowmeter; The 4-stop valve; The 5-air flue; The 6-mixing kettle; 7-steam producer; The 8-reactor; The 9-display temperature controller; The 10-heating current shows controller; The 11-peristaltic pump; 12-NH 3Gas cylinder; The 13-NO gas cylinder; The 14-HC gas cylinder; The 15-CO gas cylinder; 16-N 2Gas cylinder; 17-simulation discharging gaseous mixture inlet; 18-NH 3Inlet; The 19-steam entry; 20-reaction final vacuum outlet (leading to gas analyzer)
The NOx removal efficiency of embodiment 1 is with the situation of change of reaction temperature during Fig. 2 difference air speed;
The HC removal efficiency of embodiment 1 is with the situation of change of reaction temperature during Fig. 3 difference air speed;
The CO discharging recruitment of embodiment 1 is with the situation of change of reaction temperature during Fig. 4 difference air speed;
The NOx removal efficiency of Fig. 5 embodiment 1～6 is with the situation of change of reaction temperature;
Fig. 6 SCR catalyst performance engine evaluation system schematic diagram:
Wherein: the 21-air intake intercooler; The 22-air filter; The 23-diesel engine; The 24-reducing agent dosing valve; The 25-jet pump; 26-nozzle and woven hose; The 27-SCR catalyst converter; The 28-dynamometer machine
The specific embodiment
Below by specific embodiment step of the present invention is described in detail, but the content that the present invention is contained is not limited to following embodiment.
Embodiment 1
(1) TiO 2The preparation of precursor liquid:
Determine will be on the 1kg cordierite honeycomb ceramic carrier load coating material TiO 2
Take by weighing the 750ml butyl titanate, join in the 1500ml absolute ethyl alcohol, drip the hydrochloric acid 375ml of 10% (weight ratio) when stirring, a most back continues to stir becomes transparent, supernatant liquid up to mixture.
(2) TiO 2The coating of coating:
To clean, dried 1kg cordierite honeycomb ceramic carrier puts into the TiO that step (1) has prepared 2Flood 1h in the precursor liquid under 60 ℃, blow residual liquid in the duct after the taking-up off, dry 12h under 105 ℃ calcines 2h down at 600 ℃ again.Repeat the TiO that above-mentioned dipping, drying and calcination process prepare until step (1) 2Precursor liquid is with finishing.
(3) capacity of oxide active ingredients determines
According to Ce 2O 3: V 2O 5: WO 3: TiO 2(coating amount in step 2)=2: 1: 9: the consumption that 88 mass ratio calculates the catalyst cupport raw material is: cerous nitrate 11.07g; Ammonium metavanadate 2.57g; Ammonium tungstate 20.73g.
(4) coating of co-catalyst
Take by weighing ammonium tungstate 20.73g, it is dissolved in the pH value that adds the oxalic acid regulator solution behind the 3882ml deionized water is 5.To apply TiO in the step (2) 2Ceramic monolith put into the solution of described ammonium tungstate, oxalic acid and water, in 60 ℃ of dipping 6h down, blow the residual liquid duct in after the taking-up off, at 105 ℃ of dry 12h down, calcine 2h down at 600 ℃ again.Repeatedly repeated impregnations, drying and calcination process, up to the solution of ammonium tungstate, oxalic acid and water all with finishing.
(5) Ce 2O 3And V 2O 5The coating of active component
Take by weighing the 11.07g cerous nitrate, it is dissolved in the 1219ml deionized water; Take by weighing the 2.57g ammonium metavanadate again, it is dissolved in the 1098ml deionized water; After cerous nitrate solution and ammonium metavanadate solution mixing, the pH value that adds the oxalic acid regulator solution is 5.To apply TiO in the step (3) 2Put into the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water with the ceramic monolith of co-catalyst,, blow the residual liquid duct in after the taking-up off,, calcine 2h down at 600 ℃ again at 105 ℃ of dry 12h down in 60 ℃ of dipping 6h down.Repeatedly repeated impregnations, drying and calcination process, up to the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water all with finishing.Then the ceramic monolith behind the load master active component is calcined 4h down at 600 ℃.
Estimate embodiment 1 at NH with SCR catalyst activity laboratory evaluation device shown in Figure 1 3Catalytic performance in the-SCR reaction.Exhaust NOx concentration is 800 * 10 in the experiment -6(v/v), the concentration of CO is 650 * 10 -6(v/v), the concentration of HC (propane) is 750 * 10 -6(v/v), oxygen concentration=10% (volume ratio); NH 3With the mol equivalent proportion of NOx be 1.1: 1.The catalytic effect of 1 couple of NOx of embodiment as shown in Figure 2, and is to the catalytic effect of HC as shown in Figure 3, shown in Figure 4 to the catalytic effect of CO.
Embodiment 2
(1) TiO 2The preparation of precursor liquid:
Determine will be on the 1kg cordierite honeycomb ceramic carrier load coating material TiO 2
Take by weighing the 750ml butyl titanate, join in the 1500ml absolute ethyl alcohol, drip the hydrochloric acid 375ml of 10% (weight ratio) when stirring, a most back continues to stir becomes transparent, supernatant liquid up to mixture.
(2) TiO 2The coating of coating:
To clean, dried described 1kg cordierite honeycomb ceramic carrier puts into the TiO that step (1) has prepared 2Flood 1h in the precursor liquid under 60 ℃, blow residual liquid in the duct after the taking-up off, dry 12h under 105 ℃ calcines 2h down at 600 ℃ again.Repeat the TiO that above-mentioned dipping, drying and calcination process prepare until step (1) 2Precursor liquid is with finishing.
(3) capacity of oxide active ingredients determines
According to Ce 2O 3: V 2O 5: WO 3: TiO 2(coating amount in step 2)=1.5: 1.5: 9: the consumption that 88 mass ratio calculates the catalyst cupport raw material is: cerous nitrate 8.3g; Ammonium metavanadate 3.86g; Ammonium tungstate 20.73g.
(4) coating of co-catalyst
Take by weighing ammonium tungstate 20.73g, it is dissolved in the pH value that adds the oxalic acid regulator solution behind the 3882ml deionized water is 5.To apply TiO in the step (2) 2Ceramic monolith put into the solution of ammonium tungstate, oxalic acid and water, in 60 ℃ of dipping 6h down, blow the residual liquid duct in after the taking-up off, at 105 ℃ of dry 12h down, calcine 2h down at 600 ℃ again.Repeatedly repeated impregnations, drying and calcination process, up to the solution of ammonium tungstate, oxalic acid and water all with finishing.
(5) Ce 2O 3And V 2O 5The coating of active component
Take by weighing the 8.3g cerous nitrate, it is dissolved in the 914ml deionized water; Take by weighing the 3.86g ammonium metavanadate again, it is dissolved in the 1650ml deionized water; After cerous nitrate solution and ammonium metavanadate solution mixing, the pH value that adds the oxalic acid regulator solution is 5.To apply TiO in the step (3) 2Put into the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water with the ceramic monolith of co-catalyst,, blow the residual liquid duct in after the taking-up off,, calcine 2h down at 600 ℃ again at 105 ℃ of dry 12h down in 60 ℃ of dipping 6h down.Repeatedly repeated impregnations, drying and calcination process, up to the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water all with finishing.Then the ceramic monolith behind the load master active component is calcined 4h down at 600 ℃.
Estimate embodiment 2 at NH with SCR catalyst activity laboratory evaluation device shown in Figure 1 3Catalytic performance in the-SCR reaction.Exhaust NOx concentration is 800 * 10 in the experiment -6V/v, the concentration of CO is 650 * 10 -6V/v, the concentration of HC (propane) is 750 * 10 -6V/v, oxygen concentration=10% (volume ratio); NH 3With the mol equivalent proportion of NOx be 1.1: 1, GHSV (per hour volume space velocity)=30000h -1The catalytic effect of 2 couples of NOx of embodiment as shown in Figure 5.
Embodiment 3
(1) TiO 2The preparation of precursor liquid:
Determine will be on the 1kg cordierite honeycomb ceramic carrier load coating material TiO 2
Take by weighing the 750ml butyl titanate, join in the 1500ml absolute ethyl alcohol, drip the hydrochloric acid 375ml of 10% (weight ratio) when stirring, a most back continues to stir becomes transparent, supernatant liquid up to mixture.
(2) TiO 2The coating of coating:
To clean, dried 1kg cordierite honeycomb ceramic carrier puts into the TiO that step (1) has prepared 2Flood 1h in the precursor liquid under 60 ℃, blow residual liquid in the duct after the taking-up off, dry 12h under 105 ℃ calcines 2h down at 600 ℃ again.Repeat the TiO that above-mentioned dipping, drying and calcination process prepare until step (1) 2Precursor liquid is with finishing.
(3) capacity of oxide active ingredients determines
According to Ce 2O 3: V 2O 5: WO 3: TiO 2(coating amount in step 2)=1: 2: 9: the consumption that 88 mass ratio calculates the catalyst cupport raw material is: cerous nitrate 5.54g; Ammonium metavanadate 5.14g; Ammonium tungstate 20.73g.
(4) coating of co-catalyst
Take by weighing ammonium tungstate 20.73g, it is dissolved in the pH value that adds the oxalic acid regulator solution behind the 3882ml deionized water is 5.To apply TiO in the step (2) 2Ceramic monolith put into the solution of ammonium tungstate, oxalic acid and water, in 60 ℃ of dipping 6h down, blow the residual liquid duct in after the taking-up off, at 105 ℃ of dry 12h down, calcine 2h down at 600 ℃ again.Repeatedly repeated impregnations, drying and calcination process, up to the solution of ammonium tungstate, oxalic acid and water all with finishing.
(5) Ce 2O 3And V 2O 5The coating of active component
Take by weighing the 5.54g cerous nitrate, it is dissolved in the 610ml deionized water; Take by weighing the 5.14g ammonium metavanadate again, it is dissolved in the 2197ml deionized water; After cerous nitrate solution and ammonium metavanadate solution mixing, the pH value that adds the oxalic acid regulator solution is 5.To apply TiO in the step (3) 2Put into the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water with the ceramic monolith of co-catalyst,, blow the residual liquid duct in after the taking-up off,, calcine 2h down at 600 ℃ again at 105 ℃ of dry 12h down in 60 ℃ of dipping 6h down.Repeatedly repeated impregnations, drying and calcination process, up to the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water all with finishing.Then the ceramic monolith behind the load master active component is calcined 4h down at 600 ℃.
Estimate embodiment 3 at NH with SCR catalyst activity laboratory evaluation device shown in Figure 1 3Catalytic performance in the-SCR reaction.Exhaust NOx concentration is 800 * 10 in the experiment -6V/v, the concentration of CO is 650 * 10 -6V/v, the concentration of HC (propane) is 750 * 10 -6V/v, oxygen concentration=10% (volume ratio); NH 3With the mol equivalent proportion of NOx be 1.1: 1, GHSV (per hour volume space velocity)=30000h -1The catalytic effect of 3 couples of NOx of embodiment as shown in Figure 5.
Embodiment 4
(1) TiO 2The preparation of precursor liquid:
Determine will be on the 1kg cordierite honeycomb ceramic carrier load coating material TiO 2
Take by weighing the 758ml butyl titanate, join in the 2274ml absolute ethyl alcohol, drip the hydrochloric acid 151.6ml of 30% (weight ratio) when stirring, a most back continues to stir becomes transparent, supernatant liquid up to mixture.
(2) TiO 2The coating of coating:
To clean, dried described 1kg cordierite honeycomb ceramic carrier puts into the TiO that step (1) has prepared 2Flood 1h in the precursor liquid under 60 ℃, blow residual liquid in the duct after the taking-up off, dry 24h under 80 ℃ calcines 2h down at 600 ℃ again.Repeat the TiO that above-mentioned dipping and dry run prepare until step (1) 2Precursor liquid is with finishing.
(3) capacity of oxide active ingredients determines
According to Ce 2O 3: V 2O 5: MoO 3: TiO 2(coating amount in step 2)=1: 1: 9: the consumption that 89 mass ratio calculates the catalyst cupport raw material is: cerous nitrate 5.54g; Ammonium metavanadate 2.57g; Ammonium molybdate 22.08g.
(4) coating of co-catalyst
Take by weighing ammonium molybdate 22.08g, it is 4 that described ammonium molybdate is dissolved in the pH value that adds the oxalic acid regulator solution behind the 3573ml deionized water.To apply TiO in the step (2) 2Ceramic monolith put into the solution of ammonium molybdate, oxalic acid and water, in 60 ℃ of dipping 6h down, blow the residual liquid duct in after the taking-up off, at 80 ℃ of dry 24h down, calcine 2h down at 600 ℃ again.Repeatedly repeated impregnations, drying and calcination process, up to the solution of ammonium molybdate, oxalic acid and water all with finishing.
(5) Ce 2O 3And V 2O 5The coating of active component
Take by weighing the 5.54g cerous nitrate, it is dissolved in the 1220ml deionized water; Take by weighing the 2.57g ammonium metavanadate again, it is dissolved in the 1098ml deionized water; After cerous nitrate solution and ammonium metavanadate solution mixing, the pH value that adds the oxalic acid regulator solution is 4.To apply TiO in the step (3) 2Put into the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water with the ceramic monolith of co-catalyst,, blow the residual liquid duct in after the taking-up off,, calcine 2h down at 600 ℃ again at 80 ℃ of dry 24h down in 60 ℃ of dipping 6h down.Repeatedly repeated impregnations, drying and calcination process, up to the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water all with finishing.Then the ceramic monolith behind the load master active component is calcined 4h down at 600 ℃.
Estimate embodiment 4 at NH with SCR catalyst activity laboratory evaluation device shown in Figure 1 3Catalytic performance in the-SCR reaction.Exhaust NOx concentration is 800 * 10 in the experiment -6V/v, the concentration of CO is 650 * 10 -6V/v, the concentration of HC (propane) is 750 * 10 -6V/v, oxygen concentration=10% (volume ratio); NH 3With the mol equivalent proportion of NOx be 1.1: 1, GHSV (per hour volume space velocity)=30000h -1The catalytic effect of 4 couples of NOx of embodiment as shown in Figure 5.
Embodiment 5
(1) TiO 2The preparation of precursor liquid:
Determine will be on the 1kg cordierite honeycomb ceramic carrier load coating material TiO 2
Take by weighing the 362ml butyl titanate, join in the 1086ml absolute ethyl alcohol, drip the hydrochloric acid 180ml of 10% (weight ratio) when stirring, a most back continues to stir becomes transparent, supernatant liquid up to mixture.
(2) TiO 2The coating of coating:
To clean, dried described 1kg cordierite honeycomb ceramic carrier puts into the TiO that step (1) has prepared 2Flood 1h in the precursor liquid under 60 ℃, blow residual liquid in the duct after the taking-up off, dry 6h under 110 ℃ calcines 2h down at 500 ℃ again.Repeat the TiO that above-mentioned dipping, drying and calcination process prepare until step (1) 2Precursor liquid is with finishing.
(3) capacity of oxide active ingredients determines
According to Ce 2O 3: V 2O 5: WO 3: TiO 2(coating amount in step 2)=2: 1: 12: the consumption that 85 mass ratio calculates the catalyst cupport raw material is: cerous nitrate 5.54g; Ammonium metavanadate 1.29g; Ammonium tungstate 13.82g.
(4) coating of co-catalyst
Take by weighing ammonium tungstate 13.82g, it is dissolved in the pH value that adds the oxalic acid regulator solution behind the 3451ml deionized water is 2.To apply TiO in the step (2) 2Ceramic monolith put into the solution of ammonium tungstate, oxalic acid and water, in 60 ℃ of dipping 4h down, blow the residual liquid duct in after the taking-up off, at 110 ℃ of dry 6h down, calcine 2h down at 500 ℃ again.Repeatedly repeated impregnations, drying and calcination process, up to the solution of described ammonium tungstate, oxalic acid and water all with finishing.
(5) Ce 2O 3And V 2O 5The coating of active component
Take by weighing the 5.54g cerous nitrate, it is dissolved in the 1220ml deionized water; Take by weighing the 1.29g ammonium metavanadate again, it is dissolved in the 1103ml deionized water; After cerous nitrate solution and ammonium metavanadate solution mixing, the pH value that adds the oxalic acid regulator solution is 2.To apply TiO in the step (3) 2Put into the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water with the ceramic monolith of co-catalyst,, blow the residual liquid duct in after the taking-up off,, calcine 2h down at 500 ℃ again at 110 ℃ of dry 6h down in 60 ℃ of dipping 4h down.Repeatedly repeated impregnations, drying and calcination process, up to the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water all with finishing.Then the ceramic monolith behind the load master active component is calcined 6h down at 500 ℃.
Estimate embodiment 5 at NH with SCR catalyst activity laboratory evaluation device shown in Figure 1 3Catalytic performance in the-SCR reaction.Exhaust NOx concentration is 800 * 10 in the experiment -6V/v, the concentration of CO is 650 * 10 -6V/v, the concentration of HC (propane) is 750 * 10 -6V/v, oxygen concentration=10% (volume ratio); NH 3With the mol equivalent proportion of NOx be 1.1: 1, GHSV (per hour volume space velocity)=30000h -1The catalytic effect of 5 couples of NOx of embodiment as shown in Figure 5.
Embodiment 6
(1) TiO 2The preparation of precursor liquid:
Determine will be on the 1kg cordierite honeycomb ceramic carrier load coating material TiO 2
Take by weighing the 1189ml butyl titanate, join in the 2378ml absolute ethyl alcohol, drip the hydrochloric acid 590ml of 10% (weight ratio) when stirring, a most back continues to stir becomes transparent, supernatant liquid up to mixture.
(2) TiO 2The coating of coating:
To clean, dried described 1kg cordierite honeycomb ceramic carrier puts into the TiO that step (1) has prepared 2Flood 1h in the precursor liquid under 60 ℃, blow residual liquid in the duct after the taking-up off, dry 24h under 80 ℃ calcines 2h down at 600 ℃ again.Repeat the TiO that above-mentioned dipping, drying and calcination process prepare until step (1) 2Precursor liquid is with finishing.
(3) capacity of oxide active ingredients determines
According to Ce 2O 3: V 2O 5: WO 3: TiO 2(coating amount in step 2)=0.5: 0.5: 6: the consumption that 93 mass ratio calculates the catalyst cupport raw material is: cerous nitrate 4.15g; Ammonium metavanadate 1.93g; Ammonium tungstate 20.73g.
(4) coating of co-catalyst
Take by weighing ammonium tungstate 20.73g, it is dissolved in the pH value that adds the oxalic acid regulator solution behind the 2588ml deionized water is 6.To apply TiO in the step (2) 2Ceramic monolith put into the solution of ammonium tungstate, oxalic acid and water, in 60 ℃ of dipping 6h down, blow the residual liquid duct in after the taking-up off, at 80 ℃ of dry 24h down, calcine 2h down at 600 ℃ again.Repeatedly repeated impregnations, drying and calcination process, up to the solution of described ammonium tungstate, oxalic acid and water all with finishing.
(5) Ce 2O 3And V 2O 5The coating of active component
Take by weighing the 4.15g cerous nitrate, it is dissolved in the 914ml deionized water; Take by weighing the 1.93g ammonium metavanadate again, it is dissolved in the 1650ml deionized water; After cerous nitrate solution and ammonium metavanadate solution mixing, the pH value that adds the oxalic acid regulator solution is 6.To apply TiO in the step (3) 2Put into the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water with the ceramic monolith of co-catalyst,, blow the residual liquid duct in after the taking-up off,, calcine 2h down at 600 ℃ again at 80 ℃ of dry 24h down in 60 ℃ of dipping 6h down.Repeatedly repeated impregnations, drying and calcination process, up to the mixed solution of cerous nitrate, ammonium metavanadate, oxalic acid and deionized water all with finishing.Then the ceramic monolith behind the load master active component is calcined 4h down at 600 ℃.
Estimate embodiment 6 at NH with SCR catalyst activity laboratory evaluation device shown in Figure 1 3Catalytic performance in the-SCR reaction.Exhaust NOx concentration is 800 * 10 in the experiment -6V/v, the concentration of CO is 650 * 10 -6V/v, the concentration of HC (propane) is 750 * 10 -6V/v, oxygen concentration=10% (volume ratio); NH 3With the mol equivalent proportion of NOx be 1.1: 1, GHSV (per hour volume space velocity)=30000h -1The catalytic effect of 6 couples of NOx of embodiment as shown in Figure 5.
Embodiment 7
Apply TiO on the cordierite honeycomb ceramic carrier that in specification is 5.76L according to proportioning and the preparation method of embodiment 1 2, WO 3, V 2O 5And Ce 2O 3Etc. component; To the purifying property of NOx, the result is as shown in table 1 under the actual engine service condition for evaluation embodiment 1 on SCR catalyst performance engine evaluation system as shown in Figure 6.
Table 1 embodiment 1 in engine ESC test to true exhaust conditions under the clean-up effect of NOx
Figure A20091006901900131
The present invention has following advantage: the Ce that adopts low toxicity2O 3Part substitutes the V of high poison2O 5, reduced the ring of catalyst Border harm; Alternative catalysts has more broad active temperature scope, particularly low temperature active carrying has by a relatively large margin been arranged Height is particularly suitable for the current condition of China's urban road; Cerium is abundant at China's reserves as a kind of rare earth element, fully can Guarantee raw material supply and the cost control of the large-scale production of Novel SCR catalyst.

Claims (4)

1.Ce 2O 3And V 2O 5Dual-active component diesel vehicle removes nitrogen oxide catalyst with SCR, it is characterized in that it is framework material that catalyst adopts cordierite honeycomb ceramic carrier, with Ce 2O 3And V 2O 5Be main active component, with WO 3Or MoO 3Be cocatalyst component, with TiO 2Be coated substrate,
Wherein main active component Ce 2O 3And V 2O 5With cocatalyst component WO 3Or MoO 3And coated substrate TiO 2Mass percent be: (1～3%): (6～12%): (85～93%), mass percent sum are 100%.
2. according to the described Ce of claim 1 2O 3And V 2O 5Dual-active component diesel vehicle removes nitrogen oxide catalyst with SCR, it is characterized in that described main active component adds described cocatalyst component and adds described coated substrate TiO 2Gross mass and the mass ratio of described cordierite honeycomb ceramic carrier be (9.1～23.1%): (90.9～76.9%), the mass percent sum is 100%.
3. according to the described Ce of claim 1 2O 3And V 2O 5Dual-active component diesel vehicle removes nitrogen oxide catalyst with SCR, it is characterized in that described main active component Ce 2O 3And V 2O 5Mass percent be (30～70%): (70～30%), mass percent sum are 100%.
4.Ce 2O 3And V 2O 5Dual-active component diesel vehicle removes the nitrogen oxide catalyst preparation method with SCR, it is characterized in that concrete technology may further comprise the steps:
(1) TiO 2The preparation of precursor liquid
Determine the quality of required coating cordierite honeycomb ceramic carrier, add described cocatalyst component according to described main active component and add described coated substrate TiO again 2Gross mass and the mass ratio of described cordierite honeycomb ceramic carrier be (9.1～23.1%): (90.9～76.9%), the mass percent sum is 100%, calculates TiO 2Load capacity produces 79.88g TiO according to every 340.35g butyl titanate then 2Proportional meter calculate the quality that in precursor liquid, needs to add butyl titanate, again the mass conversion of described butyl titanate is become the volume of butyl titanate, take by weighing the butyl titanate under the described butyl titanate volume, join in the absolute ethyl alcohol of 2～3 times of described volumes, when stirring, drip concentration and be not less than 10% hydrochloric acid, continuing to stir after dripping to the greatest extent becomes transparent, supernatant liquid up to mixture, as TiO 2Precursor liquid;
(2) TiO 2The coating of coating
With described cordierite honeycomb ceramic carrier clean, after the drying, the TiO that has prepared in step (1) 2In 60 ℃ of following dipping 1h, blow the residual liquid duct in after the taking-up off in the precursor liquid, 80～110 ℃ dry down 6～24, calcine 2h down at 500～600 ℃ then, repeatedly repeated impregnations, drying and calcination process are up to described TiO 2Precursor liquid is with finishing;
(3) capacity of oxide active ingredients determines
According to the described main active component Ce of claim 3 2O 3And V 2O 5Mass percent be (30～70%): the mass ratio of (70～30%) produces 328.23g Ce according to every 908.44g cerous nitrate respectively 2O 3, every 234g ammonium metavanadate produces 182g V 2O 5And every 1602.4g ammonium tungstate produces 1391.1g WO 3Or every 1236g ammonium molybdate produces 1008gMoO 3Ratiometric conversion go out the quality of needed raw material cerous nitrate, ammonium metavanadate and ammonium tungstate or ammonium molybdate;
(4) coating of ammonium tungstate or ammonium molybdate co-catalyst
The quality that calculates according to step (3) takes by weighing ammonium tungstate or ammonium molybdate, every 16.02g ammonium tungstate or every 12.36g ammonium molybdate are dissolved in the ratio of 2000～4000ml deionized water to be mixed with deionized water, the pH value that adds the oxalic acid regulator solution then is 2～6, and step (2) has been applied TiO 2Ceramic monolith put into the solution of described ammonium tungstate or ammonium molybdate, oxalic acid and deionized water, flood 4～6h down in 60 ℃, blow residual liquid in the duct after the taking-up off, at 80～110 ℃ of down dry 6～24h, calcine 2h down at 500～600 ℃ again, repeatedly repeated impregnations, drying and calcination process, up to the solution of described ammonium tungstate (or ammonium molybdate), oxalic acid and water all with finishing;
(5) Ce 2O 3And V 2O 5The load of main active component
The quality that calculates according to step (3) takes by weighing cerous nitrate and ammonium metavanadate, the ratio that is dissolved in 500～1000ml deionized water according to every 4.54g cerous nitrate and every 1.17g ammonium metavanadate is mixed with solution respectively, the pH value that adds the oxalic acid regulator solution again is 2～6, and step (4) has been applied TiO 2Put into the solution of described cerous nitrate, ammonium metavanadate, oxalic acid and deionized water with the ceramic monolith of co-catalyst, flood 6h down in 60 ℃, blow residual liquid in the duct after the taking-up off, at 80～110 ℃ of down dry 6～24h, calcine 2h down at 500～600 ℃ again, repeatedly repeated impregnations, drying and calcination process, up to the mixed solution of described cerous nitrate, ammonium metavanadate, oxalic acid and deionized water all with finishing, then with the ceramic monolith behind the described load master active component at 500～600 ℃ of calcining 4～6h down.
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