CN102179263A - Manganese modified molecular sieve type selective catalytic reduction catalyst for diesel engine - Google Patents

Manganese modified molecular sieve type selective catalytic reduction catalyst for diesel engine Download PDF

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CN102179263A
CN102179263A CN2011100571150A CN201110057115A CN102179263A CN 102179263 A CN102179263 A CN 102179263A CN 2011100571150 A CN2011100571150 A CN 2011100571150A CN 201110057115 A CN201110057115 A CN 201110057115A CN 102179263 A CN102179263 A CN 102179263A
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molecular sieve
weight
catalyst
cordierite honeycomb
honeycomb ceramic
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CN102179263B (en
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吕刚
宋崇林
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
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Abstract

The invention discloses a manganese modified molecular sieve type selective catalytic reduction catalyst for a diesel engine. In the catalyst, a cordierite honeycomb ceramic is taken as a carrier material, main active ingredients are Mn2+ ions and manganese oxide particles entering a molecular sieve through ion exchange; and the residual non-exchanged H+ and a silicon-aluminum skeleton structure in the molecular sieve are respectively used as a cocatalyst and a coating matrix. In the molecular sieve powder subjected to ion exchange modification, the manganese element is 0.6 to 9.2 weight percent; and in the supported catalyst consisting of the cordierite honeycomb ceramic carrier and the coating, the coating is 5 to 15 weight percent. The preparation method comprises modification of the molecular sieve and preparation of the supported catalyst. In the catalyst, urea or ammonia is taken as a reducing agent, and NOx and HC is removed from exhaust of the diesel engine through selective catalytic reduction reaction. The Mn/ZSM-5 catalyst is prepared from a nontoxic and harmfulless H/ZSM-5 molecular sieve and manganous nitrate through ion exchange modification, and harm to the environment is reduced.

Description

The molecular sieve type use for diesel engine selective catalytic reduction catalysts of manganese modification
Technical field
The invention belongs to the use for diesel engine catalyst, be specifically related to a kind of manganese element modification the molecular sieve type SCR, remove the Catalysts and its preparation method of nitrogen oxide.
Background technology
Because diesel engine power is big, the thermal efficiency is high, durable, so diesel vehicle application at home is very extensive.The carbon monoxide of one diesel vehicle (CO) and hydrocarbon (HC) brake specific exhaust emission are lower, but its nitrogen oxide (NO x) and particulate (PM) discharging higher, not only destroy atmospheric environment, and the serious threat health, so the blowdown improvement technology of diesel vehicle has caused the public's common concern.With urea or ammonia is that the SCR technology of reducing agent not only has high NOx purification efficiency, and by optimizing coupling, the optimization of measure with diesel combustion, also can reduce PM discharging and fuel consume simultaneously, be one of diesel emission post-processing technology that has most promotional value.
Existing commercial SCR catalyst is many by V 2O 5-WO 3(or MoO 3)-TiO 2-ceramic monolith is formed, and such catalyst has NOx purifying property preferably in 280～500 ℃ of scopes, relatively is fit to the road operating condition of developed countries such as America and Europe.But China's urban road is crowded, and road speed is slow, and engine exhaust temperature often is lower than 280 ℃, with the efficient temperature window of catalytic component based on vanadium certain deviation is arranged; While V 2O 5Belong to highly toxic substance, bigger to human health damage.Therefore, (Selective Catalytic Reduction---SCR) catalyst becomes the urgent need of domestic the sector to adopt the low toxicity developing material to have the new selective catalytic reduction of better low-temperature catalytic activity.
Summary of the invention
The objective of the invention is, utilizing model is that 16: 1 molecular sieve is as the co-catalyst and the coating material of SCR catalyst for H/ZSM-5 and sial ratio, and the H/ZSM-5 molecular sieve is carried out ion-exchanged by manganese acetate solution, thereby provide a series of Mn/ZSM-5 molecular sieve type low toxicity SCR Catalysts and its preparation methods, this catalyst series has not only reduced the toxicity of catalyst, and has better low-temperature SCR catalytic activity than catalytic component based on vanadium.
The objective of the invention is to be achieved through the following technical solutions: the ZSM-5 molecular sieve type use for diesel engine selective catalytic reduction catalysts of manganese modification, it is characterized in that catalyst adopts cordierite honeycomb ceramic as carrier material, main active component is the Mn that enters molecular sieve by ion-exchange 2+Ion and manganese oxide particle; The H that residue is not exchanged in the molecular sieve +Ion and sial skeleton structure are respectively as co-catalyst and coated substrate.
Gross weight with described molecular sieve powder behind ion-exchanged is a benchmark, and wherein to account for percentage by weight be 0.6～9.2% to manganese element; Gross weight with cordierite honeycomb ceramic carrier and coat composed catalyst integral body is a benchmark, and it is 5～15% that its floating coat accounts for percentage by weight.
Adopting urea or ammonia is reducing agent, removes NOx and HC in the diesel exhaust gas by selective catalytic reduction reaction.
The preparation method that the present invention proposes, its concrete technology may further comprise the steps:
(1) modification of molecular sieve
With 4.9～73.5g manganese acetate (molecular formula: C 4H 6MnO 44H 2O; Molecular weight: 245.09) be dissolved in the 200ml deionized water.Weighing 15g model is then: H/ZSM-5 and sial ratio are that 16: 1 molecular sieve powder adds in the described manganese acetate solution, and reflux in 60～90 ℃ water-bath and stir 4～8h, carry out ion-exchange.
Reactant mixture after exchange finished filters, and with the pressed powder that filters out at 80～110 ℃ of down dry 6～12h, then at 550～650 ℃ of calcining 3～5h down.
To be referred to as the powder catalyst through the resulting powder catalyst of step (1).
(2) preparation of loaded catalyst
Determine the weight and the weight percentage ranges that will apply coating material of the cordierite honeycomb ceramic carrier of the load of wanting, gross weight with cordierite honeycomb ceramic carrier after the load coating and coat composed integer catalyzer is a benchmark, and it is 5～15% that its floating coat accounts for percentage by weight; The width of the weight percentage ranges of coating material is 1%.
Then, need 20～40g γ-Al according to the molecular sieve powder after every 100g modification 2O 3, 5～10g boehmite, 10～20g cerium zirconium, 5～10g polyethylene glycol and 50g nitric acid ratio, take by weighing modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol, and under agitation, with described modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol be dispersed in the salpeter solution of dilution 20 multiple proportions examples, obtains faint yellow slurry, with the sealing of gained slurry, leave standstill, obtains stable slurry after the week.
Then, the cordierite honeycomb ceramic carrier of weighing is immersed in the stable slurry, flooded 2～4 hours down, after dipping finishes at 60～90 ℃, ceramic monolith is taken out from slurries, blow residual liquid in the duct off,, calcine 2～3h down at 550～650 ℃ again at 80～110 ℃ of down dry 4～8h, after treating the loaded catalyst cooling, its weight of weighing, cooled loaded catalyst weight and cordierite honeycomb ceramic initial weight poor is the gross weight of coating.
Repeatedly repeated impregnations, drying and calcination process enter pre-determined weight percentage ranges up to the percentage by weight of coating, again with the cordierite honeycomb ceramic carrier after the load coating at 550～650 ℃ of calcining 2～3h down.
The present invention will be referred to as loaded catalyst through the resulting catalyst of step (2).
The beneficial effect of characteristics of the present invention and generation is: adopt co-catalyst and the coating material of nontoxic H/ZSM-5 molecular sieve as the SCR catalyst, the manganese ion that adopts low toxicity has simultaneously reduced the harm of catalyst to environment and human health as main active component; Simultaneously, by ion-exchanged, the high activity temperature window, particularly low temperature active that have enlarged the SCR catalyst have had raising by a relatively large margin, are particularly suitable for the low national conditions of China's city diesel vehicle exhaust temperature.
Description of drawings
Fig. 1 is a selective catalytic reduction catalysts hot laboratory evaluating apparatus schematic diagram:
Wherein: 1-air steel cylinder; 2-propane steel cylinder; The 3-NO steel cylinder; 4-NH 3Steel cylinder; 5-3 channel capacity controller; The 6-flow controller; The 7-mixing kettle; The 8-reactor; The 9-thermorelay; The 10-temperature indicator; 11-reaction final vacuum outlet (leading to gas analyzer).
Fig. 2 be the powder catalyst among the embodiment 1～6 X-ray diffraction (X-Ray Diffraction---XRD) spectrogram, abscissa is represented diffracted intensity; Ordinate is represented angle of diffraction.
Fig. 3 is that powder catalyst n Ox removal efficiency among the embodiment 1～6 is with the situation of change of reaction temperature.
Fig. 4 is that powder catalyst HC removal efficiency among the embodiment 1～6 is with the situation of change of reaction temperature.
Fig. 5 is a SCR catalyst performance engine evaluation system schematic diagram.
Wherein: the 12-diesel engine; The 13-constant displacement pump; 14-NH 3Storage tank; 15-NH 3Jet; The 16-SCR catalyst converter; The 17-dynamometer machine
Fig. 6 is NH 3/ NOx mol ratio removes performance and NH to embodiment 3 loaded catalyst NOx 3Discharge capacity influences the engine evaluation result of rule.
The specific embodiment
Below the present invention will be described in more detail by specific embodiment, but need to prove and can not limit invention which is intended to be protected with following embodiment.
The NOx catalytically active assessment test of embodiment 1～5 is what to carry out on selective catalytic reduction catalysts hot laboratory evaluating apparatus shown in Figure 1.Propane in air in the steel cylinder 1, the steel cylinder 2 and the NO in the steel cylinder 3 are that 4L/min, propane are that 1mL/min, NO are that the flow velocity of 3.6mL/min enters respectively in the mixing kettle 7 and mixes by flow-control meter 5 according to air.Mist enters in the reactor 8 more then.And the NH in the steel cylinder 4 3Gas enters reactor 8 with the flow velocity of 4.0mL/min under the control of quality controller 6, the SCR catalytic reaction takes place the catalyst surface of gaseous mixture in reactor that flows out with mixing kettle 7.The temperature range of reactor is 150-600 ℃, and by relay 9 controls, the actual temperature in the reactor is shown by temperature indicator 10.Reacted gaseous mixture enters gas analysis system after 11 mouthfuls of discharges and carries out constituent analysis.Wherein, NO concentration adopts infrared gas analyser to measure, and the gas chromatograph of hydrocarbon employing equipment flame ionization detector is measured.
Catalyst of the present invention adopts cordierite honeycomb ceramic as carrier material, and main active component is the Mn that enters molecular sieve by ion-exchange 2+Ion and manganese oxide particle; The H that residue is not exchanged in the molecular sieve +Ion and sial skeleton structure are respectively as co-catalyst and coated substrate.Gross weight with described molecular sieve powder behind ion-exchanged is a benchmark, and wherein to account for percentage by weight be 0.6～9.2% to manganese element; Gross weight with cordierite honeycomb ceramic carrier and coat composed catalyst integral body is a benchmark, and it is 5～15% that its floating coat accounts for percentage by weight.Adopting urea or ammonia is reducing agent, removes NOx and HC in the diesel exhaust gas by selective catalytic reduction reaction.
Embodiment 1
(1) modification of molecular sieve
The 4.9g manganese acetate is dissolved in the 200ml deionized water.Weighing 15g model is then: H/ZSM-5 and sial ratio are that 16: 1 molecular sieve powder adds in the described manganese acetate solution, and reflux in 60 ℃ water-bath and stir 8h, carry out ion-exchange.
Reactant mixture after exchange finished filters, and with the pressed powder that filters out at 80 ℃ of dry 12h down, then at 550 ℃ of calcining 5h down.
(2) preparation of loaded catalyst
Determine on the 1kg cordierite honeycomb ceramic carrier, to apply 5～6% coating.
Need 20g γ-Al according to the molecular sieve powder after every 100g modification 2O 3, 5g boehmite, 10g cerium zirconium, 5g polyethylene glycol (mean molecule quantity 4000) and 50g nitric acid ratio, take by weighing powder catalyst, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol, and under agitation, with described modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol be dispersed in the salpeter solution of dilution 20 multiple proportions examples, obtains faint yellow slurry.The gained slurry is sealed, leaves standstill, obtain stable slurry after the week.
The 1kg cordierite honeycomb ceramic carrier of weighing is immersed in the described stable slurry, flooded 4 hours down at 60 ℃.Dipping takes out ceramic monolith after finishing from slurries, blow residual liquid in the duct off, and dry 8h under 80 ℃ is again at 550 times calcining 3h.After treating the ceramic monolith cooling after the load, claim its weight, this weight and cordierite honeycomb ceramic initial weight poor is the gross weight of coating.
Repeatedly repeated impregnations, drying and calcination process enter pre-determined weight percentage ranges up to the percentage by weight of coating, again with the cordierite honeycomb ceramic carrier after the load coating at 550 ℃ of calcining 3h down.
Modified molecular screen powder among the embodiment 1 is 20～40 purpose particles through grinding, compressing tablet, fragmentation, screening.Modified molecular screen particle to embodiment 1 carries out the atomic absorption spectrophotometer detection, and the percetage by weight that measures Mn in the modified molecular screen is 0.6; The modified molecular screen particle is carried out the X-ray diffraction test, and the result as shown in Figure 2.
Adopt SCR catalyst activity laboratory evaluation device shown in Figure 1 that the modified molecular screen particulate burning purifying nitric oxide (NO) of described embodiment 1 and the performance of HC are estimated, the result as shown in Figure 3 and Figure 4.The ratio of reaction mixture gas rate of flow of fluid and catalyst volume is 60000h in the test -1
Through weighing and calculating, the loaded catalyst floating coat weight of embodiment 1 accounts for 5.3% of loaded catalyst gross weight.
Embodiment 2
(1) modification of molecular sieve
The 9.2g manganese acetate is dissolved in the 200ml deionized water.Weighing 15g model is then: H/ZSM-5 and sial ratio are that 16: 1 molecular sieve powder adds in the manganese acetate solution, and reflux in 75 ℃ water-bath and stir 6h, carry out ion-exchange.
Reactant mixture after exchange finished filters, and with the pressed powder that filters out at 100 ℃ of dry 10h down, then at 600 ℃ of calcining 4h down.
(2) preparation of loaded catalyst
Determine on the 1kg cordierite honeycomb ceramic carrier, to apply 10～11% coating.
Need 30g γ-Al according to the molecular sieve powder after every 100g modification 2O 3, 8g boehmite, 8g cerium zirconium, 10g polyethylene glycol (mean molecule quantity 4000) and 50g nitric acid ratio, take by weighing modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol, and under agitation, with described modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol be dispersed in the described ratio salpeter solution of 20 times of dilutions, obtains faint yellow slurry.The gained slurry is sealed, leaves standstill, obtain stable slurry after the week.
The 1kg cordierite honeycomb ceramic carrier of weighing is immersed in the described stable slurry, flooded 3 hours down at 75 ℃.Dipping takes out ceramic monolith after finishing from slurries, blow residual liquid in the duct off, and dry 6h under 100 ℃ calcines 3h down at 550 ℃ again.After treating the ceramic monolith cooling after the load, claim its weight, this weight and cordierite honeycomb ceramic initial weight poor is the gross weight of coating.
Repeatedly repeated impregnations, drying and calcination process enter pre-determined weight percentage ranges up to the percentage by weight of coating, again with the cordierite honeycomb ceramic carrier after the load coating at 550 ℃ of calcining 3h down.
Modified molecular screen powder among the embodiment 2 is 20～40 purpose particles through grinding, compressing tablet, fragmentation, screening.Modified molecular screen particle to embodiment 2 carries out the atomic absorption spectrophotometer detection, and the mass percent that measures Mn in the modified molecular screen is 1.4; The modified molecular screen particle is carried out the X-ray diffraction test, and the result as shown in Figure 2.
Adopt SCR catalyst activity laboratory evaluation device shown in Figure 1 that the modified molecular screen particulate burning purifying NO of described embodiment 2 and the performance of HC are estimated, the result as shown in Figure 3 and Figure 4.The ratio of reaction mixture gas rate of flow of fluid and catalyst volume is 60000h in the test -1
Through weighing and calculating, the loaded catalyst floating coat weight of embodiment 2 accounts for 10.2% of loaded catalyst gross weight.
Embodiment 3
(1) modification of molecular sieve
The 36.764g manganese acetate is dissolved in the 200ml deionized water.Weighing 15g model is then: H/ZSM-5 and sial ratio are that 16: 1 molecular sieve powder adds in the manganese acetate solution, and reflux in 90 ℃ water-bath and stir 4h, carry out ion-exchange.
Reactant mixture after exchange finished filters, and with the pressed powder that filters out at 100 ℃ of dry 10h down, then at 600 ℃ of calcining 4h down.
(2) preparation of loaded catalyst
Determine on the 1kg cordierite honeycomb ceramic carrier, to apply 9～10% coating.
Need 20g γ-Al according to the molecular sieve powder after every 100g modification 2O 3, 5g boehmite, 5g cerium zirconium, 5g polyethylene glycol (mean molecule quantity 4000) and 50g nitric acid ratio, take by weighing modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol, and under agitation, with described modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol be dispersed in the salpeter solution of dilution 20 multiple proportions examples, obtains faint yellow slurry.The gained slurry is sealed, leaves standstill, obtain stable slurry after the week.
The 1kg cordierite honeycomb ceramic carrier of weighing is immersed in the described stable slurry, flooded 3 hours down at 75 ℃.Dipping takes out ceramic monolith after finishing from slurries, blow residual liquid in the duct off, and dry 4h under 110 ℃ calcines 3h down at 550 ℃ again.After treating the ceramic monolith cooling after the load, claim its weight, this weight and cordierite honeycomb ceramic initial weight poor is the gross weight of coating.
Repeatedly repeated impregnations, drying and calcination process enter pre-determined weight percentage ranges up to the percentage by weight of coating, again with the cordierite honeycomb ceramic carrier after the load coating at 550 ℃ of calcining 3h down.
Modified molecular screen powder among the embodiment 3 is 20～40 purpose particles through grinding, compressing tablet, fragmentation, screening.Modified molecular screen particle to embodiment 3 carries out the atomic absorption spectrophotometer detection, and the percetage by weight that measures Mn in the modified molecular screen is 3.1; The modified molecular screen particle is carried out the X-ray diffraction test, and the result as shown in Figure 2.
Adopt SCR catalyst activity laboratory evaluation device shown in Figure 1 that the modified molecular screen particulate burning purifying NO of described embodiment 3 and the performance of HC are estimated, the result as shown in Figure 3 and Figure 4.The ratio of reaction mixture gas rate of flow of fluid and catalyst volume is 40000h in the test -1
Through weighing and calculating, the loaded catalyst floating coat weight of embodiment 3 accounts for 9.7% of loaded catalyst gross weight.
The NH that adopted as shown in Figure 5 engine test system evaluation 3/ NOx mol ratio removes performance and NH to embodiment 3 loaded catalyst NOx 3Discharge capacity influence rule.Its test method is: use the running status of dynamometer machine 17 control test engines 12, make that the delivery temperature in the SCR catalyst converter is 360 ℃, the ratio of engine exhaust flow and catalyst volume is 40000h -1 Constant displacement pump 13 is spurted into the liquefied ammonia in the storage tank 14 in the blast pipe through jet 15 with controllable flow.NH after the vaporization 3Gas with enter SCR catalyst converter 16 after the exhaust of engine 12 mixes and carry out the SCR catalytic reaction.NOx concentration and NH in the gaseous mixture of reaction back 3Concentration is measured by chemiluminescence detector.In the test, by adjusting the rotating speed control NH of constant displacement pump 3Injection rate, to adjust NH 3/ NOx mol ratio.Result of the test as shown in Figure 6.
Embodiment 4
(1) modification of molecular sieve
The 55.145g manganese acetate is dissolved in the 200ml deionized water.Weighing 15g model is then: H/ZSM-5 and sial ratio are that 16: 1 molecular sieve powder adds in the manganese acetate solution, and reflux in 75 ℃ water-bath and stir 6h, carry out ion-exchange.
Reactant mixture after exchange finished filters, and with the pressed powder that filters out at 110 ℃ of dry 6h down, then at 600 ℃ of calcining 4h down.
(2) preparation of loaded catalyst
Determine on the 1kg cordierite honeycomb ceramic carrier, to apply 14～15% coating.
Need 40g γ-Al according to the molecular sieve powder after every 100g modification 2O 3, 10g boehmite, 20g cerium zirconium, 10g polyethylene glycol (mean molecule quantity 4000) and 50g nitric acid ratio, take by weighing modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol, and under agitation, with described modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol be dispersed in the described ratio salpeter solution of 20 times of dilutions, obtains faint yellow slurry.The gained slurry is sealed, leaves standstill, obtain stable slurry after the week.
The 1kg cordierite honeycomb ceramic carrier of weighing is immersed in the described stable slurry, flooded 2 hours down at 90 ℃.Dipping takes out ceramic monolith after finishing from slurries, blow residual liquid in the duct off, and dry 4h under 110 ℃ calcines 2h down at 650 ℃ again.After treating the ceramic monolith cooling after the load, claim its weight, this weight and cordierite honeycomb ceramic initial weight poor is the gross weight of coating.
Repeatedly repeated impregnations, drying and calcination process enter pre-determined weight percentage ranges up to the percentage by weight of coating, again with the cordierite honeycomb ceramic carrier after the load coating at 650 ℃ of calcining 2h down.
Modified molecular screen powder among the embodiment 4 is 20～40 purpose particles through grinding, compressing tablet, fragmentation, screening.Modified molecular screen particle to embodiment 4 carries out the atomic absorption spectrophotometer detection, and the percetage by weight that measures Mn in the modified molecular screen is 8.6; The modified molecular screen particle is carried out the X-ray diffraction test, and the result as shown in Figure 2.
Adopt SCR catalyst activity laboratory evaluation device shown in Figure 1 that the powder catalyst granules purification NO of described embodiment 4 and the performance of HC are estimated then, the result as shown in Figure 3 and Figure 4.The ratio of gas flow rate and catalyst volume is 60000h in the test -1
Through weighing and calculating, embodiment 4 loaded catalyst floating coat weight account for 14.7% of loaded catalyst gross weight.
Embodiment 5
(1) modification of molecular sieve
The 73.527g manganese acetate is dissolved in the 200ml deionized water.Weighing 15g model is then: H/ZSM-5 and sial ratio are that 16: 1 molecular sieve powder adds in the manganese acetate solution, and reflux in 90 ℃ water-bath and stir 4h, carry out ion-exchange.
Reactant mixture after exchange finished filters, and with the pressed powder that filters out at 110 ℃ of dry 6h down, then at 650 ℃ of calcining 3h down.
(2) preparation of loaded catalyst
Determine on the 1kg cordierite honeycomb ceramic carrier, to apply 7～8% coating.
Need 20g γ-Al according to the molecular sieve powder after every 100g modification 2O 3, 5g boehmite, 10g cerium zirconium, 5g polyethylene glycol (mean molecule quantity 4000) and 50g nitric acid ratio, take by weighing modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol, and under agitation, with described powder catalyst, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol be dispersed in the described ratio salpeter solution of 20 times of dilutions, obtains faint yellow slurry.The gained slurry is sealed, leaves standstill, obtain stable slurry after the week.
The 1kg cordierite honeycomb ceramic carrier of weighing is immersed in the described stable slurry, flooded 3 hours down at 75 ℃.Dipping takes out ceramic monolith after finishing from slurries, blow residual liquid in the duct off, and dry 6h under 100 ℃ calcines 2h down at 650 ℃ again.After treating the ceramic monolith cooling after the load, claim its weight, this weight and cordierite honeycomb ceramic initial weight poor is the gross weight of coating.
Repeatedly repeated impregnations, drying and calcination process enter pre-determined weight percentage ranges up to the percentage by weight of coating, again with the cordierite honeycomb ceramic carrier after the load coating at 650 ℃ of calcining 3h down.
Modified molecular screen powder among the embodiment 5 is 20～40 purpose particles through grinding, compressing tablet, fragmentation, screening.Modified molecular screen particle to embodiment 5 carries out the atomic absorption spectrophotometer detection, and the mass percent that measures Mn in the modified molecular screen is 9.2; The modified molecular screen particle is carried out the X-ray diffraction test, and the result as shown in Figure 2.
Adopt SCR catalyst activity laboratory evaluation device shown in Figure 1 that the modified molecular screen particulate burning purifying NO of described embodiment 5 and the performance of HC are estimated, the result as shown in Figure 3 and Figure 4.The ratio of reaction mixture gas rate of flow of fluid and catalyst volume is 60000h in the test -1
Through weighing and calculating, embodiment 5 loaded catalyst floating coat weight account for 7.5% of loaded catalyst gross weight.

Claims (4)

1. the molecular sieve type use for diesel engine selective catalytic reduction catalysts of manganese modification is characterized in that catalyst adopts cordierite honeycomb ceramic as carrier material, and main active component is the Mn that enters molecular sieve by ion-exchange 2+Ion and manganese oxide particle; H+ ion that residue is not exchanged in the molecular sieve and sial skeleton structure are respectively as co-catalyst and coated substrate.
2. according to the molecular sieve type use for diesel engine selective catalytic reduction catalysts of the described manganese modification of claim 1, it is characterized in that the gross weight with described molecular sieve powder behind ion-exchanged is a benchmark, wherein to account for percentage by weight be 0.6～9.2% to manganese element; Gross weight with cordierite honeycomb ceramic carrier and coat composed catalyst integral body is a benchmark, and it is 5～15% that its floating coat accounts for percentage by weight.
3. according to the molecular sieve type use for diesel engine selective catalytic reduction catalysts of the described manganese modification of claim 1, it is characterized in that adopting urea or ammonia is reducing agent, removes NOx and HC in the diesel exhaust gas by selective catalytic reduction reaction.
4. the preparation method of the molecular sieve type use for diesel engine selective catalytic reduction catalysts of manganese modification is characterized in that concrete technology may further comprise the steps:
(1) modification of molecular sieve
4.9～73.5g manganese acetate is dissolved in the 200ml deionized water, and weighing 15g model is then: H/ZSM-5 and sial ratio are that 16: 1 molecular sieve powder adds in the manganese acetate solution, and stir 4～8h in 60～90 ℃ water-bath, carry out ion-exchange;
Reactant mixture after exchange finished filters, and with the pressed powder that filters out at 80～110 ℃ of down dry 6～12h, then at 550～650 ℃ of calcining 3～5h down;
(2) preparation of loaded catalyst
Determine the weight and the weight percentage ranges that will apply coating material of the cordierite honeycomb ceramic carrier of the load of wanting, gross weight with cordierite honeycomb ceramic carrier after the load coating and coat composed integer catalyzer is a benchmark, it is 5～15% that its floating coat accounts for percentage by weight, and the permissible variation of coating material percentage by weight is 1% to the maximum;
Then, need 20～40g γ-Al according to the molecular sieve powder after every 100g modification 2O 3, 5～10g boehmite, 10～20g cerium zirconium, 5～10g polyethylene glycol and 50g nitric acid ratio, take by weighing modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol, and under agitation, with described modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol be dispersed in the salpeter solution of dilution 20 multiple proportions examples, obtains faint yellow slurry, with the sealing of gained slurry, leave standstill, obtains stable slurry after the week;
Then, the cordierite honeycomb ceramic carrier of weighing is immersed in the stable slurry, flooded 2～4 hours down, after dipping finishes at 60～90 ℃, ceramic monolith is taken out from slurries, blow residual liquid in the duct off,, calcine 2～3h down at 550～650 ℃ again at 80～110 ℃ of down dry 4～8h, after treating the loaded catalyst cooling, its weight of weighing, cooled loaded catalyst weight and cordierite honeycomb ceramic initial weight poor is the gross weight of coating;
Repeatedly repeated impregnations, drying and calcination process enter pre-determined weight percentage ranges up to the percentage by weight of coating, again with the cordierite honeycomb ceramic carrier after the load coating at 550～650 ℃ of calcining 2～3h down.
CN2011100571150A 2011-03-10 2011-03-10 Manganese modified molecular sieve type selective catalytic reduction catalyst for diesel engine Expired - Fee Related CN102179263B (en)

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CN104338545A (en) * 2014-10-21 2015-02-11 无锡威孚环保催化剂有限公司 Effective SCR (selective catalytic reduction) catalyst applied to purification of nitrogen oxide in tail gas of diesel engine
CN105944749A (en) * 2016-05-05 2016-09-21 合肥神舟催化净化器有限公司 Modified molecular sieve main catalyst based composite oxidation catalyst for diesel engines
CN107537558A (en) * 2017-06-27 2018-01-05 中国第汽车股份有限公司 Strengthen the carried catalyst preparation method for removing NOx with grappling
CN110508318A (en) * 2019-10-22 2019-11-29 山东国瓷功能材料股份有限公司 A kind of composite denitration catalyst and its preparation method and application
CN111375445A (en) * 2018-12-29 2020-07-07 中化近代环保化工(西安)有限公司 Preparation method and application of molecular sieve-loaded manganese-based denitration catalyst
CN112275314A (en) * 2020-09-14 2021-01-29 无锡威孚环保催化剂有限公司 Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof
CN112705217A (en) * 2020-12-31 2021-04-27 深圳市天得一环境科技有限公司 Integral ozone decomposition catalyst and preparation method thereof
CN113048490A (en) * 2021-03-27 2021-06-29 洛南环亚源铜业有限公司 Hazardous waste treatment process and treatment device thereof
CN113134385A (en) * 2021-03-28 2021-07-20 桂林理工大学 Preparation method of honeycomb type ZSM-5-based coating catalyst
CN113387784A (en) * 2021-07-12 2021-09-14 山东新和成药业有限公司 Acid-base catalyst and application thereof in delta-damascenone synthesis
CN114832852A (en) * 2022-04-20 2022-08-02 柳州华锡有色设计研究院有限责任公司 Preparation method of antimony-doped modified Mn/ZSM-5 molecular sieve low-temperature denitration catalyst
CN114849704A (en) * 2022-04-12 2022-08-05 浙江通源环保科技有限公司 Preparation method of noble metal catalyst

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CN102407154A (en) * 2011-09-29 2012-04-11 浙江师范大学 Molecular sieve coating load manganese based composite oxide integrated catalyst and preparation method thereof
CN104338545A (en) * 2014-10-21 2015-02-11 无锡威孚环保催化剂有限公司 Effective SCR (selective catalytic reduction) catalyst applied to purification of nitrogen oxide in tail gas of diesel engine
CN105944749A (en) * 2016-05-05 2016-09-21 合肥神舟催化净化器有限公司 Modified molecular sieve main catalyst based composite oxidation catalyst for diesel engines
CN105944749B (en) * 2016-05-05 2018-08-24 合肥神舟催化净化器股份有限公司 Use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst
CN107537558A (en) * 2017-06-27 2018-01-05 中国第汽车股份有限公司 Strengthen the carried catalyst preparation method for removing NOx with grappling
CN107537558B (en) * 2017-06-27 2020-05-22 中国第一汽车股份有限公司 Method for preparing supported catalyst with anchored enhanced NOx removal
CN111375445B (en) * 2018-12-29 2023-09-05 中化近代环保化工(西安)有限公司 Preparation method and application of molecular sieve supported manganese-based denitration catalyst
CN111375445A (en) * 2018-12-29 2020-07-07 中化近代环保化工(西安)有限公司 Preparation method and application of molecular sieve-loaded manganese-based denitration catalyst
CN110508318A (en) * 2019-10-22 2019-11-29 山东国瓷功能材料股份有限公司 A kind of composite denitration catalyst and its preparation method and application
CN112275314A (en) * 2020-09-14 2021-01-29 无锡威孚环保催化剂有限公司 Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof
CN112705217A (en) * 2020-12-31 2021-04-27 深圳市天得一环境科技有限公司 Integral ozone decomposition catalyst and preparation method thereof
CN113048490A (en) * 2021-03-27 2021-06-29 洛南环亚源铜业有限公司 Hazardous waste treatment process and treatment device thereof
CN113134385A (en) * 2021-03-28 2021-07-20 桂林理工大学 Preparation method of honeycomb type ZSM-5-based coating catalyst
CN113387784A (en) * 2021-07-12 2021-09-14 山东新和成药业有限公司 Acid-base catalyst and application thereof in delta-damascenone synthesis
CN114849704A (en) * 2022-04-12 2022-08-05 浙江通源环保科技有限公司 Preparation method of noble metal catalyst
CN114832852A (en) * 2022-04-20 2022-08-02 柳州华锡有色设计研究院有限责任公司 Preparation method of antimony-doped modified Mn/ZSM-5 molecular sieve low-temperature denitration catalyst

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