CN102247886A - Manganese-zirconium dual metal modified selective catalytic reduction catalyst for molecular sieve type diesel engine - Google Patents

Manganese-zirconium dual metal modified selective catalytic reduction catalyst for molecular sieve type diesel engine Download PDF

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CN102247886A
CN102247886A CN2011101189229A CN201110118922A CN102247886A CN 102247886 A CN102247886 A CN 102247886A CN 2011101189229 A CN2011101189229 A CN 2011101189229A CN 201110118922 A CN201110118922 A CN 201110118922A CN 102247886 A CN102247886 A CN 102247886A
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manganese
catalyst
zirconium
catalytic reduction
selective catalytic
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CN102247886B (en
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宋崇林
吕刚
宾峰
张清茂
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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
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    • 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
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    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

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Abstract

The invention discloses a manganese-zirconium dual metal modified selective catalytic reduction catalyst for a molecular sieve type diesel engine. In the catalyst, manganese and zirconium elements enter a molecular sieve by a liquid ion exchange-immersion method; by taking the total weight of the modified powdered catalyst as reference, the manganese element accounts for 4.5 to 7.5 percent, and the zirconium element accounts for 4.5 to 15 percent; by taking the total weight of a supported catalyst as reference, a coating accounts for 5 to 15 percent; urea or ammonia is adopted as a reducing agent to remove NOx in exhaust gas of the diesel engine by virtue of selective catalytic reduction reaction; the novel SCR (selective catalytic reduction) catalyst for the diesel vehicle is prepared from non-toxic molecular sieve and low-toxic manganese and zirconium elements, so that the toxicity of the catalyst to a human body is reduced; and simultaneously a high-activity temperature window of the catalyst in the SCR reaction of the diesel vehicle is enlarged. According to the modification method, the supporting capacity is improved, the supporting proportion is more flexible and adjustable, and further optimization of the catalyst performance is facilitated.

Description

Manganese zirconium double metal modified molecular screen diesel engine selective catalytic reduction catalysts
Technical field
The invention belongs to the use for diesel engine cleaning catalyst, be specifically related to the molecular sieve type use for diesel engine catalyst of a kind of manganese, zirconium double metal modification.
Background technology
The exhaust emissions of diesel engine for automobile is one of important pollution sources at present, nitrogen oxide of its discharging (NOx) and particle (PM) serious harm health.Because the corrective measure that cylinder combustion is burnt is difficult to reduce simultaneously NOx and PM discharging, so exhaust gas aftertreatment techniques becomes the inevitable choice of Exhaust Control for Diesel Engine.With urea or ammonia is that SCR (SCR) technology of reducing agent has high NOx purification efficiency, and by with coupling, the optimization of combustion modifications measure, also can reduce the fuel consume of PM discharging and engine simultaneously, be one of the most promising efficient post-processing technology.Current business-like SCR catalyst mainly is with V 2O 5Be the loaded catalyst of major catalyst, its effective temperature window is less, and particularly minimum effective temperature is difficult to satisfy diesel vehicle under Chinese city road enforcement condition, to the actual requirement of SCR catalyst low-temperature activity about 300 ℃.While V 2O 5Belong to highly toxic substance, owing to catalyst in use unavoidably can run off, so catalytic component based on vanadium is bigger to human health damage.
At present, adopt the good SCR catalyst of low toxicity catalysis material research and development low-temperature catalytic activity, become the research focus of domestic and international association area, wherein the research of molecular sieve catalysis material is particularly active.By the exchange modification of metal pair molecular screen material, can improve the SCR catalytic performance of molecular screen material, enlarge the high activity temperature window.It is composite modified particularly to adopt multiple metal pair molecular sieve to carry out, and can bring into play the synergistic function between different metal, improves the catalytic performance of molecular sieve catalyst greatly.On the other hand, for simple liquid ion-exchange, the species of metal ion of load and load capacity are all fewer on molecular sieve, just can not enter in the type ZSM 5 molecular sieve by ion-exchange such as zirconium.But if ion-exchange and two kinds of method of modifying of dipping can be combined, not only can improve the load capacity of metal, and proportion of composing that can the flexible modulation carried metal, help simplifying the further raising of preparation technology and catalyst performance.The present invention carries out modification with manganese nitrate and zirconium nitrate mixed solution to H/ZSM-5 type molecular screen material exactly, and the molecular sieve type SCR catalyst of manganese, zirconium double metal modification is finally prepared in load through coating.
Summary of the invention
The objective of the invention is, the mixed solution that utilizes manganese nitrate and zirconium nitrate is 16: 1 molecular sieve pulverulent material for H/ZSM-5, sial ratio to model, carry out a step liquid ion-exchange-dipping modification, thereby the ZSM-5 molecular sieve type SCR powder catalyst of a series of manganese, zirconium double metal modification is provided.By the load of powder catalyst on cordierite honeycomb ceramic carrier, obtain being used for the supported SCR catalyst that diesel vehicle NOx purifies simultaneously.
The objective of the invention is to be achieved through the following technical solutions: manganese, zirconium double metal modified molecular screen diesel engine selective catalytic reduction catalysts, its manganese, zr element are to enter in the molecular sieve by liquid ion-exchange-dipping, with the gross weight through the powder catalyst after ion-exchange-dipping modification is benchmark, it is 4.5～7.5% that manganese element accounts for percentage by weight, and it is 4.5～15% that zr element accounts for percentage by weight.Gross weight with the loaded catalyst after the load coating is a benchmark, and the shared percentage by weight of its floating coat is 5～15%.This selective catalytic reduction catalysts, adopting urea or ammonia is reducing agent, removes NOx in the diesel exhaust gas by selective catalytic reduction reaction.
Manganese, zirconium double metal modified molecular screen diesel engine selective catalytic reduction catalysts, the method for its modification may further comprise the steps:
(1) 4～7g manganese nitrate and 4～15g zirconium nitrate are dissolved in the 200ml deionized water, weighing 15～18.5g model is that H/ZSM-5, sial ratio are that 16: 1 molecular sieve powder joins in the mixed solution of manganese nitrate and zirconium nitrate then, in 70～80 ℃ water-bath, reflux and stir 4～6h, carry out ion-exchange;
(2) reflux condensate device that removes in the ion-exchange step continues to add the thermal agitation dipping under 70～80 ℃, until the liquid component evaporate to dryness;
(3) with the dry 12～24h under 90～110 ℃ of the pressed powder behind ion-exchange-dipping, calcine 2～3h down at 550～650 ℃ then.
The beneficial effect of characteristics of the present invention and generation is: adopt the manganese element of nontoxic H/ZSM-5 molecular sieve and low toxicity and zr element to prepare the automobile-used SCR catalyst of novel diesel, this series powder and loaded catalyst have not only reduced the bio-toxicity of original SCR catalyst; The high activity temperature window, particularly low temperature active that have also enlarged diesel vehicle SCR reacting middle catalyst have simultaneously had raising by a relatively large margin, are particularly suitable for the low national conditions of diesel engine truck exhaust temperature in the Chinese city.In addition, one step of bimetallic liquid ion-exchange-dipping method of modifying at the ZSM-5 molecular sieve can make two kinds of carried metal proportion of composing adjustable flexibly when effectively improving content of metal, not only simplify modified technique, and helped the further optimization of catalyst performance.
Description of drawings
Fig. 1 is a selective catalytic reduction catalysts hot laboratory evaluating apparatus schematic diagram.
Wherein: 1-air steel cylinder; 2-nitrogen steel cylinder; The 3-NOx steel cylinder; The 4-NH3 steel cylinder; 5-triple channel flow 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 is the situation of change of the NOx removal efficiency of ZSM-5 molecular sieve powder catalyst after embodiment 1～4 modification with reaction temperature.
Fig. 3 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; 18-bypassing exhaust valve
Fig. 4 is the engine evaluation result of embodiment 1～4 loaded catalyst NOx purifying property.
The specific embodiment
Below by specific embodiment principle steps of the present invention is described in detail, need to prove that present embodiment is narrative, rather than determinate, can not limit protection scope of the present invention with this embodiment.
The molecular sieve type use for diesel engine selective catalytic reduction catalysts of manganese, zirconium double metal modification, it is characterized in that manganese, zr element are to enter in the molecular sieve by liquid ion-exchange-dipping, with the gross weight through the powder catalyst after ion-exchange-dipping modification is benchmark, it is 4.5～7.5% that manganese element accounts for percentage by weight, and it is 4.5～15% that zr element accounts for percentage by weight; Gross weight with the loaded catalyst after the load coating is a benchmark, and the shared percentage by weight of its floating coat is 5～15%.
It is reducing agent that the molecular sieve type use for diesel engine selective catalytic reduction catalysts of manganese, zirconium double metal modification adopts urea or ammonia, removes NOx in the diesel exhaust gas by selective catalytic reduction reaction.
The preparation method of this catalyst modification may further comprise the steps:
(1) with 4～7g manganese nitrate (molecular formula: Mn (NO 3) 24H 2O; 251.01) and 4～15g zirconium nitrate (molecular formula: Zr (NO molecular weight: 3) 45H 2O; Molecular weight: 429.32) be dissolved in the 200ml deionized water, weighing 15～18.5g model is that H/ZSM-5, sial ratio are that 16: 1 molecular sieve powder joins in the mixed solution of manganese nitrate and zirconium nitrate then, in 70～80 ℃ water-bath, reflux and stir 4～6h, carry out ion-exchange;
(2) reflux condensate device that removes in the ion-exchange step continues to add the thermal agitation dipping under 70～80 ℃, until the liquid component evaporate to dryness;
(3) with the dry 12～24h under 90～110 ℃ of the pressed powder behind ion-exchange-dipping, calcine 2～3h down at 550～650 ℃ then.
The NOx catalytically active assessment test of embodiment 1～4 modified molecular screen powder is to carry out on selective catalytic reduction catalysts hot laboratory evaluating apparatus shown in Figure 1.
Air in the steel cylinder 1～3, nitrogen and NOx are that 3L/min, nitrogen are that 3L/min, NOx are that the flow velocity of 4.8mL/min enters respectively in the mixing kettle 7 and mixes by multichannel 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 5mL/min under the control of single channel mass flow 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 infrared gas analyser after 11 mouthfuls of discharges wherein NOx is carried out quantitative analysis.In addition, the ratio of reaction mixture gas rate of flow of fluid and catalyst volume is 60000h in the setting test -1
The test of embodiment 1～4 loaded catalyst NOx catalytically active assessment is what to carry out on SCR catalyst activity engine evaluation system shown in Figure 3.
Its test method is: use the running status of dynamometer machine 17 control test engines 12, make the delivery temperature in the SCR catalyst converter reach the equilibrium temperature of prior setting successively; Meanwhile adjust bypassing exhaust valve 18, the ratio of extraction flow and catalyst volume is 60000h in the SCR catalytic converter to keep -1 Constant displacement pump 13 is with NH 3With the NOx mol ratio be that 1.05: 1 ratio is gone into the liquefied ammonia in the storage tank 14 in the blast pipe through jet 15 metered injections.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 in the gaseous mixture of reaction back is measured by chemiluminescence detector.
Consider integrality of the invention process, embodiment is divided into manganese, zirconium double metal modification and two processes of load coating.
Embodiment 1
(1) modification
5.8g manganese nitrate and 4.3g zirconium nitrate are dissolved in the 200ml deionized water, weighing 17.9g model is that H/ZSM-5, sial ratio are that 16: 1 molecular sieve powder adds in the mixed solution of manganese nitrate and zirconium nitrate then, and in 70 ℃ water-bath, reflux and stir 6h, carry out ion-exchange.Remove reflux condensate device then, continue under 70 ℃, to add the thermal agitation dipping, until the liquid component evaporate to dryness.Pressed powder behind ion-exchange-dipping behind dry 16h under 100 ℃, is calcined 3h down at 550 ℃.
(2) load
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 modified molecular screen powder, γ-Al 2O 3, boehmite, cerium zirconium and polyethylene glycol, and under agitation, with 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 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 up to the approaching pre-determined percentage by weight of the percentage by weight of coating, are calcined 3h with the cordierite honeycomb ceramic carrier after the load coating down at 550 ℃ again.
Is 20～40 purpose particles with the modified molecular screen powder through grinding, compressing tablet, fragmentation, screening.The modified molecular screen particle is carried out atomic absorption spectrophotometer detect, the percetage by weight that measures manganese in the modified molecular screen powder is 6.14%, and the percetage by weight of zirconium is 4.46%.Adopt SCR catalyst activity laboratory evaluation device shown in Figure 1, the performance of modified molecular screen particulate burning purifying NOx is estimated, the result as shown in Figure 2.
In addition, through weighing and calculating, the loaded catalyst floating coat weight of present embodiment accounts for 5.7% of loaded catalyst gross weight.Adopt SCR catalyst activity engine evaluation system shown in Figure 3, estimate the NOx catalytic purification performance of present embodiment loaded catalyst, the result as shown in Figure 4.
Embodiment 2
(1) modification
5.5g manganese nitrate and 8g zirconium nitrate are dissolved in the 200ml deionized water.Weighing 17.2g model is that H/ZSM-5, sial ratio are that 16: 1 molecular sieve powder adds in the mixed solution of manganese nitrate and zirconium nitrate then, and refluxes in 80 ℃ water-bath and stir 4h, carries out ion-exchange.Remove reflux condensate device then, continue under 80 ℃, to add the thermal agitation dipping, until the liquid component evaporate to dryness.Pressed powder behind ion-exchange-dipping behind dry 24h under 90 ℃, is calcined 3h down at 600 ℃.
(2) load
Determine on the 1kg cordierite honeycomb ceramic carrier, to apply 10～11% 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 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 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.
Is 20～40 purpose particles with the modified molecular screen powder through grinding, compressing tablet, fragmentation, screening.The modified molecular screen particle is carried out atomic absorption spectrophotometer detect, the percetage by weight that measures manganese in the modified molecular screen powder is 5.79%, and the percetage by weight of zirconium is 8.25%.Adopt SCR catalyst activity laboratory evaluation device shown in Figure 1, the performance of present embodiment modified molecular screen particulate burning purifying NOx is estimated, the result as shown in Figure 2.
In addition, through weighing and calculating, the loaded catalyst floating coat weight of present embodiment accounts for 10.4% of loaded catalyst gross weight.Adopt SCR catalyst activity engine evaluation system shown in Figure 3, estimate the NOx catalytic purification performance of loaded catalyst in the present embodiment, the result as shown in Figure 4.
Embodiment 3
(1) modification
6.8g manganese nitrate and 10g zirconium nitrate are dissolved in the 200ml deionized water.Weighing 16.5g model is that H/ZSM-5, sial ratio are that 16: 1 molecular sieve powder adds in the mixed solution of manganese nitrate and zirconium nitrate then, and refluxes in 70 ℃ water-bath and stir 6h, carries out ion-exchange.Remove reflux condensate device then, continue under 70 ℃, to add the thermal agitation dipping, until the liquid component evaporate to dryness.Pressed powder behind ion-exchange-dipping behind dry 12h under 110 ℃, is calcined 2h down at 650 ℃.
(2) load
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, 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 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 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.
Is 20～40 purpose particles with the modified molecular screen powder through grinding, compressing tablet, fragmentation, screening.The modified molecular screen particle is carried out atomic absorption spectrophotometer detect, the percetage by weight that measures manganese in the modified molecular screen powder is 7.28%, and the percetage by weight of zirconium is 10.5%.Adopt SCR catalyst activity laboratory evaluation device shown in Figure 1, the performance of the modified molecular screen particulate burning purifying NOx of present embodiment is estimated, the result as shown in Figure 2.
In addition, through weighing and calculating, the loaded catalyst floating coat weight of present embodiment accounts for 9.6% of loaded catalyst gross weight.Adopt SCR catalyst activity engine evaluation system shown in Figure 3, estimate the NOx catalytic purification performance of loaded catalyst in the present embodiment, the result as shown in Figure 4.
Embodiment 4
(1) modification
4.5g manganese nitrate and 14g zirconium nitrate are dissolved in the 200ml deionized water.Weighing 16.1g model is that H/ZSM-5, sial ratio are that 16: 1 molecular sieve powder adds in the mixed solution of described manganese nitrate and zirconium nitrate then, and refluxes in 80 ℃ water-bath and stir 4h, carries out ion-exchange.Remove reflux condensate device then, continue under 80 ℃, to add the thermal agitation dipping, until the liquid component evaporate to dryness.Pressed powder behind ion-exchange-dipping behind dry 12h under 110 ℃, is calcined 2h down at 650 ℃.
(2) load
Determine on the 1kg cordierite honeycomb ceramic carrier, to apply 14～15% 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 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 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.
Is 20～40 purpose particles with the modified molecular screen powder through grinding, compressing tablet, fragmentation, screening.The modified molecular screen particle is carried out atomic absorption spectrophotometer detect, the percetage by weight that measures manganese in the modified molecular screen powder is 4.77%, and the percetage by weight of zirconium is 14.7%.Adopt SCR catalyst activity laboratory evaluation device shown in Figure 1, the performance of the modified molecular screen particulate burning purifying NOx of present embodiment is estimated, the result as shown in Figure 2.
In addition, through weighing and calculating, the loaded catalyst floating coat weight of present embodiment accounts for 14.4% of loaded catalyst gross weight.Adopt SCR catalyst activity engine evaluation system shown in Figure 3, estimate the NOx catalytic purification performance of loaded catalyst in the present embodiment, the result as shown in Figure 4.

Claims (3)

1. manganese zirconium double metal modified molecular screen diesel engine selective catalytic reduction catalysts, it is characterized in that manganese, zr element are to enter in the molecular sieve by liquid ion-exchange-dipping, with the gross weight through the powder catalyst after ion-exchange-dipping modification is benchmark, it is 4.5～7.5% that manganese element accounts for percentage by weight, and it is 4.5～15% that zr element accounts for percentage by weight; Gross weight with the cordierite honeycomb ceramic carrier after the load coating is a benchmark, and the shared percentage by weight of its floating coat is 5～15%.
2. according to the described manganese zirconium double metal of claim 1 modified molecular screen diesel engine selective catalytic reduction catalysts, it is characterized in that adopting urea or ammonia is reducing agent, removes NOx in the diesel exhaust gas by selective catalytic reduction reaction.
3. manganese zirconium double metal modified molecular screen diesel engine selective catalytic reduction catalysts is characterized in that its modification method for preparing may further comprise the steps:
(1) 4～7g manganese nitrate and 4～15g zirconium nitrate are dissolved in the 200ml deionized water, weighing 15～18.5g model is that H/ZSM-5, sial ratio are that 16: 1 molecular sieve powder joins in the mixed solution of manganese nitrate and zirconium nitrate then, in 70～80 ℃ water-bath, reflux and stir 4～6h, carry out ion-exchange;
(2) reflux condensate device that removes in the ion-exchange step continues to add the thermal agitation dipping under 70～80 ℃, until the liquid component evaporate to dryness;
(3) with the pressed powder behind ion-exchange-dipping under 90～110 ℃, dry 12～24h is then at 550～650 ℃ of calcining 2～3h down.
CN2011101189229A 2011-05-10 2011-05-10 Manganese-zirconium dual metal modified selective catalytic reduction catalyst for molecular sieve type diesel engine Expired - Fee Related CN102247886B (en)

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CN105709813A (en) * 2016-01-22 2016-06-29 柳州市海达新型材料科技有限公司 Sulfur-resistant SCR (selective catalytic reduction) catalyst and preparation method thereof
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
CN106762041A (en) * 2016-12-28 2017-05-31 中船动力研究院有限公司 Boat diesel engine catalytic reduction device with NOx trap function
CN107029781A (en) * 2016-02-04 2017-08-11 中触媒新材料股份有限公司 Iron and cerium modified beta-molecular sieve selective reduction catalyst and preparation method and application
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

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CN101972648A (en) * 2010-09-10 2011-02-16 常州大学 Modified Mn-Zr catalyst as well as preparation method and application thereof to preparing dimethyl ether

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105709813A (en) * 2016-01-22 2016-06-29 柳州市海达新型材料科技有限公司 Sulfur-resistant SCR (selective catalytic reduction) catalyst and preparation method thereof
CN107029781A (en) * 2016-02-04 2017-08-11 中触媒新材料股份有限公司 Iron and cerium modified beta-molecular sieve selective reduction catalyst and preparation method and application
CN107029781B (en) * 2016-02-04 2019-08-09 中触媒新材料股份有限公司 Iron and cerium modified beta-molecular sieve selective reduction catalyst and preparation method and application
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
CN106762041A (en) * 2016-12-28 2017-05-31 中船动力研究院有限公司 Boat diesel engine catalytic reduction device with NOx trap function
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

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