CN106622348B - Ferrous modified molecular screen diesel engine selective catalytic reduction catalysts - Google Patents

Ferrous modified molecular screen diesel engine selective catalytic reduction catalysts Download PDF

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CN106622348B
CN106622348B CN201611000833.3A CN201611000833A CN106622348B CN 106622348 B CN106622348 B CN 106622348B CN 201611000833 A CN201611000833 A CN 201611000833A CN 106622348 B CN106622348 B CN 106622348B
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catalyst
molecular sieve
zsm
coating
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CN106622348A (en
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宋崇林
李博
吕刚
朱彦涛
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Tianjin University
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • 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 discloses a kind of ferrous modified molecular screen diesel engine selective catalytic reduction catalysts.Catalyst forms major catalyst, CeO by ferrous iron-La bimetallic-modified ZSM-5 molecular sieve2‑ZrO2Solid solution is co-catalyst, by SiO2、TiO2With γ-Al2O3Form coating basic material, 400 mesh cordierite honeycomb ceramics are catalyst carrier.Preparation process includes: preparation and the determination of supported catalyst raw material dosage, the preparation of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst and the preparation and coating of coating paste.The purification that catalyst is reacted by being packaged in catalytic reducer in diesel SCR catalytic device with the SCR of NOx to realize NOx pollutant in diesel exhaust gas.The present invention not only alleviates the environmental hazard of traditional catalyst, has contained SO3The generation of the secondary pollutions such as derivative also significantly improves the low-temperature SCR catalytic reaction activity of catalyst.

Description

Ferrous modified molecular screen diesel engine selective catalytic reduction catalysts
Technical field
The invention belongs to diesel engine vent gas purification techniques, and in particular to a kind of cleaning internal combustion engines nox in exhaust is urged Agent and preparation method thereof.
Background technique
Diesel engine is compared with other fuels and energy sources, because having outstanding advantages of loading capacity is big, the thermal efficiency is high, durable It is widely used.But due to the NOx (Nitrogen in combustion process there are more diffusion combustion, in diesel exhaust gas Oxides) and particulate matter PM (Particulate Matter) discharge amount is higher, limits it and is requiring to compare to air quality The application in stringent area.Further, since largely discharging NOx and PM in the control of diesel engine in-cylinder combustion, the control effect of discharge is difficult To meet the limitation requirement of state V, VI emission regulation of state to Emissions, exhaust gas aftertreatment techniques have become ultralow The technical measures that discharge diesel engine must use.And selective catalytic reduction SCR (Selective Catalytic Reduction) technology is current most one of efficient, most mature Diesel NOx purification techniques, meanwhile, SCR technology is also diesel oil The machine thermal efficiency provides the space further increased.Major catalyst in SCR catalyst is the core of SCR aftertreatment system, It is most active research and development focus in diesel engines at present SCR technology related fields.
Current commercialized SCR catalyst is mainly V2O5/MoO3(WO3)/TiO2/ ceramic monolith System Catalyst, such Catalyst aims are with ammonia (NH3) or urea be reducing agent SCR react, within the scope of about 300~450 DEG C have it is extremely excellent NOx purifying property.But V2O5Belong to high poison rank poisonous substance, with the long-time service of SCR catalyst, V2O5Inevitably flow It loses and enters environment, human body and animals and plants are damaged.Meanwhile V2O5The low-temperature SCR reacting catalytic performance of base SCR catalyst It is poor, the objective reality that diesel vehicle travel speed is slow, delivery temperature is low in urban road operation is not adapted to.In addition, with other Oxide type catalyst is similar, V2O5Base catalyst has stronger oxidation reaction catalysis performance, can will be in diesel exhaust gas SO2And its derivatives catalysis is oxidized to SO3Derivative, cause equip SCR system diesel engine be easy to appear discharge acid mist and after Processing system easy in inactivation, it is perishable phenomena such as.Due to V2O5Base oxide catalyst as SCR catalyst have it is clearly disadvantageous, Therefore the research and development of Novel SCR catalyst obtain extensive concern.It is studied for many years, industry has been accepted as transition metal modified molecule Sieve-type SCR catalyst is the most potential competitor of novel environmental friendly SCR catalyst, and copper modified zsm-5 zeolite Practical stage is entered with iron modified zsm-5 zeolite type SCR catalyst.But existing Cu, Fe modified molecules sieve-type SCR is urged Metallic element in agent is in most stable of high-valence state, and chemical activity is lower, is unfavorable for accordingly being catalyzed in low-temp reaction The performance of agent catalytic action.On the contrary, if metallic element is at this time using the metal-modified ZSM-5 molecular sieve material of lower valency Relatively unstable state, it is easier to valence state and structure change occur under cryogenic, to realize it to redox reaction Catalytic action.
On the other hand, although the low-temperature SCR catalytic reaction activity of lower valency metal modified molecular screen type catalyst is higher, Its high temperature SCR catalytic reaction activity does not protrude, therefore, for the SCR catalytic reaction active temperature window for extending catalyst of the present invention Mouthful, it is present invention employs the modified method of dual element, i.e., modified simultaneously with lower valency ferro element and lanthanum (La) element of high-valence state ZSM-5 molecular sieve, to realize catalyst of the present invention while there is good high and low temperature SCR reacting catalytic performance.
And with cerium oxide (CeO2), zirconium oxide (ZrO2) be representative transition metal oxide have good Oxygen storage capacity, The supply that active oxygen can be increased in low-temperature oxidation reduction reaction, urges low-temperature oxidation reduction reaction to enhance catalyst Change activity.Therefore, the present invention passes through addition CeO2-ZrO2The method of solid solution co-catalyst further increases Novel SCR catalysis The low-temperature SCR reacting catalytic performance of agent.
To sum up, for existing V2O5The deficiency of base SCR catalyst, the invention proposes ferrous elements and La element bimetallic Modified zsm-5 zeolite is major catalyst, CeO2-ZrO2Solid solution is co-catalyst, ferrous modified molecular screen diesel engine choosing Selecting property catalytic reduction catalysts and preparation method thereof.
Summary of the invention
It is an object of the present invention to provide it is a kind of suitable for diesel engine, with ferrous iron-La bimetallic-modified ZSM-5 molecular sieve As major catalyst, CeO2-ZrO2Selective catalytic reduction catalysts and preparation method thereof of the solid solution as co-catalyst.
The technical solution adopted to achieve the purpose of the present invention is: ferrous modified molecular screen diesel engine selective catalysis Reducing catalyst includes ferrous iron-La bimetallic-modified ZSM-5 molecular sieve, CeO2-ZrO2Solid solution, SiO2、TiO2、γ-Al2O3 And 400 mesh cordierite honeycomb ceramics carriers, it further include n-hexane, polyethylene glycol, nitric acid, sodium hydroxide solution, glacial acetic acid, urine Plain solution etc..Major catalyst is formed by ferrous iron-La bimetallic-modified ZSM-5 molecular sieve, wherein Fe element and La element respectively with FeO oligomer and La2O3The form of oligomer is dispersed in the surface and micropore of ZSM-5 molecular sieve, and FeO, La2O3And The mass percent of ZSM-5 molecular sieve is respectively as follows: 5~12%/3~8%/92~80%, and the sum of mass percent is 100%.
By CeO2-ZrO2Solid solution forms co-catalyst, CeO2And ZrO2Mass percent be respectively as follows: 70~80%/30 ~20%.
By SiO2、TiO2With γ-Al2O3Collectively constitute the coating basic material of catalyst, SiO2、TiO2With γ-Al2O3's Mass percent is respectively as follows: 20~30%/70~40%/10~30%.
The major catalyst that is made of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve, by CeO2-ZrO2Solid solution composition helps Catalyst, by SiO2、TiO2With γ-Al2O3The coating basic material of composition, collectively constitutes catalyst coatings.Wherein major catalyst, The mass percent of co-catalyst and coating basic material is respectively as follows: 10~20%/10~20%/80~60%.
Ferrous modified molecular screen diesel engine is formed with 400 mesh cordierite honeycomb ceramics carriers by catalyst coatings selectively to urge Change reducing catalyst, catalyst coatings are coated on the cordierite honeycomb by carrier of the cordierite honeycomb ceramic carrier as catalyst On ceramic monolith, the mass percent of catalyst coatings and the cordierite honeycomb ceramic carrier is respectively as follows: 10~30%/90~ 70%.
The sum of above-mentioned all constituent elements or the mass percent of component are 100%.
The preparation of ferrous modified molecular screen diesel engine selective catalytic reduction catalysts and carrying method, concrete technology packet Include following 4 steps:
(1) preparation and the determination of supported catalyst raw material dosage；
(2) preparation of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst；
(3) preparation of coating paste；
(4) coating of coating paste.
The features of the present invention and its beneficial effect of generation are: using ferrous iron-La bimetallic-modified ZSM-5 molecular sieve main reminder Agent substitutes the V in conventional diesel engine SCR catalyst2O5Major catalyst not only alleviates the environmental hazard of traditional catalyst, SO is contained3The generation of the secondary pollutions such as derivative also significantly improves the low-temperature SCR catalytic reaction activity of catalyst, and High temperature SCR reacting catalytic performance is realized not deteriorate.And the CeO with good oxygen storage capacity2-ZrO2Solid solution co-catalyst Addition, further enhances the low-temperature SCR reacting catalytic performance of catalyst entirety.In addition, SiO in coating basic material2With γ- Al2O3Addition, further promote storage oxygen compound Oxygen storage capacity raising and coating stability and firmness enhancing.
Detailed description of the invention
Fig. 1 is SCR catalyst catalytic performance engine evaluation system schematic diagram.
Wherein: 1- dynamometer machine；2- shaft coupling；3- tests diesel engine；4- inlet air flow meter；5- air inlet air conditioning；6- reducing agent Spray electronic control system；7- exhaust sampling port A；8- temperature sensor A；9- urea storage tank；10- reducing agent jet pump；11- is also Former agent nozzle；12- temperature sensor B；13- selective catalytic reduction catalyst；14- temperature sensor C；15- exhaust sampling port B；16- axial flow blower；17- engine exhaust analyzer；18- exhaust gas sampling switches clack box.
Fig. 2 be using SCR catalyst catalytic performance engine evaluation system, SCR catalyst central temperature be 250 DEG C, Air speed is 30000h-1Steady state condition when, during the lower diesel exhaust gas SCR of Examples 1 to 5 prepared catalyst catalysis reacts, The purification efficiency of NOx.
Fig. 3 be using SCR catalyst catalytic performance engine evaluation system, SCR catalyst central temperature be 350 DEG C, Air speed is 60000h-1Steady state condition when, during the lower diesel exhaust gas SCR of Examples 1 to 5 prepared catalyst catalysis reacts, The purification efficiency of NOx.
Fig. 4 is to utilize SCR catalyst catalytic performance engine evaluation system, in the circulation ESC test of European steady state test, In diesel exhaust gas SCR reaction under the catalysis of Examples 1 to 5 prepared catalyst, the purification efficiency of NOx.
Specific embodiment
Below in conjunction with attached drawing and by specific embodiment, technical scheme of the present invention will be further described.It needs Illustrate be the embodiment be it is narrative, and non-limiting, the content that is covered of the present invention is not limited to following implementations Example.
Ferrous modified molecular screen diesel engine selective catalytic reduction catalysts include ferrous iron-La (lanthanum) bimetallic-modified ZSM-5 molecular sieve, CeO2(cerium oxide)-ZrO2(zirconium oxide) solid solution, SiO2(silica), TiO2(titanium dioxide), γ- Al2O3(aluminum oxide) and 400 mesh cordierite honeycomb ceramics carriers etc..By ferrous iron-La bimetallic-modified ZSM-5 molecular sieve Major catalyst is formed, wherein Fe (iron) element and La element are respectively with FeO (ferrous oxide) oligomer and La2O3(lanthana) is low The form of polymers is dispersed in the surface and micropore of ZSM-5 molecular sieve.FeO,La2O3And the quality percentage of ZSM-5 molecular sieve Than being respectively as follows: 5~12%/3~8%/92~80%.
By CeO2-ZrO2Solid solution forms co-catalyst, CeO2And ZrO2Mass percent are as follows: 70~80%/30~ 20%.By SiO2、TiO2With γ-Al2O3Collectively constitute the coating basic material of catalyst, SiO2、TiO2With γ-Al2O3Quality Percentage is respectively as follows: 20~30%/70~40%/10~30%.SiO in its floating coat basic material2From as coating The SiO generated after the silica solution calcining of adhesive2, TiO2From pure matter TiO2Powder, γ-Al2O3From pure matter γ-Al2O3Powder Body.
The major catalyst that is made of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve, by CeO2-ZrO2Solid solution composition helps Catalyst, by SiO2、TiO2With γ-Al2O3The coating basic material of composition, collectively constitutes catalyst coatings, wherein major catalyst, The mass percent of co-catalyst and coating basic material is respectively as follows: 10~20%/10~20%/80~60%.
Ferrous modified molecular screen diesel engine is formed with 400 mesh cordierite honeycomb ceramics carriers by catalyst coatings selectively to urge Change reducing catalyst, carrier of the 400 mesh cordierite honeycomb ceramics carriers as catalyst, and needs for catalyst coatings to be coated on On 400 mesh cordierite honeycomb ceramics carriers, and the mass percent of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers is distinguished Are as follows: 10~30%/90~70%.
The sum of above-mentioned all constituent elements or the mass percent of component are 100%.
The preparation of ferrous modified molecular screen diesel engine selective catalytic reduction catalysts and carrying method, specifically include with Lower step:
(1) preparation and the determination of supported catalyst raw material dosage
According to aforementioned each proportion, separately design out FeO in major catalyst ferrous iron-La bimetallic-modified ZSM-5 molecular sieve, La2O3With the mass percent of ZSM-5 molecular sieve；CeO in co-catalyst2And ZrO2Mass percent；Major catalyst is helped and is urged The mass percent of agent and coating basic material；SiO in coating basic material2、TiO2With γ-Al2O3Mass percent； The mass percent range of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers；And planned allocation coating paste produces The quality of catalyst coatings.
According to fixed each ratio, FeO, the La consumed needed for preparing catalyst is calculated separately out2O3, ZSM-5 molecule Sieve, CeO2、ZrO2, the generated SiO of silica solution2, pure matter TiO2, pure matter γ-Al2O3Quality.In conjunction with every 198.8g FeCl2·4H2O prepares 71.8g FeO, every 866.0g La (NO3)3·6H2O prepares 325.8g La2O3, every 434.1g Ce (NO3)3·6H2O prepares 172.1g CeO2, every 429.3g Zr (NO3)4·5H2O prepares 123.2g ZrO2Ratio, calculate Prepare the FeCl consumed needed for catalyst2·4H2O、La(NO3)3·6H2O、Ce(NO3)3·6H2O、Zr(NO3)4·5H2The matter of O Amount.According to SiO in silica solution2Actual mass percentages calculate prepares coating slurries needed for consume silica solution quality； According still further to the ratio of the corresponding 200~300ml n-hexane of every 100g ferrous iron-La bimetallic-modified ZSM-5 molecular sieve, preparation is calculated The volume of the n-hexane consumed needed for ferrous iron-La bimetallic-modified ZSM-5 molecular sieve.According to every 100g catalyst coatings need 5~ The ratio of polyethylene glycol and 25~50g nitric acid that 15g average molecular weight is 20000, calculates and disappears needed for prepares coating slurry The polyethylene glycol of consumption and the quality of nitric acid.
(2) preparation of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst
Weigh the FeCl for having determined that quality2·4H2O、La(NO3)3·6H2O and ZSM-5 molecular sieve pour into them together It has determined that in the n-hexane of volume, 2~4h of strong stirring is under He protective atmosphere to form uniform suspension, then still in He Uniform suspension is evaporated n-hexane in 60~70 DEG C of water-baths under protective atmosphere.It will be evaporated the powder after liquid again in roaster In, under He protective atmosphere, 500 DEG C are warming up to the speed of 5~10 DEG C/min, and still roast at 500 DEG C under He protective atmosphere Burn 4~6h.After sample is cooling, is crushed, is ground into that partial size is spare less than the little particle of 100 mesh, this is ferrous iron-La pairs Metal-modified ZSM-5 molecular sieve major catalyst.
(3) preparation of coating paste
By ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst obtained and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder, pure matter TiO2Powder, silica solution, polyethylene glycol, nitric acid are added to matter Amount be equivalent to plan prepare in 10~15 times of catalyst coatings gross mass of deionized water, homogeneous slurry is sufficiently stirred into.With The pH value that the sodium hydroxide solution or glacial acetic acid of 1mol/L adjusts homogeneous slurry is 3~4.By homogeneous slurry on wet grinding mill It is ground to D50 partial size to be in 1.0~1.2 micron ranges, then again stirs the homogeneous slurry after grinding at 60~80 DEG C 16~for 24 hours to get arrive coating paste.
(4) coating of coating paste
Design the quality of the 400 mesh cordierite honeycomb ceramics carrier for the catalyst coatings of being applied；It weighs and has determined that matter The 400 mesh cordierite honeycomb ceramics carrier of cylinder of amount, ceramic monolith is immersed in 60~80 DEG C of the coating paste, and Guarantee that the upper surface of ceramic monolith is slightly above slurry liquid level.After slurries promote all ducts full of carrier naturally, by carrier It is taken out from slurry, blows residual fluid in duct off, dry 6~12h at 80~110 DEG C, then 2 are calcined at 500~600 DEG C ~4h.Above-mentioned dipping, drying and calcination process 2~3 times are repeated to get to ferrous modified molecular screen diesel engine selective catalysis Reducing catalyst.
The ferrous modified molecular screen diesel engine selective catalytic reduction catalysts obtained by above-mentioned steps are pacified after encapsulated Loaded in diesel engine exhaust port, pass through catalysis NOx and reducing agent (NH3Or urea) SCR reaction purification diesel engine exhaust in NOx pollutant.
Embodiment 1
(1) preparation and the determination of supported catalyst raw material dosage
In the major catalyst ferrous iron-La bimetallic-modified ZSM-5 molecular sieve for designing 1 prepared catalyst of embodiment, FeO, La2O3It is respectively as follows: 12%:8%:80% with the mass percent of ZSM-5 molecular sieve.CeO in co-catalyst2And ZrO2Quality Percentage is respectively as follows: 80%/20%.The mass percent of major catalyst, co-catalyst and coating basic material are as follows: 10%: 10%:80%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively as follows: 30%:40%:30%. It is 20000 polyethylene glycol and 50g nitric acid that every 100g catalyst coatings, which need 10g average molecular weight,；The double gold of every 100g ferrous iron-La Belong to modified zsm-5 zeolite and needs 300ml n-hexane.
Raw material dosage needed for calculating preparation 2000g catalyst coatings according to conversion scale: frerrous chloride [FeCl2·4H2O] 66.5g, lanthanum nitrate [La (NO3)3·6H2O] 42.5g, ZSM-5 molecular sieve 160g, cerous nitrate [Ce (NO3)3·6H2O]403.6g、 Zirconium nitrate [Zr (NO3)4·5H2O] 139.4g, n-hexane 600ml, nitric acid 1000g, the polyethylene glycol that average molecular weight is 20000 The generated SiO of 200g, silica solution2480g, pure matter TiO2Powder 640g, pure matter γ-Al2O3Powder 480g.SiO in silica solution2's Mass content is 25%, thus calculates and needs silica solution 1920g.
(2) preparation of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst
Weigh the FeCl for having determined that quality2·4H2O、La(NO3)3·6H2O and ZSM-5 molecular sieve pour into them together It has determined that in the n-hexane of volume, under He protective atmosphere then strong stirring 4h is still protected in He with forming uniform suspension Uniform suspension is evaporated n-hexane in 65 DEG C of water-baths under shield atmosphere.It will be evaporated the powder after liquid again in roaster, He Under protective atmosphere, 500 DEG C are warming up to 5 DEG C/min, and in 500 DEG C of roasting 6h still under He protective atmosphere.After sample is cooling, It crushed, be ground into that partial size is spare less than the little particle of 100 mesh, this is ferrous iron-La bimetallic-modified ZSM-5 molecular sieve master Catalyst.
(3) preparation of coating paste
By ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst obtained and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder, pure matter TiO2Powder, silica solution, polyethylene glycol, nitric acid are added In 20000g deionized water, homogeneous slurry is sufficiently stirred into.It is homogenized with the sodium hydroxide solution of 1mol/L or glacial acetic acid adjusting The pH value of liquid is 3~4.Homogeneous slurry is ground to D50 partial size to be in 1.0~1.2 micron ranges on wet grinding mill, so Homogeneous slurry after grinding is stirred to 20h at 70 DEG C again afterwards to get coating paste is arrived.
(4) coating of coating paste
The cylindrical 400 mesh cordierite honeycomb ceramics carriers of 1kg are weighed, the coating that honeycomb ceramic carrier is immersed in 70 DEG C is starched In material, and guarantee that the upper surface of ceramic monolith is slightly above slurry liquid level.After slurries promote all ducts full of carrier naturally, Carrier is taken out from slurry, blows residual fluid in duct off, the dry 12h at 90 DEG C, then 2h is calcined at 600 DEG C.It repeats Above-mentioned dipping, drying and calcination process 3 times are to get to ferrous modified molecular screen diesel engine selective catalytic reduction catalysts.
The ferrous modified molecular screen diesel engine selective catalysis obtained using 1 catalyst preparation carrying method of embodiment is also Raw catalyst, the mass percent of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers are as follows: 28~30%/72~70%, matter Measuring the sum of percentage is 100%.
Embodiment 2
(1) preparation and the determination of supported catalyst raw material dosage
In the major catalyst ferrous iron-La bimetallic-modified ZSM-5 molecular sieve for designing 2 prepared catalyst of embodiment, FeO, La2O3It is respectively as follows: 5%:3%:92% with the mass percent of ZSM-5 molecular sieve.CeO in co-catalyst2And ZrO2Quality hundred Ratio is divided to be respectively as follows: 70%/30%.The mass percent of major catalyst, co-catalyst and coating basic material are as follows: 20%:20%: 60%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively as follows: 20%:70%:10%.Often It is 20000 polyethylene glycol and 25g nitric acid that 100g catalyst coatings, which need 15g average molecular weight,；Every 100g ferrous iron-La bimetallic Modified zsm-5 zeolite needs 200ml n-hexane.
Raw material dosage needed for calculating preparation 2000g catalyst coatings according to conversion scale: FeCl2·4H2O 55.4g、La (NO3)3·6H2O 31.9g, ZSM-5 molecular sieve 368g, Ce (NO3)3·6H2O 706.3g、Zr(NO3)4·5H2O 418.1g、 N-hexane 800ml, nitric acid 500g, average molecular weight by 20000 Liquid Macrogol g, silica solution generate SiO2It is 240g, pure Matter TiO2Powder 840g, pure matter γ-Al2O3Powder 120g.SiO in silica solution2Mass content be 25%, thus calculate need Want silica solution 960g.
(2) preparation of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst
Weigh the FeCl for having determined that quality2·4H2O、La(NO3)3·6H2O and ZSM-5 molecular sieve pour into them together It has determined that in the n-hexane of volume, under He protective atmosphere then strong stirring 2h is still protected in He with forming uniform suspension Uniform suspension is evaporated n-hexane in 60 DEG C of water-baths under shield atmosphere.It will be evaporated the powder after liquid again in roaster, He Under protective atmosphere, 500 DEG C are warming up to 10 DEG C/min, and still roast 4h at 500 DEG C under He protective atmosphere.It is cooling to sample Afterwards, it crushed, be ground into that partial size is spare less than the little particle of 100 mesh, this is ferrous iron-La bimetallic-modified ZSM-5 molecule Sieve major catalyst.
(3) preparation of coating paste
By ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst obtained and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder, pure matter TiO2Powder, silica solution, polyethylene glycol, nitric acid are added In 30000g deionized water, homogeneous slurry is sufficiently stirred into.It is homogenized with the sodium hydroxide solution of 1mol/L or glacial acetic acid adjusting The pH value of liquid is 3~4.Homogeneous slurry is ground to D50 partial size to be in 1.0~1.2 micron ranges on wet grinding mill, so The homogeneous slurry after grinding is stirred at 60 DEG C again afterwards for 24 hours to get to coating paste.
(4) coating of coating paste
The cylindrical 400 mesh cordierite honeycomb ceramics carriers of 1kg are weighed, the coating that honeycomb ceramic carrier is immersed in 60 DEG C is starched In material, and guarantee that the upper surface of ceramic monolith is slightly above slurry liquid level.After slurries promote all ducts full of carrier naturally, Carrier is taken out from slurry, blows residual fluid in duct off, the dry 6h at 110 DEG C, then 4h is calcined at 500 DEG C.It repeats Above-mentioned dipping, drying and calcination process 3 times are to get to ferrous modified molecular screen diesel engine selective catalytic reduction catalysts.
The ferrous modified molecular screen diesel engine selective catalysis obtained using 2 catalyst preparation carrying method of embodiment is also Raw catalyst, the mass percent of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers are as follows: 19~21%/81~79%, matter Measuring the sum of percentage is 100%.
Embodiment 3
(1) preparation and the determination of supported catalyst raw material dosage
In the major catalyst ferrous iron-La bimetallic-modified ZSM-5 molecular sieve for designing 3 prepared catalyst of embodiment, FeO, La2O3It is respectively as follows: 10%:5%:85% with the mass percent of ZSM-5 molecular sieve.CeO in co-catalyst2And ZrO2Quality Percentage is respectively as follows: 80%/20%.The mass percent of major catalyst, co-catalyst and coating basic material is respectively as follows: 20%:15%:65%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively as follows: 25%:45%: 30%.It is 20000 polyethylene glycol and 30g nitric acid that every 100g catalyst coatings, which need 5g average molecular weight,；Every 100g ferrous iron-La Bimetallic-modified ZSM-5 molecular sieve needs 250ml n-hexane.
Raw material dosage needed for calculating preparation 2000g catalyst coatings according to conversion scale: FeCl2·4H2O 110.8g、La (NO3)3·6H2O 53.2g, ZSM-5 molecular sieve 340g, Ce (NO3)3·6H2O 605.4g、Zr(NO3)4·5H2O 209.1g、 N-hexane 1000ml, nitric acid 600g, average molecular weight by 20000 polyethylene glycol 100g, silica solution generate SiO2 325g、 Pure matter TiO2Powder 585g, pure matter γ-Al2O3Powder 390g.SiO in silica solution2Mass content be 25%, thus calculate Need silica solution 1300g.
(2) preparation of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst
Weigh the FeCl for having determined that quality2·4H2O、La(NO3)3·6H2O and ZSM-5 molecular sieve pour into them together It has determined that in the n-hexane of volume, under He protective atmosphere then strong stirring 3h is still protected in He with forming uniform suspension The uniform suspension is evaporated n-hexane in 70 DEG C of water-baths under shield atmosphere.It will be evaporated the powder after liquid again in roaster In, under He protective atmosphere, 500 DEG C are warming up to 5 DEG C/min, and still roast 6h at 500 DEG C under He protective atmosphere.To sample It after cooling, crushed, be ground into that partial size is spare less than the little particle of 100 mesh, this is ferrous iron-La bimetallic-modified ZSM-5 Molecular sieve major catalyst.
(3) preparation of coating paste
By ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst obtained and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder, pure matter TiO2Powder, silica solution, polyethylene glycol, nitric acid are added In 25000g deionized water, homogeneous slurry is sufficiently stirred into.It is homogenized with the sodium hydroxide solution of 1mol/L or glacial acetic acid adjusting The pH value of liquid is 3~4.Homogeneous slurry is ground to D50 partial size to be in 1.0~1.2 micron ranges on wet grinding mill, so Homogeneous slurry after grinding is stirred to 16h at 80 DEG C again afterwards to get coating paste is arrived.
(4) coating of coating paste
The cylindrical 400 mesh cordierite honeycomb ceramics carriers of 1kg are weighed, the honeycomb ceramic carrier is immersed in 80 DEG C of institute It states in coating paste, and guarantees that the upper surface of ceramic monolith is slightly above slurry liquid level.Promote the institute full of carrier naturally to slurries After having duct, carrier is taken out from slurry, blows residual fluid in duct off, the dry 10h at 100 DEG C, then forged at 500 DEG C Burn 4h.Repeat above-mentioned dipping, drying and calcination process 3 times to get to ferrous modified molecular screen diesel engine selective catalysis also Raw catalyst.
The ferrous modified molecular screen diesel engine selective catalysis obtained using 3 catalyst preparation carrying method of embodiment is also Raw catalyst, the mass percent of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers are as follows: 25~27%/75~73%, matter Measuring the sum of percentage is 100%.
Embodiment 4
(1) preparation and the determination of supported catalyst raw material dosage
In the major catalyst ferrous iron-La bimetallic-modified ZSM-5 molecular sieve for designing 4 prepared catalyst of embodiment, FeO, La2O3It is respectively as follows: 12%:8%:80% with the mass percent of ZSM-5 molecular sieve.CeO in co-catalyst2And ZrO2Quality Percentage is respectively as follows: 70%/30%.The mass percent of major catalyst, co-catalyst and coating basic material is respectively as follows: 15%:15%:70%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively as follows: 25%:50%: 25%.It is 20000 polyethylene glycol and 30g nitric acid that every 100g catalyst coatings, which need 10g average molecular weight,；Every 100g ferrous iron- La bimetallic-modified ZSM-5 molecular sieve needs 250ml n-hexane.
Raw material dosage needed for calculating preparation 2000g catalyst coatings according to conversion scale: FeCl2·4H2O 99.7g、La (NO3)3·6H2O 63.8g, ZSM-5 molecular sieve 240g, Ce (NO3)3·6H2O 529.7g、Zr(NO3)4·5H2O 313.6g、 N-hexane 750ml, nitric acid 600g, average molecular weight by 20000 polyethylene glycol 200 g, silica solution generate SiO2It is 350g, pure Matter TiO2Powder 750g, pure matter γ-Al2O3Powder 350g.SiO in silica solution2Mass content be 25%, thus calculate need Want silica solution 1400g.
(2) preparation of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst
Weigh the FeCl for having determined that quality2·4H2O、La(NO3)3·6H2O and ZSM-5 molecular sieve pour into them together It has determined that in the n-hexane of volume, under He protective atmosphere then strong stirring 3h is still protected in He with forming uniform suspension The uniform suspension is evaporated n-hexane in 65 DEG C of water-baths under shield atmosphere.It will be evaporated the powder after liquid again in roaster In, under He protective atmosphere, 500 DEG C are warming up to 8 DEG C/min, and still roast 6h at 500 DEG C under He protective atmosphere.To sample It after cooling, crushed, be ground into that partial size is spare less than the little particle of 100 mesh, this is ferrous iron-La bimetallic-modified ZSM-5 Molecular sieve major catalyst.
(3) preparation of coating paste
By ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst obtained and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder, pure matter TiO2Powder, silica solution, polyethylene glycol, nitric acid are added In 25000g deionized water, homogeneous slurry is sufficiently stirred into.It is homogenized with the sodium hydroxide solution of 1mol/L or glacial acetic acid adjusting The pH value of liquid is 3~4.Homogeneous slurry is ground to D50 partial size to be in 1.0~1.2 micron ranges on wet grinding mill, so The homogeneous slurry after grinding is stirred at 60 DEG C again afterwards for 24 hours to get to coating paste.
(4) coating of coating paste
The cylindrical 400 mesh cordierite honeycomb ceramics carriers of 1kg are weighed, the coating that honeycomb ceramic carrier is immersed in 60 DEG C is starched In material, and guarantee that the upper surface of ceramic monolith is slightly above slurry liquid level.After slurries promote all ducts full of carrier naturally, Carrier is taken out from slurry, blows residual fluid in duct off, the dry 6h at 110 DEG C, then 4h is calcined at 500 DEG C.It repeats Above-mentioned dipping, drying and calcination process 2 times are to get to ferrous modified molecular screen diesel engine selective catalytic reduction catalysts.
The ferrous modified molecular screen diesel engine selective catalysis obtained using 4 catalyst preparation carrying method of embodiment is also Raw catalyst, the mass percent of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers are as follows: 15~17%/85~83%, matter Measuring the sum of percentage is 100%.
Embodiment 5
(1) preparation and the determination of supported catalyst raw material dosage
In the major catalyst ferrous iron-La bimetallic-modified ZSM-5 molecular sieve for designing 5 prepared catalyst of embodiment, FeO, La2O3It is respectively as follows: 10%:5%:85% with the mass percent of ZSM-5 molecular sieve.CeO in co-catalyst2And ZrO2Quality Percentage are as follows: 80%/20%.The mass percent of major catalyst, co-catalyst and coating basic material is respectively as follows: 20%: 20%:60%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively as follows: 30%:50%:20%. It is 20000 polyethylene glycol and 30g nitric acid that every 100g catalyst coatings, which need 10g average molecular weight,；The double gold of every 100g ferrous iron-La Belong to modified zsm-5 zeolite and corresponds to 250ml n-hexane.
Raw material dosage needed for calculating preparation 2000g catalyst coatings according to conversion scale: FeCl2·4H2O 110.8g、La (NO3)3·6H2O 53.2g, ZSM-5 molecular sieve 340g, Ce (NO3)3·6H2O 807.2g、Zr(NO3)4·5H2O 278.8g、 N-hexane 1000ml, nitric acid 600g, average molecular weight by 20000 polyethylene glycol 200 g, silica solution generate SiO2 360g、 Pure matter TiO2Powder 600g, pure matter γ-Al2O3Powder 240g.SiO in silica solution2Mass content be 25%, thus calculate Need silica solution 1440g.
(2) preparation of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst
Weigh the FeCl for having determined that quality2·4H2O、La(NO3)3·6H2O and ZSM-5 molecular sieve pour into them together It has determined that in the n-hexane of volume, under He protective atmosphere then strong stirring 4h is still protected in He with forming uniform suspension The uniform suspension is evaporated n-hexane in 65 DEG C of water-baths under shield atmosphere.It will be evaporated the powder after liquid again in roaster In, under He protective atmosphere, 500 DEG C are warming up to 5 DEG C/min, and still roast 6h at 500 DEG C under He protective atmosphere.To sample It after cooling, crushed, be ground into that partial size is spare less than the little particle of 100 mesh, this is ferrous iron-La bimetallic-modified ZSM-5 Molecular sieve major catalyst.
(3) preparation of coating paste
By ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst obtained and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder, pure matter TiO2Powder, silica solution, polyethylene glycol, nitric acid are added In 30000g deionized water, homogeneous slurry is sufficiently stirred into.It is homogenized with the sodium hydroxide solution of 1mol/L or glacial acetic acid adjusting The pH value of liquid is 3~4.Homogeneous slurry is ground to D50 partial size to be in 1.0~1.2 micron ranges on wet grinding mill, so Homogeneous slurry after grinding is stirred to 20h at 70 DEG C again afterwards to get coating paste is arrived.
(4) coating of coating paste
The cylindrical 400 mesh cordierite honeycomb ceramics carriers of 1kg are weighed, the coating that honeycomb ceramic carrier is immersed in 70 DEG C is starched In material, and guarantee that the upper surface of ceramic monolith is slightly above slurry liquid level.After slurries promote all ducts full of carrier naturally, Carrier is taken out from slurry, blows residual fluid in duct off, the dry 9h at 100 DEG C, then 3h is calcined at 550 DEG C.It repeats Above-mentioned dipping, drying and calcination process 2 times are to get to ferrous modified molecular screen diesel engine selective catalytic reduction catalysts.
The ferrous modified molecular screen diesel engine selective catalysis obtained using 5 catalyst preparation carrying method of embodiment is also Raw catalyst, the mass percent of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers are as follows: 11~13%/89~87%, matter Measuring the sum of percentage is 100%.
Using SCR catalyst catalytic performance engine evaluation system shown in FIG. 1, urge prepared by the embodiment 1-5 Urea-SCR the reacting catalytic performance of agent is evaluated.It needs for embodiment 1-5 prepared catalyst to be respectively cut, respectively before test From being combined into 5L cylinder integral catalyzer, and processing is packaged to the cylindrical integral catalyzer for cutting, being combined into. Test method are as follows:
(1) steady state condition is tested: using dynamometer machine 1 and 2 Control experiment diesel engine of shaft coupling (CY4102 diesel engine) 3 Torque and revolving speed, successively adjust extraction flow and the ratio of catalyst volume is respectively 30000h-1And 60000h-1, and successively control The temperature of 13 central point of SCR catalyst processed is respectively 250 DEG C and 350 DEG C, carries out urea-SCR and reacts purified treatment.
In test, electronic control system 6 is sprayed by reducing agent and adjusts reducing agent jet pump 10 and reductant nozzle 11 Reducing agent jet velocity guarantees that reducing agent (urea liquid) decomposes obtained NH3Substance withdrawl syndrome and exhaust in NOx object The ratio of the amount concentration of matter is 1:1.
SCR catalyst handles forward and backward diesel exhaust gas respectively through exhaust sampling port A7 and exhaust sampling port B15 and row Gas sampling switching clack box 18 enters engine exhaust analyzer 17 and carries out NOx concentration analysis, and the gas after NOx is analyzed passes through Axial flow blower 16 gives off laboratory.Exhaust temperature before and after temperature sensor A8 and temperature sensor C14 measurement SCR catalyst Degree, and the temperature at temperature sensor B12 measurement SCR catalyst center.The measured temperature and inlet air flow of 3 temperature sensors The charge flow rate measured value of meter 4 provides feedback parameter for the control strategy that reducing agent sprays electronic control system 6.
Using SCR catalyst catalytic performance engine evaluation system, SCR catalyst central temperature is 250 DEG C, air speed is 30000h-1When and SCR catalyst central temperature be 350 DEG C, air speed 60000h-1When, Examples 1 to 5 prepared catalyst In urea-SCR reaction under catalysis, the purification efficiency difference of NOx is as shown in Figures 2 and 3.
(2) ESC is tested: using SCR catalyst catalytic performance engine evaluation system, and GB according to national standards 17691-2005 " automobile-used compression-ignited, gaseous fuel spark-ignition engine and automobile exhaust pollutant discharge limit value and measurement method (Chinese III, IV, V stage) " specified in ESC testing regulations, evaluation Examples 1 to 5 prepared catalyst to test diesel engine The clean-up effect of NOx pollutant, evaluation result are as shown in Figure 4 in tail gas.
Ferrous modified molecular screen diesel engine selective catalytic reduction catalysts, have good low temperature reacting catalytic performance and Wide active temperature windows add CeO2-ZrO2Solid solution as co-catalyst, urge by the low-temperature SCR reaction that can enhance catalyst entirety Change performance.SiO is added2With γ-Al2O3, can promote the raising of coating storage oxygen compound Oxygen storage capacity, and enhance the steady of coating Qualitative and firmness.

Claims (3)

1. ferrous modified molecular screen diesel engine selective catalytic reduction catalysts, it is characterised in that: changed by ferrous iron-La bimetallic Property ZSM-5 molecular sieve form major catalyst, wherein Fe element and La element are respectively with FeO oligomer and La2O3The form of oligomer It is dispersed in the surface and micropore of ZSM-5 molecular sieve, and FeO, La2O3And the mass percent difference of ZSM-5 molecular sieve Are as follows: 5~12%/3~8%/92~80%, the sum of mass percent is 100%；
By CeO2-ZrO2Solid solution forms co-catalyst, and CeO2And ZrO2Mass percent be respectively as follows: 70~80%/30 ~20%, the sum of mass percent is 100%；
By SiO2、TiO2With γ-Al2O3Collectively constitute the coating basic material of catalyst, and SiO2、TiO2With γ-Al2O3Matter Amount percentage is respectively as follows: 20~30%/70~40%/10~30%, and the sum of mass percent is 100%；Meanwhile coating basis SiO in material2The SiO generated after the silica solution calcining as binders for coatings2, the TiO2From pure matter TiO2Powder Body, the γ-Al2O3From pure matter γ-Al2O3Powder;
The major catalyst that is made of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve, by CeO2-ZrO2The co-catalysis of solid solution composition Agent, by SiO2、TiO2With γ-Al2O3The coating basic material of composition, collectively constitutes catalyst coatings, and wherein major catalyst, help The mass percent of catalyst and coating basic material is respectively as follows: 10~20%/10~20%/80~60%, mass percent The sum of be 100%；
Ferrous modified molecular screen diesel engine selective catalysis is formed also by catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers Raw catalyst, carrier of the 400 mesh cordierite honeycomb ceramics carriers as catalyst, and need catalyst coatings coated on 400 mesh On cordierite honeycomb ceramic carrier, and the mass percent of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers is respectively as follows: 10 ~30%/90~70%, the sum of mass percent is 100%.
2. a kind of preparation of ferrous modified molecular screen diesel engine selective catalytic reduction catalysts described in accordance with the claim 1 Method, it is characterized in that: specific preparation method the following steps are included:
(1) determination of catalyst raw material dosage is prepared
It is respectively matched according to determined by claim 1, separately designs out major catalyst ferrous iron-La bimetallic-modified ZSM-5 molecule FeO, La in sieve2O3With the mass percent of ZSM-5 molecular sieve；CeO in co-catalyst2And ZrO2Mass percent；Main catalytic Agent, co-catalyst and coating basic material mass percent；SiO in coating basic material2、TiO2With γ-Al2O3Quality Percentage；The mass percent range of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers；And planned allocation coating paste Produce the quality of catalyst coatings；
FeO, La of consumption needed for preparing catalyst are calculated separately out according to fixed each ratio2O3, ZSM-5 molecular sieve, CeO2、ZrO2, the generated SiO of silica solution2, pure matter TiO2, pure matter γ-Al2O3Quality；In conjunction with every 198.8 g FeCl2· 4H2O prepares 71.8g FeO, every 866.0g La (NO3)3·6H2O prepares 325.8g La2O3, every 434.1g Ce (NO3)3· 6H2O prepares 172.1g CeO2, every 429.3g Zr (NO3)4·5H2O prepares 123.2g ZrO2Ratio, calculate preparation and urge The FeCl consumed needed for agent2·4H2O、La(NO3)3·6H2O、Ce(NO3)3·6H2O、Zr(NO3)4·5H2The quality of O；According to SiO in silica solution2Actual mass percentages calculate prepares coating slurries needed for consume silica solution quality；According still further to every The ratio of corresponding 200~300 mL n-hexanes of 100g ferrous iron-La bimetallic-modified ZSM-5 molecular sieve, calculates preparation ferrous iron-La The volume of the n-hexane consumed needed for bimetallic-modified ZSM-5 molecular sieve；Need 5~15g average according to every 100g catalyst coatings The ratio of polyethylene glycol and 25~50g nitric acid that molecular weight is 20000, calculates the poly- second consumed needed for prepares coating slurry The quality of two pure and mild nitric acid；
(2) preparation of ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst
Weigh the FeCl for having determined that quality2▪4H2O、La(NO3)3▪6H2O and ZSM-5 molecular sieve, they are poured into together and is had determined that In the n-hexane of volume, under He protective atmosphere then 2~4h of strong stirring still protects gas in He to form uniform suspension Uniform suspension is evaporated n-hexane in 60~70 DEG C of water-baths under atmosphere；It will be evaporated the powder after liquid again in roaster, He Under protective atmosphere, be warming up to 500 DEG C with the speed of 5~10 DEG C/min, and still under He protective atmosphere at 500 DEG C roasting 4~ 6h；After sample is cooling, is crushed, is ground into that partial size is spare less than the little particle of 100 mesh, this is ferrous iron-La bimetallic Modified zsm-5 zeolite major catalyst；
(3) preparation of coating paste
By ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalyst obtained and the Ce (NO for having determined that quality3)3▪6H2O、 Zr(NO3)4▪5H2O, pure matter γ-Al2O3Powder, pure matter TiO2Powder, silica solution, polyethylene glycol, that nitric acid is added to quality is suitable In plan prepare 10~15 times of catalyst coatings gross mass deionized water in, homogeneous slurry is sufficiently stirred into；With 1mol/L's The pH value that sodium hydroxide solution or glacial acetic acid adjust homogeneous slurry is 3~4；Homogeneous slurry is ground on wet grinding mill D50 partial size is in 1.0~1.2 micron ranges, then the homogeneous slurry after grinding stirs to 16 at 60~80 DEG C again~ For 24 hours to get arrive coating paste；
(4) coating of coating paste
Design the quality of the 400 mesh cordierite honeycomb ceramics carrier for the catalyst coatings of being applied；It weighs and has determined that quality Cylindrical 400 mesh cordierite honeycomb ceramics carriers, ceramic monolith are immersed in 60~80 DEG C of the coating paste, and guarantee The upper surface of ceramic monolith is slightly above slurry liquid level；After slurries promote all ducts full of carrier naturally, by carrier from slurry Taken out in material, blow residual fluid in duct off, dry 6~12h at 80~110 DEG C, then at 500~600 DEG C calcining 2~ 4h；Repeat above-mentioned dipping, drying and calcination process 2~3 times to get to ferrous modified molecular screen diesel engine selective catalysis also Raw catalyst.
3. a kind of application of ferrous iron modified molecular screen diesel engine selective catalytic reduction catalysts, it is characterized in that: according to right It is required that modified point of ferrous iron that the preparation method of the 2 ferrous modified molecular screen diesel engine selective catalytic reduction catalysts obtains Sub- sieve-type diesel engine selective catalytic reduction catalysts are packaged in diesel engine selective catalytic reduction catalyst, and by urinate Plain solution is the nitrogen oxide pollutant in the selective catalytic reduction reaction purification of diesel tail gas of reducing agent.
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