CN106622348A - Ferrous modified molecular sieve type diesel engine selective catalytic reduction catalyst - Google Patents

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

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CN106622348A
CN106622348A CN201611000833.3A CN201611000833A CN106622348A CN 106622348 A CN106622348 A CN 106622348A CN 201611000833 A CN201611000833 A CN 201611000833A CN 106622348 A CN106622348 A CN 106622348A
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catalyst
zsm
ferrous
diesel engine
molecular sieve
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CN106622348B (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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    • 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

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Abstract

The invention discloses a ferrous modified molecular sieve type diesel engine selective catalytic reduction catalyst. The catalyst is composed of a main catalyst, an auxiliary catalyst, a coating base material and a catalyst carrier, wherein a ferrous-La bimetallic modified ZSM-5 molecular sieve serves as the main catalyst; a CeO2-ZrO2 solid solution serves as the auxiliary catalyst; the coating base material is composed of SiO2, TiO2 and gamma-Al2O3; and a 400-mesh cordierite honeycomb ceramic serves as the catalyst carrier. A preparation process comprises the following steps: preparing and confirming the dosage of the supported catalyst raw materials; preparing the main catalyst, namely, the ferrous-La bimetallic modified ZSM-5 molecular sieve; and preparing the coating slurry and coating. The catalyst is packaged in a diesel engine SCR catalytic converter and is used for catalyzing the SCR reaction of the reducing agent and NOx, so as to realize the purification of NOx pollutants in the exhaust gas of the diesel engine. According to the invention, the environmental harm of the traditional catalyst is reduced, the generation of the secondary pollutants, such as SO3 derivatives, is restrained, and the low-temperature SCR reaction catalytic activity of the catalyst is obviously improved.

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 technology
Diesel engine compared with other fuels and energy sources, because with loading capacity is big, the thermal efficiency is high, the outstanding advantages such as durable It is widely used.But NOx (the Nitrogen due to there is more diffusion combustion in combustion process, in diesel exhaust gas Oxides) and particulate matter PM (Particulate Matter) discharge capacity is higher, limit it air quality is being required to compare The application in strict area.Further, since a large amount of discharge NOx and PM in the control of diesel engine in-cylinder combustion, the control effect hardly possible of discharge To meet the restriction requirement of state V, the Abgasgesetz of state VI to Emissions, exhaust gas aftertreatment techniques have become ultralow The discharge diesel engine technical measures to be adopted.And SCR SCR (Selective Catalytic Reduction) technology is one of Diesel NOx purification techniques most efficient, most ripe at present, meanwhile, SCR technology is also diesel oil The machine thermal efficiency provides the space further improved.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 association area.
At present business-like SCR catalyst is mainly V2O5/MoO3(WO3)/TiO2/ ceramic monolith System Catalyst, such Catalyst aims are with ammonia (NH3) or carbamide for reducing agent SCR react, in the range of about 300～450 DEG C have it is extremely excellent NOx purifying properties.But V2O5Belong to high poison rank poisonous substance, with the life-time service of SCR catalyst, V2O5Inevitably flow Lose and enter environment, human body and animals and plants are damaged.Meanwhile, V2O5The low-temperature SCR reacting catalytic performance of base SCR catalyst It is poor, it is impossible to adapt to the objective reality that diesel vehicle travel speed is slow, delivery temperature is low in urban road operation.Additionally, and other Oxide type catalyst is similar to, V2O5Base catalyst has stronger oxidation reaction catalysis performance, can be by diesel exhaust gas SO2And its derivatives catalysis are oxidized to SO3Derivant, cause equip SCR system diesel engine easily occur discharge acid mist and after The phenomenon such as processing system easy in inactivation, perishable.Due to V2O5Base oxide catalyst have as SCR catalyst it is clearly disadvantageous, Therefore the research and development of Novel SCR catalyst obtain extensive concern.Jing is studied for many years, and 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 had been enter into ferrum 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 its chemism is relatively low, and is unfavorable for accordingly being catalyzed in low-temp reaction The performance of agent catalytic action.If conversely, using the metal-modified ZSM-5 molecular sieve material of lower valency, now metallic element is in Relatively unstable state, it is easier to valence state and structure change occur under cryogenic, so as 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 reactions activity is not projected, therefore, it is the SCR catalytic reaction active temperature windows for extending catalyst of the present invention Mouthful, present invention employs the modified method of dual element, i.e., it is simultaneously modified with lanthanum (La) element of lower valency ferrum element and high-valence state ZSM-5 molecular sieve, to realize that catalyst of the present invention has good high and low temperature SCR reacting catalytic performances simultaneously.
And with cerium oxide (CeO2), zirconium oxide (ZrO2) it is that the transition metal oxide of representative has good Oxygen storage capacity, The supply of active oxygen can be increased in low-temperature oxidation reduction reaction, low-temperature oxidation reduction reaction is urged so as to strengthen catalyst Change activity.Therefore, the present invention is by adding CeO2-ZrO2The method of solid solution promoter, further improves Novel SCR catalysis The low-temperature SCR reacting catalytic performance of agent.
To sum up, for existing V2O5The deficiency of base SCR catalyst, the present invention proposes ferrous element and La element bimetallics Modified zsm-5 zeolite is major catalyst, CeO2-ZrO2Solid solution is promoter, ferrous modified molecular screen diesel engine choosing Selecting property catalytic reduction catalysts and preparation method thereof.
The content 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 sieves As major catalyst, CeO2-ZrO2Selective catalytic reduction catalysts and preparation method thereof of the solid solution as promoter.
To realize that the technical scheme that the purpose of the present invention is adopted is：Ferrous modified molecular screen diesel engine selective catalysis Reducing catalyst, comprising ferrous iron-La bimetallic-modified ZSM-5 molecular sieves, CeO2-ZrO2Solid solution, SiO2、TiO2、γ-Al2O3 And 400 mesh cordierite honeycomb ceramics carriers, also including normal hexane, Polyethylene Glycol, nitric acid, sodium hydroxide solution, glacial acetic acid, urine Plain solution etc..Major catalyst is constituted by ferrous iron-La bimetallic-modified ZSM-5 molecular sieves, wherein Fe elements and La elements 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：5～12%/3～8%/92～80%, mass percent sum is 100%.
By CeO2-ZrO2Solid solution constitutes promoter, CeO2And ZrO2Mass percent be respectively：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：20～30%/70～40%/10～30%.
The major catalyst that is made up of ferrous iron-La bimetallic-modified ZSM-5 molecular sieves, by CeO2-ZrO2What solid solution was constituted helps Catalyst, by SiO2、TiO2With γ-Al2O3The coating basic material of composition, collectively constitutes catalyst coatings.Wherein major catalyst, The mass percent of promoter and coating basic material is respectively：10～20%/10～20%/80～60%.
Ferrous modified molecular screen diesel engine selectivity is constituted by catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers to urge Change reducing catalyst, catalyst coatings are coated on the cordierite honeycomb by cordierite honeycomb ceramic carrier as the carrier of catalyst On ceramic monolith, catalyst coatings are respectively with the mass percent of the cordierite honeycomb ceramic carrier：10～30%/90～ 70%.
The mass percent sum of above-mentioned all constituent elements or component is 100%.
The preparation of ferrous modified molecular screen diesel engine selective catalytic reduction catalysts and carrying method, concrete technology bag Include following 4 steps：
(1) preparation and the determination of supported catalyst raw material dosage；
(2) preparation of ferrous iron-La bimetallic-modifieds ZSM-5 molecular sieve major catalyst；
(3) preparation of coating paste；
(4) coating of coating paste.
The beneficial effect of of the invention the characteristics of and its generation is：Sponsored using ferrous iron-La bimetallic-modified ZSM-5 molecular sieves 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 derivant, also significantly improves the low-temperature SCR catalytic reaction activity of catalyst, and Realize high temperature SCR reacting catalytic performances not deteriorate.And there is the CeO of good oxygen storage capacity2-ZrO2Solid solution promoter Addition, further enhancing the overall low-temperature SCR reacting catalytic performance of catalyst.Additionally, SiO in coating basic material2With γ- Al2O3Addition, further promote storage oxygen compound Oxygen storage capacity raising and coating stability and firmness enhancing.
Description of the drawings
Fig. 1 is SCR catalyst catalytic performance electromotor evaluation system schematic diagram.
Wherein：1- dynamometer machines；2- shaft couplings；3- tests diesel engine；4- inlet air flow gauge；5- air inlet air conditionings；6- reducing agents Injection electronic control system；7- exhaust gas sampling mouth A；8- temperature sensor A；9- urea storage tanks；10- reducing agent ejector pumpes；11- is also Former agent nozzle；12- temperature sensor B；13- selective catalytic reduction catalysts；14- temperature sensor C；15- exhaust gas sampling mouths B；16- axial flow blowers；17- engine exhaust analysers；18- exhaust gas samplings switch clack box.
Fig. 2 be using SCR catalyst catalytic performance electromotor 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 the prepared catalyst of embodiment 1～5 catalysis reacts, The purification efficiency of NOx.
Fig. 3 be using SCR catalyst catalytic performance electromotor 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 the prepared catalyst of embodiment 1～5 catalysis reacts, The purification efficiency of NOx.
Fig. 4 is to utilize SCR catalyst catalytic performance electromotor evaluation system, when European steady state test circulation ESC is tested, In diesel exhaust gas SCR reactions under the catalysis of the prepared catalyst of embodiment 1～5, the purification efficiency of NOx.
Specific embodiment
Below in conjunction with accompanying drawing and by specific embodiment, technical scheme is further described.Need Illustrate be the embodiment be narrative, rather than determinate, the content that covered of the present invention is not limited to following enforcements Example.
Ferrous modified molecular screen diesel engine selective catalytic reduction catalysts, comprising ferrous iron-La (lanthanum) bimetallic-modified ZSM-5 molecular sieve, CeO2(cerium oxide)-ZrO2(zirconium oxide) solid solution, SiO2(silicon dioxide), TiO2(titanium dioxide), γ- Al2O3(aluminium sesquioxide) and 400 mesh cordierite honeycomb ceramics carriers etc..By ferrous iron-La bimetallic-modified ZSM-5 molecular sieves Composition major catalyst, wherein Fe (ferrum) elements and La elements 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：5～12%/3～8%/92～80%.
By CeO2-ZrO2Solid solution constitutes promoter, CeO2And ZrO2Mass percent be：70～80%/30～ 20%.By SiO2、TiO2With γ-Al2O3Collectively constitute the coating basic material of catalyst, SiO2、TiO2With γ-Al2O3Quality Percentage ratio is respectively：20～30%/70～40%/10～30%.SiO in its floating coat basic material2From as coating The SiO generated after the Ludox calcining of binding agent2, TiO2From pure matter TiO2Powder body, γ-Al2O3From pure matter γ-Al2O3Powder Body.
The major catalyst that is made up of ferrous iron-La bimetallic-modified ZSM-5 molecular sieves, by CeO2-ZrO2What solid solution was constituted helps Catalyst, by SiO2、TiO2With γ-Al2O3The coating basic material of composition, collectively constitutes catalyst coatings, wherein major catalyst, The mass percent of promoter and coating basic material is respectively：10～20%/10～20%/80～60%.
Ferrous modified molecular screen diesel engine selectivity is constituted by catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers to urge Change reducing catalyst, 400 mesh cordierite honeycomb ceramics carriers and need to be coated on catalyst coatings as the carrier of catalyst On 400 mesh cordierite honeycomb ceramics carriers, and the mass percent difference of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers For：10～30%/90～70%.
The mass percent sum of above-mentioned all constituent elements or component is 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 proportioning, separately design out FeO in major catalyst ferrous iron-La bimetallic-modified ZSM-5 molecular sieves, La2O3With the mass percent of ZSM-5 molecular sieve；CeO in promoter2And ZrO2Mass percent；Major catalyst, help and urge The mass percent of agent and coating basic material；SiO in coating basic material2、TiO2With γ-Al2O3Mass percent； The mass percent scope of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers；And planned allocation coating paste can be generated The quality of catalyst coatings.
According to fixed each ratio, calculate prepare FeO, the La consumed needed for catalyst respectively2O3, ZSM-5 molecules Sieve, CeO2、ZrO2, Ludox generate SiO2, 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, per 434.1g Ce (NO3)3·6H2O prepares 172.1g CeO2, per 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 Ludox2Actual mass percentages calculate the quality of the Ludox consumed needed for prepares coating serosity； According still further to the ratio of every 100g ferrous irons-La bimetallic-modifieds ZSM-5 molecular sieve correspondence 200～300ml normal hexane, preparation is calculated The volume of the normal hexane consumed needed for ferrous iron-La bimetallic-modifieds ZSM-5 molecular sieve.According to every 100g catalyst coatings need 5～ 15g mean molecule quantities are the ratio of 20000 Polyethylene Glycol and 25～50g nitric acid, calculate and disappear needed for prepares coating slurry The Polyethylene Glycol of consumption and the quality of nitric acid.
(2) preparation of ferrous iron-La bimetallic-modifieds 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 In having determined that the normal hexane of volume, under He protective atmospheres 2～4h of strong stirring to form uniform suspension, then still in He Uniform suspension is evaporated into normal hexane in 60～70 DEG C of water-baths under protective atmosphere.The powder after liquid will be evaporated again in roaster In, under He protective atmospheres, 500 DEG C, and the still roasting at 500 DEG C under He protective atmospheres are warming up to the speed of 5～10 DEG C/min Burn 4～6h.After sample cooling, crushed, ground to form that particle diameter is standby less than the little particle of 100 mesh, this is ferrous iron-La couple Metal-modified ZSM-5 molecular sieve major catalyst.
(3) preparation of coating paste
By obtained ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalysts and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder body, pure matter TiO2Powder body, Ludox, Polyethylene Glycol, nitric acid are added to matter Amount equivalent to plan prepare in the deionized water of 10～15 times of catalyst coatings gross mass, be sufficiently stirred for uniformly serosity.With It is 3～4 that the sodium hydroxide solution of 1mol/L or glacial acetic acid adjust the pH value of homogeneous slurry.By homogeneous slurry on wet grinding mill D50 particle diameters are ground in 1.0～1.2 micrometer ranges, then again stir the homogeneous slurry after grinding at 60～80 DEG C 16～24h, that is, obtain coating paste.
(4) coating of coating paste
Design the quality of the 400 mesh cordierite honeycomb ceramics carrier of to be applied catalyst coatings；Weigh and have determined that matter The mesh cordierite honeycomb ceramics carrier of cylinder 400 of amount, ceramic monolith is immersed in 60～80 DEG C of the coating paste, and The upper surface for ensureing ceramic monolith is slightly above slurry liquid level.After serosity lifts all ducts full of carrier naturally, by carrier Take out from slurry, blow residual fluid in duct off, 6～12h is dried at 80～110 DEG C, then 2 are calcined at 500～600 DEG C ～4h.The above-mentioned dipping of repetition, drying and calcination process 2～3 times, that is, obtain 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, encapsulated rear peace Loaded in diesel engine exhaust port, by being catalyzed NOx and reducing agent (NH3Or carbamide) SCR reaction purification diesel engine aerofluxuss 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 sieves of the prepared catalyst of design embodiments 1, FeO, La2O3It is respectively with the mass percent of ZSM-5 molecular sieve：12%:8%:80%.CeO in promoter2And ZrO2Quality Percentage ratio is respectively：80%/20%.The mass percent of major catalyst, promoter and coating basic material is：10%: 10%:80%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively：30%:40%:30%. The Polyethylene Glycol and 50g nitric acid that 10g mean molecule quantities are 20000 is needed per 100g catalyst coatings；Double gold per 100g ferrous irons-La Category modified zsm-5 zeolite needs 300ml normal hexane.
Preparation 2000g catalyst coatings needed raw material consumptions are calculated according to conversion scale：Ferrous chloride [FeCl2·4H2O] 66.5g, Lanthanum (III) 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, normal hexane 600ml, nitric acid 1000g, the Polyethylene Glycol that mean molecule quantity is 20000 200g, Ludox generate SiO2480g, pure matter TiO2Powder body 640g, pure matter γ-Al2O3Powder body 480g.SiO in Ludox2's Mass content is 25%, and thus calculating needs Ludox 1920g.
(2) preparation of ferrous iron-La bimetallic-modifieds 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 In having determined that the normal hexane of volume, under He protective atmospheres strong stirring 4h to form uniform suspension, then still He protect Uniform suspension is evaporated into normal hexane in 65 DEG C of water-baths under shield atmosphere.The powder after liquid will be evaporated again in roaster, He Under protective atmosphere, 500 DEG C are warming up to 5 DEG C/min, and still under He protective atmospheres in 500 DEG C of roasting 6h.After sample cooling, Crushed, grind to form particle diameter less than 100 mesh little particle it is standby, this is ferrous iron-La bimetallic-modified ZSM-5 molecular sieve masters Catalyst.
(3) preparation of coating paste
By obtained ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalysts and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder body, pure matter TiO2Powder body, Ludox, Polyethylene Glycol, nitric acid are added In 20000g deionized waters, uniformly serosity is sufficiently stirred for.Adjusted with the sodium hydroxide solution of 1mol/L or glacial acetic acid and be homogenized The pH value of liquid is 3～4.Homogeneous slurry is ground to into D50 particle diameters in 1.0～1.2 micrometer ranges, so on wet grinding mill Again the homogeneous slurry after grinding stirred into 20h at 70 DEG C afterwards, that is, obtain coating paste.
(4) coating of coating paste
1kg 400 mesh cordierite honeycomb ceramics carriers of cylinder are weighed, honeycomb ceramic carrier is immersed in into 70 DEG C of coating slurry In material, and ensure that the upper surface of ceramic monolith is slightly above slurry liquid level.After serosity lifts all ducts full of carrier naturally, Carrier is taken out from slurry, residual fluid in duct is blown off, 12h is dried at 90 DEG C, then 2h is calcined at 600 DEG C.Repeat Above-mentioned dipping, drying and calcination process 3 times, that is, obtain ferrous modified molecular screen diesel engine selective catalytic reduction catalysts.
The ferrous modified molecular screen diesel engine selective catalysis obtained using the catalyst preparation carrying method of embodiment 1 are also Raw catalyst, catalyst coatings are with the mass percent of 400 mesh cordierite honeycomb ceramics carriers：28～30%/72～70%, matter Amount percentage ratio sum 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 sieves of the prepared catalyst of design embodiments 2, FeO, La2O3It is respectively with the mass percent of ZSM-5 molecular sieve：5%:3%:92%.CeO in promoter2And ZrO2Quality hundred Ratio is divided to be respectively：70%/30%.The mass percent of major catalyst, promoter and coating basic material is：20%:20%: 60%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively：20%:70%:10%.Often 100g catalyst coatings need the Polyethylene Glycol and 25g nitric acid that 15g mean molecule quantities are 20000；Per 100g ferrous iron-La bimetallics Modified zsm-5 zeolite needs 200ml normal hexane.
Preparation 2000g catalyst coatings needed raw material consumptions are calculated 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、 Normal hexane 800ml, nitric acid 500g, mean molecule quantity by 20000 Liquid Macrogol g, Ludox generate SiO2It is 240g, pure Matter TiO2Powder body 840g, pure matter γ-Al2O3Powder body 120g.SiO in Ludox2Mass content be 25%, thus calculate need Want Ludox 960g.
(2) preparation of ferrous iron-La bimetallic-modifieds 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 In having determined that the normal hexane of volume, under He protective atmospheres strong stirring 2h to form uniform suspension, then still He protect Uniform suspension is evaporated into normal hexane in 60 DEG C of water-baths under shield atmosphere.The powder after liquid will be evaporated again in roaster, He Under protective atmosphere, with 10 DEG C/min 500 DEG C are warming up to, and still under He protective atmospheres at 500 DEG C roasting 4h.Treat that sample is cooled down Afterwards, crushed, grind to form particle diameter less than 100 mesh little particle it is standby, this is ferrous iron-La bimetallic-modified ZSM-5 molecules Sieve major catalyst.
(3) preparation of coating paste
By obtained ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalysts and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder body, pure matter TiO2Powder body, Ludox, Polyethylene Glycol, nitric acid are added In 30000g deionized waters, uniformly serosity is sufficiently stirred for.Adjusted with the sodium hydroxide solution of 1mol/L or glacial acetic acid and be homogenized The pH value of liquid is 3～4.Homogeneous slurry is ground to into D50 particle diameters in 1.0～1.2 micrometer ranges, so on wet grinding mill Again the homogeneous slurry after grinding stirred into 24h at 60 DEG C afterwards, that is, obtain coating paste.
(4) coating of coating paste
1kg 400 mesh cordierite honeycomb ceramics carriers of cylinder are weighed, honeycomb ceramic carrier is immersed in into 60 DEG C of coating slurry In material, and ensure that the upper surface of ceramic monolith is slightly above slurry liquid level.After serosity lifts all ducts full of carrier naturally, Carrier is taken out from slurry, residual fluid in duct is blown off, 6h is dried at 110 DEG C, then 4h is calcined at 500 DEG C.Repeat Above-mentioned dipping, drying and calcination process 3 times, that is, obtain ferrous modified molecular screen diesel engine selective catalytic reduction catalysts.
The ferrous modified molecular screen diesel engine selective catalysis obtained using the catalyst preparation carrying method of embodiment 2 are also Raw catalyst, catalyst coatings are with the mass percent of 400 mesh cordierite honeycomb ceramics carriers：19～21%/81～79%, matter Amount percentage ratio sum 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 sieves of the prepared catalyst of design embodiments 3, FeO, La2O3It is respectively with the mass percent of ZSM-5 molecular sieve：10%:5%:85%.CeO in promoter2And ZrO2Quality Percentage ratio is respectively：80%/20%.The mass percent of major catalyst, promoter and coating basic material is respectively： 20%:15%:65%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively：25%:45%: 30%.The Polyethylene Glycol and 30g nitric acid that 5g mean molecule quantities are 20000 is needed per 100g catalyst coatings；Per 100g ferrous iron-La Bimetallic-modified ZSM-5 molecular sieve needs 250ml normal hexane.
Preparation 2000g catalyst coatings needed raw material consumptions are calculated 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、 Normal hexane 1000ml, nitric acid 600g, mean molecule quantity by 20000 Polyethylene Glycol 100g, Ludox generate SiO2 325g、 Pure matter TiO2Powder body 585g, pure matter γ-Al2O3Powder body 390g.SiO in Ludox2Mass content be 25%, thus calculate Need Ludox 1300g.
(2) preparation of ferrous iron-La bimetallic-modifieds 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 In having determined that the normal hexane of volume, under He protective atmospheres strong stirring 3h to form uniform suspension, then still He protect The uniform suspension is evaporated into normal hexane in 70 DEG C of water-baths under shield atmosphere.The powder after liquid will be evaporated again in roaster In, under He protective atmospheres, with 5 DEG C/min 500 DEG C are warming up to, and still under He protective atmospheres at 500 DEG C roasting 6h.Treat sample After cooling, crushed, grind to form particle diameter less than 100 mesh little particle it is standby, this is ferrous iron-La bimetallic-modifieds ZSM-5 Molecular sieve major catalyst.
(3) preparation of coating paste
By obtained ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalysts and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder body, pure matter TiO2Powder body, Ludox, Polyethylene Glycol, nitric acid are added In 25000g deionized waters, uniformly serosity is sufficiently stirred for.Adjusted with the sodium hydroxide solution of 1mol/L or glacial acetic acid and be homogenized The pH value of liquid is 3～4.Homogeneous slurry is ground to into D50 particle diameters in 1.0～1.2 micrometer ranges, so on wet grinding mill Again the homogeneous slurry after grinding stirred into 16h at 80 DEG C afterwards, that is, obtain coating paste.
(4) coating of coating paste
1kg 400 mesh cordierite honeycomb ceramics carriers of cylinder are weighed, the honeycomb ceramic carrier is immersed in into 80 DEG C of institute In stating coating paste, and ensure that the upper surface of ceramic monolith is slightly above slurry liquid level.Treat that serosity lifts the institute full of carrier naturally After having duct, carrier is taken out from slurry, blow residual fluid in duct off, 10h is dried at 100 DEG C, then forged at 500 DEG C Burn 4h.The above-mentioned dipping of repetition, drying and calcination process 3 times, that is, obtain ferrous modified molecular screen diesel engine selective catalysis also Raw catalyst.
The ferrous modified molecular screen diesel engine selective catalysis obtained using the catalyst preparation carrying method of embodiment 3 are also Raw catalyst, catalyst coatings are with the mass percent of 400 mesh cordierite honeycomb ceramics carriers：25～27%/75～73%, matter Amount percentage ratio sum 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 sieves of the prepared catalyst of design embodiments 4, FeO, La2O3It is respectively with the mass percent of ZSM-5 molecular sieve：12%:8%:80%.CeO in promoter2And ZrO2Quality Percentage ratio is respectively：70%/30%.The mass percent of major catalyst, promoter and coating basic material is respectively： 15%:15%:70%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively：25%:50%: 25%.The Polyethylene Glycol and 30g nitric acid that 10g mean molecule quantities are 20000 is needed per 100g catalyst coatings；Ferrous per 100g- La bimetallic-modified ZSM-5 molecular sieves need 250ml normal hexane.
Preparation 2000g catalyst coatings needed raw material consumptions are calculated 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、 Normal hexane 750ml, nitric acid 600g, mean molecule quantity by 20000 polyethylene glycol 200 g, Ludox generate SiO2It is 350g, pure Matter TiO2Powder body 750g, pure matter γ-Al2O3Powder body 350g.SiO in Ludox2Mass content be 25%, thus calculate need Want Ludox 1400g.
(2) preparation of ferrous iron-La bimetallic-modifieds 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 In having determined that the normal hexane of volume, under He protective atmospheres strong stirring 3h to form uniform suspension, then still He protect The uniform suspension is evaporated into normal hexane in 65 DEG C of water-baths under shield atmosphere.The powder after liquid will be evaporated again in roaster In, under He protective atmospheres, with 8 DEG C/min 500 DEG C are warming up to, and still under He protective atmospheres at 500 DEG C roasting 6h.Treat sample After cooling, crushed, grind to form particle diameter less than 100 mesh little particle it is standby, this is ferrous iron-La bimetallic-modifieds ZSM-5 Molecular sieve major catalyst.
(3) preparation of coating paste
By obtained ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalysts and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder body, pure matter TiO2Powder body, Ludox, Polyethylene Glycol, nitric acid are added In 25000g deionized waters, uniformly serosity is sufficiently stirred for.Adjusted with the sodium hydroxide solution of 1mol/L or glacial acetic acid and be homogenized The pH value of liquid is 3～4.Homogeneous slurry is ground to into D50 particle diameters in 1.0～1.2 micrometer ranges, so on wet grinding mill Again the homogeneous slurry after grinding stirred into 24h at 60 DEG C afterwards, that is, obtain coating paste.
(4) coating of coating paste
1kg 400 mesh cordierite honeycomb ceramics carriers of cylinder are weighed, honeycomb ceramic carrier is immersed in into 60 DEG C of coating slurry In material, and ensure that the upper surface of ceramic monolith is slightly above slurry liquid level.After serosity lifts all ducts full of carrier naturally, Carrier is taken out from slurry, residual fluid in duct is blown off, 6h is dried at 110 DEG C, then 4h is calcined at 500 DEG C.Repeat Above-mentioned dipping, drying and calcination process 2 times, that is, obtain ferrous modified molecular screen diesel engine selective catalytic reduction catalysts.
The ferrous modified molecular screen diesel engine selective catalysis obtained using the catalyst preparation carrying method of embodiment 4 are also Raw catalyst, catalyst coatings are with the mass percent of 400 mesh cordierite honeycomb ceramics carriers：15～17%/85～83%, matter Amount percentage ratio sum 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 sieves of the prepared catalyst of design embodiments 5, FeO, La2O3It is respectively with the mass percent of ZSM-5 molecular sieve：10%:5%:85%.CeO in promoter2And ZrO2Quality Percentage ratio is：80%/20%.The mass percent of major catalyst, promoter and coating basic material is respectively：20%: 20%:60%.In coating basic material, SiO2、TiO2With γ-Al2O3Mass percent be respectively：30%:50%:20%. The Polyethylene Glycol and 30g nitric acid that 10g mean molecule quantities are 20000 is needed per 100g catalyst coatings；Double gold per 100g ferrous irons-La Category modified zsm-5 zeolite correspondence 250ml normal hexane.
Preparation 2000g catalyst coatings needed raw material consumptions are calculated 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、 Normal hexane 1000ml, nitric acid 600g, mean molecule quantity by 20000 polyethylene glycol 200 g, Ludox generate SiO2 360g、 Pure matter TiO2Powder body 600g, pure matter γ-Al2O3Powder body 240g.SiO in Ludox2Mass content be 25%, thus calculate Need Ludox 1440g.
(2) preparation of ferrous iron-La bimetallic-modifieds 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 In having determined that the normal hexane of volume, under He protective atmospheres strong stirring 4h to form uniform suspension, then still He protect The uniform suspension is evaporated into normal hexane in 65 DEG C of water-baths under shield atmosphere.The powder after liquid will be evaporated again in roaster In, under He protective atmospheres, with 5 DEG C/min 500 DEG C are warming up to, and still under He protective atmospheres at 500 DEG C roasting 6h.Treat sample After cooling, crushed, grind to form particle diameter less than 100 mesh little particle it is standby, this is ferrous iron-La bimetallic-modifieds ZSM-5 Molecular sieve major catalyst.
(3) preparation of coating paste
By obtained ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalysts and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder body, pure matter TiO2Powder body, Ludox, Polyethylene Glycol, nitric acid are added In 30000g deionized waters, uniformly serosity is sufficiently stirred for.Adjusted with the sodium hydroxide solution of 1mol/L or glacial acetic acid and be homogenized The pH value of liquid is 3～4.Homogeneous slurry is ground to into D50 particle diameters in 1.0～1.2 micrometer ranges, so on wet grinding mill Again the homogeneous slurry after grinding stirred into 20h at 70 DEG C afterwards, that is, obtain coating paste.
(4) coating of coating paste
1kg 400 mesh cordierite honeycomb ceramics carriers of cylinder are weighed, honeycomb ceramic carrier is immersed in into 70 DEG C of coating slurry In material, and ensure that the upper surface of ceramic monolith is slightly above slurry liquid level.After serosity lifts all ducts full of carrier naturally, Carrier is taken out from slurry, residual fluid in duct is blown off, 9h is dried at 100 DEG C, then 3h is calcined at 550 DEG C.Repeat Above-mentioned dipping, drying and calcination process 2 times, that is, obtain ferrous modified molecular screen diesel engine selective catalytic reduction catalysts.
The ferrous modified molecular screen diesel engine selective catalysis obtained using the catalyst preparation carrying method of embodiment 5 are also Raw catalyst, catalyst coatings are with the mass percent of 400 mesh cordierite honeycomb ceramics carriers：11～13%/89～87%, matter Amount percentage ratio sum is 100%.
Using the SCR catalyst catalytic performance electromotor evaluation system shown in Fig. 1, to urging prepared by embodiment 1-5 Carbamide-SCR the reacting catalytic performances of agent are evaluated.Need to be respectively cut embodiment 1-5 prepared catalyst before test, respectively From 5L cylinder integral catalyzers are combined into, and the cylindrical integral catalyzer to cutting, being combined into is packaged process. Test method is：
(1) steady state condition test：Using dynamometer machine 1 and the Control experiment diesel engine of shaft coupling 2 (CY4102 diesel engines) 3 Moment of torsion and rotating speed, successively adjust extraction flow and the ratio of catalyst volume is respectively 30000h-1And 60000h-1, and successively control The temperature of the central point of SCR catalyst processed 13 is respectively 250 DEG C and 350 DEG C, carries out carbamide-SCR reaction purified treatment.
In test, electronic control system 6 is sprayed by reducing agent and adjusts reducing agent ejector pump 10 and reductant nozzle 11 Reducing agent jet velocity, it is ensured that reducing agent (urea liquid) decomposes the NH for obtaining3Substance withdrawl syndrome and aerofluxuss in NOx thing The ratio of the amount concentration of matter is 1:1.
The forward and backward diesel exhaust gas difference Jing exhaust gas sampling mouth A7 of SCR catalyst process and exhaust gas sampling mouth B15 and row Gas sampling switching clack box 18 carries out NOx concentration analysis into engine exhaust analyser 17, and the gas Jing after NOx analyses passes through Axial flow blower 16 gives off test chamber.Aerofluxuss temperature before and after temperature sensor A8 and temperature sensor C14 measurement SCR catalysts Degree, and the temperature at temperature sensor B12 measurement SCR catalysts center.The measured temperature and inlet air flow of 3 temperature sensors The charge flow rate measured value of gauge 4 provides feedback parameter for the control strategy that reducing agent sprays electronic control system 6.
Using SCR catalyst catalytic performance electromotor evaluation system, SCR catalyst central temperature be 250 DEG C, air speed be 30000h-1When and SCR catalyst central temperature be 350 DEG C, air speed be 60000h-1When, the prepared catalyst of embodiment 1～5 In carbamide-SCR reactions under catalysis, the purification efficiency of NOx is respectively as shown in Figures 2 and 3.
(2) ESC tests：Using SCR catalyst catalytic performance electromotor evaluation system, and according to standard GB/T 17691-2005《Automobile-used compression-ignited, gaseous fuel spark-ignition engine and automobile exhaust pollutant discharge limit value and measuring method (Chinese III, IV, V stage)》Specified in ESC testing regulationss, evaluate the prepared catalyst of embodiment 1～5 to test diesel engine The clean-up effect of NOx pollutant in tail gas, evaluation result is as shown in Figure 4.
Ferrous modified molecular screen diesel engine selective catalytic reduction catalysts, with good low temperature reacting catalytic performance and Wide active temperature windows, add CeO2-ZrO2Solid solution can strengthen the overall low-temperature SCR reaction of catalyst and urge as promoter Change performance.Add SiO2With γ-Al2O3, coating can be promoted to store up the raising of oxygen compound Oxygen storage capacity, and strengthen the steady of coating Qualitative and firmness.

Claims (7)

1. ferrous modified molecular screen diesel engine selective catalytic reduction catalysts, divide comprising ferrous iron-La bimetallic-modifieds ZSM-5 Son sieve, CeO2-ZrO2Solid solution, SiO2、TiO2、γ-Al2O3And 400 mesh cordierite honeycomb ceramics carriers, also including just oneself Alkane, Polyethylene Glycol, nitric acid, sodium hydroxide solution, glacial acetic acid, urea liquid, it is characterised in that：By ferrous iron-La bimetallic-modifieds ZSM-5 molecular sieve constitutes major catalyst, and wherein Fe elements and La elements are respectively with FeO oligomer and La2O3The form of oligomer is equal It is even to be scattered in the surface and micropore of ZSM-5 molecular sieve, and FeO, La2O3And the mass percent of ZSM-5 molecular sieve is respectively：5 ～12%/3～8%/92～80%, mass percent sum is 100%.
2., according to the ferrous modified molecular screen diesel engine selective catalytic reduction catalysts described in claim 1, its feature exists In：By the CeO2-ZrO2Solid solution constitutes promoter, and CeO2And ZrO2Mass percent be respectively：70～80%/ 30～20%, mass percent sum is 100%.
3., according to the ferrous modified molecular screen diesel engine selective catalytic reduction catalysts described in claim 1, its feature exists In：By the SiO2、TiO2With γ-Al2O3Collectively constitute the coating basic material of catalyst, and SiO2、TiO2With γ-Al2O3's Mass percent is respectively：20～30%/70～40%/10～30%, mass percent sum is 100%；Meanwhile, coating base SiO in plinth material2The SiO generated after the Ludox calcining as binders for coatings2, the TiO2From pure matter TiO2 Powder body, the γ-Al2O3From pure matter γ-Al2O3Powder body.
4., according to the ferrous modified molecular screen diesel engine selective catalytic reduction catalysts described in claim 1, its feature exists In：The major catalyst that is made up of the ferrous iron-La bimetallic-modified ZSM-5 molecular sieves, by CeO2-ZrO2What solid solution was constituted helps Catalyst, by SiO2、TiO2With γ-Al2O3The coating basic material of composition, collectively constitutes catalyst coatings, and wherein main catalytic The mass percent of agent, promoter and coating basic material is respectively：10～20%/10～20%/80～60%, quality hundred It is 100% to divide than sum.
5., according to the ferrous modified molecular screen diesel engine selective catalytic reduction catalysts described in claim 1, its feature exists In：Ferrous modified molecular screen diesel engine selectivity is constituted by the catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers to urge Change reducing catalyst, 400 mesh cordierite honeycomb ceramics carriers and need to be coated on catalyst coatings as the carrier of catalyst On 400 mesh cordierite honeycomb ceramics carriers, and the mass percent difference of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers For：10～30%/90～70%, mass percent sum is 100%.
6. a kind of ferrous modified molecular screen diesel engine selective catalytic reduction catalysts according to described in Claims 1 to 5 Prepare and carrying method, it is characterized in that：Concrete preparation and carrying method technique are comprised the following steps：
(1) preparation and the determination of supported catalyst raw material dosage
According to each proportioning described in claim 1 to 5, major catalyst ferrous iron-La bimetallic-modified ZSM-5 molecular sieves are separately designed out Middle FeO, La2O3With the mass percent of ZSM-5 molecular sieve；CeO in promoter2And ZrO2Mass percent；Main catalytic The mass percent of agent, promoter and coating basic material；SiO in coating basic material2、TiO2With γ-Al2O3Quality Percentage ratio；The mass percent scope of catalyst coatings and 400 mesh cordierite honeycomb ceramics carriers；And planned allocation coating paste The quality of catalyst coatings can be generated；
FeO, the La consumed needed for catalyst is prepared according to having determined that aforementioned each ratio is calculated respectively2O3, ZSM-5 molecular sieve, CeO2、ZrO2, Ludox generate SiO2, 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, per 434.1g Ce (NO3)3· 6H2O prepares 172.1g CeO2, per 429.3g Zr (NO3)4·5H2O prepares 123.2g ZrO2Ratio, calculate preparation catalysis The FeCl consumed needed for agent2·4H2O、La(NO3)3·6H2O、Ce(NO3)3·6H2O、Zr(NO3)4·5H2The quality of O；According to silicon SiO in colloidal sol2Actual mass percentages calculate the quality of the Ludox consumed needed for prepares coating serosity；According still further to every The ratio of 100g ferrous iron-La bimetallic-modifieds ZSM-5 molecular sieve correspondence 200～300ml normal hexane, calculates preparation ferrous iron-La The volume of the normal hexane consumed needed for bimetallic-modified ZSM-5 molecular sieve；Need 5～15g average according to every 100g catalyst coatings Molecular weight is the ratio of 20000 Polyethylene Glycol and 25～50g nitric acid, calculates the poly- second consumed needed for prepares coating slurry The quality of glycol and nitric acid；
(2) preparation of ferrous iron-La bimetallic-modifieds 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 true In determining the normal hexane of volume, under He protective atmospheres 2～4h of strong stirring to form uniform suspension, then still He protect Uniform suspension is evaporated into normal hexane in 60～70 DEG C of water-baths under atmosphere；The powder after liquid will be evaporated again in roaster, Under He protective atmospheres, 500 DEG C, and the still roasting 4 at 500 DEG C under He protective atmospheres are warming up to the speed of 5～10 DEG C/min ～6h；After sample cooling, crushed, ground to form that particle diameter is standby less than the little particle of 100 mesh, it is double golden that this is ferrous iron-La Category modified zsm-5 zeolite major catalyst；
(3) preparation of coating paste
By obtained ferrous iron-La bimetallic-modified ZSM-5 molecular sieve major catalysts and the Ce (NO for having determined that quality3)3· 6H2O、Zr(NO3)4·5H2O, pure matter γ-Al2O3Powder body, pure matter TiO2Powder body, Ludox, Polyethylene Glycol, nitric acid are added to matter Amount equivalent to plan prepare in the deionized water of 10～15 times of catalyst coatings gross mass, be sufficiently stirred for uniformly serosity；With It is 3～4 that the sodium hydroxide solution of 1mol/L or glacial acetic acid adjust the pH value of homogeneous slurry；By homogeneous slurry on wet grinding mill D50 particle diameters are ground in 1.0～1.2 micrometer ranges, then again stir the homogeneous slurry after grinding at 60～80 DEG C 16～24h, that is, obtain coating paste；
(4) coating of coating paste
Design the quality of the 400 mesh cordierite honeycomb ceramics carrier of to be applied catalyst coatings；Weigh and have determined that quality Cylindrical 400 mesh cordierite honeycomb ceramics carriers, ceramic monolith is immersed in 60～80 DEG C of the coating paste, and is ensured The upper surface of ceramic monolith is slightly above slurry liquid level；After serosity lifts all ducts full of carrier naturally, by carrier from slurry In material take out, blow residual fluid in duct off, at 80～110 DEG C be dried 6～12h, then at 500～600 DEG C calcining 2～ 4h；The above-mentioned dipping of repetition, drying and calcination process 2～3 times, that is, obtain ferrous modified molecular screen diesel engine selective catalysis also Raw catalyst.
7., according to the ferrous modified molecular screen diesel engine selective catalytic reduction catalysts described in claim 6, it is characterized in that： The ferrous modified molecular screen diesel engine selective catalytic reduction catalysts obtained by the step are packaged in diesel engine selectivity In catalyst reduction catalyst device, and by the selective catalytic reduction reaction purification of diesel tail gas with urea liquid as reducing agent Nitrogen oxides pollution thing.
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