CN105944749A - Modified molecular sieve main catalyst based composite oxidation catalyst for diesel engines - Google Patents

Modified molecular sieve main catalyst based composite oxidation catalyst for diesel engines Download PDF

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CN105944749A
CN105944749A CN201610297377.7A CN201610297377A CN105944749A CN 105944749 A CN105944749 A CN 105944749A CN 201610297377 A CN201610297377 A CN 201610297377A CN 105944749 A CN105944749 A CN 105944749A
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catalyst
coating
major catalyst
pure matter
quality
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CN105944749B (en
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吕颂
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Catalytic Cleaner Co Ltd Of Hefei Divine Boat
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Catalytic Cleaner Co Ltd Of Hefei Divine Boat
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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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/504—ZSM 5 zeolites

Abstract

The invention discloses a modified molecular sieve main catalyst based composite oxidation catalyst for diesel engines. The composite oxidation catalyst comprises: a main catalyst, i.e. a binary metal modified ZSM-5 molecular sieve catalyst formed by copper chloride, zirconium nitrate, and a modified ZSM-5 type molecular sieve material; a cocatalyst composed of pure CeO2 and pure ZrO2; and a coating material composed of SiO2 and gamma-Al2O3, and the main catalyst, the cocatalyst and the coating material are applied uniformly to a 400-mesh cordierite honeycomb ceramic carrier. The specific preparation and loading method includes the four steps: determination of the amounts of raw materials for preparation and loading of the catalyst; preparation of the main catalyst; preparation of the coating slurry; and application of the coating slurry. According to the invention, the composite oxidation catalyst is employed to replace noble metal catalysts, the catalyst production cost is significantly reduced, the oxidation reaction catalytic performance of the catalyst is improved, and also the sulfur resistance and thermal aging resistance of the catalyst are greatly improved.

Description

Use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst
Technical field
The invention belongs to use for diesel engine catalyst, be specifically related to the catalysis of a kind of compound oxidizing with modified molecular screen as major catalyst Agent and prepare carrying method, for the purification of Emissions.
Background technology
Diesel engine, because the thermal efficiency is high, loading capacity is big, is at home and abroad widely used.But the particulate matter in its tail gas (Particulate Matter-PM) discharge capacity is higher, and the operation of massive diesel-fuel car can cause the rising of inspirable particle concentration. Owing to the aerodynamic diameter of these particulate matters is generally less than 2.5 microns, small particle diameter has higher specific surface area, can Carrier as multiple pathogenetic bacteria is inhaled into, and health causes bigger potential hazard.Hydrocarbon (HC) of engine emission It is not only poisonous, harmful gas with carbon monoxide (CO), but also is the precursor of Atmospheric particulates, it is possible to promote haze ring The formation in border.
For controlling the discharge of diesel engine pollutant, people have developed multiple emission aftertreatment technology in order to outside the machine that discharges pollutants Purify.Such as diesel oxidation catalyst (Diesel Oxident Catalyst-DOC), diesel particulate filter (Diesel Particulate Filter-DPF), SCR (Selective Catalytic Reduction-SCR) technology etc..Wherein, DOC is that cost is minimum, structure is the simplest, application the most widest Diesel Engine After-treatment Technology, design, mate good DOC is respectively provided with good clean-up effect to HC, CO and PM of diesel engine.Oxidation catalyst and coated technique thereof are DOC The core of technology, directly decides DOC to the purifying property of pollutant and service life.At present, commercial applications is put into DOC nearly all use noble metal as major catalyst, not only higher to the oxidation activity of HC, CO and microgranule, and the type Major catalyst relatively costly, high temperature easy-sintering, and sulfur resistance is poor.Therefore, exploitation high activity, low cost, resistance to SO_2 Strong and that high-temperature stability is good Novel main catalyst becomes the research and development focus of Emissions control field.
The present invention is directed to the defect of existing oxidation catalyst based on noble metal major catalyst, it is proposed that with binary metal modified molecules Use for diesel engine compound oxidizing catalyst that sieve is major catalyst and preparation method thereof.
Summary of the invention
It is an object of the present invention to provide a kind of use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst and Prepare carrying method.
Technical scheme is divided into composition and method two parts of preparation load of compound oxidizing catalyst.
Use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst, has: copper chloride, zirconium nitrate, ZSM-5 Molecular sieve, CuO, ZrO2、CeO2、SiO2、γ-Al2O3, 400 mesh cordierite honeycomb ceramics carriers, normal hexane, poly-second two Alcohol and nitric acid.By copper chloride, zirconium nitrate and modified ZSM-5 type molecular sieve material, it is thus achieved that binary metal modified ZSM-5 Molecular sieve type catalyst is as major catalyst.Wherein Cu element and Zr element are respectively with copper oxide oligomer and zirconium oxide oligomer Form be dispersed in surface and the micropore of type ZSM 5 molecular sieve.Copper oxide oligomer, zirconium oxide oligomer and ZSM-5 The mass percent of type molecular sieve is: 3.0～6.0%/2.0～6.0%/95.0～88.0%, and the percentage ratio sum of gross mass is 100%.By pure matter CeO2With pure matter ZrO2Composition promoter, by SiO2With γ-Al2O3Composition coating material, and by sponsoring Agent, promoter and coating material collectively constitute coating.
Pure matter CeO2With pure matter ZrO2Mass percent be: 50～80%/50～20%, the percentage ratio sum of gross mass is 100%.
SiO2With γ-Al2O3Mass percent be: 20～30%/80～70%, the percentage ratio sum of gross mass is 100%.
SiO in coating material2The SiO generated after calcining from Ludox2.γ-Al in coating material2O3Respectively from pure matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3.Pure matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3, its matter Amount percentage ratio is: 70～100%/30～0%, the percentage ratio sum of gross mass is 100%.
Binary metal modified zsm-5 zeolite type major catalyst, by pure matter CeO2With pure matter ZrO2The promoter that collectively constitutes, And by SiO2With γ-Al2O3The mass percent of the coating material collectively constituted is: 20～30%/10～20%/70～50%, The percentage ratio sum of gross mass is 100%.
By 400 mesh cordierite honeycomb ceramics as carrier, aforementioned major catalyst, promoter and coating material collectively constitute Coating, be coated on 400 mesh cordierite honeycomb ceramics carriers.Coating and the quality hundred of 400 mesh cordierite honeycomb ceramics carriers Proportion by subtraction is: 10～30%/90～70%, and the percentage ratio sum of gross mass is 100%.
The preparation of use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst and carrying method, concrete technology bag Include four steps: (1) prepares and the determination of supported catalyst raw material dosage；(2) preparation of major catalyst；(3) coating paste Preparation；(4) coating of coating paste.Described in detail individually below:
(1) preparation and the determination of supported catalyst raw material dosage
According to aforementioned each proportioning, separately design out CuO oligomer, ZrO in major catalyst2Oligomer and type ZSM 5 molecular sieve The mass percent of each constituent element；Pure matter CeO in promoter2With pure matter ZrO2Mass percent；Major catalyst, co-catalysis Agent and the mass percent of coating material；SiO in coating material2With γ-Al2O3, whole γ-Al2O3In pure matter γ-Al2O3With aluminum γ-the Al generated after colloidal sol calcining2O3Mass percent；Coating and the mass percent scope of cordierite honeycomb ceramic carrier；Meter Draw configuration coating slurry and can generate the quality of coating.
According to having determined that the ratio of each constituent element, calculate major catalyst respectively, promoter, coating material, Ludox are generated SiO2, pure matter γ-Al2O3, Alumina gel generated γ-Al2O3Quality, in conjunction with every 170.5g copper chloride prepare 79.5g oxidation It is unchanged that copper oligomer, every 429.3g zirconium nitrate prepare 123.2g zirconium oxide oligomer, ZSM-5 molecular sieve quality, calculates system The copper chloride of the required consumption of standby major catalyst, zirconium nitrate, the quality of ZSM-5 molecular sieve.Corresponding according to every 100g major catalyst The ratio of 200～300ml normal hexane, calculates the quality preparing the required normal hexane consumed of major catalyst；It is coated with according to every 100g Polyethylene Glycol and the ratio of 25～50g nitric acid that layer needs 5～15g mean molecule quantities to be 20000, calculates preparation coating slurry The required Polyethylene Glycol consumed of liquid and the quality of nitric acid；And according to SiO in Ludox2Actual mass percentage ratio, in Alumina gel Al2O3Actual mass percentage ratio and pure matter γ-Al2O3Quality is unchanged, calculates and prepares the required silicon consumed of coating slurry Colloidal sol, Alumina gel and pure matter γ-Al2O3Quality.
(2) preparation of major catalyst
Weigh and have determined that the copper chloride of quality, zirconium nitrate, ZSM-5 molecular sieve, they are poured into together and has determined that the just own of quality In alkane, strong stirring 2～4 hours.Then the suspension of mix homogeneously is evaporated in 60～70 DEG C of water-baths normal hexane, then will It is evaporated the powder after liquid to put in roaster.Under He atmosphere, with the ramp of 5～10 DEG C/min to 500 DEG C, and Roasting 4～8h at 500 DEG C.Until sample cool down after, is pulverized, grind to form particle diameter be less than the 100 little granules of purpose standby, this It is metal modified molecular screen major catalyst powder.
(3) preparation of coating paste
The metal modified molecular screen major catalyst powder that will have prepared, and have determined that pure matter CeO of quality2, pure matter ZrO2, pure Matter γ-Al2O3, Alumina gel, Ludox, Polyethylene Glycol and nitric acid, adding quality is coating gross mass 5～the deionization of 10 times In water, continuous stirring makes powder be evenly dispersed in liquid becomes slurry.It is ground to put down on wet grinding mill by this slurry again All particle diameters are 1.0～1.2 micrometer ranges, then sealed by gained slurry, stand, obtain stable slurry after one week.
(4) load of coating paste
Take the quality cylinder 400 mesh cordierite honeycomb ceramics carrier impregnation less than coating gross mass in the stable slurry of 60～80 DEG C In, and ensure that the upper surface of ceramic monolith is slightly above slurry liquid level, and behind all ducts that serosity promotes full carrier naturally, will Carrier takes out from slurry, blows residual liquid in duct off, is dried 6～12h at 80～110 DEG C, then at 500～550 DEG C Calcining 2～4h, repeats above-mentioned dipping, dry and calcination process 2～3 times, and wherein last calcining is to calcine at 600 DEG C 4h, i.e. obtains use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst.
The use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst that will be obtained by above-mentioned steps, is packaged in bavin HC, CO and PM pollutant in oil machine oxidation catalyzer, in purification diesel engine aerofluxus.
Feature and the generation thereof of the present invention provide the benefit that: utilize low cost, high activity, the copper of high resistance to SO_2, zirconium double metal Modified zsm-5 zeolite replacement noble metal, as the major catalyst of diesel oxidation catalyst, not only significantly reduces catalyst Production cost, also can be greatly improved sulfur resistance and the thermal ageing resistant performance of catalyst, extend making of diesel oxidation catalyst Use the life-span.Additionally, on catalyst preparation process, use solid liposome nanoparticle method based on normal hexane suspension process as sponsoring The preparation method of agent not only shortens the preparation time of major catalyst, but also achieves the accurate control of modified metal load capacity.
Accompanying drawing explanation
Fig. 1 is that diesel oxidation catalyst pollutant purification performance engine evaluates system schematic.
Wherein: 1-dynamometer machine；2-tests diesel engine；3-inlet air flow gauge；4-air inlet air conditioning；5-electronic control unit (ECU)； 6-exhaust gas temperature sensor；7-diesel oxidation catalyst (DOC) front gaseous contaminant sample tap；Before 8-DOC, particulate matter takes Sample mouth；9-DOC；Gaseous contaminant sample tap after 10-DOC；Particulate matter sample tap after 11-DOC；12-particulate matter dilution tunnel Sampler；13-gas analyser.
Fig. 2 is to utilize described diesel oxidation catalyst pollutant purification performance engine to evaluate system, and in Europe, steady state test follows HC pollutant in the embodiment 1 obtained in ring (European steady state cycle-ESC) test～5 pairs of diesel exhaust gases Clean-up effect.
Fig. 3 is to utilize described diesel oxidation catalyst pollutant purification performance engine to evaluate system, obtains in ESC tests Embodiment 1～5 pairs of diesel exhaust gases in the clean-up effect of CO pollutant.
Fig. 4 is to utilize described diesel oxidation catalyst pollutant purification performance engine to evaluate system, obtains in ESC tests Embodiment 1～the clean-up effect of 5 pairs of diesel engine discharged particles (PM).
Fig. 5 be utilize described diesel oxidation catalyst pollutant purification performance engine evaluate system, 2510r/min, 100% Under the steady state condition of load, test the embodiment 1～the average cleanup effect of 5 pairs of diesel engine PM pollutant obtained for 1 hour.
Detailed description of the invention
Below by way of combining accompanying drawing and specific embodiment, technical scheme is further described.Need explanation Be described embodiment be narrative, rather than determinate, the content that the present invention is contained is not limited to following embodiment.
Technical scheme is divided into the composition of catalyst and method two parts of preparation load to be explained.
The technical scheme of the composition of catalyst is:
Use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst, its composition is: by CuCl2·2H2O and Zr(NO3)4·5H2O and modified ZSM-5 type molecular sieve material, it is thus achieved that binary metal modified zsm-5 zeolite type catalyst (i.e. by copper chloride, zirconium nitrate mixed solution, ZSM-5 molecular sieve material is modified, it is thus achieved that binary metal as major catalyst Modified zsm-5 zeolite material).Wherein Cu element and Zr element are respectively with copper oxide oligomer and the shape of zirconium oxide oligomer Formula is dispersed in surface and the micropore of type ZSM 5 molecular sieve.Copper oxide oligomer, zirconium oxide oligomer and ZSM-5 The mass percent of type molecular sieve is: 3.0～6.0%/2.0～6.0%/95.0～88.0%, and the percentage ratio sum of gross mass is 100%, by pure matter CeO2With pure matter ZrO2Composition promoter, by SiO2With γ-Al2O3Composition coating material, and by sponsoring Agent, promoter and coating material collectively constitute coating.
By pure matter CeO2With pure matter ZrO2The promoter of composition, its pure matter CeO2With pure matter ZrO2Mass percent be: 50～80%/50～20%, the percentage ratio sum of gross mass is 100%.
By SiO2With γ-Al2O3The coating material of composition, its SiO2With γ-Al2O3Mass percent be: 20～30%/80～ 70%, the percentage ratio sum of gross mass is 100%.
SiO in coating material2The SiO generated after calcining from Ludox2；γ-Al in described coating material2O3Respectively from Pure matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3, pure matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3's Mass percent is: 70～100%/30～0%, and the percentage ratio sum of gross mass is 100%.
By binary metal modified zsm-5 zeolite type major catalyst, by pure matter CeO2With pure matter ZrO2The co-catalysis collectively constituted Agent and by SiO2With γ-Al2O3The mass percent of the coating material collectively constituted is: 20～30%/10～20%/70～ 50%, the percentage ratio sum of gross mass is 100%.
By 400 mesh cordierite honeycomb ceramics as carrier, major catalyst, promoter and the coating material painting collectively constituted Layer, is coated on 400 mesh cordierite honeycomb ceramics carriers, and the percent mass of coating and 400 mesh cordierite honeycomb ceramics carriers Ratio is: 10～30%/90～70%, and the percentage ratio sum of gross mass is 100%.
Use for diesel engine based on modified molecular screen major catalyst is collectively constituted compound by major catalyst, promoter and coating material The coating of oxidation catalyst and it needs to coating is coated on 400 mesh cordierite honeycomb ceramics carriers.
The method describing the preparation load of this catalyst below by way of specific embodiment in detail.
Embodiment 1
(1) preparation and the determination of supported catalyst raw material dosage
CuO oligomer, ZrO in design major catalyst2The mass percent of oligomer and ZSM-5 molecular sieve is: 6%:6%: 88%；Pure matter CeO in promoter2With pure matter ZrO2Mass percent be: 80%:20%；Major catalyst, promoter And the mass percent of coating material is: 20%:15%:65%；In coating material, SiO2With γ-Al2O3Percent mass Ratio is: 20%:80%；All γ-Al2O3In pure matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3Mass percent For: 70%:30%；Polyethylene Glycol that every 100g coating needs 15g mean molecule quantity to be 20000 and 50g nitric acid；Every 100g Major catalyst needs 300ml normal hexane.
Calculate according to conversion scale and prepare 2000g coating needed raw material consumption: copper chloride 51.4g, zirconium nitrate 83.6g, ZSM-5 Molecular sieve 352g, normal hexane 1200ml, pure matter CeO2240g, pure matter ZrO2The generated SiO of 60g, Ludox2260g, pure Matter γ-Al2O3728g, Alumina gel generated γ-Al2O3312g；Consumption nitric acid 1000g, mean molecule quantity are the poly-second of 20000 Glycol 300g.
SiO in the Ludox that the present embodiment is used2Mass content is 25%, thus calculates and needs Ludox 1040g；This reality Execute Al in the Alumina gel that example is used2O3Content be 10.8%, thus calculate and need Alumina gel 2888.9g.
(2) preparation of major catalyst
Weigh the CuCl having determined that quality2·2H2O、Zr(NO3)4·5H2O, ZSM-5 molecular sieve, pour into it together and have determined that In the normal hexane of volume, strong stirring 4 hours, then the suspension of mix homogeneously is evaporated normal hexane in 65 DEG C of water-baths. Powder after being evaporated liquid again is put in roaster, under He atmosphere, with the ramp of 5 DEG C/min to 500 DEG C, and Roasting 8h at 500 DEG C.Until sample cool down after, is pulverized, grind to form particle diameter be less than the 100 little granules of purpose standby.This It is metal modified molecular screen major catalyst powder.
(3) preparation of coating paste
By the major catalyst powder prepared and pure matter CeO having determined that quality2, pure matter ZrO2, pure matter γ-Al2O3, Alumina gel, Ludox, Polyethylene Glycol, nitric acid add in 20000g deionized water, and continuous stirring makes powder be evenly dispersed in liquid.Again Above-mentioned slurry is ground on wet grinding mill D50 particle diameter be in 1.0～1.2 micrometer ranges, then gained slurry is sealed, Stand, after one week, obtain stable slurry.
(4) coating of coating paste
Take the cylinder 400 mesh cordierite honeycomb ceramics carrier impregnation of 1kg in the stable slurry of 80 DEG C, and ensure ceramic monolith Upper surface be slightly above slurry liquid level.Behind all ducts that serosity promotes full carrier naturally, carrier is taken out from slurry, Blow residual liquid in duct off, at 90 DEG C, be dried 12h, then at 550 DEG C, calcine 2h.Repeat above-mentioned dipping, be dried and forge Burning process 3 times.Wherein last calcining is calcining 4h at 600 DEG C, i.e. obtains bavin based on modified molecular screen major catalyst Oil machine compound oxidizing catalyst.
Use the diesel oil based on modified molecular screen major catalyst that coating paste preparation and carrying method described in embodiment 1 prepare Machine is with in compound oxidizing catalyst, and coating with the mass percent of 400 mesh cordierite honeycomb ceramics carriers is: 11～13%/ 89～87%, mass percent sum is 100%.
Embodiment 2
(1) preparation and the determination of supported catalyst raw material dosage
CuO oligomer, ZrO in design major catalyst2The mass percent of oligomer and ZSM-5 molecular sieve is: 3%:2%: 95%；Pure matter CeO in promoter2With pure matter ZrO2Mass percent be: 50%:50%；Major catalyst, promoter And the mass percent of coating material is: 30%:20%:50%；In coating material, SiO2With γ-Al2O3Percent mass Ratio is: 30%:70%；All γ-Al2O3In pure matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3Mass percent For: 80%:20%；Polyethylene Glycol that every 100g coating needs 15g mean molecule quantity to be 20000 and 25g nitric acid；Every 100g Major catalyst needs 200ml normal hexane.
Calculate according to conversion scale and prepare 2000g coating needed raw material consumption: copper chloride 38.6g, zirconium nitrate 41.8g, ZSM-5 Molecular sieve 570g, normal hexane 1200ml, pure matter CeO2200g, pure matter ZrO2The generated SiO of 200g, Ludox2 300g、 Pure matter γ-Al2O3560g, Alumina gel generated γ-Al2O3140g, nitric acid 500g, mean molecule quantity are the Polyethylene Glycol of 20000 300g。
SiO in the Ludox that the present embodiment is used2Mass content be 25%, thus calculate and need Ludox 1200g；This Al in the Alumina gel that embodiment is used2O3Mass content be 10.8%, thus calculate and need Alumina gel 1296.3g.
(2) preparation of major catalyst
Weigh the CuCl having determined that quality2·2H2O、Zr(NO3)4·5H2O, ZSM-5 molecular sieve, pour into it together and have determined that In the normal hexane of quality, strong stirring 2 hours, then the suspension of mix homogeneously is evaporated normal hexane in 60 DEG C of water-baths.Again Powder after being evaporated liquid is put in roaster, under He atmosphere, with the ramp of 10 DEG C/min to 500 DEG C, and Roasting 4h at 500 DEG C.Until sample cool down after, is pulverized, grind to form particle diameter be less than the 100 little granules of purpose standby.This is Metal modified molecular screen major catalyst powder.
(3) preparation of coating paste
By the major catalyst powder prepared and pure matter CeO having determined that quality2, pure matter ZrO2, pure matter γ-Al2O3, Alumina gel, Ludox, Polyethylene Glycol, nitric acid add in 16000g deionized water, and continuous stirring makes powder be evenly dispersed in liquid.Again Above-mentioned slurry is ground on wet grinding mill D50 particle diameter be in 1.0～1.2 micrometer ranges, then gained slurry is sealed, Stand, after one week, obtain stable slurry.
(4) coating of coating paste
Take the cylinder 400 mesh cordierite honeycomb ceramics carrier impregnation of 1kg in the described stable slurry of 60 DEG C, and ensure pottery The upper surface of carrier is slightly above slurry liquid level.Behind all ducts that serosity promotes full carrier naturally, carrier is taken from slurry Go out, blow residual liquid in duct off, at 110 DEG C, be dried 6h, then at 500 DEG C, calcine 4h.Repeat above-mentioned dipping, be dried With calcination process 3 times.Wherein last calcining is calcining 4h at 600 DEG C, i.e. obtains based on modified molecular screen major catalyst Use for diesel engine compound oxidizing catalyst.
Use the diesel oil based on modified molecular screen major catalyst that coating paste preparation and carrying method described in embodiment 2 prepare Machine is with in compound oxidizing catalyst, and coating with the mass percent of 400 mesh cordierite honeycomb ceramics carriers is: 24～26%/ 76～74%, mass percent sum is 100%.
Embodiment 3
(1) preparation and the determination of supported catalyst raw material dosage
CuO oligomer, ZrO in design major catalyst2The mass percent of oligomer and ZSM-5 molecular sieve is: 5%:5%: 90%；Pure matter CeO in promoter2With pure matter ZrO2Mass percent be: 60%:40%；Major catalyst, promoter And the mass percent of coating material is: 25%:15%:60%；In coating material, SiO2With γ-Al2O3Percent mass Ratio is: 25%:75%；All γ-Al2O3In pure matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3Mass percent For: 80%:20%；Polyethylene Glycol that every 100g coating needs 10g mean molecule quantity to be 20000 and 40g nitric acid；Every 100g Major catalyst needs 250ml normal hexane.
Calculate according to conversion scale and prepare 2000g coating needed raw material consumption: copper chloride 53.6g, zirconium nitrate 87.1g, ZSM-5 Molecular sieve 450g, normal hexane 1250ml, pure matter CeO2180g, pure matter ZrO2The generated SiO of 120g, Ludox2 300g、 Pure matter γ-Al2O3720g, Alumina gel generated γ-Al2O3180g, nitric acid 800g, mean molecule quantity are the Polyethylene Glycol of 20000 200g。
SiO in the Ludox that the present embodiment is used2Mass content be 25%, thus calculate and need Ludox 1200g；This Al in the Alumina gel that embodiment is used2O3Mass content be 10.8%, thus calculate and need Alumina gel 1666.7g.
(2) preparation of major catalyst
Weigh the CuCl having determined that quality2·2H2O、Zr(NO3)4·5H2O, ZSM-5 molecular sieve, pour into it together and have determined that In the normal hexane of quality, strong stirring 3 hours, then the suspension of mix homogeneously is evaporated normal hexane in 70 DEG C of water-baths.Again Powder after being evaporated liquid is put in roaster, under He atmosphere, with the ramp of 5 DEG C/min to 500 DEG C, and Roasting 6h at 500 DEG C.Until sample cool down after, is pulverized, grind to form particle diameter be less than the 100 little granules of purpose standby.This is Metal modified molecular screen major catalyst powder.
(3) preparation of coating paste
By the major catalyst powder prepared and pure matter CeO having determined that quality2, pure matter ZrO2, pure matter γ-Al2O3, Alumina gel, Ludox, Polyethylene Glycol, nitric acid add in 10000g deionized water, and continuous stirring makes powder be evenly dispersed in liquid.Again Above-mentioned slurry is ground on wet grinding mill D50 particle diameter be in 1.0～1.2 micrometer ranges, then gained slurry is sealed, Stand, after one week, obtain stable slurry.
(4) coating of coating paste
Take the cylinder 400 mesh cordierite honeycomb ceramics carrier impregnation of 1kg in the described stable slurry of 70 DEG C, and ensure pottery The upper surface of carrier is slightly above slurry liquid level.Behind all ducts that serosity promotes full carrier naturally, carrier is taken from slurry Go out, blow residual liquid in duct off, at 100 DEG C, be dried 10h, then at 500 DEG C, calcine 3h.Repeat above-mentioned dipping, be dried With calcination process 3 times, wherein last calcining is calcining 4h at 600 DEG C, i.e. obtains based on modified molecular screen major catalyst Use for diesel engine compound oxidizing catalyst.
Use the diesel oil based on modified molecular screen major catalyst that coating paste preparation and carrying method described in embodiment 3 prepare Machine is with in compound oxidizing catalyst, and coating with the mass percent of 400 mesh cordierite honeycomb ceramics carriers is: 18～20%/ 82～80%, mass percent sum is 100%.
Embodiment 4
(1) preparation and the determination of supported catalyst raw material dosage
CuO oligomer, ZrO in design major catalyst2The mass percent of oligomer and ZSM-5 molecular sieve is: 5%:5%: 90%；Pure matter CeO in promoter2With pure matter ZrO2Mass percent be: 50%:50%；Major catalyst, promoter And the mass percent of coating material is: 20%:20%:60%；In coating material, SiO2With γ-Al2O3Percent mass Ratio is: 30%:70%；All γ-Al2O3In pure matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3Mass percent For: 100%:0%；Polyethylene Glycol that every 100g coating needs 5g mean molecule quantity to be 20000 and 30g nitric acid；Every 100g Major catalyst needs 250ml normal hexane.
Calculate according to conversion scale and prepare 2000g coating needed raw material consumption: copper chloride 42.9g, zirconium nitrate 69.7g, ZSM-5 Molecular sieve 360g, normal hexane 1000ml, pure matter CeO2200g, pure matter ZrO2The generated SiO of 200g, Ludox2 360g、 Pure matter γ-Al2O3Powder 840g, nitric acid 600g, mean molecule quantity are the Polyethylene Glycol 100g of 20000.The present embodiment is used SiO in Ludox2Mass content be 25%, thus calculate and need Ludox 1200g；The Alumina gel that the present embodiment is used Consumption be 0g.
(2) preparation of major catalyst
Weigh the CuCl having determined that quality2·2H2O、Zr(NO3)4·5H2They are poured into the most true by O, ZSM-5 molecular sieve together Determine in the normal hexane of quality, strong stirring 3 hours, then the suspension of mix homogeneously is evaporated normal hexane in 65 DEG C of water-baths. Powder after being evaporated liquid again is placed in roaster, under He atmosphere, is warming up to 500 DEG C with 8 DEG C/min, and at 500 DEG C Lower roasting 8h.Until sample cool down after, is pulverized, grind to form particle diameter be less than the 100 little granules of purpose standby.This is metal and changes Property molecular sieve major catalyst powder.
(3) preparation of coating paste
By the major catalyst powder prepared and pure matter CeO having determined that quality2, pure matter ZrO2, pure matter γ-Al2O3, Ludox, Polyethylene Glycol, nitric acid add in 20000g deionized water, and continuous stirring makes powder be evenly dispersed in liquid.Again by above-mentioned slurry Material is ground to D50 particle diameter on wet grinding mill and is in 1.0～1.2 micrometer ranges, is then sealed by gained slurry, stands, Stable slurry is obtained after one week.
(4) coating of coating paste
Take 400 mesh cordierite honeycomb ceramics carrier impregnation of suitable shape and quality in the described stable slurry of 70 DEG C, and ensure The upper surface of ceramic monolith is slightly above slurry liquid level.Behind all ducts that serosity promotes full carrier naturally, by carrier from slurry Middle taking-up, blows residual liquid in duct off, is dried 6h, then calcines 2h at 550 DEG C at 110 DEG C.Repeat above-mentioned dipping, Being dried and calcination process 2 times, wherein last calcining is calcining 4h at 600 DEG C, i.e. obtains sponsoring based on modified molecular screen The use for diesel engine compound oxidizing catalyst of agent.
Use the diesel oil based on modified molecular screen major catalyst that coating paste preparation and carrying method described in embodiment 4 prepare Machine is with in compound oxidizing catalyst, and coating with the mass percent of 400 mesh cordierite honeycomb ceramics carriers is: 10～12%/ 90～88%, mass percent sum is 100%.
Embodiment 5
(1) preparation and the determination of supported catalyst raw material dosage
CuO oligomer, ZrO in design major catalyst2The mass percent of oligomer and ZSM-5 molecular sieve is: 6%:6%: 88%；Pure matter CeO in promoter2With pure matter ZrO2Mass percent be: 70%:30%；Major catalyst, promoter And the mass percent of coating material is: 25%:15%:60%；In coating material, SiO2With γ-Al2O3Percent mass Ratio is: 30%:70%；All γ-Al2O3In pure matter γ-Al2O3γ-the Al generated after powder and Alumina gel calcining2O3Quality it Ratio is: 75%:25%；Polyethylene Glycol that every 100g coating needs 10g mean molecule quantity to be 20000 and 30g nitric acid；Often 100g major catalyst needs 250ml normal hexane.
Calculate according to conversion scale and prepare 2000g coating needed raw material consumption: copper chloride 64.3g, zirconium nitrate 104.5g, ZSM-5 Molecular sieve 440g, normal hexane 1250ml, pure matter CeO2210g, pure matter ZrO2The generated SiO of 90g, Ludox2360g, pure Matter γ-Al2O3Powder 630g, Alumina gel generated γ-Al2O3210g, nitric acid 600g, mean molecule quantity are the poly-second of 20000 Glycol 200g.
SiO in the Ludox that the present embodiment is used2Mass content be 25%, thus calculate and need Ludox 1440g；This Al in the Alumina gel that embodiment is used2O3Mass content be 10.8%, thus calculate and need Alumina gel 1944.4g.
(2) preparation of major catalyst
Weigh the CuCl having determined that quality2·2H2O、Zr(NO3)4·5H2They are poured into the most true by O, ZSM-5 molecular sieve together Determine in the normal hexane of volume, strong stirring 4 hours, then the suspension of mix homogeneously is evaporated normal hexane in 65 DEG C of water-baths. Powder after being evaporated liquid again is put in roaster, under He atmosphere, with the ramp of 5 DEG C/min to 500 DEG C, and Roasting 6h at 500 DEG C.Until sample cool down after, is pulverized, grind to form particle diameter be less than the 100 little granules of purpose standby.This It is metal modified molecular screen major catalyst powder.
(3) preparation of coating paste
By the major catalyst powder prepared and pure matter CeO having determined that quality2, pure matter ZrO2, pure matter γ-Al2O3, Alumina gel, Ludox, Polyethylene Glycol, nitric acid add in 20000g deionized water, and continuous stirring makes powder be evenly dispersed in liquid.Again Above-mentioned slurry is ground on wet grinding mill D50 particle diameter be in 1.0～1.2 micrometer ranges, then gained slurry is sealed, Stand, after one week, obtain stable slurry.
(4) coating of coating paste
Take the cylinder 400 mesh cordierite honeycomb ceramics carrier impregnation of 1kg in the described stable slurry of 80 DEG C, and ensure pottery The upper surface of carrier is slightly above slurry liquid level.Behind all ducts that serosity promotes full carrier naturally, carrier is taken from slurry Go out, blow residual liquid in duct off, at 100 DEG C, be dried 9h, then at 550 DEG C, calcine 2h.Repeat above-mentioned dipping, be dried With calcination process 3 times, wherein last calcining is calcining 4h at 600 DEG C, i.e. obtains based on modified molecular screen major catalyst Use for diesel engine compound oxidizing catalyst.
Use the diesel oil based on modified molecular screen major catalyst that coating paste preparation and carrying method described in embodiment 1 prepare Machine is with in compound oxidizing catalyst, and coating with the mass percent of 400 mesh cordierite honeycomb ceramics carriers is: 20～22%/ 80～78%, mass percent sum is 100%.
The diesel oxidation catalyst pollutant purification performance engine shown in Fig. 1 is used to evaluate system, to described 5 embodiments HC, CO and PM pollutant purification performance be evaluated, result is as shown in Figure 2-5.
Test diesel engine model is CY4102-C3B, and its test method is:
(1) ESC test: use described diesel oxidation catalyst pollutant purification performance engine to evaluate system, and according to state Family standard GB 17691-2005 " automobile-used compression-ignited, gaseous fuel spark-ignition engine and automobile exhaust pollutant discharge limit value and Measuring method (China III, IV, V stage) " in the ESC test cycle of regulation evaluate embodiment 1～the 5 couples of diesel engine CO, The clean-up effect of HC and PM pollutant, result is the most as shown in Figure 2,3, 4.
(2) steady state condition test: the rotating speed using dynamometer machine 1 Control experiment electromotor 2 is 2510rpm, load is 100%. The aerofluxus of test engine is after the process of diesel oxidation catalyst 9, and it is dilute that the sampled mouth of a portion 11 enters particulate matter Release passage sampler 12.Particulate matter dilution tunnel sampler needed to install the most weighed just prothyl before being passed through engine exhaust The filter paper of amount, and engine exhaust passes through filter paper, the particulate matter in aerofluxus in particulate matter dilution tunnel sampler after dilution Just it is intercepted on filter paper.After continuous sampling 1h, take out filter paper and filter paper is weighed.Sample the difference of forward and backward filter paper quality It is the quality of exhaust particulate.Additionally, some sampled mouth of tail gas 10 after diesel oxidation catalyst processes enters Enter exhaust gas analyzer 13, to realize the on-line measurement of HC and CO concentration of emission.
On the other hand, in diesel oxidation catalyst pollutant purification performance engine evaluation system, microgranule dilution tunnel samples System and emission analyzer can be sampled mouth 7 the most respectively and sample tap 8 measures HC, CO and PM discharge capacity before DOC, And by the comparison of the forward and backward three kinds of pollutant discharge amounts of DOC, calculating, determine the DOC transformation efficiency to three kinds of pollutant, Result is as shown in Figure 5.

Claims (8)

1. use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst, has: copper chloride, zirconium nitrate, ZSM-5 Type molecular sieve, CuO, ZrO2、CeO2、SiO2、γ-Al2O3, 400 mesh cordierite honeycomb ceramics carriers, normal hexane, poly-second Glycol and nitric acid, is characterized in that: by copper chloride, zirconium nitrate and modified ZSM-5 type molecular sieve material, it is thus achieved that binary Metal-modified ZSM-5 molecular sieve type catalyst is as major catalyst, and wherein Cu element and Zr element are respectively with copper oxide oligomer With the form of zirconium oxide oligomer, be dispersed in surface and the micropore of type ZSM 5 molecular sieve, wherein copper oxide oligomer, The mass percent of zirconium oxide oligomer and type ZSM 5 molecular sieve is: 3.0～6.0%/2.0～6.0%/95.0～88.0%, The percentage ratio sum of gross mass is 100%；By pure matter CeO2With pure matter ZrO2Composition promoter；By SiO2With γ-Al2O3 Composition coating material；And collectively constituted coating by major catalyst, promoter and coating material.
2., according to the use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst described in claim 1, it is special Levy and be: be described by pure matter CeO2With pure matter ZrO2The promoter of composition, its pure matter CeO2With pure matter ZrO2Percent mass Ratio is: 50～80%/50～20%, and the percentage ratio sum of gross mass is 100%.
3., according to the use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst described in claim 1, it is special Levy and be: be described by SiO2With γ-Al2O3The coating material of composition, its SiO2With γ-Al2O3Mass percent be: 20～30% / 80～70%, the percentage ratio sum of gross mass is 100%.
4., according to the use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst described in claim 1, it is special Levy and be: the SiO in described coating material2The SiO generated after calcining from Ludox2；γ-Al in described coating material2O3Point Not from pure matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3, pure matter γ-Al2O3Generate after calcining with Alumina gel γ-Al2O3Mass percent be: 70～100%/30～0%, the percentage ratio sum of gross mass is 100%.
5., according to the use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst described in claim 1, it is special Levy and be: by described binary metal modified zsm-5 zeolite type major catalyst, by pure matter CeO2With pure matter ZrO2Collectively constitute Promoter and by SiO2With γ-Al2O3The mass percent of the coating material collectively constituted is: 20～30%/10～20% / 70～50%, the percentage ratio sum of gross mass is 100%.
6., according to the use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst described in claim 1, it is special Levy and be: by described 400 mesh cordierite honeycomb ceramics as carrier, described common by major catalyst, promoter and coating material With the coating of composition, it is coated on 400 mesh cordierite honeycomb ceramics carriers, and coating and 400 mesh cordierite honeycomb ceramics carriers Mass percent be: 10～30%/90～70%, the percentage ratio sum of gross mass is 100%.
7. the system according to use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst described in claim 1 Standby and carrying method, is characterized in that: concrete technology comprises the following steps:
(1) preparation and the determination of supported catalyst raw material dosage
According to each proportioning described in claim 1 to 5, separately design out CuO oligomer, ZrO in major catalyst2Oligomer and The mass percent of each constituent element of type ZSM 5 molecular sieve；Pure matter CeO in promoter2With pure matter ZrO2Mass percent；Main The mass percent of catalyst, promoter and coating material；SiO in coating material2With γ-Al2O3, whole γ-Al2O3In pure Matter γ-Al2O3γ-the Al generated after calcining with Alumina gel2O3Mass percent；Coating and the quality of cordierite honeycomb ceramic carrier Percentage range；Planned allocation coating slurry can generate the quality of coating；
According to having determined that the ratio of each constituent element, calculate major catalyst respectively, promoter, coating material, Ludox are generated SiO2, pure matter γ-Al2O3, Alumina gel generated γ-Al2O3Quality；79.5g oxidation is prepared in conjunction with every 170.5g copper chloride It is unchanged that copper oligomer, every 429.3g zirconium nitrate prepare 123.2g zirconium oxide oligomer, ZSM-5 molecular sieve quality, calculates system The copper chloride of the required consumption of standby major catalyst, zirconium nitrate, the quality of ZSM-5 molecular sieve；Corresponding according to every 100g major catalyst The ratio of 200～300ml normal hexane, calculates the quality preparing the required normal hexane consumed of major catalyst；It is coated with according to every 100g Polyethylene Glycol and the ratio of 25～50g nitric acid that layer needs 5～15g mean molecule quantities to be 20000, calculates preparation coating slurry The required Polyethylene Glycol consumed of liquid and the quality of nitric acid；And according to SiO in Ludox2Actual mass percentage ratio, in Alumina gel Al2O3Actual mass percentage ratio and pure matter γ-Al2O3Quality is unchanged, calculates and prepares the required silicon consumed of coating slurry Colloidal sol, Alumina gel and pure matter γ-Al2O3Quality；
(2) preparation of major catalyst
Weigh and have determined that the copper chloride of quality, zirconium nitrate, ZSM-5 molecular sieve, they are poured into together and has determined that the just own of quality In alkane, strong stirring 2～4 hours, then the suspension of mix homogeneously is evaporated in 60～70 DEG C of water-baths normal hexane, then will It is evaporated the powder after liquid and puts in roaster, under He atmosphere, with the ramp of 5～10 DEG C/min to 500 DEG C, and Roasting 4～8h at 500 DEG C, until sample cool down after, is pulverized, grind to form particle diameter be less than the 100 little granules of purpose standby, This is metal modified molecular screen major catalyst powder；
(3) preparation of coating paste
The metal modified molecular screen major catalyst powder that will have prepared, and have determined that pure matter CeO of quality2, pure matter ZrO2, pure Matter γ-Al2O3, Alumina gel, Ludox, Polyethylene Glycol and nitric acid, adding quality is coating gross mass 5～the deionization of 10 times In water, continuous stirring makes powder be evenly dispersed in liquid becomes slurry, then is ground on wet grinding mill by described slurry Mean diameter is 1.0～1.2 micrometer ranges, is then sealed by gained slurry, stands, obtains stable slurry after one week；
(4) load of coating paste
Take quality less than described stable in 60～80 DEG C of the cylinder 400 mesh cordierite honeycomb ceramics carrier impregnation of coating gross mass In slurry, and ensure that the upper surface of ceramic monolith is slightly above slurry liquid level, behind all ducts that serosity promotes full carrier naturally, Carrier is taken out from slurry, blows residual liquid in duct off, at 80～110 DEG C, be dried 6～12h, then at 500～550 DEG C Lower calcining 2～4h, repeats above-mentioned dipping, dry and calcination process 2～3 times, and wherein last calcining is to forge at 600 DEG C Burn 4h, i.e. obtain use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst.
8., according to the use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst described in claim 1, it is special Levy and be: the use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst that step described in claim 7 is obtained, It is packaged in diesel oxidation catalyst, HC, CO and PM pollutant in purification diesel engine aerofluxus.
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