CN110215931A - Cupric molecular screen material and preparation method thereof and catalyst - Google Patents
Cupric molecular screen material and preparation method thereof and catalyst Download PDFInfo
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- CN110215931A CN110215931A CN201910573325.1A CN201910573325A CN110215931A CN 110215931 A CN110215931 A CN 110215931A CN 201910573325 A CN201910573325 A CN 201910573325A CN 110215931 A CN110215931 A CN 110215931A
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- 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
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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
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7215—Zeolite Beta
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/723—CHA-type, e.g. Chabazite, LZ-218
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
This application involves vehicle maintenance service fields, in particular to a kind of cupric molecular screen material and preparation method thereof and catalyst.When preparation, complex copper solutions are uniformly mixed with molecular sieve, close copper ion and copper atom and molecular sieve bond in complex copper solutions, obtain suspension；Suspension is dried in air atmosphere, in 400 DEG C of -500 DEG C of roasting powders, cupric molecular screen material to be made after powder.Load carriers are carried out, catalyst is obtained.This catalyst activity is high, can be improved the purification efficiency of the nitrogen oxides in vehicle exhaust.This method is loaded over a molecular sieve using complex copper, improves catalytic activity.And preparation method is simple, compares the preparation method of the SCR catalyst of the synthetic zeolite of common supported copper or iron transition metal at present, does not filter and cleaning process, therefore preparation section is simple, is conducive to improve production efficiency.
Description
Technical field
This application involves vehicle maintenance service fields, in particular to a kind of cupric molecular screen material and its preparation side
Method and catalyst.
Background technique
It is that the ammonia for decomposing aqueous solution of urea carries out instead as reducing agent and automobile exhaust gas in automobile exhaust gas processing
It answers, in the process, needs to use NOxSelective catalysis reduction (reduction of commonly known as SCR catalyst, i.e. selective catalysis "
The abbreviation of Selective Catalytic Reduction ").
But the preparation method of the SCR catalyst of the synthetic zeolite of transition metal such as supported copper or iron common at present, system
Standby step is complicated, needs filtering and cleaning process, production efficiency is low, and catalyst activity obtained is low.
Summary of the invention
The embodiment of the present application is designed to provide a kind of cupric molecular screen material and preparation method thereof and catalyst,
It is intended to improve the problem that existing SCR catalyst activity is low, preparation step is complicated.
In a first aspect, the application provides a kind of technical solution:
A kind of preparation method of cupric molecular screen material, comprising:
Complex copper solutions are uniformly mixed with molecular sieve, make copper ion in complex copper solutions and copper atom and molecular sieve key
In conjunction with obtaining suspension；
Suspension is dried as after powder, in air atmosphere, in 400 DEG C -500 DEG C of roasting powders 2.0-5.0 hours.
Over a molecular sieve using complex copper load, it so that having loaded more in conjunction with copper on molecular sieve, improves catalysis and lives
Property.This preparation method step is simple, compares the SCR catalyst of the synthetic zeolite of common at present supported copper or iron transition metal
Preparation method, do not filter and cleaning process, therefore preparation section is simple, be conducive to improve production efficiency.
In the other embodiments of the application, above-mentioned complex copper solutions are by the way that copper ion complexing agent is mixed hair with mantoquita
Raw complex reaction is made.
In the other embodiments of the application, above-mentioned copper ion complexing agent is selected from triethanolamine；Mantoquita is selected from copper acetate；
The molar ratio of triethanolamine and copper acetate is 0.6~0.65.
In the other embodiments of the application, in the above-mentioned step for being uniformly mixed complex copper solutions with molecular sieve, copper is former
The mass ratio of son and molecular sieve is 0.021~0.025.
In the other embodiments of the application, the above-mentioned step for being uniformly mixed complex copper solutions with molecular sieve include: by
Complex copper solutions react -5 hours 3 hours with molecular sieve slurry agitation.
Second aspect, the application provide a kind of technical solution:
A kind of catalyst, the catalyst include as made from the preparation method of above-mentioned cupric molecular screen material containing copper molecule
Sieve material；And
Carrier, cupric molecular screen material are supported on carrier；The material of carrier is selected from cordierite ceramic, silicon carbide, inorganic
Fiber or any one metal；
Optionally, above-mentioned catalyst further include mass fraction be 1.5%-2.5% nanometer Aluminum sol, mass fraction be
The Nano silica sol and mass fraction of 2%-5% is the cellulose of 0.2%-0.04%.
The catalyst, for restoring the nitrogen oxides in vehicle exhaust, high catalytic efficiency.
In the other embodiments of the application, the BET specific surface area of above-mentioned catalyst is 50m2/ g~80m2/g。
The third aspect, the application provide a kind of technical solution:
A kind of cupric molecular screen material, the cupric molecular screen material include molecular sieve and loaded article, and loaded article is supported on point
On son sieve；The content of loaded article is the 2.1%~2.5% of molecular sieve quality；Loaded article includes copper atom and copper ion；Wherein,
Above-mentioned copper ion includes combining copper ion and free copper ion, and the content in conjunction with copper ion is the 50%-70% of loaded article content,
Above-mentioned copper ion includes Cu2+And Cu+。
The content of the cupric molecular screen material combination copper is high, and when for restoring the nitrogen oxides in vehicle exhaust, catalysis is lived
Property it is high.
In the other embodiments of the application, SiO in above-mentioned molecular sieve2/Al2O3Molar ratio in the above-mentioned molecular sieve of 6-12
Selected from h-type zeolite molecular sieve；
Optionally, in molecular sieve of the h-type zeolite molecular sieve selected from BEA, MFI, CHA, AEI, FAU, LTA or AFX structure
At least one.
In the other embodiments of the application, the average grain diameter of above-mentioned cupric molecular screen material is 2.5 μm~3.0 μm.
The beneficial effect of cupric molecular screen material provided by the embodiments of the present application and preparation method thereof and catalyst includes:
Over a molecular sieve using complex copper load, it so that having loaded more in conjunction with copper on molecular sieve, improves catalysis and lives
Property.This preparation method step is simple, compares the SCR catalyst of the synthetic zeolite of common at present supported copper or iron transition metal
Preparation method, do not filter and cleaning process, therefore preparation section is simple, be conducive to improve production efficiency.Using this side
Cupric molecular screen material made from method has good high/low temperature activity, in vehicle maintenance service, can effectively improve nitrogen
Oxide purification efficiency.
Detailed description of the invention
Technical solution in ord to more clearly illustrate embodiments of the present application, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only some embodiments of the application, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the result schematic diagram that catalyst provided by the embodiments of the present application carries out engine bench test；
Fig. 2 is NO of the catalyst provided by the embodiments of the present application under different other conditionsxPurification result schematic diagram.
Specific embodiment
To keep the purposes, technical schemes and advantages of the embodiment of the present application clearer, below in conjunction with the embodiment of the present application
In attached drawing, the technical scheme in the embodiment of the application is clearly and completely described, it is clear that described embodiment is
Some embodiments of the present application, instead of all the embodiments.The application being usually described and illustrated herein in the accompanying drawings is implemented
The component of example can be arranged and be designed with a variety of different configurations.
Therefore, the detailed description of the embodiments herein provided in the accompanying drawings is not intended to limit below claimed
Scope of the present application, but be merely representative of the selected embodiment of the application.Based on the embodiment in the application, this field is common
Technical staff's every other embodiment obtained without creative efforts belongs to the model of the application protection
It encloses.
Term " first ", " second ", " third " etc. are only used for distinguishing description, are not understood to indicate or imply relatively heavy
The property wanted.
The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
The application embodiment provides a kind of cupric molecular screen material.The cupric molecular screen material is by the way that complex copper is molten
Liquid is mixed to get with molecular sieve.
In some embodiments of the application, which includes molecular sieve and loaded article, and loaded article is negative
It carries over a molecular sieve；The content of loaded article is the 2.1%~2.5% of molecular sieve quality.Loaded article includes copper atom and copper ion.
Still optionally further, the content for loading loaded article over a molecular sieve is the 2.2%~2.4% of molecular sieve quality.
Still optionally further, the content for loading loaded article over a molecular sieve is the 2.3% of molecular sieve quality.
In some embodiments of the application, copper ion includes combining copper ion and free copper ion, in conjunction with copper ion
Content be loaded article content 50%-70%.
It still optionally further, is the 55%-65% of loaded article content in conjunction with the content of copper ion.Still optionally further, it ties
The content for closing copper ion is the 60% of loaded article content.
In some embodiments of the application, copper ion includes Cu2+And Cu+。
In some embodiments of the application, SiO in molecular sieve2/Al2O3Molar ratio in 6-12.It is further optional
Ground, SiO in molecular sieve2/Al2O3Molar ratio in 7-11.Still optionally further, SiO in molecular sieve2/Al2O3Molar ratio in 8-
10.Still optionally further, SiO in molecular sieve2/Al2O3Molar ratio 9.
In some embodiments of the application, molecular sieve is selected from h-type zeolite molecular sieve.H-type zeolite molecular sieve has
Excellent heat resistance.Using h-type zeolite molecular sieve, so that cupric molecular screen material obtained has lasting heat resistance,
Even if under the high temperature conditions, being also able to maintain good catalytic activity, thus be preferably applied to reduction vehicle exhaust in NO and
NO2。
Still optionally further, h-type zeolite molecular sieve is selected from BEA, MFI, CHA, AEI, FAU, LTA or AFX type structure
At least one of molecular sieve.Still optionally further, h-type zeolite molecular sieve is selected from H-SSZ-13 type structure.H-SSZ-13 type knot
Structure zeolite molecular sieve has very excellent heat resistance, can greatly improve the continuous heat resistance of cupric molecular screen material, protects
Card cupric molecular screen material has good catalytic activity under high temperature environment.
It should be noted that above-mentioned SiO2/Al2O3Molar ratio 6-12 circular ring structure zeolite molecular sieve, name according to
It is distinguished according to the structural code of international zeolite association (Internat1nal Zeolite Associat1n).Specifically: BEA type knot
Structure (such as β as maximum oxygen number of rings 12)；MFI type structure (such as: the ZSM -5 as maximum oxygen number of rings 10)；CHA type (example
Alumina silicate based compound, phosphatic silicoaluminophosphate based compound such as: the SSZ-13 that maximum oxygen number of rings is 8)；FAU type structure
(such as: the SAP0-37 that maximum oxygen number of rings is 12)；AEI type structure (such as: the SAP0-18 that maximum oxygen number of rings is 8)；CHA type
Structure (such as: SAPO -34, SAPO -44, SAPO -47 of the maximum oxygen number of rings for 8)；LTA structure (such as: maximum oxygen number of rings
SAPO -42 for 8)；AFX structure (such as: the SAPO -56 that maximum oxygen number of rings is 8) etc..
Further, X-ray diffraction analysis is utilized to above-mentioned h-type zeolite molecular sieve, asks brilliant from X-ray diffraction pattern
Lattice interplanar distance (d), with the X-ray diffraction pattern database or I of international synthetic zeolite association (3) D (Internat1nal
Centre forDiffract1n Data；Diffraction data International Center) PDF (Powder Diffract1n File；Powder
Diffraction File) collect data compare identification, it is as a result as follows:
Add hydrogen BEA type synthetic zeolite (Miller indices: 101) d=11.4168 [A]；
Add hydrogen MFI type synthetic zeolite (Miller indices: 011) d=11.1323 [A]；
Add hydrogen CHA type synthetic zeolite (Miller indices: 100) d=9.4076 [A].
In some embodiments of the application, the average grain diameter of cupric molecular screen material is 2.5 μm~3.0 μm.
In some embodiments of the application, the BET specific surface area of cupric molecular screen material is 550m2/g-650m2/g。
Embodiment further provides the preparation methods of above-mentioned cupric molecular screen material by the application, comprising:
Step S1, complex copper solutions are prepared.
Complex copper solutions are made by the way that copper ion complexing agent to be mixed to generation complex reaction with mantoquita.
By preparing complex copper solutions, using complex copper in conjunction with molecular sieve, the higher molecular sieve of activity can be obtained and urged
Agent material.
In some embodiments of the application, copper ion complexing agent is selected from triethanolamine；Mantoquita is selected from copper acetate.By three
Ethanol amine and copper acetate mixing, carry out complex reaction, complex copper solutions are made.In triethanolamine, due to there is orphan on nitrogen-atoms
To electronics, triethanolamine has alkalescent, can generate salt with inorganic acid or organic acid reaction, thus can be complexed cupric from
Son.
Still optionally further, the molar ratio of triethanolamine and copper acetate is 0.6~0.65.Still optionally further, three ethyl alcohol
The molar ratio of amine and copper acetate is 0.61~0.64.Still optionally further, the molar ratio of triethanolamine and copper acetate be 0.62~
0.63。
The preparation step of complex copper solutions for example may include: to take appropriate amount of deionized water, by triethanolamine and deionized water
Mixing, is warmed to 40 DEG C~60 DEG C, is sufficiently stirred 20~30 minutes, and triethanolamine solution is made.Optionally, triethanolamine with go
The mass ratio of ionized water is 1:5.Appropriate amount of deionized water is taken, acetic acid copper solution, optionally, the matter of copper acetate and deionized water are configured
Amount is than being 1:4.Then, according to triethanolamine: the molar ratio of copper acetate are as follows: 0.6~0.65:1 slowly adds acetic acid copper solution
Enter into triethanolamine solution and (optionally, be slowly added to according to 20 minutes time), continues to maintain the temperature at 40 DEG C~60 DEG C,
It is stirred to react 0.5-3h.
In other optional embodiments of the application, above-mentioned copper ion complexing agent can choose other alcamines complexings
Agent, such as monoethanolamine, diethanol amine etc..Above-mentioned mantoquita can choose other mantoquitas, such as copper acetate etc..
Step S2, complex copper solutions are uniformly mixed with molecular sieve.For example, step S1 is obtained complex copper solutions and molecule
Sieve is mutually mixed, and is stirred until homogeneous.
It is mutually mixed by the way that step S1 is obtained complex copper solutions with molecular sieve, so that copper ion in complex copper solutions,
Copper atom and molecular sieve bond are closed, i.e., copper atom and copper ion load over a molecular sieve.
In some embodiments of the application, when complex copper solutions are uniformly mixed with molecular sieve, copper atom and molecule
The mass ratio of sieve is 0.021~0.025.Still optionally further, when complex copper solutions being uniformly mixed with molecular sieve, copper atom with
The mass ratio of molecular sieve is 0.022~0.024.Still optionally further, when complex copper solutions being uniformly mixed with molecular sieve, copper is former
The mass ratio of son and molecular sieve is 0.023.
It further, is that complex copper is made using the method for stirring by the step that complex copper solutions are uniformly mixed with molecular sieve
Solution and molecular sieve are stirred to react -5 hours 3 hours.Still optionally further, step complex copper solutions being uniformly mixed with molecular sieve
It suddenly is so that complex copper solutions and molecular sieve is stirred to react 3.0h~5.0h using the method for stirring.
Specifically, the mass ratio for controlling copper atom and molecular sieve is 0.021 when complex copper solutions are mixed with molecular sieve
~0.025, that is, control the mass ratio 0.06~0.10 of complex copper and molecular sieve.Complex copper solutions are carried out hygrometric state with molecular sieve to mix
It closes, and is stirred to react 3.0h~5.0h.Optionally, when hygrometric state mixes, molecular sieve is blank molecular sieve, and according to molecular sieve: being gone
Ionized water=30-40:60-70 mass ratio is mixed, and is stirred evenly, and molecular sieve slurry is made；Then, by prepared network
It closes copper solution and the most fierce position of the following mass transfer exchange of molecular sieve slurry liquid level, injection time is entered by peristaltic pump direct injection
It is optionally a hour, and continues 3.0~5.0h of stirring.
It in other alternative-embodiments, can be according to molecule when complex copper solutions being mixed with molecular sieve progress hygrometric state
Sieve: deionized water=32-38:62-68 mass ratio is mixed, and molecular sieve slurry is made.Still optionally further, by complex copper
When solution is mixed with molecular sieve progress hygrometric state, can be according to molecular sieve: deionized water=33-37:63-67 mass ratio be mixed
It closes, molecular sieve slurry is made.Still optionally further, when complex copper solutions and molecular sieve being carried out hygrometric state and mixing, can according to point
Son sieve: deionized water=34-36:64-66 mass ratio is mixed, and molecular sieve slurry is made.Still optionally further, above-mentioned system
When the sub- screening the pulp material of back-up, according to molecular sieve: deionized water=38:62 mass ratio, by molecular sieve powder be slowly added into from
In sub- water, stirring is to being mixed thoroughly.
Further, in some embodiments of the application, above-mentioned molecular sieve selects SiO2/Al2O3Molar ratio
(abbreviation silica alumina ratio) is the zeolite molecular sieve of the circular ring structure within the scope of 6-12.Still optionally further, molecular sieve is boiled selected from Hydrogen
Stone molecular sieve.Still optionally further, h-type zeolite molecular sieve is selected from point of BEA, MF1, CHA, AE1, FAU, LTA, AFX type structure
At least one of son sieve.
Step S3, suspension made from step S2 is dried in air atmosphere, to be roasted in 400 DEG C -500 DEG C after powder
It burns powder 2.0-5.0 hours.
As drying suspension made from step S2 for after powder, in air atmosphere, in 400 DEG C of -500 DEG C of roasting powder
Body 2.0-5.0 hours, it can be improved the combination effect of copper atom, copper ion and molecular sieve, make copper atom, copper ion and molecular sieve
It is fixedly combined.
Still optionally further, suspension made from step S2 is dried as after powder, in air atmosphere, in 420 DEG C-
480 DEG C roasting powder 2.5-4.5 hours.Still optionally further, suspension made from step S2 is dried as after powder, in air
Under atmosphere, in 450 DEG C -470 DEG C of roasting powders 3.0-4.0 hours.
In some embodiments of the application, it is using expansion drying that suspension made from step S2, which is dried as powder,
Method be dried.Specifically, can be presented preferable after suspension made from step S2 is adjusted solid content
Mobility, then by spraying flash dryer, be dried at 100 DEG C~150 DEG C.Still optionally further, pass through spraying flash distillation
When dry, temperature control is at 110 DEG C~140 DEG C.When still optionally further, by spraying expansion drying, temperature control is at 120 DEG C~130 DEG C.
It is dried by using the method for expansion drying, can be realized complex copper and molecular sieve by complexation reaction and live
Property site fast shaping, to realize the generation of 50~70% combination copper.
In some embodiments of the application, roasting powder made from above-mentioned expansion drying is that the powder that will be dried is sent into
Rotary calcining furnace, control temperature are roasted within the scope of 400~500 DEG C, and in the process control air flow rate of roasting,
Calcining time is about 2.0h~5.0h.Still optionally further, when roasting powder made from above-mentioned expansion drying, control temperature
Roasted within the scope of 420 DEG C~480 DEG C, and in the process control air flow rate of roasting, calcining time be about 2.2h~
4.8h.Still optionally further, when roasting powder made from above-mentioned expansion drying, temperature is controlled within the scope of 430 DEG C~460 DEG C
It is roasted, and in the process control air flow rate of roasting, calcining time is about 2.4h~4.6h.
By roasting, it is 50~70% that the content ratio of copper is combined in the molecular sieve catalytic agent material of cupric obtained.Knot
The raising for closing the content of copper, can effectively improve the activity of molecular sieve catalytic agent material, and then improves it and restore NO and NO2's
Efficiency.
The average grain diameter control of cupric molecular screen material obtained above is 2.5 μm~3.0 μm.Cupric obtained above point
The particle size determination of son sieve material is measured using laser diffraction formula hondrometer, and 1.544 refractive index, particle addition are specially selected
The shading rate that amount is 13~15%, is dispersed using ultrasonic wave, and jitter time is three minutes.The volume of particle diameter distribution is accumulative
50% partial size (D50) is 2.5~3.0 μm and meets the requirements.
By the way that the size controlling of cupric molecular screen material obtained above at 2.5 μm~3.0 μm, can be greatlyd improve
The catalytic activity of cupric molecular screen material improves NO and NO in reduction vehicle exhaust2Catalytic efficiency.
The preparation method of the cupric molecular screen material compares the synthetic zeolite of common at present supported copper or iron transition metal
SCR catalyst preparation method, do not filter and cleaning process, therefore preparation section is simple, be conducive to improve production efficiency.
The application embodiment also provides a kind of catalyst, which includes such as cupric molecular screen material obtained above
And carrier.Cupric molecular screen material is supported on carrier.
By the way that carrier is arranged, reaction gas (NO and NO in vehicle exhaust is enabled to2) contacted with catalyst it is even closer.
Further, cupric molecular screen material is supported on carrier.Further, the material of carrier is made pottery selected from cordierite
Any one in porcelain, silicon carbide, inorfil or metal.Still optionally further, carrier be selected from cordierite ceramic 400-4 and
Cordierite ceramic 600-3, whole wall-flow type SDPF carrier, inorfil or any one metal that material is silicon carbide.Into
Optionally, the honeycomb that carrier is selected from porous cordierite flows through type monolith carrier to one step, and specially 400-4 and 600-3's is straight-through
Formula carrier.Still optionally further, carrier is selected from 300/12 silicon carbide entirety wall-flow type SDPF carrier.
Still optionally further, above-mentioned when being supported on cupric molecular screen material on carrier, cupric molecular screen material is in carrier
On bearing capacity be 140g/L~160g/L.For example, the honeycomb as made from cordierite flows through the case where type monolith carrier carrying
Under, cupric molecular screen material carries out NO and NO2When reduction, cupric molecular screen material is born according to the load capacity of 140~160g/L
It is loaded on carrier, can guarantee the enough durabilities of catalyst, and guarantee higher transformation efficiency, and cost is relatively low.
Further, it is the nanometer Aluminum sol of 1.5%-2.5%, quality point that cupric molecular screen material, which further includes mass fraction,
The cellulose that the Nano silica sol and mass fraction that number is 2%-5% are 0.2%-0.04%.Contain copper zeolite for improving
The firmness of the connection of material and carrier.Still optionally further, it is 1.8%-2.0% that cupric molecular screen material, which further includes mass fraction,
Nanometer Aluminum sol, mass fraction be 2.5%-4.5% Nano silica sol and mass fraction be 0.5%-0.1% fiber
Element.It is bonding with carrier secured to can be improved cupric molecular screen material by addition nanometer Aluminum sol, nano-silicon and cellulose
Property.
In some embodiments of the application, it is configured to cupric molecular screen material that nanometer Aluminum sol is added after solution, receives
Rice silicon and cellulose support mixed slurry, and mixed slurry is ground to the particle size range of needs.Optionally, using Horizontal sand
Grinding machine is ground, and specially uses partial size for the zirconium oxide bead of 1.0~1.2mm, and grinding chamber volume is 0.5L, zirconium pearl loading
It is the 70~75% of total volume, power 2.2kw is ground to the granularity of requirement.
Further, the BET specific surface area of the catalyst is 50m2/ g~80m2/g.BET specific surface area is higher, has good
Good catalytic activity.NO and NO with low temperature active and hydrothermal durability2Purifying property, to 180 DEG C or less engine exhausts
Ratio NO:NO2The NO of value >=50%xPurifying rate up to 80% or more.
The feature of the application and performance are described in further detail with reference to embodiments:
Embodiment 1
It is obtained in this way the present embodiment provides a kind of catalyst:
Step S1: select the silica alumina ratio of CHA structure for 22 H-SSZ-13 zeolitic material as molecular sieve.Firstly, pressing
It is 1:5 according to triethanolamine and the mass ratio of deionized water, is warmed to 40 DEG C, is sufficiently stirred 20 minutes, triethanolamine solution is made.
It is 1:4 according to copper acetate and the mass ratio of deionized water, acetic acid copper solution is made.Secondly, according to triethanolamine: copper acetate rubs
Acetic acid copper solution is added in triethanolamine solution than being 0.6:1, continues to be kept for 40 DEG C, be stirred to react 2.0h, network is made by you
Close copper solution.Again, according to molecular sieve: deionized water=40:60 mass ratio is mixed, and is stirred evenly, and molecular sieve is made
Slurry.It is 0.021:1 according to the mass ratio of copper atom and molecular sieve, complex copper solutions is entered by peristaltic pump direct injection and are divided
The sub- following mass transfer of screening the pulp feed liquid surface exchanges most fierce position, one hour of injection time, is stirred for 3.0h after having injected, makes network
The copper ion and copper atom and molecular sieve bond closed in copper solution closes, and obtains suspension.
Step S2: by suspension by spraying flash dryer, being dried at 100 DEG C, and powder is made.Then, by powder
Body is sent into rotary calcining furnace, and under conditions of being passed through air, in 400 DEG C of roasting 5h, cupric molecular screen material is made.
Step S3: cupric molecular screen material is mixed with deionized water, and it is 30% containing copper zeolite that mass fraction, which is made,
The nanometer Aluminum sol that mass fraction is 10%, mass fraction 30% are added in Xiang Hantong molecular screen material solution for material solution
Alkaline nano silica solution, and the gross mass for controlling nanometer Aluminum sol and alkaline nano silica solution is cupric molecular screen material quality
2.0%；The hydroxymethyl cellulose that mass fraction is 0.2% is finally added, the quality of hydroxymethyl cellulose is containing copper molecule
The 0.1% of quality of materials is sieved, mixed slurry is made.Then, mixed slurry is ground to 2.5 by granularity D50 using grinder
Micron.Finally, the mixed slurry after grinding is coated on carrier cordierite ceramic 600-3, the dry upper carrying capacity that increases weight of control coating
For 160g/L；Using drying and roasting, molding obtains finished catalyst.
Embodiment 2
It is obtained in this way the present embodiment provides a kind of catalyst:
Step S1: select the silica alumina ratio of BEA structure for 22 H-SSZ-13 zeolitic material as molecular sieve.Firstly, pressing
It is 1:5 according to triethanolamine and the mass ratio of deionized water, is warmed to 60 DEG C, is sufficiently stirred 30 minutes, triethanolamine solution is made.
It is 1:5 according to copper acetate and the mass ratio of deionized water, acetic acid copper solution is made.Secondly, according to triethanolamine: copper acetate rubs
Acetic acid copper solution is added in triethanolamine solution than being 0.65:1, continues to be kept for 60 DEG C, be stirred to react 3h, network is made by you
Close copper solution.Again, according to molecular sieve: deionized water=40:60 mass ratio is mixed, and is stirred evenly, and molecular sieve is made
Slurry.It is 0.025:1 according to the mass ratio of copper atom and molecular sieve, complex copper solutions is entered by peristaltic pump direct injection and are divided
The sub- following mass transfer of screening the pulp feed liquid surface exchanges most fierce position, one hour of injection time, is stirred for 5h after having injected, makes to be complexed
Copper ion and copper atom and molecular sieve bond in copper solution close, and obtain suspension.
Step S2: by suspension by spraying flash dryer, being dried at 150 DEG C, and powder is made.Then, by powder
Body is sent into rotary calcining furnace, and under conditions of being passed through air, in 500 DEG C of roasting 2.0h, cupric molecular screen material is made.
Step S3: cupric molecular screen material is mixed with deionized water, and it is 30% containing copper zeolite that mass fraction, which is made,
The nanometer Aluminum sol that mass fraction is 2.5%, mass fraction 5% are added in Xiang Hantong molecular screen material solution for material solution
Alkaline nano silica solution, and the gross mass for controlling nanometer Aluminum sol and alkaline nano silica solution is cupric molecular screen material quality
5.0%；The hydroxymethyl cellulose that mass fraction is 0.04% is finally added, the quality of hydroxymethyl cellulose is containing copper molecule
The 0.4% of quality of materials is sieved, mixed slurry is made.Then, mixed slurry is ground to 3.0 by granularity D50 using grinder
In micron range.Finally, the mixed slurry after grinding is coated on carrier cordierite ceramic 400-4, the dry weight gain of control coating
Upper carrying capacity is 140g/L；Using drying and roasting, molding obtains finished catalyst.
Embodiment 3
It is obtained in this way the present embodiment provides a kind of catalyst:
Step S1: select the silica alumina ratio of BEA structure for 22 H-SSZ-13 zeolitic material as molecular sieve.Firstly, pressing
It is 1:5 according to triethanolamine and the mass ratio of deionized water, is warmed to 60 DEG C, is sufficiently stirred 30 minutes, triethanolamine solution is made.
It is 1:5 according to copper acetate and the mass ratio of deionized water, acetic acid copper solution is made.Secondly, according to triethanolamine: copper acetate rubs
Acetic acid copper solution is added in triethanolamine solution than being 0.62:1, continues to be kept for 60 DEG C, be stirred to react 3h, network is made by you
Close copper solution.Again, according to molecular sieve: deionized water=40:60 mass ratio is mixed, and is stirred evenly, and molecular sieve is made
Slurry.It is 0.024:1 according to the mass ratio of copper atom and molecular sieve, complex copper solutions is entered by peristaltic pump direct injection and are divided
The sub- following mass transfer of screening the pulp feed liquid surface exchanges most fierce position, one hour of injection time, is stirred for 4h after having injected, makes to be complexed
Copper ion and copper atom and molecular sieve bond in copper solution close, and obtain suspension.
Step S2: by suspension by spraying flash dryer, being dried at 150 DEG C, and powder is made.Then, by powder
Body is sent into rotary calcining furnace, and under conditions of being passed through air, in 450 DEG C of roasting 3h, cupric molecular screen material is made.
Step S3: cupric molecular screen material is mixed with deionized water, and it is 30% containing copper zeolite that mass fraction, which is made,
The nanometer Aluminum sol that mass fraction is 2.5%, mass fraction 5% are added in Xiang Hantong molecular screen material solution for material solution
Alkaline nano silica solution, and the gross mass for controlling nanometer Aluminum sol and alkaline nano silica solution is cupric molecular screen material quality
5.0%；The hydroxymethyl cellulose that mass fraction is 0.04% is finally added, the quality of hydroxymethyl cellulose is containing copper molecule
The 0.4% of quality of materials is sieved, mixed slurry is made.Then, mixed slurry is ground to 2.6 by granularity D50 using grinder
In micron range.Finally, the mixed slurry after grinding is coated on carrier cordierite ceramic 400-4, the dry weight gain of control coating
Upper carrying capacity is 150g/L；Using drying and roasting, molding obtains finished catalyst.
Embodiment 4
It is obtained in this way the present embodiment provides a kind of catalyst:
Step S1: select the silica alumina ratio of MFI structure for 22 H-SSZ-13 zeolitic material as molecular sieve.Firstly, pressing
It is 1:5 according to triethanolamine and the mass ratio of deionized water, is warmed to 60 DEG C, is sufficiently stirred 30 minutes, triethanolamine solution is made.
It is 1:5 according to copper acetate and the mass ratio of deionized water, acetic acid copper solution is made.Secondly, according to triethanolamine: copper acetate rubs
Acetic acid copper solution is added in triethanolamine solution than being 0.62:1, continues to be kept for 60 DEG C, be stirred to react 3h, network is made by you
Close copper solution.Again, according to molecular sieve: deionized water=40:60 mass ratio is mixed, and is stirred evenly, and molecular sieve is made
Slurry.It is 0.024:1 according to the mass ratio of copper atom and molecular sieve, complex copper solutions is entered by peristaltic pump direct injection and are divided
The sub- following mass transfer of screening the pulp feed liquid surface exchanges most fierce position, one hour of injection time, is stirred for 4h after having injected, makes to be complexed
Copper ion and copper atom and molecular sieve bond in copper solution close, and obtain suspension.
Step S2: by suspension by spraying flash dryer, being dried at 150 DEG C, and powder is made.Then, by powder
Body is sent into rotary calcining furnace, and under conditions of being passed through air, in 450 DEG C of roasting 3h, cupric molecular screen material is made.
Step S3: cupric molecular screen material is mixed with deionized water, and it is 30% containing copper zeolite that mass fraction, which is made,
The nanometer Aluminum sol that mass fraction is 2.5%, mass fraction 5% are added in Xiang Hantong molecular screen material solution for material solution
Alkaline nano silica solution, and the gross mass for controlling nanometer Aluminum sol and alkaline nano silica solution is cupric molecular screen material quality
5.0%；The hydroxymethyl cellulose that mass fraction is 0.04% is finally added, the quality of hydroxymethyl cellulose is containing copper molecule
The 0.4% of quality of materials is sieved, mixed slurry is made.Then, mixed slurry is ground to 2.7 by granularity D50 using grinder
In micron range.Finally, the mixed slurry after grinding is coated on carrier cordierite ceramic 400-4, the dry weight gain of control coating
Upper carrying capacity is 155g/L；Using drying and roasting, molding obtains finished catalyst.
Comparative example
A kind of copper-based molecular sieve catalyst is provided.It is made using the method for traditional Copper Ion Exchange, according to the following steps
It carries out:
Step 1: select the silica alumina ratio of CHA structure for 22 H-SSZ-13 molecular sieve as zeolitic material.Firstly, according to
Molecular sieve: deionized water=30:70 ratio calculates molecular sieve and water consumption, calculates according to copper concentration is 0.15-0.225M
The dosage of copper acetate；It is that deionized water → copper acetate → molecular sieve material addition stirs in stainless steel hold in proper order according to order
These materials are added in device, while controlling PH 4.5~5.0；
Step 2: suspension prepared by step 1 is sealed heating, controlled at 60~80 DEG C, to carry out ion
Exchange step, control time are 2.0~3.0h；
Step 3: carrying out filter press washing, and until not having the appearance of obvious blue solution, water consumption is molecular sieve: deionization
Water=10:90, washing times are three times；Then according to Step 1: Step 2: step 3 carries out a copper load and washing again；
Step 4: carrying out finished catalyst production, and controlling carrying capacity on coating is 140~160g/L.
Experimental example
The performance for the copper-based molecular sieve catalyst that catalyst made from embodiment 1-4 and comparative example provide is examined
It surveys.
1, engine bench test experiment is carried out to the catalyst that embodiment 1-4 is provided, tests NOxPurification efficiency.Rack is east wind
Six engine pedestal of DDi75 state.Test result is shown in Fig. 1.
It will be seen from figure 1 that the catalyst of embodiment 1-4 offer is 84.4% in 180 DEG C of efficiency；200 DEG C of efficiency are
95.7%；550 DEG C of efficiency are 93%.Efficiency is preferable.Illustrate that the activity of catalyst obtained is high.
2, the purification of nitrogen oxides for the copper-based molecular sieve catalyst that the catalyst that embodiment 1 provides is provided with comparative example
It can be carried out comparison.
1 ingredient comparative analysis result of table
| Molecular screen material | Producer | Copper uploads mode | Carrying capacity (ICP measurement) on copper | Bearing capacity | |
| Embodiment 1 | H-SSZ-13 (Si/Al=22) | German Clariant | Triethanolamine complex copper | 2.3% | 160g/L |
| Comparative example 1 | H-SSZ-13 (Si/Al=22) | German Clariant | Copper Ion Exchange | 2.3% | 160g/L |
The copper-based molecular sieve catalyst that the catalyst and comparative example provide embodiment 1 provides carries out purification of nitrogen oxides
It can test, it is as a result as follows.
The catalyst that embodiment 1 is provided is with the concentration (capacity) shown in defined temperature and space velocity contact table 2
Mixed gas, the concentration of the upstream relative to catalyst measure the concentration in downstream, the purifying rate as nitrogen oxides.Experiment knot
Fruit is shown in Table 3.
2 test gas condition of table
The initial NO of 3 catalyst of tablexPurifying property result
| NOxPurification efficiency | ||||
| 170℃ | 180℃ | 200℃ | 550℃ | |
| Embodiment 1 | 70% | 85% | 95% | 92% |
| Comparative example 1 | 50% | 70% | 86% | 83% |
As can be seen from Table 3, the purification efficiency of catalyst made from conventional method, each temperature section of low temperature, high temperature is low
In the purification efficiency of catalyst provided by the embodiments of the present application, illustrate that the activity of catalyst provided by the embodiments of the present application improves.
3, for NO:NO2Ratio difference test the difference of catalyst efficiency, so that demonstration needs to guarantee NO:NO2≥
50%, it just can ensure that the preferable low temperature high temperature efficiency of catalyst.Using three kinds of different test gas (table 4- table 6) to embodiment
1 catalyst provided carries out purification of nitrogen oxides performance test, and the results are shown in attached figure 2.
The details of the first test gas are shown in Table 4:
4 test gas condition of table
Modulation NO:NO2Ratio, increase NO2Ratio, the details of second of test gas are shown in Table 5:
5 test gas condition of table
Modulation NO:NO2Ratio, increase NO2Ratio, modulation NO:NO2Ratio, increase NO2Ratio, the third examination
The details for testing gas are shown in Table 6:
6 test gas condition of table
The result of the purification of nitrogen oxides efficiency of the catalyst provided using these three test gas testing example 1 is shown in attached
Fig. 1, from attached drawing 1 it can be seen that
1., work as NO:NO2In the case of >=50%, NO2Accounting is bigger, and purification efficiency is higher, especially under low-temperature condition；
2., work as NO2In the case of accounting > 50%, irregular variation is presented in the purification efficiency of catalyst, and efficiency is unsatisfactory for wanting
It asks.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of preparation method of cupric molecular screen material characterized by comprising
Complex copper solutions are uniformly mixed with molecular sieve, make copper ion in complex copper solutions and copper atom with the molecular sieve
Bond is closed, and suspension is obtained；
The suspension is dried in air atmosphere, it is small to roast the powder 2.0-5.0 in 400 DEG C -500 DEG C after powder
When.
2. the preparation method of cupric molecular screen material according to claim 1, which is characterized in that
The complex copper solutions are made by the way that copper ion complexing agent to be mixed to generation complex reaction with mantoquita.
3. the preparation method of cupric molecular screen material according to claim 2, which is characterized in that
The copper ion complexing agent is selected from triethanolamine；The mantoquita is selected from copper acetate；
The molar ratio of the triethanolamine and the copper acetate is 0.6~0.65.
4. the preparation method of cupric molecular screen material according to claim 1, which is characterized in that
In the step that complex copper solutions are uniformly mixed with molecular sieve, the mass ratio of copper atom and molecular sieve is 0.021~
0.025。
5. the preparation method of cupric molecular screen material according to claim 1, which is characterized in that
The step that complex copper solutions are uniformly mixed with molecular sieve includes: that complex copper solutions and molecular sieve slurry agitation are anti-
It answers -5 hours 3 hours.
6. a kind of catalyst, which is characterized in that the catalyst includes as described in any one in claim 1-5 containing copper zeolite
Cupric molecular screen material made from the preparation method of material；And
Carrier, the cupric molecular screen material load is on the carrier；The material of the carrier is selected from cordierite ceramic, carbonization
Silicon, inorfil or any one metal；
Optionally, the catalyst further includes that the nano aluminum that the mass fraction that is carried on the carrier is 1.5%-2.5% is molten
The cellulose that the Nano silica sol and mass fraction that glue, mass fraction are 2%-5% are 0.2%-0.04%.
7. catalyst according to claim 6, which is characterized in that
The BET specific surface area of the catalyst is 50m2/ g~80m2/g。
8. a kind of cupric molecular screen material, which is characterized in that
The cupric molecular screen material includes molecular sieve and the loaded article for being carried on the molecular sieve, and the content of the loaded article is
The 2.1%~2.5% of the molecular sieve quality；The loaded article includes copper atom and copper ion；
Wherein, the copper ion includes combining copper ion and free copper ion, and the content of the combination copper ion is the load
The 50%-70% of object content；The copper ion includes Cu2+And Cu+。
9. cupric molecular screen material according to claim 8, which is characterized in that
SiO in the molecular sieve2/Al2O3Molar ratio in 6-12；
The molecular sieve is selected from h-type zeolite molecular sieve；
Optionally, in the molecular sieve of the h-type zeolite molecular sieve selected from BEA, MFI, CHA, AEI, FAU, LTA or AFX structure
At least one.
10. cupric molecular screen material according to claim 8, which is characterized in that
The average grain diameter of the cupric molecular screen material is 2.5 μm~3.0 μm.
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| WO2021082140A1 (en) * | 2019-10-29 | 2021-05-06 | 山东国瓷功能材料股份有限公司 | Cu-cha copper-containing molecular sieve, and catalyst and use thereof |
| CN114904567A (en) * | 2022-01-20 | 2022-08-16 | 安徽艾可蓝环保股份有限公司 | Environment-friendly copper-based SCR catalyst and preparation method thereof |
| CN116474842A (en) * | 2023-04-06 | 2023-07-25 | 济南大学 | Method for preparing metal-based small-pore molecular sieve by ion capturing method, and obtained product and application |
| CN117380255A (en) * | 2023-12-05 | 2024-01-12 | 河北华特汽车部件有限公司 | Preparation method and application of catalyst for purifying nitrogen oxides |
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