CN110451521A - Preparation method, the preparation method of SCR catalyst of Beta molecular sieve - Google Patents
Preparation method, the preparation method of SCR catalyst of Beta molecular sieve Download PDFInfo
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- 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
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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- 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
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- 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
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The invention belongs to chemical industry to catalyze and synthesize field, and in particular to preparation method, the preparation method of SCR catalyst of Beta molecular sieve.Then preparation method of the invention adds mixed templates and silicon source, forms gel the following steps are included: by the mixing of silicon source, inorganic base, water and crystal seed, through crystallization, ammonium exchange, roasting, obtain the Beta molecular sieve；Wherein, the mixed templates include at least one two amido alkane and at least one tetraethyl amine cation organic amine.
Description
Technical field
The invention belongs to chemical industry to catalyze and synthesize field, and in particular to preparation method, the system of SCR catalyst of Beta molecular sieve
Preparation Method.
Background technique
Beta molecular sieve is the micro porous molecular sieve material of a kind of wide aperture, high silicon, contains 12 yuan three-dimensional of duct.Due to it
Have the characteristics that high thermal stability, chemical stability, strong acidic site, hydrophobicity and large aperture, is commonly used for catalysis reaction.But it is high
High synthesis cost limits being widely used for Beta molecular sieve.
The Beta molecular sieve partial size synthesized at present is generally smaller, so that requiring in industrial production solid-liquid separating equipment severe
It carves, constrains the mass production of Beta molecular sieve.
Patent US5164169 discloses a kind of synthetic method of big partial size Beta molecular sieve, and the patent is with tertiary amines chemical combination
Object is that chelating agent synthesizes large-sized Beta molecular sieve, but the tertiary amine compounds are toxic and water-soluble bad, easily
Volatilization, is easily destroyed environment in commercial process.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation methods of Beta molecular sieve, the system of SCR catalyst
Preparation Method.
According to an aspect of the present invention, a kind of preparation method of Beta molecular sieve is provided, comprising the following steps:
Silicon source, inorganic base, water and crystal seed are mixed, mixed templates and silicon source are then added, gel is formed, through crystalline substance
Change, ammonium exchange, roasting, obtains the Beta molecular sieve；
Wherein, the mixed templates include that at least one two amido alkane and at least one tetraethyl amine cation are organic
Amine.
According to embodiment of the present invention, the two amidos alkane is selected from pentanediamine, hexamethylene diamine, heptamethylene diamine or pungent two
One of amine or more than one.
According to embodiment of the present invention, the tetraethyl amine cation organic amine be selected from tetraethyl ammonium hydroxide,
One of tetraethylammonium bromide, etamon chloride or tetraethyl ammonium iodide or more than one.
Further, the two amidos alkane be selected from one of hexamethylene diamine or heptamethylene diamine or more than one, the tetrem
Base amine cation organic amine be selected from one of tetraethyl ammonium hydroxide or tetraethylammonium bromide or more than one.
According to embodiment of the present invention, in the mixed templates, the tetraethyl amine cation organic amine with
The mass ratio of the two amidos alkane is 1:(0.01-3).
Further, the mass ratio of the tetraethyl amine cation organic amine and the two amidos alkane is 1:(0.5-1).
According to embodiment of the present invention, the inorganic base is in sodium hydroxide, potassium hydroxide, lithium hydroxide
It is one or more kinds of；The silicon source is selected from one of alkaline silica sol, neutral silica solution, solid silicone, waterglass or one
Kind or more；Source of aluminium be selected from one of aluminum sulfate, aluminum nitrate, boehmite, aluminium chloride, sodium metaaluminate, aluminium oxide or
More than one.
According to embodiment of the present invention, SiO in silicon source2: Al in silicon source2O3: inorganic base: mixed templates: water
Molar ratio is 1:(0.001~0.1): (0.005~0.2): (0.01~0.1): (5~20).
According to embodiment of the present invention, the process of the crystallization are as follows: by the gel with the liter of 1~10 DEG C/min
Warm rate is warming up to 120~190 DEG C, crystallization 12~96 hours.
Further, the process of the crystallization are as follows: the gel is warming up to 150 with the heating rate of 1~10 DEG C/min
~180 DEG C, crystallization 12~48 hours.
According to embodiment of the present invention, the ammonium exchange is carried out using ammonium exchange reagent, and the ammonium exchanges reagent
Selected from one of ammonium chloride, ammonium sulfate, ammonium nitrate or more than one.
According to another aspect of the present invention, a kind of Beta molecular sieve is provided, the Beta molecular sieve is using according to this
The invention method is prepared.
According to another aspect of the present invention, a kind of preparation method of SCR catalyst is provided, wherein used Beta
Molecular sieve is prepared using method as described above.
According to embodiment of the present invention, the preparation method of SCR catalyst includes: to make using method as described above
The molecular sieve carried metal ion of the Beta being prepared, obtains the SCR catalyst.
According to embodiment of the present invention, can be the method for the molecular sieve carried metal ion of Beta by Beta points
Son sieve is mixed with metal ion solution.
According to embodiment of the present invention, the metal ion contained by metal ion solution is bivalent cupric ion, two
One of valence cobalt ions, bivalent nickel ion, trivalent cerium ion, monovalence silver ion, divalent palladium ion or more than one.
According to embodiment of the present invention, metal ion solution is the nitric acid solution of metal ion, metal ion
Sulfuric acid solution etc..Such as copper nitrate, cobalt nitrate, nickel nitrate, cerous nitrate, silver nitrate, palladium nitrate, copper sulphate, cobaltous sulfate, sulfuric acid
Nickel, cerous sulfate, silver sulfate, palladium sulfate etc..
According to embodiment of the present invention, the concentration of metal ion solution is 0.1mol/L-0.5mol/L；SCR is urged
In agent, the mass percent of metal ion is 1%-5%.
The invention has the following advantages: being obtained a kind of with high-specific surface area using preparation method of the invention
Big partial size Beta molecular sieve.The specific surface area of the Beta molecular sieve of the method for the present invention preparation is up to 700~900m2/ g, partial size
Up to 1 μm or more, be conducive to the processes such as separation, washing of Beta molecular sieve pulp in commercial process.
The preparation method of Beta molecular sieve of the invention also has reduction synthesis cost, shortening crystallization time etc. excellent simultaneously
Point.
SCR catalyst obtained from prepared by the method Beta molecular sieve has high hydrothermal stability and high tail gas
Catalytic performance.
Specific embodiment
Specific embodiment is only the description of the invention, without constituting the limitation to the content of present invention, below in conjunction with
Invention is further explained and description for specific embodiment.
The present invention provides a kind of preparation methods of Beta molecular sieve, the preparation method of SCR catalyst.
The present invention provides a kind of preparation methods of Beta molecular sieve, comprising the following steps:
Silicon source, inorganic base, water and crystal seed are mixed, mixed templates and silicon source are then added, gel is formed, through crystalline substance
Change, ammonium exchange, roasting, obtains the Beta molecular sieve；
Wherein, the mixed templates include that at least one two amido alkane and at least one tetraethyl amine cation are organic
Amine.
Specifically, preparation method may comprise steps of:
Gel preparation: (a) tetraethyl amine cation organic amine and two cheap amido alkane are mixed in a certain ratio
Even formation mixed templates；(b) silicon source, inorganic base, water and crystal seed are mixed；(c) mixed templates and silicon source is added, obtains one
Determine the aluminosilicate gels of molar ratio；
Crystallization: by the sample crystallization of the aluminosilicate gels, then separating, washing, drying, molecular screen primary powder is obtained；
Above-mentioned molecular screen primary powder: being exchanged the mixing of reagent aqueous solution with ammonium, heated by ammonium exchange, and stirring thereafter hands over ion
Sample after changing separated, washed, is dried and is obtained sieve sample；
Roasting: above-mentioned sieve sample is roasted, the Beta zeolite product after being roasted.
In preparation method of the present invention, in gel preparation course, the sequence of step (a) and step (b) is interchangeable.
According to embodiment of the present invention, by tetraethyl amine cation organic amine and two amido alkane in room temperature to 90
It is mixed at a temperature of DEG C, forms mixed templates.Hybrid mode, which can be, to be stirred, such as mechanical stirring, magnetic agitation etc..
Using preparation method of the invention, a kind of big partial size Beta molecular sieve with high-specific surface area is obtained.This hair
The specific surface area of the Beta molecular sieve of bright method preparation is up to 700~900m2/ g, partial size are conducive to industrialize up to 1 μm or more
The processes such as separation, washing of Beta molecular sieve pulp in production process.The preparation method of Beta molecular sieve of the invention is gone back simultaneously
Have many advantages, such as to reduce synthesis cost, shorten crystallization time.
According to embodiment of the present invention, the two amidos alkane is selected from pentanediamine, hexamethylene diamine, heptamethylene diamine or pungent two
One of amine or more than one.
According to embodiment of the present invention, the tetraethyl amine cation organic amine be selected from tetraethyl ammonium hydroxide,
One of tetraethylammonium bromide, etamon chloride or tetraethyl ammonium iodide or more than one.
Further, the two amidos alkane be selected from one of hexamethylene diamine or heptamethylene diamine or more than one, the tetrem
Base amine cation organic amine be selected from one of tetraethyl ammonium hydroxide or tetraethylammonium bromide or more than one.
According to embodiment of the present invention, in the mixed templates, the tetraethyl amine cation organic amine with
The mass ratio of the two amidos alkane is 1:(0.01-3).
Further, the mass ratio of the tetraethyl amine cation organic amine and the two amidos alkane is 1:(0.5-1).
Applicants have discovered that only with two amido alkane as template when, using method such as of the invention, can not obtain
Beta molecular sieve.
According to embodiment of the present invention, the inorganic base is in sodium hydroxide, potassium hydroxide, lithium hydroxide
It is one or more kinds of；The silicon source is selected from one of alkaline silica sol, neutral silica solution, solid silicone, waterglass or one
Kind or more；Source of aluminium be selected from one of aluminum sulfate, aluminum nitrate, boehmite, aluminium chloride, sodium metaaluminate, aluminium oxide or
More than one.
According to embodiment of the present invention, SiO in silicon source2: Al in silicon source2O3: inorganic base: mixed templates: water
Molar ratio is 1:(0.001~0.1): (0.005~0.2): (0.01~0.1): (5~20).In the present invention, the dosage of water is body
The total amount of all water in system.
According to embodiment of the present invention, the process of the crystallization are as follows: by the gel with the liter of 1~10 DEG C/min
Warm rate is warming up to 120~190 DEG C, crystallization 12~96 hours.
Further, the process of the crystallization are as follows: the gel is warming up to 150 with the heating rate of 1~10 DEG C/min
~180 DEG C, crystallization 12~48 hours.According to embodiment of the present invention, crystallization time be, for example, 12 hours, 15 hours,
18 hours, 20 hours, 24 hours, 28 hours, 30 hours, 36 hours, 40 hours, 45 hours, 48 hours etc..
According to embodiment of the present invention, the ammonium exchange is carried out using ammonium exchange reagent, and the ammonium exchanges reagent
Selected from one of ammonium chloride, ammonium sulfate, ammonium nitrate or more than one.
The present invention also provides a kind of Beta molecular sieve, the Beta molecular sieve is using method according to the present invention
It is prepared.
The present invention also provides a kind of preparation methods of SCR catalyst, wherein used Beta molecular sieve is using such as
What the upper method was prepared.
According to embodiment of the present invention, the preparation method of SCR catalyst includes: to make using method as described above
The molecular sieve carried metal ion of the Beta being prepared, obtains the SCR catalyst.
According to embodiment of the present invention, can be the method for the molecular sieve carried metal ion of Beta by Beta points
Son sieve is mixed with metal ion solution.
According to embodiment of the present invention, the metal ion contained by metal ion solution is bivalent cupric ion, two
One of valence cobalt ions, bivalent nickel ion, trivalent cerium ion, monovalence silver ion, divalent palladium ion or more than one.
According to embodiment of the present invention, metal ion solution is the nitric acid solution of metal ion, metal ion
Sulfuric acid solution etc..Such as copper nitrate, cobalt nitrate, nickel nitrate, cerous nitrate, silver nitrate, palladium nitrate, copper sulphate, cobaltous sulfate, sulfuric acid
Nickel, cerous sulfate, silver sulfate, palladium sulfate etc..
According to embodiment of the present invention, the concentration of metal ion solution is 0.1mol/L-0.5mol/L；SCR is urged
In agent, the mass percent of metal ion is 1%-5%.
SCR catalyst obtained from prepared by the method Beta molecular sieve has high hydrothermal stability and high tail gas
Catalytic performance.
Embodiments of the present invention are further explained and are illustrated with reference to embodiments.
In the present invention, the hydrothermal stability of test molecule sieve is tested by hydrothermal aging, in tail gas clean-up evaluating apparatus
Evaluate the tail gas clean-up effect of SCR catalyst.
Embodiment 1
Firstly, taking 0.46gNaOH, 1g sodium metaaluminate to stir in water sufficiently at 25 DEG C, adding 5.16g hybrid template
Then 27g silica gel is added in agent (mass ratio=1:1 of tetraethyl ammonium hydroxide and hexamethylene diamine) and 0.3g crystal seed while stirring, move
Enter in stainless steel cauldron.It is warming up to 140 DEG C and at the uniform velocity stirs crystallization 48 hours, then collect, wash, is dry, ammonium exchange, roasting
It burns, obtains Beta molecular sieve.
Beta molecular sieve is characterized through SEM, BET etc., and wherein D50=0.5 μm, specific surface area 898m2/g.Beta molecular sieve with
Copper nitrate solution (concentration 0.15mol/L) mixing, obtains the SCR catalyst of loaded Cu ion, examines in tail gas clean-up evaluating apparatus
Its catalytic performance is surveyed, 85% is all larger than to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.It is examined in hydrothermal aging device
Survey hydrothermal aging stability, overall catalytic performance declines only 6% after aging 20 hours at 800 DEG C.
Embodiment 2
At 25 DEG C, takes 0.56gNaOH, 2g sodium metaaluminate that stirring in 30.9g water is added and sufficiently, add 9.16g hybrid guided mode
Then 27g silica gel is added in plate agent (mass ratio=1:1 of tetraethylammonium bromide and heptamethylene diamine) and 0.3g crystal seed while stirring, move
Enter in stainless steel cauldron.It is warming up to 160 DEG C and mixing speed at the uniform velocity stir crystallization 36 hours, then collect, wash, is dry
Dry, ammonium exchange, roasting, obtain Beta molecular sieve.
Beta molecular sieve is characterized through SEM, BET etc., and wherein D50=0.63 μm, specific surface area 833m2/g。
Beta molecular sieve is mixed with nickel sulfate solution (concentration 0.2mol/L), obtains the SCR catalyst of load Ni ion, In
Tail gas clean-up evaluating apparatus detects its catalytic performance, is greater than 86% to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.
Hydrothermal aging stability is detected in hydrothermal aging device, overall catalytic performance declines 4% after aging 20 hours at 800 DEG C.
Embodiment 3
At 25 DEG C, takes 0.56gNaOH, 2g sodium metaaluminate that stirring in 30.9g water is added and sufficiently, add 5.16g hybrid guided mode
Then 27g silicon is added in plate agent (mass ratio=1:0.5 of tetraethyl ammonium hydroxide and hexamethylene diamine) and 0.3g crystal seed while stirring
Glue moves into stainless steel cauldron.It is warming up to 160 DEG C and at the uniform velocity stir crystallization 36 hours, then collect, wash, is dry,
Ammonium exchange, roasting, obtain Beta molecular sieve.
Beta molecular sieve is characterized through XRF, BET, Particle Size Analyzer etc., and wherein D50=0.84 μm, specific surface area 788m2/g。
Beta molecular sieve is mixed with copper nitrate solution (concentration 0.3mol/L), the SCR catalyst of loaded Cu ion is obtained, in tail gas clean-up
Evaluating apparatus detects its catalytic performance, is greater than 84% to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.It is old in hydro-thermal
Detection hydrothermal aging stability is set in makeup, and overall catalytic performance declines 3% after aging 20 hours at 800 DEG C.
Embodiment 4
At 25 DEG C, takes 0.56gNaOH, 2g sodium metaaluminate that stirring in 30.9g water is added and sufficiently, add 5.16g hybrid guided mode
Then 27g silica gel is added in plate agent (mass ratio=1:2 of tetraethylammonium bromide and hexamethylene diamine) and 0.3g crystal seed while stirring, move
Enter in stainless steel cauldron.It is warming up to 180 DEG C and at the uniform velocity stir crystallization 12 hours, then collect, wash, dry, ammonium is handed over
It changes, roast, obtain Beta molecular sieve.
Beta molecular sieve is characterized through SEM, XRF, BET etc., and wherein D50=1.33 μm, specific surface area 718m2/g.Beta points
Son sieve is mixed with silver nitrate solution (concentration 0.25mol/L), obtains the SCR catalyst of loaded Ag ion, is evaluated in tail gas clean-up
Device detects its catalytic performance, is greater than 83% to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.It is filled in hydrothermal aging
Detection hydrothermal aging stability is set, overall catalytic performance declines 5% after aging 20 hours at 800 DEG C.
Embodiment 5
Same as Example 1, difference is only that mixed templates used are etamon chloride, heptamethylene diamine (mass ratio
For 1:0.5).
Beta molecular sieve is characterized through SEM, XRF, BET etc., and wherein D50=0.53 μm, specific surface area 883m2/g.Beta points
Son sieve is mixed with cerous nitrate solution (concentration 0.4mol/L), obtains the SCR catalyst of load C e ion, is evaluated and is filled in tail gas clean-up
It sets and detects its catalytic performance, 86% is greater than to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.In hydrothermal aging device
Hydrothermal aging stability is detected, overall catalytic performance declines 4% after aging 20 hours at 800 DEG C.
Embodiment 6
Same as Example 1, difference is only that mixed templates used are tetraethyl ammonium iodide, octamethylenediamine (mass ratio
For 1:1.5).
Beta molecular sieve is characterized through SEM, XRF, BET etc., and wherein D50=0.52 μm, specific surface area 892m2/g.Beta points
Son sieve is mixed with copper nitrate solution (concentration 0.5mol/L), obtains the SCR catalyst of loaded Cu ion, is evaluated and is filled in tail gas clean-up
It sets and detects its catalytic performance, 85% is greater than to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.In hydrothermal aging device
Hydrothermal aging stability is detected, overall catalytic performance declines 5% after aging 20 hours at 800 DEG C.
Embodiment 7
Same as Example 1, difference is only that mixed templates used are etamon chloride, hexamethylene diamine (mass ratio
For 1:2.5).
Beta molecular sieve is characterized through SEM, XRF, BET etc., and wherein D50=0.51 μm, specific surface area 895m2/g.Beta points
Son sieve is mixed with silver nitrate solution (concentration 0.2mol/L), obtains the SCR catalyst of loaded Ag ion, is evaluated and is filled in tail gas clean-up
It sets and detects its catalytic performance, 84% is greater than to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.In hydrothermal aging device
Hydrothermal aging stability is detected, overall catalytic performance declines 5% after aging 20 hours at 800 DEG C.
Embodiment 8
Same as Example 1, difference is only that mixed templates used are tetraethyl ammonium iodide, hexamethylene diamine (mass ratio
For 1:0.1).
Beta molecular sieve is characterized through SEM, XRF, BET etc., and wherein D50=0.48 μm, specific surface area 902m2/g.Beta points
Son sieve is mixed with cobalt nitrate solution (concentration 0.15mol/L), obtains the SCR catalyst of load C o ion, is evaluated in tail gas clean-up
Device detects its catalytic performance, is greater than 86% to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.It is filled in hydrothermal aging
Detection hydrothermal aging stability is set, overall catalytic performance declines 4% after aging 20 hours at 800 DEG C.
Comparing embodiment 1
Identical as the method for embodiment 1, difference is only that template used is 5.16g tetraethyl ammonium hydroxide, crystallization
Time 72 hours.
Beta molecular sieve is characterized through SEM, XRF, BET etc., and wherein D50=0.3 μm, specific surface area 918m2/g.Beta molecule
Sieve is mixed with copper nitrate solution (concentration 0.15mol/L), obtains the SCR catalyst of loaded Cu ion, is evaluated and is filled in tail gas clean-up
It sets and detects its catalytic performance, 80% is all larger than to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.It is filled in hydrothermal aging
Detection hydrothermal aging stability is set, overall catalytic performance declines 44% after aging 20 hours at 800 DEG C.
Comparing embodiment 2
Identical as the method for embodiment 2, difference is only that template used is 9.16g tetraethylammonium bromide, when crystallization
Between 72 hours.
Beta molecular sieve is characterized through SEM, XRF, BET etc., and wherein D50=0.6 μm, specific surface area 842m2/g.Beta molecule
Sieve is mixed with nickel nitrate solution (concentration 0.2mol/L), the SCR catalyst of load Ni ion is obtained, in tail gas clean-up evaluating apparatus
Its catalytic performance is detected, 80% is greater than to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.It is examined in hydrothermal aging device
Hydrothermal aging stability is surveyed, overall catalytic performance declines 41% after aging 20 hours at 800 DEG C.
Comparing embodiment 3
Identical as the method for embodiment 5, difference is only that template used is 5.16g etamon chloride, when crystallization
Between 72 hours.
Beta molecular sieve is characterized through SEM, XRF, BET etc., and wherein D50=0.51 μm, specific surface area 887m2/g.Beta points
Son sieve is mixed with cerous nitrate solution (concentration 0.4mol/L), obtains the SCR catalyst of load C e ion, is evaluated and is filled in tail gas clean-up
It sets and detects its catalytic performance, 80% is greater than to the conversion ratio of NO in 200 DEG C and 600 DEG C as the result is shown.In hydrothermal aging device
Hydrothermal aging stability is detected, overall catalytic performance declines 47% after aging 20 hours at 800 DEG C.
The comparison of embodiment according to the present invention and comparing embodiment, it can be seen that use mixed templates of the invention
The beta molecular sieve of preparation have big partial size, higher specific surface area, hydrothermal stability is more preferable, tail gas catalyzed performance is higher.
Comparing embodiment 4
Identical as the method for embodiment 1, difference is only that template machine agent used is 5.16g tetraethyl ammonium hydroxide and oneself
Diamines, mass ratio are greater than 1:3.
Sample is characterized through SEM, XRF, BET etc., and sample is the mixed crystal containing ZSM-22 and ZSM-5 molecular sieve, wherein D50=
1.54 μm or so, specific surface area≤514m2/g.Sample detects its catalytic performance in tail gas clean-up evaluating apparatus after loading, knot
55% is respectively less than to the conversion ratio of NO when fruit is shown in 200 DEG C and 600 DEG C, is stablized in hydrothermal aging device detection hydrothermal aging
Property, overall catalytic performance declines 48% or so after aging 20 hours at 800 DEG C.
In the description of above embodiment, particular features, structures, materials, or characteristics can be at any one or more
It can be combined in any suitable manner in a embodiment or example.
Obviously, those skilled in the art can carry out various modification and variations without departing from the essence of the application to the application
Mind and range.In this way, if these modifications and variations of the application belong to the range of the claim of this application and its equivalent technologies
Within, then the application is also intended to include these modifications and variations.
Claims (10)
1. a kind of preparation method of Beta molecular sieve, which comprises the following steps:
Silicon source, inorganic base, water and crystal seed are mixed, mixed templates and silicon source are then added, gel is formed, through crystallization, ammonium
Exchange, roasting, obtain the Beta molecular sieve；
Wherein, the mixed templates include at least one two amido alkane and at least one tetraethyl amine cation organic amine.
2. preparation method according to claim 1, which is characterized in that the two amidos alkane be selected from pentanediamine, hexamethylene diamine,
One of heptamethylene diamine or octamethylenediamine or more than one.
3. preparation method according to claim 1, which is characterized in that the tetraethyl amine cation organic amine is selected from tetrem
One of base ammonium hydroxide, tetraethylammonium bromide, etamon chloride or tetraethyl ammonium iodide or more than one.
4. preparation method according to claim 1, which is characterized in that the two amidos alkane is selected from hexamethylene diamine or heptamethylene diamine
One of or more than one, the tetraethyl amine cation organic amine is in tetraethyl ammonium hydroxide or tetraethylammonium bromide
One or more.
5. preparation method according to claim 1, which is characterized in that in the mixed templates, the tetraethyl amine sun
The mass ratio of ion organic amine and the two amidos alkane is 1:(0.01-3).
6. preparation method according to claim 1, which is characterized in that in the mixed templates, the tetraethyl amine sun
The mass ratio of ion organic amine and the two amidos alkane is 1:(0.5-1).
7. preparation method according to claim 1, which is characterized in that the inorganic base be selected from sodium hydroxide, potassium hydroxide,
One of lithium hydroxide or more than one；The silicon source is selected from alkaline silica sol, neutral silica solution, solid silicone, waterglass
One of or more than one；Source of aluminium is selected from aluminum sulfate, aluminum nitrate, boehmite, aluminium chloride, sodium metaaluminate, oxidation
One of aluminium or more than one.
8. preparation method according to claim 1, which is characterized in that SiO in silicon source2: Al in silicon source2O3: inorganic base: mixed
Shuttering agent: the molar ratio of water is 1:(0.001~0.1): (0.005~0.2): (0.01~0.1): (5~20).
9. preparation method according to claim 1, which is characterized in that the process of the crystallization are as follows: by the gel with 1~
The heating rate of 10 DEG C/min is warming up to 120~190 DEG C, crystallization 12~96 hours.
10. a kind of preparation method of SCR catalyst, which is characterized in that prepare Beta molecule used in the SCR catalyst
Sieve is prepared using such as the described in any item methods of claim 1-9.
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