CN104209141B - A kind of Cu-SAPO-34 molecular sieve catalyst, preparation method and its usage - Google Patents
A kind of Cu-SAPO-34 molecular sieve catalyst, preparation method and its usage Download PDFInfo
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Abstract
The invention provides a kind of Cu SAPO 34 molecular sieve catalyst, preparation method and its usage.Said method comprising the steps of: boehmite is added in deionized water and is stirred, it is subsequently adding the one in aerosil or Ludox and orthophosphoric acid, after mixing, add copper sulfate and TEPA, after being sufficiently stirred for, add diethylamine, triethylamine or n-propylamine.To stir crystallization in the hydrothermal reaction kettle of gel loading completely, then room temperature cooling, separates solid crystallized product with mother solution, and washing is to neutral, dry, in atmosphere 600～850 DEG C of roastings, obtains Cu SAPO 34 molecular sieve catalyst.The present invention uses a step hydrothermal synthesis method to prepare Cu SAPO 34 molecular sieve catalyst, and by controlling copper sulfate TEPA, aerosil or the input amount of Ludox and sintering temperature, obtains NH3SCR catalysis activity and the molecular sieve catalyst of hydrothermal stability excellence.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of Cu-SAPO-34 molecular sieve catalyst, preparation
Method and application thereof.
Background technology
With NH3For reducing agent Selective Catalytic Reduction of NO x i.e. NH3-SCR technology, at catalytic elimination NOx
During there is particularly important effect, its key core is the exploitation of SCR catalyst system.Due to bavin
The spies such as oil car operating condition is changeable, exhaust gas temperature change amplitude big, tail gas composition is complicated, changes in flow rate is fast
Point, excellent automotive catalyst need to possess following performance: has higher catalytic activity, water at wide temperature window
Heat stability is high, mechanical strength SO high, anti-2High-speed ability strong with HC poisoning capability, anti-is strong.And
The most conventional V2O5-WO3(MoO3)/TiO2Although catalyst commercial Application is for many years, but there are still
Temperature window is narrower for some shortcomings that self cannot overcome, such as operation, high temperature time N2O generates in a large number and causes
N2Generate selectivity decline, SO2To SO3Aoxidize serious and active component V2O5There is bio-toxicity, danger
Evil health etc..Therefore, novel non-vanadium NH is developed3-SCR catalyst system becomes scientific research personnel and NOx
The focus of emission control worker research.
Small pore molecular sieve Cu-SAPO-34 is provided simultaneously with high activity, high N due to it2Selectivity and excellent water
Heat stability and anti-HC poisoning capability and receive significant attention.The Cu-SAPO-34 of major part report divides at present
Son sieve all uses mantoquita presoma and SAPO-34 molecular sieve to carry out ion exchange and prepares.Ion exchange
Relate to exchanging, filter, the process such as washing, and due to SAPO-34 molecular sieve pore passage size and exchange capacity
Limiting, Cu load capacity to be improved needs repeated exchanged step or extends swap time, largely limits
The research of Cu-SAPO-34 molecular sieve and application.
CN 102259895A discloses and divides as template synthesis phosphorus sial using metal-amine-complex for a kind of
The method of son sieve.The method is that boehmite or aluminium hydroxide are added deionized water, is added dropwise over phosphoric acid,
Amorphous silica is added after stirring；After being mixed, it is sequentially added into divalent metal salt and organic amine, makes gel
PH value reach between 7～9, stir after 12 hours under room temperature, load crystallization in reactor, will
Solid crystallized product washing, to neutral, obtain molecular sieve powder after drying, then 550 DEG C of roastings, obtains
Remove the zeolite product of template agent removing.But, if copper content is too high, easily form more CuO, high
There is non-selective oxidation reduction NH in temperature section (350-550 DEG C)3, cause catalysis activity and N2Selectivity drops
Low.If sintering temperature is on the low side, the organic amine as template can not be removed completely, causes the knot of molecular sieve
Crystalline substance degree is relatively low, and specific surface area and pore volume are less than normal, and catalysis activity also can reduce.
Summary of the invention
For the problem of prior art, an object of the present invention is to provide a kind of Cu-SAPO-34 molecule
The preparation method of sieve catalyst, the catalyst using the method to obtain has the NH of excellence3-SCR is catalyzed activity
And hydrothermal stability.
In order to achieve the above object, present invention employs following technical scheme:
The preparation method of a kind of Cu-SAPO-34 molecular sieve catalyst, said method comprising the steps of:
(1) boehmite is added in deionized water it is stirred, be subsequently adding aerosil or silicon
Any one and orthophosphoric acid in colloidal sol, adds copper sulfate and TEPA, after being sufficiently stirred for after mixing
Add diethylamine, triethylamine or n-propylamine；
(2) will stir crystallization in the hydrothermal reaction kettle of gel loading completely, after crystallization completes, room temperature is cold
But, solid crystallized product is separated with mother solution, be washed with deionized to neutrality, be dried, then at air
In 600～850 DEG C of roastings, i.e. obtain Cu-SAPO-34 molecular sieve catalyst；
In the method, the consumption controlling each reactant makes possess following quality proportioning pass in reaction system
System, i.e.
Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is
1:1.14:0.25～0.8:75:0.04～0.5:3.4.Wherein, organic amine is diethylamine, triethylamine or n-propylamine.
In the preparation process of Cu-SAPO-34 molecular sieve catalyst, sintering temperature directly affects molecular sieve
Degree of crystallinity and catalysis activity；Transition metal copper is different because of its load capacity, the state of copper and distribution difference thereof, leads
Cause NH3-SCR catalysis activity and hydrothermal stability have larger difference；Silicone content and the mode of replacement are to a certain degree
On affect structural stability and the hydrothermal stability of catalyst.The present invention uses a step hydrothermal synthesis method to prepare
Cu-SAPO-34 molecular sieve catalyst, and next by controlling the input amount of copper sulfate-TEPA further
Control the input amount that copper load capacity is 0～10wt% (not including 0), aerosil or Ludox to control
Silicone content is 600～850 DEG C in 7～11wt% and control sintering temperature, to obtain NH3-SCR is catalyzed activity
The molecular sieve catalyst excellent with hydrothermal stability.
In the present invention, Al is controlled2O3、P2O5、SiO2、H2O, copper sulfate-TEPA and organic amine
Mol ratio be 1:1.14:0.65:75:0.04:3.4,1:1.14:0.65:75:0.08:3.4,
1:1.14:0.65:75:0.12:3.4、1:1.14:0.65:75:0.2:3.4、1:1.14:0.65:75:0.3:3.4、
1:1.14:0.65:75:0.5:3.4、1:1.14:0.25:75:0.12:3.4、1:1.14:0.45:75:0.12:3.4、
1:1.14:0.65:75:0.12:3.4,1:1.14:0.8:75:0.12:3.4, wherein, organic amine is diethylamine, triethylamine
Or n-propylamine.
Preferably, Al is controlled2O3、P2O5、SiO2、H2Rubbing of O, copper sulfate-TEPA and organic amine
That ratio is 1:1.14:0.65:75:0.08～0.3:3.4, and the load capacity of the copper of the molecular sieve catalyst now obtained is
3.14～5.57%, preferably 1:1.14:0.65:75:0.12:3.4, the load of the copper of the molecular sieve catalyst now obtained
Amount is 3.44wt%.
Preferably, Al is controlled2O3、P2O5、SiO2、H2Rubbing of O, copper sulfate-TEPA and organic amine
That ratio is 1:1.14:0.25～0.65:75:0.12:3.4, and the silicone content of the molecular sieve catalyst now obtained is
7.36～10.13%, preferably 1:1.14:0.45:75:0.12:3.4, the silicone content of the molecular sieve catalyst now obtained
For 8.48wt%.
Preferably, the temperature of crystallization is 150～200 DEG C, such as 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C,
175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C or 195 DEG C, preferably 180 DEG C.
Preferably, the temperature of crystallization is 24～72 hours, such as 28 hours, 35 hours, 40 hours, 45
Hour, 50 hours, 55 hours, 60 hours, 65 hours or 70 hours, preferably 72 hours.
In the present invention, described dry temperature is 80-120 DEG C, and the time being dried is 6-18 hour, preferably
Described dry temperature is 100 DEG C, and the time being dried is 12 hours.
In the present invention, sintering temperature for example, 620 DEG C, 640 DEG C, 660 DEG C, 680 DEG C, 700 DEG C,
720 DEG C, 740 DEG C, 760 DEG C, 780 DEG C, 800 DEG C, 820 DEG C or 840 DEG C, the most described sintering temperature is
700～800 DEG C, further preferred 700 DEG C.
In the present invention, roasting time is 3～8 hours, preferably 5 hours.
In the present invention, the heating rate in roasting process is 0.5-2 DEG C/min, preferably 1 DEG C/min.
As the preferred technical solution of the present invention, the preparation side of a kind of Cu-SAPO-34 molecular sieve catalyst
Method, said method comprising the steps of:
Boehmite is added in deionized water and is stirred, be subsequently adding aerosil or Ludox
In any one and orthophosphoric acid, after mixing, add copper sulfate and TEPA, add after being sufficiently stirred for
Diethylamine, triethylamine or n-propylamine；
To stir crystallization in the hydrothermal reaction kettle of gel loading completely, after crystallization completes, room temperature cools down, will
Solid crystallized product separates with mother solution, is washed with deionized to neutrality, is dried, exists the most in atmosphere
700 DEG C of roastings, i.e. obtain Cu-SAPO-34 molecular sieve catalyst；
In the method, Al is controlled2O3、P2O5、SiO2、H2O, copper sulfate-TEPA and organic amine
Mol ratio be 1:1.14:0.45:75:0.12:3.4, wherein, organic amine is diethylamine, triethylamine or positive third
Amine, the load capacity of the copper of the molecular sieve catalyst now obtained is 3.44wt%, and silicone content is 8.48wt%.
The catalyst using this optimal technical scheme to obtain has catalysis activity and the hydrothermal stability of excellence, its
There is in 200～500 DEG C the NO higher than 80%xConversion ratio, at 750 DEG C, 10%H2O hydrothermal aging 16
Hour or 800 DEG C, 10%H2After O hydrothermal aging 16 hours, the catalyst obtained in 200～500 DEG C still
There is the NO higher than 80%xConversion ratio.Therefore, in technique scheme, by controlling the addition of raw material
Measure and sintering temperature 700 DEG C, and then control copper load capacity is 3.44wt%, silicone content 8.48wt%, this point
Son sieve shows the NH of excellence3-SCR catalysis activity and hydrothermal stability.
The two of the purpose of the present invention are to provide a kind of Cu-SAPO-34 prepared by method as defined above
Molecular sieve catalyst.
The three of the purpose of the present invention are to provide a kind of Cu-SAPO-34 molecular sieve catalyst as above
Purposes, it is used for NH3-SCR reacts.
Compared with the prior art, there is advantages that
The Cu-SAPO-34 molecular sieve catalyst of the present invention uses a step hydrothermal synthesis method to prepare, the most easily
Control, activity component load quantity can regulate in (0-10%) in a big way.
Additionally, the Cu-SAPO-34 molecular sieve catalyst of preparation has the NH of excellence after preferably3-SCR lives
Property and hydrothermal stability, structural integrity and good catalysis still can be kept after 800 DEG C of hydrothermal agings to live
Property.
Accompanying drawing explanation
Fig. 1 is the NO of embodiment 1 catalystxConversion ratio evaluation figure；
Fig. 2 is the N of embodiment 1 catalyst2Selective evaluation figure；
Fig. 3 is the XRD figure of embodiment 1 catalyst；
Fig. 4 is the NO before and after the hydrothermal aging of embodiment 1 catalystxConversion ratio evaluation figure；
Fig. 5 is the NO of embodiment 2 catalystxConversion ratio evaluation figure；
Fig. 6 is the XRD figure of embodiment 2 catalyst；
Fig. 7 is the NO of embodiment 3 catalystxConversion ratio evaluation figure；
Fig. 8 is the NO of embodiment 4 catalystxConversion ratio evaluation figure.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
In the present invention, the evaluation of catalyst is adopted with the following method:
Take Cu-SAPO-34 molecular sieve catalyst, 40-60 mesh, be respectively put into catalyst activity evaluating apparatus,
Activity rating is carried out in fixed bed reactors.Simulated flue gas consists of (500ppm NH3, 500ppm
NO, 5%O2), N2For Balance Air, total flow is 500mL/min, and reaction velocity is 400000h-1。
Embodiment 1
Boehmite is added in deionized water and is stirred, be subsequently adding aerosil or Ludox
In any one and orthophosphoric acid, after mixing, add copper sulfate and TEPA, add after being sufficiently stirred for
Diethylamine, triethylamine or n-propylamine；
Gel completely will be stirred and load in hydrothermal reaction kettle 180 DEG C of crystallization 72 hours, after crystallization completes
Room temperature cools down, and is separated with mother solution by solid crystallized product, is washed with deionized to neutrality, and 100 DEG C are dried
12 hours, roasting the most in atmosphere, sintering temperature was 700 DEG C, and in roasting process, heating rate is 1 DEG C
/ min, roasting time is 5 hours, obtains Cu-SAPO-34 molecular sieve catalyst.
The consumption controlling each reactant makes possess following quality proportion relation in reaction system:
Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is
1:1.14:0.65:75:0.08～0.5:3.4, make the load capacity of copper be respectively 2.19%, 3.14%, 3.44%,
5.02%, 5.57% and 9.50%, wherein, organic amine is diethylamine, triethylamine or n-propylamine.
It is the catalytic performance test figure of the molecular sieve catalyst of the load capacity of different Cu shown in Fig. 1～4, this chart
Bright, the molecular sieve of different Cu load capacity shows different catalysis activity, N2Selectivity and hydrothermal stability,
Wherein, optimal copper load capacity is 3.44%.
Embodiment 2
Boehmite is added in deionized water and is stirred, be subsequently adding aerosil or Ludox
In any one and orthophosphoric acid, after mixing, add copper sulfate and TEPA, add after being sufficiently stirred for
Diethylamine, triethylamine or n-propylamine；
Gel completely will be stirred and load in hydrothermal reaction kettle 180 DEG C of crystallization 72 hours, after crystallization completes
Room temperature cools down, and is separated with mother solution by solid crystallized product, is washed with deionized to neutrality, and 100 DEG C are dried
12 hours, carrying out roasting the most at different temperatures, in roasting process, heating rate is 1 DEG C
/ min, roasting time is 5 hours, obtains Cu-SAPO-34 molecular sieve catalyst.
In the method, the consumption controlling each reactant makes possess following quality proportioning pass in reaction system
System:
Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is
1:1.14:0.65:75:0.12:3.4, make the load capacity of copper be respectively 3.44%, wherein, organic amine be diethylamine,
Triethylamine or n-propylamine.
Fig. 5 and 6 be respectively sintering temperature be the catalysis that 600 DEG C, 700 DEG C, 800 DEG C and 850 DEG C of roastings obtain
The catalytic performance test figure of agent, this figure shows, in difference on the basis of being 3.44wt% selecting copper load capacity
At a temperature of carry out roasting, the degree of crystallinity of molecular sieve and catalysis activity there is some difference, it is contemplated that economical because of
Element, 700 DEG C is optimum calcination temperature.
Embodiment 3
Boehmite is added in deionized water and is stirred, be subsequently adding aerosil or Ludox
In any one and orthophosphoric acid, after mixing, add copper sulfate and TEPA, add after being sufficiently stirred for
Diethylamine, triethylamine or n-propylamine；
Gel completely will be stirred and load in hydrothermal reaction kettle 180 DEG C of crystallization 72 hours, after crystallization completes
Room temperature cools down, and is separated with mother solution by solid crystallized product, is washed with deionized to neutrality, and 100 DEG C are dried
12 hours, carrying out roasting at 700 DEG C the most in atmosphere, in roasting process, heating rate is 1 DEG C/min, roasting
The burning time is 5 hours, i.e. obtains Cu-SAPO-34 molecular sieve catalyst.
In the method, the consumption controlling each reactant makes possess following quality proportioning pass in reaction system
System: Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is
1:1.14:0.25～0.8:75:0.12:3.4, makes silicone content be respectively 7.36%, 8.48%, 10.13% and
10.75%, wherein, organic amine is diethylamine, triethylamine or n-propylamine.
Fig. 7 is the catalytic performance test figure of the catalyst of different silicone content, and this figure shows, loads at optimal copper
Amount 3.44% and the different silicone contents of regulation on the basis of optimum calcination temperature 700 DEG C, silicone content is at about 8.48wt%
The catalysis activity of molecular sieve catalyst optimum.
Embodiment 4
Boehmite is added in deionized water and is stirred, be subsequently adding aerosil or Ludox
In any one and orthophosphoric acid, after mixing, add copper sulfate and TEPA, add after being sufficiently stirred for
Diethylamine, triethylamine or n-propylamine；
Gel completely will be stirred and load in hydrothermal reaction kettle 180 DEG C of crystallization 72 hours, after crystallization completes
Room temperature cools down, and is separated with mother solution by solid crystallized product, is washed with deionized to neutrality, and 100 DEG C are dried
12 hours, carrying out roasting at 700 DEG C the most in atmosphere, in roasting process, heating rate is 1 DEG C/min, roasting
The burning time is 5 hours, i.e. obtains Cu-SAPO-34 molecular sieve catalyst.
In the method, the consumption controlling each reactant makes possess following quality proportioning pass in reaction system
System: Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is
1:1.14:0.45:75:0.12:3.4, making copper load capacity is 3.44%, and silicone content is 8.48%, wherein, organic amine
For diethylamine, triethylamine or n-propylamine.
Fig. 8 is the catalytic performance test figure of catalyst, and this figure shows, selects copper load capacity 3.44%, roasting
Temperature 700 DEG C, silicone content 8.48% prepares Cu-SAPO-34 molecular sieve, and this molecular sieve shows excellence
NH3-SCR catalysis activity and hydrothermal stability.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention
It is not limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed ability real
Execute.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to product of the present invention
The equivalence of each raw material is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the guarantor of the present invention
Within the scope of protecting scope and disclosure.
Claims (19)
1. the preparation method of a Cu-SAPO-34 molecular sieve catalyst, it is characterised in that said method comprising the steps of:
(1) boehmite is added in deionized water it is stirred, any one and the orthophosphoric acid being subsequently adding in aerosil or Ludox, after mixing, add copper sulfate and TEPA, after being sufficiently stirred for, add diethylamine, triethylamine or n-propylamine；
(2) will stir crystallization in the hydrothermal reaction kettle of gel loading completely, after crystallization completes, room temperature cools down, and is separated with mother solution by solid crystallized product, it is washed with deionized to neutrality, it is dried, the most in atmosphere 700～780 DEG C of roastings, obtains Cu-SAPO-34 molecular sieve catalyst；
In the method, the consumption controlling each reactant makes possess following quality proportion relation in reaction system, i.e.
Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is 1:1.14:0.25～0.8:75:0.04～0.5:3.4, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
2. preparation method as claimed in claim 1, it is characterised in that control Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is 1:1.14:0.65:75:0.04～0.5:3.4, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
3. preparation method as claimed in claim 2, it is characterised in that control Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is 1:1.14:0.65:75:0.12:3.4.
4. preparation method as claimed in claim 1, it is characterised in that control Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is 1:1.14:0.25～0.8:75:0.12:3.4, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
5. preparation method as claimed in claim 4, it is characterised in that control Al2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is 1:1.14:0.45:75:0.12:3.4.
6. preparation method as claimed in claim 1, it is characterised in that the temperature of described crystallization is 150～200 DEG C.
7. preparation method as claimed in claim 6, it is characterised in that the temperature of described crystallization is 180 DEG C.
8. preparation method as claimed in claim 1, it is characterised in that the time of described crystallization is 24～72 hours.
9. preparation method as claimed in claim 8, it is characterised in that the time of described crystallization is 72 hours.
10. preparation method as claimed in claim 1, it is characterised in that described dry temperature is 80-120 DEG C, and the time being dried is 6-18 hour.
11. preparation methoies as claimed in claim 10, it is characterised in that described dry temperature is 100 DEG C, the time being dried is 12 hours.
12. preparation methoies as claimed in claim 1, it is characterised in that sintering temperature is 700 DEG C.
13. preparation methoies as claimed in claim 1, it is characterised in that the time of described roasting is 3-8 hour.
14. preparation methoies as claimed in claim 13, it is characterised in that the time of described roasting is 5 hours.
15. preparation methoies as claimed in claim 1, it is characterised in that the heating rate in described roasting process is 0.5-2 DEG C/min.
16. preparation methoies as claimed in claim 15, it is characterised in that the heating rate in described roasting process is 1 DEG C/min.
17. preparation methoies as claimed in claim 1, it is characterised in that said method comprising the steps of:
Boehmite is added in deionized water and is stirred, any one and the orthophosphoric acid being subsequently adding in aerosil or Ludox, after mixing, add copper sulfate and TEPA, after being sufficiently stirred for, add diethylamine, triethylamine or n-propylamine；
To stir crystallization in the hydrothermal reaction kettle of gel loading completely, after crystallization completes, room temperature cools down, and is separated with mother solution by solid crystallized product, it is washed with deionized to neutrality, it is dried, the most in atmosphere 700 DEG C of roastings, obtains Cu-SAPO-34 molecular sieve catalyst；
In the method, Al is controlled2O3、P2O5、SiO2、H2The mol ratio of O, copper sulfate-TEPA and organic amine is 1:1.14:0.45:75:0.12:3.4, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
The Cu-SAPO-34 molecular sieve catalyst that 18. 1 kinds are prepared by preparation method as described in one of claim 1-17.
The purposes of 19. 1 kinds of Cu-SAPO-34 molecular sieve catalysts as claimed in claim 18, it is used for NH3-SCR reacts.
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| CN111437876B (en) * | 2020-04-21 | 2023-11-14 | 河北大学 | Cu-SAPO-34 molecular sieve catalyst, and preparation method and application thereof |
| CN111617801A (en) * | 2020-07-08 | 2020-09-04 | 黑龙江大学 | Preparation method of hierarchical porous Cu/SAPO-34 catalyst |
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| CN112916026B (en) * | 2021-01-28 | 2023-04-21 | 盐城工学院 | Catalyst for preparing glyoxal by catalytic oxidation of ethylene glycol and preparation method thereof |
| CN113680381A (en) * | 2021-08-18 | 2021-11-23 | 四川泸天化股份有限公司 | Preparation method and application of bifunctional molecular sieve catalyst |
| CN115869998A (en) * | 2022-12-12 | 2023-03-31 | 大连海事大学 | Cu-SAPO-34 catalyst, and preparation method and application thereof |
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| CN101176851A (en) * | 2007-11-02 | 2008-05-14 | 中国化学工程集团公司 | Method for synthesizing silicon aluminum orthophosphate molecular sieve using white bole |
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| US9475040B2 (en) * | 2012-12-10 | 2016-10-25 | GM Global Technology Operations LLC | Synthesis of Cu/SAPO-34 with variable copper loadings |
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