CN108097301A - One kind is used for NH3Composite catalyst of-SCR reactions and its preparation method and application - Google Patents
One kind is used for NH3Composite catalyst of-SCR reactions and its preparation method and application Download PDFInfo
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- 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
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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
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Abstract
The present invention provides one kind to be used for NH3Composite catalyst of SCR reactions and its preparation method and application, the composite catalyst is using molecular sieve as carrier, to load to the transition metal on molecular sieve by ion exchange as active component.The method of the present invention includes：It is mixed first by molecular sieve with the salting liquid of transition metal and carries out ion-exchange reactions, then through separation of solid and liquid and roasting, obtain AEI molecular sieve catalysts.The advantages of nontoxic raw materials that the present invention uses is harmless, and preparation method is simple and practicable, and prepared catalyst has catalytic activity height, N2O growing amounts are low, and operation temperature window is wide, the features such as adapting to high-speed reaction condition, are adapted to using exhaust gas from diesel vehicle as the mobile source tail-gas of representative and stationary source flue gas nitrogen oxide catalytic purification.
Description
Technical field
The invention belongs to field of environment pollution control, are related to a kind of for NH3The composite catalyst and its system of-SCR reactions
Preparation Method and purposes more particularly to one kind are used for NH3AEI molecular sieve catalysts and preparation method thereof of-SCR reactions and in movement
The purposes of the catalytic purification of source tail-gas and/or stationary source nitrogen oxides in effluent.
Background technology
Nitrogen oxides (NOx) is the important pollutant in atmosphere pollution, it can cause acid rain, haze, photochemical fog etc.
Great environmental problem not only has ecological environment significant damage, while also jeopardizes human health, and therefore, the removal of NOx is current
The most important thing of environmental protection.At present, with NH3For reducing agent Selective Catalytic Reduction of NO x (NH3- SCR) because of its conversion rate of NOx
Height, the N of generation2There is no secondary pollution, the advantages such as reaction temperature is low have been widely used for stationary source denitrating flue gas and diesel vehicle
Tail gas clean-up.
Efficient NH3- SCR catalyst is the core of the technology.At present, V2O5-WO3(MoO3)/TiO2There is system catalysis to live
High, the anti-SO of property2The characteristics of poisoning performance is good, has been widely used in NH3In-SCR reactions.But the system still have it is all
More problems, such as：Action pane is narrow, high temperature N2Selectivity is low, active component V has bio-toxicity.And the nothing researched and developed at present
Harmless non-V catalyst such as oxide catalyst Ce-W, Fe-Ti of poison, using ZSM-5 and beta molecular sieves as the Cu bases or Fe of carrier
Based molecular sieve catalyst etc. is all different degrees of, and there is temperature operating window is narrow, hydrothermal stability is poor and HC poisoning capability differences etc.
Problem.
In recent years, had high catalytic activity and the high hydro-thermal steady simultaneously with the CHA small pore molecular sieve catalysts for being configured as representing
It is qualitative, it receives significant attention, and has been applied to exhaust gas from diesel vehicle NOx purifications.Such as CN101065321A and CN 105314648A
It discloses for NH3The CHA configuration molecular sieve catalysts of-SCR.But at present using CHA as the molecular sieve catalyst valency of configuration
Lattice are expensive, and hydrothermal stability still needs to be further improved.
Therefore, exploitation has catalytic activity height, temperature operating window is wide, price is excellent honest and clean and possesses high hydrothermal stability
Catalyst faces huge challenge.
The content of the invention
The purpose of the invention is to overcome existing NH3Temperature operating window existing for-SCR molecular sieve catalysts is narrow, water
The problems such as thermal stability difference and poor HC poisoning capabilities, provides a kind of for NH3The composite catalyst of-SCR reactions and its preparation side
Method and purposes, it is especially a kind of to be used for NH3AEI molecular sieve catalysts and preparation method thereof of-SCR reactions and in mobile source tail-gas
And/or the purposes of the catalytic purification of stationary source nitrogen oxides in effluent.
In order to achieve the above objectives, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of composite catalyst, the composite catalyst is using molecular sieve as carrier, to pass through
The transition metal that ion exchange is loaded on molecular sieve is active component.
Below as currently preferred technical solution, but not as the limitation of technical solution provided by the invention, pass through
Following technical scheme can preferably reach and realize the technical purpose and advantageous effect of the present invention.
Preferably, the specific surface area of the composite catalyst is 350m2/ g~800m2/ g, such as 350m2/g、500m2/g、
600m2/g、700m2/ g or 800m2/ g etc., it is not limited to cited numerical value, other interior unrequited numbers of the numberical range
It is worth equally applicable.
As the optimal technical scheme of composite catalyst of the present invention, the molecular sieve is AEI molecular sieves.
In this optimal technical scheme, the composite catalyst be using rich aluminium profiles AEI molecular sieves as carrier, using transition metal as
The AEI molecular sieve catalysts of active component are a kind of available for NH3- SCR realizes the catalyst of efficient catalytic.Wherein, AEI
Molecular sieve is similar to CHA structure, all has three-dimensional octatomic ring (0.38nm × 0.38nm) pore passage structure, arrangement interlaced with each other, by
Hexatomic ring is connected with four-membered ring.Unlike, double hexatomic rings are distributed in mirror symmetry in AEI structures, and double six in CHA structure
Yuan of rings parallel distribution.Specific structure possessed by AEI molecular sieves is determined in NH3Before there is preferable application in-SCR fields
Scape.
Preferably, the AEI molecular sieves are rich aluminium profiles AEI molecular sieves, and the silica alumina ratio Si/Al of the richness aluminium profiles AEI is 15
~2, such as 15,13,10,8,6,4 or 2 etc., it is not limited to cited numerical value, other are unrequited in the numberical range
Numerical value is equally applicable, is preferably 12~5.
Preferably, the transition metal is any one in copper, iron, cerium or manganese or at least two combination, described group
It closes typical case but non-limiting examples has：The combination of the combination of the combination of copper and iron, iron and cerium, copper and cerium, the group of copper, iron and cerium
It closes, the combination of copper and manganese, the combination of iron and manganese, combination of copper, iron and manganese etc., is preferably copper and/or iron.It is of the present invention at least
During two kinds of transition metal combinations, the mixing ratio of various transition metal is not construed as limiting, can be arbitrary proportion.
Preferably, the active component account for the 1%~10% of composite catalyst gross mass, such as 1%, 2%, 3%, 4%,
5%th, 6%, 7%, 8%, 9% or 10% etc., it is not limited to cited numerical value, other are unrequited in the numberical range
Numerical value is equally applicable, is preferably 2%~5%.
In the present invention, the load capacity of active component can be by adjusting transition metal salt solution on the composite catalyst
The number of concentration and/or ion-exchange reactions is adjusted.
Second aspect, the present invention provide the preparation method of composite catalyst as described in relation to the first aspect, the described method includes
Following steps：
(1) molecular sieve with the salting liquid of transition metal is mixed and carries out ion exchange, obtain mixed liquor；
(2) separation of solid and liquid is carried out to the mixed liquor that step (1) obtains, obtains solid mixture；
(3) solid mixture obtained to step (2) roasts, and obtains composite catalyst.
In the method for the present invention, step (1) described ion-exchange reactions can carry out repeatedly, load capacity as needed
It is adjusted.
It is molten by adjusting the number and/or transition metal salt of step (1) described ion-exchange reactions in the method for the present invention
The concentration of liquid can regulate and control the load capacity of the active component on composite catalyst.
As the optimal technical scheme of the method for the invention, the salting liquid of step (1) described transition metal is mantoquita, iron
Any one in salt, cerium salt or manganese salt or at least two salting liquids combined.The combination is typical but non-limiting examples have：
The combination of mantoquita and molysite, the combination of molysite and cerium salt, the combination of mantoquita and cerium salt, the combination of mantoquita, molysite and cerium salt, mantoquita
With the combination of manganese salt, the combination of molysite and manganese salt, the combination of mantoquita, molysite and manganese salt etc., be preferably mantoquita and/or molysite salt
Solution.
Preferably, the salting liquid of step (1) described transition metal is：The sulfate liquor of transition metal, transition metal
In the Acetate Solution of nitrate solution or transition metal any one or at least two combination.The combination is typical but non-
Limitative examples have：The combination of the sulfate liquor of transition metal and the nitrate solution of transition metal, the nitric acid of transition metal
The combination of the Acetate Solution of salting liquid and transition metal, the sulfate liquor of transition metal, the nitrate solution of transition metal
With the combination of the Acetate Solution of transition metal etc..
Preferably, the concentration of the salting liquid of step (1) described transition metal is 0.01mol/L~1.0mol/L, it is preferable that
The concentration of the salting liquid of step (1) described transition metal is 0.01mol/L~1.0mol/L, such as 0.01mol/L, 0.05mol/
L, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.7mol/L or 1.0mol/L etc., it is not limited to cited numerical value, it should
Other unrequited numerical value are equally applicable in numberical range.Its load capacity as needed is adjusted.
In the present invention, the concentration of the salting liquid of transition metal is one of factor for influencing AEI molecular sieve catalysts.Compared with
Molecular sieve (such as AEI molecular sieves), the excessive concentration of the salting liquid of transition metal or too low all can finally influence urging for catalyst
Change performance.It is illustrated by taking AEI molecular sieves as an example：For the AEI molecular sieves of certain mass, if the salting liquid of transition metal is dense
Low (less than 0.01mol/L) is spent, the activity component load quantity on AEI molecular sieves can be made very few, reduce the middle low temperature of catalyst
Catalytic activity；And the excessive concentration (be higher than 1.0mol/L) of the salting liquid of transition metal, can make the metal loaded on molecular sieve from
Son is excessively high, reunites in roasting process, and causing AEI molecular sieve catalysts, catalytic performance reduces under the high temperature conditions.
Preferably, step (1) described molecular sieve is AEI molecular sieves, is preferably rich aluminium profiles AEI molecular sieves, the richness aluminium profiles
The silica alumina ratio Si/Al of AEI is 15~2, is preferably 12~5.
Preferably, the ratio between the quality of step (1) described molecular sieve and the volume of salting liquid of transition metal are 1g:(20mL
~200mL), such as 1g:50mL、1g:70mL、1g:100mL、1g:130mL、1g:150mL、1g:170mL or 1g:200mL etc.,
It is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable, are preferably 1g:(50mL
~100mL).
Preferably, the reaction temperature condition of step (1) described ion-exchange reactions be 20 DEG C~80 DEG C, such as 20 DEG C, 30
DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C etc., it is not limited to cited numerical value, other are not arranged in the numberical range
The numerical value of act is equally applicable.In the present invention, the ion-exchange reaction temperature condition is to influence AEI molecular sieve catalyst performances
One of factor, compared with AEI molecular sieves, the temperature excessively high (being higher than 80 DEG C) of ion exchange can cause transition metal ions to gather,
And reunite in roasting process, reduce the catalytic performance of AEI molecular sieve catalysts under the high temperature conditions.The temperature mistake of ion exchange
Low (be less than 20 DEG C) can cause on AEI molecular sieve catalysts that activity component load quantity is very few, reduce the middle low temperature active of catalyst.
Preferably, step (1) described ion-exchange reactions carries out under agitation.
Preferably, the reaction time of step (1) described ion-exchange reactions is 5h~for 24 hours, for example, 5h, 8h, 12h, 14h,
16h, 18h, 20h, 22h or for 24 hours etc., it is not limited to cited numerical value, other unrequited numerical value in the numberical range
It is equally applicable.
Preferably, the mode of step (2) described separation of solid and liquid includes but not limited to any one in filtering, filter or centrifuging
Kind or at least two combination.
As the optimal technical scheme of the method for the invention, the method is additionally included in after step (2) separation of solid and liquid
Step (2) ' is carried out before step (3) roasting：Solid mixture is washed and is dried.
Preferably, step (2) ' in, 80 DEG C~105 DEG C of the temperature of the drying, for example, 80 DEG C, 83 DEG C, 85 DEG C, 87 DEG C,
90 DEG C, 93 DEG C, 95 DEG C, 97 DEG C, 100 DEG C or 105 DEG C etc., it is not limited to cited numerical value, in the numberical range other
Unrequited numerical value is equally applicable, is preferably 100 DEG C.
Preferably, step (2) ' in, the drying time be 12h~36h, such as 12h, 14h, 16h, 18h, 20h, 22h,
For 24 hours, 26h, 28h, 30h, 32h, 34h or 36h etc., it is not limited to cited numerical value, interior other of the numberical range do not arrange
The numerical value of act is equally applicable, is preferably 12h.
As the optimal technical scheme of the method for the invention, the temperature of step (3) described roasting is 450 DEG C~650 DEG C,
Such as 450 DEG C, 470 DEG C, 500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C, 600 DEG C, 630 DEG C or 650 DEG C etc., it is not limited to listed
The numerical value of act, other interior unrequited numerical value of the numberical range are equally applicable.
In the present invention, calcination temperature is also one of factor for influencing AEI molecular sieve catalysts.Compared with molecular sieve (such as
AEI molecular sieves), calcination temperature is too low or the excessively high catalyst performance that can all influence catalyst.It is said by taking AEI molecular sieves as an example
It is bright：If calcination temperature is too low (being less than 450 DEG C), sulfate, nitrate or acetate can be made to residue in catalyst surface, covering is lived
Property site, so as to reduce the catalytic performance of AEI molecular sieve catalysts.If calcination temperature is excessively high (being higher than 650 DEG C), molecular sieve can be made
The metal ion of upper load occurs migration on AEI molecular sieves in roasting process and reunites, and further aoxidizes, simultaneously
The configuration of AEI molecular sieves is destroyed, and be easy to cause the inactivation of catalyst, reduces the catalytic of AEI molecular sieve catalysts
Energy.
Preferably, step (3) described roasting time is 3h~8h, such as 3h, 4h, 5h, 6h, 7h or 8h etc., but simultaneously not only
It is limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) salting liquid of AEI molecular sieves and the transition metal of concentration 0.01mol/L~1.0mol/L is pressed into quality and volume
Than for 1g:(20mL~200mL) is mixed, and carries out ion-exchange reactions under agitation in 20 DEG C~80 DEG C, and reaction 5h~
For 24 hours, mixed liquor is obtained；
(2) step (1) is obtained mixed liquor to filter, obtains solid mixture；
(3) solid mixture that step (2) obtains is washed, after drying 12h~36h at 80 DEG C~105 DEG C,
3h~8h is roasted at 450 DEG C~650 DEG C, obtains AEI molecular sieve catalysts.
The third aspect, the present invention provide the purposes of composite catalyst as described in relation to the first aspect, and the composite catalyst is used
In catalytic purification of nitroxide field, preferably make the carrier in composite catalyst for AEI molecular sieves, more preferably catalysis is imitated to realize
Fruit.
Preferably, the composite catalyst is used for NH3- SCR reacts.
Preferably, the composite catalyst is used to move source tail-gas and/or the catalysis of stationary source nitrogen oxides in effluent is net
Change.
Compared with the prior art, the present invention has the advantages that：
(1) composite catalyst (such as AEI molecular sieve catalysts) of the present invention has wider temperature operating window, can
To keep more than 80% nitrogen oxide removal efficiency in the range of 200 DEG C~650 DEG C.
(2) composite catalyst (such as AEI molecular sieve catalysts) of the present invention has high-specific surface area and more active sites
Point compared with other species sieve catalysts, has stronger thermal stability and water-resistance and excellent N2Generation selection
Property,
(3) composite catalyst of the present invention will not make health and ecological environment using nontoxic component
Into harm, preparation method is simple and practicable.
(4) composite catalyst of the present invention especially AEI molecular sieve catalysts, it is net particularly suitable for motor-vehicle tail-gas
Change and stationary source flue gas low-temperature denitration.
Description of the drawings
Fig. 1 is the catalytic activity figure of catalyst described in present example 1；
Fig. 2 is the N of catalyst described in present example 12O generation figures；
Fig. 3 is the catalytic activity figure of catalyst described in present example 2；
Fig. 4 is the N of catalyst described in present example 22O generation figures.
Specific embodiment
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
Specific embodiment of the invention part provides a kind of for NH3- SCR reaction AEI molecular sieve catalysts and its
Preparation method and purposes, the AEI molecular sieve catalysts are using AEI molecular sieves as carrier, and ion exchange transition metal is as activity
Component.
In the present invention, " the ion exchange transition metal " refers to：The transition gold on molecular sieve is loaded to by ion exchange
Belong to.
Its preparation method comprises the following steps：
(1) AEI molecular sieves with the salting liquid of transition metal are mixed and carries out ion-exchange reactions, obtain mixed liquor；
(2) mixed liquor for obtaining step (1) carries out separation of solid and liquid, obtains solid mixture；
(3) solid mixture that step (2) obtains is roasted, obtains AEI molecular sieve catalysts.
It is below present invention typical case but non-limiting example：
Embodiment 1：
It present embodiments provides a kind of for NH3AEI molecular sieve catalysts of-SCR reactions and its preparation method and application,
The AEI molecular sieve catalysts are using AEI molecular sieves as carrier, and ion exchange metal copper is as active component.
Its preparation method is：
(1) copper-bath of 0.1mol/L is prepared, rich aluminium profiles AEI molecular sieves are mixed with copper-bath, wherein AEI
The quality of molecular sieve and the volume ratio of copper-bath are 1g:80mL stirs 12h progress ion-exchange reactions at 25 DEG C, obtains
To mixed liquor；
(2) mixed liquor that step (1) obtains is filtered and washs 3 times and obtain filter cake；
(3) filter cake that step (2) obtains is put into baking oven and dries 12h in 100 DEG C, then in 550 DEG C in Muffle furnace
Roasting 5h obtains the powdered Cu-AEI catalyst with AEI configurations, by catalyst tabletting obtained, grinding, sieving, takes 20
~40 mesh are spare.
Gained Cu-AEI catalyst is used for NH3- SCR reacts, and the composition of wherein reaction mixture gas is：[NO]=[NH3]=
500ppm, [O2]=5%, [H2O]=5%, N2As Balance Air, total gas flow rate 500mL/min, reaction temperature is at 150 DEG C
~550 DEG C.
The usage amount for taking catalyst is respectively 25mg, 50mg and 100mg, and corresponding air speed is respectively 800,000h-1、400,
000h-1And 200,000h-1, corresponding condition number is respectively A, B and C.NO and NH3And by-product N2O and NO2Utilize
Infrared-gas pond measures.
The catalytic activity of gained catalyst carries out on fixed reaction bed, until reaction carries out measuring reaction gas to stable state
Composition, under tri- kinds of test cases of A, B and C, the catalytic activity of catalyst is as shown in Figure 1, N2The growing amount of O is as shown in Figure 2.
As seen from Figure 1, the catalyst has the catalytic activity of excellent nitrogen oxides.In condition B and C situation
Under, the catalyst in 200 DEG C~550 DEG C temperature ranges, the conversion ratio of nitrogen oxides is more than 80%.Even very
In the case of severe condition A, which can also keep more than 80% nitrogen oxygen in 225 DEG C~550 DEG C temperature ranges
Compound conversion ratio.
As seen from Figure 2, in 150 DEG C~550 DEG C temperature ranges, N in the case of three kinds2The growing amount of O is all in 10ppm
Hereinafter, there is excellent N2Selectivity.The catalyst described above has very excellent NH3- SCR catalytic performances.
Embodiment 2：
It present embodiments provides a kind of for NH3AEI molecular sieve catalysts of-SCR reactions and its preparation method and application,
The AEI molecular sieve catalysts are using AEI molecular sieves as carrier, and carried metal copper is as active component.
Its preparation method is the preparation method in reference embodiment 1, difference lies in：Prepare 0.3mol/L's in step (1)
Copper nitrate solution, and the quality of AEI molecular sieves and the volume ratio of copper nitrate solution are 1g:50mL stirs 8h progress at 50 DEG C
Ion-exchange reactions.
Gained Cu-AEI catalyst is used for NH3- SCR reacts, reaction condition and the reaction condition phase in embodiment 1
Together, catalytic activity test method is in the same manner as in Example 1.Under tri- kinds of test cases of A, B and C, the catalytic activity of catalyst
As shown in figure 3, N2The growing amount of O is as shown in Figure 4.
By this example catalyst it can be seen from Fig. 3 and Fig. 4 in 225 DEG C~550 DEG C temperature ranges, tri- kinds of items of A, B and C
More than 80% NO conversion ratios, while the N generated can be kept under part2The content of O all in below 10ppm, has excellent N2Choosing
Selecting property.
Embodiment 3：
It present embodiments provides a kind of for NH3AEI molecular sieve catalysts of-SCR reactions and its preparation method and application,
The AEI molecular sieve catalysts are using AEI molecular sieves as carrier, and carried metal iron is as active component.
Its preparation method is the preparation method in reference embodiment 1, difference lies in：Prepare 0.1mol/L's in step (1)
Iron nitrate solution, and the quality of AEI molecular sieves and the volume ratio of iron nitrate solution are 1g:100mL, stirred at 35 DEG C for 24 hours into
Row ion-exchange reactions.
Gained Fe-AEI catalyst is used for NH3- SCR reacts, reaction condition and the reaction condition phase in embodiment 1
Together, catalytic activity test method is in the same manner as in Example 1.
Fe-AEI catalyst obtained by the present embodiment in condition C, the catalyst in 250 DEG C~450 DEG C temperature
In the range of degree, the conversion ratio of nitrogen oxides is more than 60%；In 150 DEG C~550 DEG C temperature ranges, N in the case of three kinds2O's
Growing amount all in below 15ppm, has very excellent NH3- SCR catalytic performances.
Embodiment 4：
It present embodiments provides a kind of for NH3AEI molecular sieve catalysts of-SCR reactions and its preparation method and application,
The AEI molecular sieve catalysts are using AEI molecular sieves as carrier, and carried metal copper and cerium are as active component.
Its preparation method is the preparation method in reference embodiment 1, difference lies in：Prepare in step (1) 0.1mol/L and
The copper nitrate of 0.1mol/L and cerous nitrate mixed solution, and the quality of AEI molecular sieves and the volume ratio of mixed solution are 1g:
150mL stirs 30h progress ion-exchange reactions at 25 DEG C.
Gained Cu/Ce-AEI catalyst is used for NH3- SCR reacts, reaction condition and the reaction condition in embodiment 1
Identical, catalytic activity test method is in the same manner as in Example 1.
Gained Cu/Ce-AEI catalyst is used for NH3- SCR reacts, reaction condition and the reaction condition in embodiment 1
Identical, catalytic activity test method is in the same manner as in Example 1.
Cu/Ce-AEI catalyst obtained by the present embodiment in condition C, the catalyst at 200 DEG C~500 DEG C
In temperature range, the conversion ratio of nitrogen oxides is more than 80%；In 150 DEG C~550 DEG C temperature ranges, N in the case of three kinds2O
Output all in below 10ppm, there is very excellent NH3- SCR catalytic performances.
Embodiment 5：
It present embodiments provides a kind of for NH3AEI molecular sieve catalysts of-SCR reactions and its preparation method and application,
The AEI molecular sieve catalysts are using AEI molecular sieves as carrier, and carried metal copper is as active component.
Its preparation method is the preparation method in reference embodiment 1, difference lies in：Calcination temperature is 650 in step (3)
DEG C, roasting time 6h.
Gained Cu-AEI catalyst is used for NH3- SCR reacts, reaction condition and the reaction condition phase in embodiment 1
Together, catalytic activity test method is in the same manner as in Example 1.
Gained Cu-AEI catalyst is used for NH3- SCR reacts, in condition C, the catalyst 200 DEG C~
In 550 DEG C of temperature ranges, the conversion ratio of nitrogen oxides is more than 80%；In 150 DEG C~550 DEG C temperature ranges, three kinds of situations
Lower N2The growing amount of O all in below 10ppm, has very excellent NH3- SCR catalytic performances.
Comparative example 1：
This comparative example provides a kind of for NH3The CHA configuration molecular sieve catalysts of-SCR reactions, are obtained from commercial channels
.
Use it for NH3- SCR reacts, and reaction condition is identical with the reaction condition in embodiment 1, and catalytic activity is surveyed
Method for testing is in the same manner as in Example 1.
The catalyst in condition C, the catalyst in 450 DEG C~550 DEG C high temperature ranges, nitrogen oxides
Conversion ratio is only up to 80%, and the more herein described AEI catalyst of performance is poor.
Comparative example 2：
This comparative example provides a kind of for NH3The AEI configuration molecular sieve catalysts of-SCR reactions, the AEI molecular sieves
Catalyst is using AEI molecular sieves as carrier, and carried metal copper is as active component.
Its preparation method is the preparation method in reference embodiment 1, difference lies in：Copper-bath is dense in step (1)
It spends for the excessive concentration of 1.2mol/L, i.e. copper-bath.
Gained Cu-AEI catalyst is used for NH3- SCR reacts, reaction condition and the reaction condition phase in embodiment 1
Together, catalytic activity test method is in the same manner as in Example 1.
The catalyst in condition C, the catalyst in 400 DEG C~550 DEG C high temperature ranges, nitrogen oxides
Conversion ratio is only up to 80%, the N generated in the case of three kinds2The all extra 10ppm of O content, it is seen that since active component is excessive, hair
It is raw to reunite, and then decline the high-temperature selective of catalyst.
Comparative example 3：
This comparative example provides a kind of for NH3The AEI configuration molecular sieve catalysts of-SCR reactions, the AEI molecular sieves
Catalyst is using AEI molecular sieves as carrier, and carried metal copper is as active component.
Its preparation method is the preparation method in reference embodiment 1, difference lies in：Copper-bath is dense in step (1)
It spends for 0.005mol/L, i.e. the concentration of copper-bath is too low.
By gained Cu-AEI catalyst, it is used for NH3- SCR reacts, reaction condition and the reaction condition phase in embodiment 1
Together, catalytic activity test method is in the same manner as in Example 1.
In the case of the catalysts conditions C, the catalyst in 150 DEG C~350 DEG C temperature ranges, nitrogen oxides turn
Rate is only up to 76%；It can be seen that active component is very little, low temperature active is caused to be decreased obviously.
Comparative example 4：
This comparative example provides a kind of for NH3The AEI configuration molecular sieve catalysts of-SCR reactions, the AEI molecular sieves
Catalyst is using AEI molecular sieves as carrier, and carried metal copper is as active component.
Its preparation method is the preparation method in reference embodiment 1, difference lies in：Calcination temperature is 400 in step (3)
DEG C, i.e., calcination temperature is relatively low.
By gained Cu-AEI catalyst, it is used for NH3- SCR reacts, reaction condition and the reaction condition phase in embodiment 1
Together, catalytic activity test method is in the same manner as in Example 1.
In the case of the catalysts conditions C, the catalyst in 150 DEG C~550 DEG C temperature ranges, nitrogen oxides turn
Rate is only up to 85%, it is seen that catalytic performance is decreased obviously.
Comparative example 5：
This comparative example provides a kind of for NH3The AEI configuration molecular sieve catalysts of-SCR reactions, the AEI molecular sieves
Catalyst is using AEI molecular sieves as carrier, and carried metal copper is as active component.
Its preparation method is the preparation method in reference embodiment 1, difference lies in：Calcination temperature is 750 in step (3)
DEG C, i.e., calcination temperature is higher.
By gained Cu-AEI catalyst, it is used for NH3- SCR reacts, reaction condition and the reaction condition phase in embodiment 1
Together, catalytic activity test method is in the same manner as in Example 1.
In the case of the catalysts conditions C, the catalyst in 400 DEG C~550 DEG C temperature ranges, nitrogen oxides is most
High conversion is only 75%；In 350 DEG C~500 DEG C temperature ranges, N in the case of three kinds2The extra 15ppm of growing amount of O, it is seen that
It roasts at an excessive temperature, catalyst surface active component is made to reunite, and then makes N2Selectivity reduces.
Summary embodiment and comparative example can be seen that AEI molecular sieve catalysts of the present invention with wider temperature
Action pane is spent, higher nitrogen oxide removal efficiency can be kept in the range of 200 DEG C~550 DEG C, and nitrogen oxides is gone
Except rate is up to more than 80%；Meanwhile AEI molecular sieve catalysts of the present invention have high-specific surface area and more active sites, with
Other species sieve catalysts are compared with stronger thermal stability and water-resistance and excellent N2Generation selectivity.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of composite catalyst, which is characterized in that the composite catalyst is using molecular sieve as carrier, to be born by ion exchange
The transition metal being downloaded on molecular sieve is active component.
2. composite catalyst according to claim 1, which is characterized in that the specific surface area of the composite catalyst is
350m2/ g~800m2/g。
3. composite catalyst according to claim 1 or 2, which is characterized in that the molecular sieve is AEI molecular sieves；
Preferably, the AEI molecular sieves are rich aluminium profiles AEI molecular sieves, and the silica alumina ratio Si/Al of the richness aluminium profiles AEI is 15~2,
Preferably 12~5.
4. according to claim 1-3 any one of them composite catalysts, which is characterized in that the transition metal is copper, iron, cerium
In manganese any one or at least two combination, be preferably copper and/or iron；
Preferably, the active component accounts for the 1%~10% of composite catalyst gross mass, is preferably 2%~5%.
5. such as the preparation method of claim 1-4 any one of them composite catalysts, which is characterized in that the method is ion
Exchange process specifically includes following steps：
(1) molecular sieve with the salting liquid of transition metal is mixed and carries out ion exchange, obtain mixed liquor；
(2) separation of solid and liquid is carried out to the mixed liquor that step (1) obtains, obtains solid mixture；
(3) solid mixture obtained to step (2) roasts, and obtains composite catalyst.
6. according to the method described in claim 5, it is characterized in that, the salting liquid of step (1) described transition metal is mantoquita, iron
Any one in salt, cerium salt or manganese salt or at least two salting liquids combined are preferably the salting liquid of mantoquita and/or molysite；
Preferably, the salting liquid of step (1) described transition metal is：The sulfate liquor of transition metal, the nitric acid of transition metal
In the Acetate Solution of salting liquid or transition metal any one or at least two combination；
Preferably, the concentration of the salting liquid of step (1) described transition metal is 0.01mol/L~1.0mol/L；
Preferably, step (1) described molecular sieve is AEI molecular sieves, is preferably rich aluminium profiles AEI molecular sieves, the richness aluminium profiles AEI's
Silica alumina ratio Si/Al is 15~2, is preferably 12~5；
Preferably, the ratio between the quality of step (1) described molecular sieve and the volume of salting liquid of transition metal are 1g:(20mL~
200mL), it is preferably 1g:(50mL~100mL)；
Preferably, the reaction temperature condition of step (1) described ion-exchange reactions is 20 DEG C~80 DEG C；
Preferably, step (1) described ion-exchange reactions carries out under agitation；
Preferably, the reaction time of step (1) described ion-exchange reactions is 5h~for 24 hours.
7. method according to claim 5 or 6, which is characterized in that the mode of step (2) described separation of solid and liquid for filter,
Filtering or centrifugation in any one or at least two combination；
Preferably, step (3) roasting carries out step (2) ' before after the method is additionally included in step (2) separation of solid and liquid：It is right
Solid mixture is washed and dried；
Preferably, step (2) ' in, 80 DEG C~105 DEG C of the temperature of the drying is preferably 100 DEG C；
Preferably, step (2) ' in, the drying time is 12h~36h, is preferably 12h.
8. according to claim 5-7 any one of them methods, which is characterized in that the temperature of step (3) described roasting is 450 DEG C
~650 DEG C；
Preferably, step (3) described roasting time is 3h~8h.
9. according to claim 5-8 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) it is by quality and volume ratio by AEI molecular sieves and the salting liquid of the transition metal of concentration 0.01mol/L~1.0mol/L
1g:(20mL~200mL) is mixed, and carries out ion-exchange reactions under agitation in 20 DEG C~80 DEG C, and reaction 5h~for 24 hours, it obtains
To mixed liquor；
(2) step (1) is obtained mixed liquor to filter, obtains solid mixture；
(3) solid mixture that step (2) obtains is washed, after drying 12h~36h at 80 DEG C~105 DEG C, 450
DEG C~650 DEG C at roast 3h~8h, obtain AEI molecular sieve catalysts.
10. such as the purposes of claim 1-4 any one of them composite catalysts, which is characterized in that the composite catalyst is used
In catalytic purification of nitroxide field；
Preferably, the composite catalyst is used for NH3- SCR reacts；
Preferably, the composite catalyst is used to move the catalytic purification of source tail-gas and/or stationary source nitrogen oxides in effluent.
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| CN113070097A (en) * | 2021-03-29 | 2021-07-06 | 中国科学院生态环境研究中心 | NO for ammonia selective catalytic reductionxCopper-based catalyst and preparation method thereof |
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