CN109647501A - A kind of multi-stage porous Fe- beta-molecular sieve catalyst and its preparation method and application - Google Patents
A kind of multi-stage porous Fe- beta-molecular sieve catalyst and its preparation method and application Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The present invention relates to a kind of multi-stage porous Fe- beta-molecular sieve catalyst and its preparation method and application；The preparation method obtains multi-stage porous beta-molecular sieve using organic amine aqueous solution hydro-thermal process beta-molecular sieve, multi-stage porous Fe- beta-molecular sieve catalyst is then obtained by ion exchange, when catalyst prepared by the present invention is used as ammonia selective catalyst reduction of nitrogen oxides, it is significantly improved relative to catalytic activity of the simple Fe- beta-molecular sieve catalyst being prepared using ion-exchange within the temperature range of 150-225 DEG C, it can reach 78%, and its anti-C in 225 DEG C of transformation efficiency of the oxides of nitrogen3H6The performance of poisoning also significantly improves.
Description
Technical field
The present invention relates to catalysis material fields more particularly to a kind of multi-stage porous Fe- beta-molecular sieve catalyst and preparation method thereof
And purposes.
Background technique
NO in atmospherexMostly come from the tails such as discharge gas and motor vehicles, the steamer for the related industrial process that burns
The discharge of gas is the major reason for causing the environmental pollutions such as acid rain, photochemical fog, haze.Currently, NOxThe main side of removal
Method has NOxStore reduction method and ammonia selective catalytic reduction.Wherein, ammonia selective catalytic reduction has removal efficiency
It the advantages that high, at low cost, receives significant attention.And the key studied ammonia selective catalytic reduction is catalyst.
In numerous molecular sieve catalysts, modified molecular sieve catalyst is due to excellent activity and selectivity, wide active window
And high high-temp stability, it is considered to have the catalyst of the ammonia selective catalytic reduction of actual application prospect.Cu base
It is the system of current most study with Fe based molecular sieve catalyst.Cu based molecular sieve has excellent cryogenic property, but it is high
Warm activity and sulfur resistance need to be further increased, Fe based molecular sieve catalyst (Fe- beta-molecular sieve catalyst and Fe-ZSM-5 points
Sub- sieve catalyst) activity be concentrated mainly on 300-500 DEG C of high temperature region, removed in 200-300 DEG C of middle low-temperature region
NOxEfficiency it is undesirable.
CN107029781A discloses a kind of iron and cerium modified beta-molecular sieve selective reduction catalyst and preparation method and answers
With, Template-free method synthesizing low silicon aluminium than beta-zeolite molecular sieve as catalyst substrates component, using liquid ion exchange-dipping side
Formula introduces Fe and Ce ion, on the basis of the total weight by the modified powder catalyst of ion exchange-dipping, Fe element
Accounting for weight percent is 0.5-8.0%, and it is 0.5-6.0% that Ce element, which accounts for weight percent,；Beta-zeolite molecular sieve silica alumina ratio (mole
Compare nSiO2/nAl2O3) range is 7.8-20, the catalyst contains NO for handlingxAir-flow；Catalyst obtained by this scheme is urged
Change that active temperature windows are narrow, 250 DEG C of whens reach the maximum value of transformation efficiency of the oxides of nitrogen, and subsequent activity is begun to decline, and catalyst
Preparation process it is complicated, higher cost.
CN105314647A discloses a kind of sial β or ferrosilicon beta-molecular sieve, the catalysis of purifying vehicle exhaust as made from it
Agent and their preparation method and application；Its method for preparing ferrosilicon beta-molecular sieve include (1) match colloidal sol: mixed templates and
Alkali and water add source of iron and silicon source, stir evenly between 25-45 DEG C；(2) colloidal sol of step (1) is taken, 0.1-5wt% weight is added
(relative to SiO in silicon source2Weight) crystal seed, be added in autoclave pressure, stir, crystallization 2-6 days at 135-155 DEG C, (3) general
The product filtering that step (2) obtains in above-mentioned preparation method, is then washed, then carries out sour exchange with dilute acid soln；(4) will
The product of step (3) carries out high-temperature calcination and obtains the ferrosilicon beta-molecular sieve, and the preparation method of this scheme is complicated, higher cost, and
Catalyst low-temperature activity obtained is poor.
CN102513145A discloses a kind of for NO in acrylonitrile oxidized tail gasxThe Fe molecular sieve SCR catalyst of purification
And preparation method；It is using commercial ZSM-5 molecular sieve, Y type molecular sieve, ferrierite or beta-molecular sieve as carrier, using infusion process
Or ion-exchange introduces mass fraction 0.3-10.0%Fe3+For active component, and introduce 0.5-8.0%M (lanthanum La or cobalt Co)
As modification component；Fe- beta-molecular sieve catalyst obtained by this scheme is poor in 250 DEG C of activity below, and catalyst preparation process
Complexity, higher cost.
Although above-mentioned document provides the preparation method of some Fe- beta-molecular sieve catalyst, but there are still catalyst preparations
Process is complicated, higher cost, and the problem that catalyst low-temperature activity is poor or temperature window is narrow, therefore develops a kind of simple system
The low temperature active that Preparation Method improves catalyst has great importance.
Summary of the invention
The purpose of the present invention is to provide a kind of multi-stage porous Fe- beta-molecular sieve catalyst and its preparation method and application；It is described
Preparation method obtains multi-stage porous beta-molecular sieve using organic amine aqueous solution hydro-thermal process beta-molecular sieve, is then obtained by ion exchange
The catalyst is used as the catalyst of catalysis ammonia selective catalyst reduction of nitrogen oxides by multi-stage porous Fe- beta-molecular sieve catalyst
When, the Fe- beta-molecular sieve catalyst that is prepared relative to simple ion-exchange is within the temperature range of 150-225 DEG C
Catalytic activity significantly improves, and can reach 78%, and its anti-C in 225 DEG C of transformation efficiency of the oxides of nitrogen3H6The performance of poisoning
It significantly improves.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of multi-stage porous Fe- beta-molecular sieve catalyst, the method packet
Include following steps:
(1) multi-stage porous beta-molecular sieve is obtained using organic amine aqueous solution processing beta-molecular sieve；
(2) Fe is loaded on the multi-stage porous beta-molecular sieve that step (1) obtains by ion exchange, obtains the multi-stage porous Fe-
Beta-molecular sieve catalyst.
The present invention increases the knot of the duct inside beta-molecular sieve using the method for organic amine aqueous solution hydro-thermal process beta-molecular sieve
Structure, the multi-stage porous beta-molecular sieve being prepared contain the cellular structure of different scale, have micro porous molecular sieve crystal excellent simultaneously
On the one hand the excellent diffusion transport performance of different hydrothermal stability and mesoporous material, above structure increase reactant molecule in hole
On the other hand diffusion rate in road provides more ion exchange sites on beta-molecular sieve surface for Fe, to be conducive to
More reactivity sites are provided for catalysis reaction, improve the activity of catalysis reaction；Multi-stage porous Fe- β of the present invention points
The multi-stage porous Fe- beta-molecular sieve catalyst that sub- sieve catalyst preparation method is prepared is prepared into relative to simple ion-exchange
To the specific surface area of Fe- beta-molecular sieve catalyst increase, the load capacity of Fe also improves under identical ion exchange conditions
, catalytic activity within the temperature range of 150-225 DEG C also significantly improves.
Preferably, the silica alumina ratio of step (1) described beta-molecular sieve be 10-50, such as 10,12,15,17,20,22,25,27,
30,35,40,45 or 50 etc., preferably 20-30, preferably 25.
Preferably, the organic amine in organic amine aqueous solution includes tetraethyl ammonium hydroxide, triethylamine, diethanol amine
In di-n-propylamine any one or at least two mixture, the mixture illustratively includes tetraethyl ammonium hydroxide
With the mixture of triethylamine, the mixture of diethanol amine and di-n-propylamine or triethylamine and the mixture of diethanol amine etc.,
Preferably tetraethyl ammonium hydroxide.
The present invention can make part beta-molecular sieve in hydrothermal treatment process using template of the organic amine as beta-molecular sieve
Dissolution, and recrystallized using this organic amine as template, the hierarchical porous structure of micropore-mesopore (macropore) is formed, compared to nothing
Machine alkali process has apparent advantage, and the latter handles the destruction and collapsing for often leading to molecular sieve structure.
Preferably, in organic amine aqueous solution organic amine concentration be 0.1-1mol/L, such as 0.1mol/L,
0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or
1mol/L etc., preferably 0.3mol/L.
Preferably, step (1) the organic amine aqueous solution processing beta-molecular sieve method the following steps are included:
(a) beta-molecular sieve is mixed with organic amine aqueous solution, is stirred；
(b) hydro-thermal process is carried out to the product that step (a) obtains；
(c) product that step (b) obtains is filtered, is washed, dried, roasting obtains the multi-stage porous beta-molecular sieve.
Preferably, the ratio between the quality of step (a) beta-molecular sieve and the volume of organic amine aqueous solution are 0.033-0.1g/
ML, such as 0.033g/mL, 0.04g/mL, 0.05g/mL, 0.06g/mL, 0.07g/mL, 0.08g/mL, 0.09g/mL or 0.1g/
ML etc..
Preferably, the temperature of step (b) hydro-thermal process is 120-150 DEG C, such as 120 DEG C, 125 DEG C, 130 DEG C, 135
DEG C, 140 DEG C, 145 DEG C or 150 DEG C etc., preferably 140 DEG C.
Preferably, the time of step (b) hydro-thermal process is 24-168h；Such as 24 hours, 36h, 48h, 60h, 72h,
84h, 96h, 108h, 120h, 132h, 144h or 168h etc., preferably 72h.
The present invention makes beta-molecular sieve that dissolution-recrystallization occur using hydro-thermal process, to form hierarchical porous structure.
Preferably, the temperature of step (c) roasting be 450-600 DEG C, such as 450 DEG C, 480 DEG C, 500 DEG C, 550 DEG C,
570 DEG C or 600 DEG C etc., preferably 550 DEG C.
Preferably, the time of step (c) roasting be 3-10h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h etc.,
Preferably 5h.
Preferably, the heating rate of step (c) roasting be 1-5 DEG C/min, such as 1 DEG C/min, 2 DEG C/min, 3 DEG C/
Min, 4 DEG C/min or 5 DEG C/min etc., preferably 2 DEG C/min.
Preferably, step (2) described ion exchange method the following steps are included:
(a ') mixes the multi-stage porous beta-molecular sieve that step (1) is prepared with molysite aqueous solution, and stirring carries out ion friendship
It changes；
The product that (b ') obtains step (a ') is filtered, and is washed, dry, and roasting obtains the multi-stage porous Fe- beta molecule
Sieve catalyst.
Preferably, the molysite in step (a ') described molysite aqueous solution includes frerrous chloride, ferrous sulfate, ferric nitrate or two
In luxuriant iron any one or at least two mixture, the mixture illustratively includes frerrous chloride and ferrous sulfate
Mixture, the mixture or ferrocene of ferric nitrate and ferrous sulfate, the mixture of frerrous chloride and ferric nitrate etc..
Preferably, the concentration of step (a ') described molysite aqueous solution be 0.01-0.25mol/L, such as 0.01mol/L,
0.03mol/L、0.05mol/L、0.08mol/L、0.13mol/L、0.15mol/L、0.17mol/L、0.2mol/L、0.22mol/
L or 0.25mol/L etc., preferably 0.05mol/L.
Preferably, the ratio between the quality of step (a ') described multi-stage porous beta-molecular sieve and the volume of molysite aqueous solution are 0.004-
0.0067g/mL, such as 0.004g/mL, 0.005g/mL, 0.006g/mL or 0.0067g/mL etc., preferably 0.005g/mL.
Preferably, it is -90 DEG C of room temperature that step (a ') stirring, which carries out the temperature of ion exchange, preferably 60-80 DEG C, example
Such as 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C, further preferably 80 DEG C.
Preferably, it is 5-48h that step (a ') stirring, which carries out the time of ion exchange, for example, 5h, 7h, 10h, 15h,
18h, for 24 hours, 28h, 32h, 36h, 40h, 44h or 48h etc., preferably for 24 hours.
Preferably, the temperature of step (b ') described roasting be 400-600 DEG C, such as 400 DEG C, 430 DEG C, 450 DEG C, 470 DEG C,
500 DEG C, 520 DEG C, 550 DEG C, 570 DEG C or 600 DEG C etc., preferably 500 DEG C.
Preferably, the time of step (b ') described roasting be 3-10h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h etc.,
Preferably 3h.
Preferably, the heating rate of step (b ') described roasting is 1-10 DEG C/min, such as 1 DEG C/min, 2 DEG C/min, 3
DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/min, preferably 5 DEG C/
min。
As the present invention preferably technical solution, the preparation method packet of multi-stage porous Fe- beta-molecular sieve catalyst of the present invention
Include following steps:
The tetraethyl ammonium hydroxide that beta-molecular sieve and concentration that silica alumina ratio is 10-50 are 0.1-1mol/L by (1 ') it is water-soluble
Liquid is mixed according to the ratio of 0.033-0.1g/mL；
The product that (2 ') obtains step (1 ') hydro-thermal process 24-168h at a temperature of 120-150 DEG C；
The product that (3 ') obtains step (2 ') is filtered, and is washed, and drying then roasts 3-10h at 450-600 DEG C
Obtain the multi-stage porous beta-molecular sieve；
The multi-stage porous beta-molecular sieve and concentration that (4 ') step (3 ') is prepared are 0.01-0.25mol/L molysite aqueous solution
It is mixed according to the ratio of 0.004-0.0067g/mL, stirring carries out ion exchange 5-48h at 60-80 DEG C；
The product that (5 ') obtains step (4 ') is filtered, and is washed, dry, finally roasts 3-10h at 400-600 DEG C
Obtain the multi-stage porous Fe- beta-molecular sieve catalyst.
Second aspect, the present invention provides the multi-stage porous Fe- beta-molecular sieves that preparation method as described in relation to the first aspect is prepared
Catalyst.
The low temperature active of multi-stage porous Fe- beta-molecular sieve catalyst of the present invention is prepared relative to only with ion-exchange
Catalytic activity of Fe- beta-molecular sieve catalyst within the temperature range of 150-225 DEG C significantly improves, in 150-550 DEG C of temperature
It is 100% to the selectivity of nitrogen in section, and its anti-C3H6The performance of poisoning also significantly improves.
The third aspect, the present invention provides the multi-stage porous Fe- beta-molecular sieve catalyst as described in second aspect to select as ammonia
The purposes of the catalyst of selecting property catalyzing and reducing nitrogen oxides.
Preferably, the multi-stage porous Fe- beta-molecular sieve catalyst as the mobile source tail-gas of ammonia selective catalytic reduction and/
Or the catalyst of stationary source nitrogen oxides in effluent.
Compared with the existing technology, the present invention at least has the advantages that
(1) the multi-stage porous Fe- beta molecule that the preparation method of multi-stage porous Fe- beta-molecular sieve catalyst of the present invention is prepared
Sieve catalyst has bigger BET specific surface area relative to the Fe- beta-molecular sieve catalyst that simple ion-exchange is prepared,
And it also significantly improves the load capacity of Fe；
(2) the multi-stage porous Fe- beta molecule that the preparation method of multi-stage porous Fe- beta-molecular sieve catalyst of the present invention is prepared
The Fe- beta-molecular sieve catalyst that sieve catalyst is prepared relative to simple ion-exchange is within the temperature range of 150-225 DEG C
Catalytic activity significantly improve, in 225 DEG C of transformation efficiency of the oxides of nitrogen i.e. up to 78%；
(3) the Fe- β that multi-stage porous Fe- beta-molecular sieve catalyst of the present invention is prepared relative to simple ion-exchange
Molecular sieve catalyst, anti-C3H6The performance of poisoning also significantly improves；
(4) preparation method of multi-stage porous Fe- beta-molecular sieve catalyst of the present invention is simple, at low cost, is easy to industrialize and answer
With.
Detailed description of the invention
Fig. 1 is the activity for the catalyst ammonia nitrogen oxides reduction that the embodiment of the present invention 1 and comparative example 1 are prepared
Compare figure；
Fig. 2 is the process for the catalyst ammonia nitrogen oxides reduction that the embodiment of the present invention 1 and comparative example 1 are prepared
In figure is compared to the selectivity of nitrogen；
Fig. 3 is that the catalyst that the embodiment of the present invention 1 and comparative example 1 are prepared is free of C in reaction gas3H6With contain C3H6
Under conditions of catalysis ammonia nitrogen oxides reduction expression activitiy figure.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) by silica alumina ratio be 25 beta-molecular sieve and 60mL concentration be 0.3mol/L tetraethyl ammonium hydroxide aqueous solution by
According to the ratio mixing of 0.05g/mL, 1h is stirred；
(2) by the product of step (1) at a temperature of 140 DEG C hydro-thermal process 72h；
(3) product of step (2) is filtered, is washed to neutrality, in 100 DEG C of drying 12h, then roasted at 550 DEG C
It burns 5h and obtains the multi-stage porous beta-molecular sieve；
(4) the multi-stage porous beta-molecular sieve that step (3) is prepared is that 0.05mol/L frerrous chloride is water-soluble with 200mL concentration
Liquid is mixed according to the ratio of 0.005g/mL, and stirring carries out ion exchange for 24 hours at 80 DEG C；
(5) product that step (4) obtains is filtered, is washed to neutrality, then the dry 12h at 100 DEG C, finally exists
5h is roasted at 500 DEG C and obtains the multi-stage porous Fe- beta-molecular sieve catalyst, is marked as multi-stage porous Fe- β.
The structured data and Fe content for the multi-stage porous Fe- beta-molecular sieve catalyst that the present embodiment is prepared are as shown in table 1；
Its activity figure for being catalyzed ammonia nitrogen oxides reduction is as shown in figures 1 and 3, right during catalysis ammonia nitrogen oxides reduction
The selectivity of nitrogen is as shown in Fig. 2, nitrogen oxides of the multi-stage porous Fe- beta-molecular sieve catalyst obtained by the present embodiment at 225 DEG C turns
Rate is as shown in table 2.
Embodiment 2
The present embodiment the difference from embodiment 1 is that: the silica alumina ratio of beta-molecular sieve is replaced with 50 by 25, by 0.3mol/L
Tetraethyl ammonium hydroxide aqueous solution replace with the aqueous triethylamine of isometric 0.5mol/L；Step (2) described hydro-thermal
The temperature of processing replaces with 150 DEG C, and the time of hydro-thermal process replaces with 48h；The temperature of step (3) described roasting replaces with 600
℃；Step (4) the 0.05mol/L ferrous chloride aqueous solution replaces with isometric 0.05mol/L ferrous sulfate aqueous solution；It will
The temperature of the ion exchange of step (4) replaces with 60 DEG C, and other conditions are identical compared with Example 1.
Transformation efficiency of the oxides of nitrogen of the multi-stage porous Fe- beta-molecular sieve catalyst obtained by the present embodiment at 225 DEG C is as shown in table 2.
Embodiment 3
The present embodiment the difference from embodiment 1 is that: the tetraethyl ammonium hydroxide aqueous solution of 0.3mol/L is replaced with
The diethanol amine aqueous solution of the 0.5mol/L of volume；The temperature of step (2) described hydro-thermal process replaces with 120 DEG C, step (2) institute
The time for stating hydro-thermal process replaces with 120h；Step (3) described calcining time replaces with 8h；The 0.05mol/L chlorination of step (4)
Ferrous aqueous solution replaces with isometric 0.1mol/L iron nitrate aqueous solution；The ion-exchange temperature of step (4) is replaced with 70
DEG C, other conditions are identical compared with Example 1.
Transformation efficiency of the oxides of nitrogen of the multi-stage porous Fe- beta-molecular sieve catalyst obtained by the present embodiment at 225 DEG C is as shown in table 2.
Embodiment 4
The present embodiment the difference from embodiment 1 is that: the tetraethyl ammonium hydroxide aqueous solution of 0.3mol/L is replaced with
The aqueous solution of the di-n-propylamine of the 0.8mol/L of volume；The 0.05mol/L ferrous chloride aqueous solution of step (4) replaces in equal volume
0.1mol/L ferrocene aqueous solution；The ion-exchange temperature of step (4) is replaced with into room temperature, the maturing temperature of step (5) replaces
It is changed to 450 DEG C.
Transformation efficiency of the oxides of nitrogen of the multi-stage porous Fe- beta-molecular sieve catalyst obtained by the present embodiment at 225 DEG C is as shown in table 2.
Comparative example 1
This comparative example is only with (4) the step of embodiment 1 and step (5), and by the multi-stage porous beta-molecular sieve in step (4)
The beta-molecular sieve without organic amine aqueous solution hydro-thermal process in 1 step of embodiment (1) of quality such as replace with；Other conditions with
Embodiment 1 is identical, and gained catalyst is labeled as Fe- β.
The structured data and Fe content of Fe- beta catalyst obtained by this comparative example are as described in Table 1；It is catalyzed ammonia and restores nitrogen oxygen
The activity figure of compound is as shown in figures 1 and 3；It such as schemes the selective figure of nitrogen during being catalyzed ammonia nitrogen oxides reduction
Shown in 2；Transformation efficiency of the oxides of nitrogen of the Fe- beta catalyst obtained by this comparative example at 225 DEG C is as shown in table 2.
The method for carrying out activity rating to catalyst made from embodiment 1-4 and comparative example 1 is the catalyst for taking 40-60 mesh
Particle carries out the experiment of catalysis ammonia nitrogen oxides reduction on fixed bed reactors.
Without C3H6Test condition under, the air inlet of experiment forms are as follows: [NO]=[NH3]=500ppm, [O2]=5%, N2
Make Balance Air, total gas flow rate 500mL/min, gas space velocity (Gas hourly spacevelocity, GHSV) is
200000h-1, 150-550 DEG C of reaction temperature.
Contain C3H6Test condition under, the air inlet of experiment forms are as follows: [NO]=[NH3]=500ppm, [C3H6]=
500ppm, [O2]=5%, N2Make Balance Air, total gas flow rate 500mL/min, gas space velocity 200000h-1, reaction temperature
150-550℃；1 gained catalyst of embodiment is containing C3H6Test condition under test result labeled as multi-stage porous Fe- β+
C3H6, 1 gained catalyst of comparative example containing C3H6Test condition under test result be labeled as Fe- β+C3H6。
Analysis method: NO and NH3And by-product N2O、NO2Content utilize infrared gas analyser (Nicolet
Antaris IGS) measurement.
Fig. 1 is the activity for the catalyst ammonia nitrogen oxides reduction that the embodiment of the present invention 1 and comparative example 1 are prepared
Compare figure；As seen from the figure, under the same reaction conditions, it compared to the Fe- β of comparative example 1, is made by preparation method of the present invention
The low temperature active of multi-stage porous Fe- β significantly improve.
Fig. 2 is the process for the catalyst ammonia nitrogen oxides reduction that the embodiment of the present invention 1 and comparative example 1 are prepared
In figure is compared to the selectivity of nitrogen；As seen from the figure, the multi-stage porous Fe- β that embodiment 1 is prepared is in entire reaction process
In nitrogen selective reach 100%, illustrate the catalyst suitable for stationary source and moving source nitrogen oxide in tail gas
Purification, the especially purification of nitrogen oxides at low temperatures illustrate that the present invention improves catalyst by introducing multi-stage porous beta-molecular sieve
The method of cryogenic property is feasible.
Fig. 3 is that the catalyst that the embodiment of the present invention 1 and comparative example 1 are prepared is free of C in reaction gas3H6With contain C3H6
Under conditions of catalysis ammonia nitrogen oxides reduction expression activitiy figure；As seen from the figure, under same reaction conditions, compared to comparison
The Fe- β of example 1, the anti-C of multi-stage porous Fe- β as made from preparation method of the present invention3H6Poisoning capability is enhanced.
The structured data and Fe content for the catalyst that embodiment 1 and comparative example 1 are prepared are as described in Table 1；
Table 1
Multi-stage porous Fe- β ratio Fe- β has bigger external surface area as can be seen from Table 1, illustrates water-soluble by organic amine
Liquid processing introduces multi-stage porous on beta-molecular sieve, and under equal conditions carries out ion exchange, and the Fe on multi-stage porous Fe- β contains
Amount is higher, illustrates that the multi-stage porous introduced provides more ion-exchange sites, this is also the reason of activity improves.
Reaction gas is free of C3H6Under conditions of, the nitrogen oxides of embodiment 1-4 and 1 gained catalyst of comparative example at 225 DEG C
Conversion ratio is as shown in table 2.
Table 2
Comparative example 1-4 is with comparative example 1 as can be seen that the low temperature active through organic amine aqueous solution processing rear catalyst is bright
It is aobvious to be promoted, illustrate that the hierarchical porous structure formed on beta-molecular sieve is handled using organic amine aqueous solution to be conducive to improve catalysis really
The catalytic activity of agent.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of preparation method of multi-stage porous Fe- beta-molecular sieve catalyst, which is characterized in that the described method comprises the following steps:
(1) multi-stage porous beta-molecular sieve is obtained using organic amine aqueous solution processing beta-molecular sieve；
(2) Fe is loaded on the multi-stage porous beta-molecular sieve that step (1) obtains by ion exchange, obtains the multi-stage porous Fe- β points
Sub- sieve catalyst.
2. preparation method as described in claim 1, which is characterized in that the silica alumina ratio of step (1) described beta-molecular sieve is 10-50,
Preferably 20-30, further preferably 25；
Preferably, the organic amine in organic amine aqueous solution includes tetraethyl ammonium hydroxide, triethylamine, diethanol amine or two
In n-propylamine any one or at least two mixture, preferably tetraethyl ammonium hydroxide；
Preferably, the concentration of organic amine is 0.1-1mol/L, preferably 0.3mol/L in organic amine aqueous solution.
3. preparation method as claimed in claim 1 or 2, which is characterized in that described organic β points of amine aqueous solution processing of step (1)
Son sieve method the following steps are included:
(a) beta-molecular sieve is mixed with organic amine aqueous solution, is stirred；
(b) hydro-thermal process is carried out to the product that step (a) obtains；
(c) product that step (b) obtains is filtered, is washed, dried, roasting obtains the multi-stage porous beta-molecular sieve.
4. preparation method as claimed in claim 3, which is characterized in that the quality and organic aqueous amine of step (a) beta-molecular sieve
The ratio between volume of solution is 0.033-0.1g/mL；
Preferably, the temperature of step (b) hydro-thermal process is 120-150 DEG C, preferably 140 DEG C；
Preferably, the time of step (b) hydro-thermal process is 24-168h；Preferably 72h.
5. preparation method as described in claim 3 or 4, which is characterized in that the temperature of step (c) roasting is 450-600
DEG C, preferably 550 DEG C；
Preferably, the time of step (c) roasting is 3-10h, preferably 5h；
Preferably, the heating rate of step (c) roasting is 1-5 DEG C/min, preferably 2 DEG C/min.
6. preparation method as described in any one in claim 1-5, which is characterized in that the method for step (2) described ion exchange
The following steps are included:
(a ') mixes the multi-stage porous beta-molecular sieve that step (1) is prepared with molysite aqueous solution, and stirring carries out ion exchange；
The product that (b ') obtains step (a ') is filtered, and is washed, dry, and roasting obtains the multi-stage porous Fe- beta-molecular sieve and urges
Agent.
7. preparation method as claimed in claim 6, which is characterized in that the molysite in step (a ') described molysite aqueous solution includes
In frerrous chloride, ferrous sulfate, ferric nitrate or ferrocene any one or at least two mixture；
Preferably, the concentration of step (a ') described molysite aqueous solution is 0.01-0.25mol/L, preferably 0.05mol/L；
Preferably, the ratio between the quality of step (a ') described multi-stage porous beta-molecular sieve and the volume of molysite aqueous solution are 0.004-
0.0067g/mL, preferably 0.005g/mL；
Preferably, it is -90 DEG C of room temperature that step (a ') stirring, which carries out the temperature of ion exchange, preferably 60-80 DEG C, further
Preferably 80 DEG C；
Preferably, step (a ') stirring carries out the time of ion exchange for 5-48h, preferably for 24 hours；
Preferably, the temperature of step (b ') described roasting is 400-600 DEG C, preferably 500 DEG C；
Preferably, the time of step (b ') described roasting is 3-10h, preferably 3h；
Preferably, the heating rate of step (b ') described roasting is 1-10 DEG C/min, preferably 5 DEG C/min.
8. such as the described in any item preparation methods of claim 1-7, which is characterized in that the preparation method comprises the following steps:
(1 ') by silica alumina ratio be 10-50 beta-molecular sieve and concentration be 0.1-1mol/L tetraethyl ammonium hydroxide aqueous solution by
According to the ratio mixing of 0.033-0.1g/mL；
The product that (2 ') obtains step (1 ') hydro-thermal process 24-168h at a temperature of 120-150 DEG C；
The product that (3 ') obtains step (2 ') is filtered, and is washed, drying, is then roasted 3-10h at 450-600 DEG C and is obtained
The multi-stage porous beta-molecular sieve；
Multi-stage porous beta-molecular sieve that (4 ') step (3 ') is prepared and concentration be 0.01-0.25mol/L molysite aqueous solution according to
The ratio of 0.004-0.0067g/mL mixes, and stirring carries out ion exchange 5-48h at 60-80 DEG C；
The product that (5 ') obtains step (4 ') is filtered, and is washed, dry, is finally roasted 3-10h at 400-600 DEG C and is obtained
The multi-stage porous Fe- beta-molecular sieve catalyst.
9. the multi-stage porous Fe- beta-molecular sieve catalyst being prepared such as the described in any item preparation methods of claim 1-8.
10. multi-stage porous Fe- beta-molecular sieve catalyst as claimed in claim 9 is as ammonia selective catalyst reduction of nitrogen oxides
Catalyst purposes；
Preferably, the multi-stage porous Fe- beta-molecular sieve catalyst moves source tail-gas as ammonia selective catalytic reduction and/or consolidates
Determine the catalyst of source nitrogen oxides in effluent.
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