CN105964295A - Manganese-rich Mn-SAPO-34 molecular sieve catalyst as well as preparation method and application thereof - Google Patents
Manganese-rich Mn-SAPO-34 molecular sieve catalyst as well as preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011572 manganese Substances 0.000 title claims abstract description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 69
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 17
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 229940043279 diisopropylamine Drugs 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 claims description 14
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 claims description 14
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 239000010413 mother solution Substances 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 2
- 239000012452 mother liquor Substances 0.000 abstract 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229940086542 triethylamine Drugs 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 27
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
-
- 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
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/65—Catalysts not containing noble metals
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a manganese-rich Mn-SAPO-34 molecular sieve catalyst as well as a preparation method and application thereof. The method comprises the following steps: mixing orthophosphoric acid with deionized water to obtain a mixture I, adding pseudo-boehmite into the mixture I, and adding silica sol after the pseudo-boehmite is uniformly mixed with the mixture I to obtain a mixture II; adding a manganese acetate solution into the mixture II, dropwise adding triethylamine and diisopropylamine into the mixture II after stirring, introducing the completely stirred gel into a hydrothermal reaction kettle to crystallize, and then cooling the hydrothermal reaction kettle at a room temperature; and separating a solid crystallized product from mother liquor, carrying out washing until the mother liquor is neutral, carrying out drying, and carrying out roasting at a temperature being 500-600 DEG C in air, thereby obtaining the manganese-rich Mn-SAPO-34 molecular sieve catalyst. According to the manganese-rich Mn-SAPO-34 molecular sieve catalyst disclosed by the invention, a one-step hydro-thermal synthesis process is adopted, and the adding amount and roasting temperatures of manganese acetate, triethylamine, diisopropylamine and silica sol are controlled to obtain the manganese-rich Mn-SAPO-34 molecular sieve catalyst, so that the dispersibility of active ingredients is improved, and the catalyst shows an excellent low-temperature NH3-SCR property at a low-temperature section (lower than 250 DEG C).
Description
Technical field
The invention belongs to environmental conservation and environmental catalysis field, the Mn-SAPO-34 molecular sieve being specifically related to a kind of rich manganese is urged
Agent and preparation method thereof and purposes.
Background technology
Nitrogen oxides (NOx) it is one of main atmosphere pollution.In addition to being directly detrimental to health, or generate ozone
One of important presoma thing, be also to form the major reason that region gray haze and fine particle etc. pollute.Nitrogen oxides main source
In the burning of Fossil fuel, according to statistics, the 66.7% of whole nation Industrial Nitrogen oxide emissions comes from electric power, heating power produces and supplies
Ying Ye, is the discharge rich and influential family of China's nitrogen oxides, and wherein Thermal Power Generation Industry nitrogen oxides contribution margin is maximum, and therefore, power industry is
China controls the major fields of discharged nitrous oxides.In numerous nitrogen oxides pollution control technology, SCR
(SCR) gas denitrifying technology is ripe effectively, extensively applies in coal-fired plant flue gas purification process.
Catalyst is the key of SCR gas denitrifying technology, and current business SCR catalyst is mainly V2O5–WO3
(MoO3)/TiO2Catalyst series, its active temperature windows is 300-450 DEG C, owing to required temperature is higher, SCR denitration device
Before being typically disposed in dedusting and desulfurizer, thus catalyst is vulnerable to washing away and blocking of dust, service life reduction.And by denitration
When device is placed in after dedusting and desulfurizer, then need the requirement installing smoke pre-heating device additional with satisfied catalysis activity.Therewith
Comparing, low-temperature SCR catalyst can work at less than 300 DEG C, and the denitrification apparatus being therefore equipped with low-temperature SCR catalyst is permissible
After being directly installed on dedusting and desulfurizer, there is preferable economic benefit.
There is rule and the molecular sieve catalyst of uniform pore passage structure, because of the activity temperature that its higher catalysis is active and wider
Degree scope and receive much attention in SCR technology, wherein SAPO-34 be SAPO Series Molecules sieve in one, there is CHA type
Topological structure, belongs to pore type molecular sieve.In recent years, due to SAPO-34 molecular sieve, there is suitable acidic acid amount and its rule
Whole pore passage structure, as active component can be made during carrier to be preferably dispersed in its surface, it has extensively at catalytic field
Application.Some scholars also studied the application in SCR of the SAPO-34 molecular sieve, Fe/SAPO-34 and Cu-SAPO-34 divides
In SCR, all do not show the activity of excellence.
A kind of method preparing Cu-SAPO-34 denitrating catalyst disclosed in CN102409141A, the method will intend thin water aluminum
Stone adds in deionized water and is stirred, the one being subsequently adding in Ludox and orthophosphoric acid, add after mixing copper sulfate and
TEPA, and add diethylamine, triethylamine or n-propylamine after being sufficiently stirred for.Gel completely will be stirred and load hydro-thermal reaction
Crystallization in still, then room temperature cooling, separates solid crystallized product with mother solution, and washing, to neutral, is dried, and roasting obtains Cu-
SAPO-34 molecular sieve catalyst.But Cu-SAPO-34 denitrating catalyst is primarily directed to the NO of moving source tail gasxRemoving,
Bigger difference is there is with the flue gas environment of stationary source (such as coal-burning power plant) in the temperature window that its catalyst runs with service condition.
Therefore, the present invention is directed to the problem that stationary source denitrating flue gas exists, by the Mn-of a step Hydrothermal Synthesis richness manganese
SAPO-34 molecular sieve catalyst, improves the dispersibility of active component, adds specific surface area and the acid of catalyst simultaneously
Property so that catalyst shows the low temperature NH of excellence in low-temperature zone (less than 250 DEG C)3-SCR performance.
Summary of the invention
For the problem of prior art, it is an object of the invention to provide a kind of rich manganese Mn-SAPO-34 molecular sieve catalyst and
Its preparation method and purposes, the catalyst using the method to obtain has excellent low temperature NH3-SCR is catalyzed activity.
Present invention employs following technical scheme.
The preparation method of the Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese, said method comprising the steps of:
(1) orthophosphoric acid is mixed with deionized water, is subsequently adding boehmite, to be mixed uniformly after add Ludox, wait to mix
Add manganese acetate solution after closing uniformly, after being sufficiently stirred for, drip organic amine template triethylamine and diisopropylamine；
(2) step (1) gained is stirred crystallization, then room temperature cooling in the hydrothermal reaction kettle of gel loading completely, solid is tied
Brilliant product separates with mother solution, and washing, to neutral, is dried, 500～600 DEG C of roastings in atmosphere, obtains the Mn-SAPO-of a kind of rich manganese
34 molecular sieve catalysts；In the method, the consumption controlling each reactant makes each material in reaction system possess following proportioning
Relation, by 1.0mol boehmite, 1.0mol orthophosphoric acid, 1.0mol Ludox, 1.0mol manganese acetate, 1.0mol triethylamine and
0.5molAl used respectively by 1.0mol diisopropylamine2O3、0.5molP2O5、1.0molSiO2, 1.0molMnO, 1.0molTEA and
1.0molDIPA represent (herein " by 1.0 boehmite 0.5Al2O3Represent " refer to contain in 1.0mol boehmite
There is 0.5molAl2O3), i.e.
Al2O3、P2O5、H2O、SiO2, the mol ratio of MnO, TEA, DIPA be 1:1:80:(0.2～1.0): (0.05～0.6):
(1.0～3.5): (0～1.5).
In the preparation process of the Mn-SAPO-34 molecular sieve catalyst of rich manganese, sintering temperature directly affects the knot of molecular sieve
Crystalline substance degree and catalysis activity, transition metal manganese is different because of its load capacity, the state of manganese and distribution difference thereof, causes low-temperature SCR to be catalyzed
Activity has larger difference, silicone content and replacement mode to affect structure and the surface acidity of catalyst to a certain extent, to low
Temperature SCR catalysis activity also has considerable influence.The present invention uses the Mn-SAPO-34 molecular sieve of the rich manganese of step hydrothermal synthesis method preparation
Catalyst, and be 0～15 wt%, molten by silicon by control manganese acetate, triethylamine input amount controlling manganese load capacity further
It is 500～600 DEG C that glue input amount controls silicone content at 5～15 wt% and control sintering temperature, to obtain the Mn-of Fu Meng
The molecular sieve catalyst of SAPO-34 low-temperature SCR superior activity.
In the present invention, major control Al2O3、P2O5、H2O、SiO2, the mol ratio of MnO, TEA, DIPA be 1:1:80:
(0.2～1.0): (0.05～0.6): (1.0～3.5): (0～1.5), are preferably in a proportion of 1:1:80:0.6:0.4:1.5:1.5.
Preferably, control hydrothermal crystallizing temperature, the temperature of crystallization is 190～210 DEG C, be respectively preferably 190 DEG C, 200
DEG C and 210 DEG C.
Preferably, control hydrothermal crystallizing time, the hydrothermal crystallizing time is 24～96 hours, be respectively preferably 24 hours,
48 hours and 96 hours.
Preferably, controlling the temperature being dried, dry temperature is 100～120 DEG C, preferably 100 DEG C respectively, 110 DEG C and
120 ℃.The time being dried is 6～15 hours.
Preferably, controlling sintering temperature, sintering temperature is 500～600 DEG C, further preferred 500 DEG C, 550 DEG C and 600
℃。
Preferably, controlling roasting time, roasting time is 3～9 hours, is respectively preferably 3 hours, 6 hours and 9 hours.
Preferably, controlling the heating rate of roasting, the heating rate in roasting process is 0.5～1.5 DEG C/min, the most excellent
Select 0.5 DEG C/min, 1 DEG C/min and 1.5 DEG C/min.
As the preferred technical solution of the present invention, the preparation method of the Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese,
Said method comprising the steps of: after being mixed with a certain amount of deionized water by orthophosphoric acid, be then slowly added into boehmite,
To be mixed uniformly after add Ludox, to be mixed uniformly after add the manganese acetate solution of certain mass mark, drip after being sufficiently stirred for
Add triethylamine and diisopropylamine；
To stir crystallization in the hydrothermal reaction kettle of gel loading completely, then room temperature cooling, divides solid crystallized product with mother solution
From, washing, to neutral, is dried, in atmosphere 550 DEG C of roastings；
In the method, Al is controlled2O3、P2O5、H2O、SiO2, the mol ratio of MnO, TEA, DIPA be 1:1:80:0.6:0.4:
1.5:1.5.
The Mn-SAPO-34 molecular sieve catalyst using preferred method to prepare has the low temperature NH of excellence3-SCR urges
Changing activity, it has the NO higher than 90% in 200～400 DEG C x Conversion ratio and N2Selectivity, reacts 12 hours at 250 DEG C,
Still there is higher SCR activity.Therefore, in technique scheme, by Control architecture agent, Ludox, manganese addition with
And sintering temperature 550 DEG C, prepare the Mn-SAPO-34 molecular sieve catalyst of Fu Meng, this molecular sieve shows the low temperature of excellence
NH3-SCR catalysis activity and stability.
The Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese prepared by made as described above method.
The purposes of the Mn-SAPO-34 molecular sieve catalyst of above-described a kind of rich manganese, it takes off for stationary source flue gas
Nitre, i.e. low temperature NH3-SCR reacts.
Compared with the prior art, there is advantages that
The Mn-SAPO-34 molecular sieve catalyst of the rich manganese of the present invention uses a step hydrothermal synthesis method to prepare, simple and controlled, lives
Property component manganese load capacity can regulate in a big way, the Mn-SAPO-34 molecule of rich manganese prepared by the method for the present invention
Sieve catalyst, improves the dispersibility of active component so that catalyst shows the low temperature of excellence in low-temperature zone (less than 250 DEG C)
NH3-SCR performance.
Accompanying drawing explanation
Fig. 1 is the NO of the catalyst that embodiment 1 prepares x Conversion ratio activity rating figure；
Fig. 2 is the NO of the catalyst that embodiment 2 prepares x Conversion ratio activity rating figure；
Fig. 3 is the NO of the catalyst that embodiment 3 prepares x Conversion ratio activity rating figure；
Fig. 4 is the NO of the catalyst that embodiment 4 prepares x Conversion ratio activity rating figure；
Fig. 5 is the NO of the catalyst that embodiment 5 prepares x Conversion ratio activity rating figure；
Fig. 6 is the NO of the catalyst that embodiment 6 prepares x Conversion ratio activity rating figure；
Fig. 7 is the N of the catalyst that embodiment 4 prepares2Selective evaluation figure；
Fig. 8 is the estimation of stability figure of the catalyst that embodiment 4 prepares；
Fig. 9 is that the catalyst that embodiment 4 prepares obtains XRD figure.
Detailed description of the invention
Mn-SAPO-34 molecular sieve catalyst that the invention provides a kind of rich manganese and preparation method thereof and purposes, knot below
The present invention will be further described to close detailed description of the invention.But embodiments of the present invention are not limited to this, if any the most dated
Technological parameter, can refer to routine techniques and carry out.
In the present invention, the evaluation of catalyst is adopted with the following method: take the Mn-SAPO-34 molecular sieve catalytic of 0.90 mL
Agent, 40-60 mesh, it is respectively put into catalyst activity evaluating apparatus, uses laboratory simulation flue gas condition, by embodiment and comparative example
The catalyst of preparation is placed in quartz ampoule fixed bed reactors and carries out activity rating, with NH3For reducing gases, test condition is: NO
And O2Volume fraction be respectively 0.1% and 5%, ammonia nitrogen is Balance Air than for 1:1, Ar, and air speed is 40,000h-1。NO x Analysis
Use U.S.'s Thermo Fisher42i-HL flue gas analyzer, N2Test use GC9560 gas chromatograph, packed column 5A divides
Son sieve.
Embodiment 1
After weighing the deionized water mixing of orthophosphoric acid that 13.835 g mass fractions are 85% and 70.710 g, the most slowly add
Enter 8.880 g boehmites, a certain amount of Ludox (SiO of rear addition to be mixed2With Al2O3Molar ratio be 0.6
Time, the consumption of Ludox is 7.211 g), to be mixed uniformly after add the manganese acetate solution that 7.350 g mass fractions are 20%, fill
Template triethylamine 18.821 g is dripped after dividing stirring；
Carrying out crystallization at 200 DEG C by stirring during gel loads hydrothermal reaction kettle completely, crystallization time is 48 hours, so
Rear room temperature cools down, and is separated with mother solution by solid crystallized product, and washing is to neutral, and 110 DEG C are dried 12 hours, in atmosphere with 1
DEG C/min is warmed up to 550 DEG C of roastings 6 hours, obtains the Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese；
In the method, the consumption controlling each reactant makes possess following proportion relation, i.e. Al in reaction system2O3、P2O5、
H2O、SiO2, the mol ratio of MnO, TEA, DIPA be 1:1:80:0.2～1.0:0.1:3.0:0, wherein SiO2With Al2O3Mole
Ratio controls 0.2,0.4,0.6,0.8,1.0.
Being the catalytic performance test figure of the molecular sieve catalyst of different Si content shown in Fig. 1, this figure shows, different Si content
Mn-SAPO-34 molecular sieve show different catalysis activity, wherein, optimal SiO2With Al2O3Molar ratio be 0.6.
Embodiment 2
After weighing the orthophosphoric acid that mass fraction is 85% of 13.835 g and the deionized water mixing of 53.070 g, the most slowly
Adding 8.880 g boehmites, the uniform rear Ludox adding 7.211 g to be mixed, rear addition to be mixed is a certain amount of
Mass fraction is manganese acetate solution (MnO and Al of 20%2O3When being 0.4, the quality of corresponding manganese acetate solution is 29.400 g),
Template triethylamine 18.821 g is dripped after being sufficiently stirred for；
Carrying out crystallization at 200 DEG C by stirring during gel loads hydrothermal reaction kettle completely, crystallization time is 48 hours,
Then room temperature cooling, separates solid crystallized product with mother solution, and washing is to neutral, and 110 DEG C are dried 12 hours, in atmosphere with 1
DEG C/min is warmed up to 550 DEG C of roastings 6 hours, obtains the Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese；
In the method, the consumption controlling each reactant makes possess following proportion relation, i.e. Al in reaction system2O3、P2O5、
H2O、SiO2, the mol ratio of MnO, TEA, DIPA be 1:1:80:0.6:0.1～0.6:3.0:0, wherein MnO and Al2O3Ratio
Control 0.1,0.2,0.4,0.6.
Being the catalytic performance test figure of the molecular sieve catalyst of different Mn content shown in Fig. 2, Activity evaluation shows, no
Different catalysis activity, wherein, optimal manganese acetate and Al is shown with the Mn-SAPO-34 molecular sieve of Mn content2O3Ratio be
0.4。
Embodiment 3
After weighing the orthophosphoric acid that mass fraction is 85% of 13.835 g and the deionized water mixing of 53.070 g, the most slowly
Add 8.880 g boehmites, the uniform rear Ludox adding 7.211 g to be mixed, rear addition 29.400 to be mixed
G mass fraction is the manganese acetate solution of 20%, drips template triethylamine 15.786 g and diisopropylamine 3.035 after being sufficiently stirred for
g；
Carrying out crystallization at 200 DEG C by stirring during gel loads hydrothermal reaction kettle completely, crystallization time is 48 hours,
Then room temperature cooling, separates solid crystallized product with mother solution, and washing is to neutral, and 110 DEG C are dried 12 hours, in atmosphere with 1
DEG C/min is warmed up to 550 DEG C of roastings 6 hours, obtains the Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese；
In the method, the consumption controlling each reactant makes possess following quality proportion relation, i.e. Al in reaction system2O3、
P2O5、H2O、SiO2, the mol ratio of MnO, TEA, DIPA be 1:1:80:0.6:0.4:2.6:0.5.
It it is the catalytic of molecular sieve catalyst obtained after interpolation organic amine template DIPA in preparation process shown in Fig. 3
Can evaluate figure, Activity evaluation shows, after adding organic amine template DIPA, Mn-SAPO-34 molecular sieve catalyst has more
Good low-temperature denitration activity.
Embodiment 4
After weighing the orthophosphoric acid that mass fraction is 85% of 13.835 g and the deionized water mixing of 53.070 g, the most slowly
Add 8.880 g boehmites, the uniform rear Ludox adding 7.211 g to be mixed, rear addition 29.400 to be mixed
G mass fraction is the manganese acetate solution of 20%, drips template triethylamine 9.110 g and diisopropylamine 9.110 after being sufficiently stirred for
g；
Carrying out crystallization at 200 DEG C by stirring during gel loads hydrothermal reaction kettle completely, crystallization time is 48 hours,
Then room temperature cooling, separates solid crystallized product with mother solution, and washing is to neutral, and 110 DEG C are dried 12 hours, in atmosphere with 1
DEG C/min is warmed up to 550 DEG C of roastings 6 hours, obtains the Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese；
In the method, the consumption controlling each reactant makes possess following quality proportion relation, i.e. Al in reaction system2O3、
P2O5、H2O、SiO2, the mol ratio of MnO, TEA, DIPA be 1:1:80:0.6:0.4:1.5:1.5.
Fig. 4 is the catalytic performance test figure of the catalyst that the present embodiment prepares, and this figure shows: select manganese acetate and Al2O3's
Ratio is 0.4, sintering temperature 550 DEG C, and the mol ratio of TEA, DIPA is the Mn-SAPO-34 molecule that 1.5:1.5 prepares Fu Meng
Sieve, this molecular sieve shows the low temperature NH of excellence3-SCR is catalyzed activity.Fig. 7 Yu Fig. 8 is respectively the catalyst that the present embodiment prepares
N2Selectivity and catalyst stability test, evaluation result shows: manganese acetate and Al2O3Ratio be 0.4, sintering temperature 550
DEG C, the mol ratio of TEA, DIPA is the Mn-SAPO-34 molecular sieve that 1.5:1.5 prepares Fu Meng, not only shows the NO of excellence x
Conversion ratio, and show excellent N2Selectivity and catalyst stability.Fig. 9 is the XRD of the catalyst that the present embodiment prepares
Characterization test, analysis shows, the present embodiment is prepared the Mn-SAPO-34 molecular sieve of Fu Meng and had good chabasie topology knot
Structure, and degree of crystallinity is preferable.
Embodiment 5
After weighing the orthophosphoric acid that mass fraction is 85% of 13.835 g and the deionized water mixing of 53.070 g, the most slowly
Add 8.880 g boehmites, the uniform rear Ludox adding 7.211 g to be mixed, rear addition 29.400 to be mixed
G mass fraction is the manganese acetate solution of 20%, drips template triethylamine 9.110 g and diisopropylamine 9.110 after being sufficiently stirred for
g；
Carrying out crystallization at 190 DEG C by stirring during gel loads hydrothermal reaction kettle completely, crystallization time is 24 hours,
Then room temperature cooling, separates solid crystallized product with mother solution, and washing is to neutral, and 100 DEG C are dried 12 hours, in atmosphere with
0.5 DEG C/min is warmed up to 500 DEG C of roastings 3 hours, obtains the Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese；
In the method, the consumption controlling each reactant makes possess following quality proportion relation, i.e. Al in reaction system2O3、
P2O5、H2O、SiO2, the mol ratio of MnO, TEA, DIPA be 1:1:80:0.6:0.4:1.5:1.5.
Fig. 5 is the catalytic performance test figure of the catalyst that the present embodiment prepares, and this figure shows: change molecule in preparation process
The preparation conditions such as the crystallization time of sieve catalyst, crystallization temperature (in particular such as reducing crystallization temperature) can significantly affect catalyst
Denitration activity, compared with the low-temperature denitration of the catalyst of embodiment 4 preparation, the low-temperature denitration of the catalyst that the present embodiment prepares is lived
Property is clearly worse.
Embodiment 6
After weighing the orthophosphoric acid that mass fraction is 85% of 13.835 g and the deionized water mixing of 53.070 g, the most slowly
Add 8.880 g boehmites, the uniform rear Ludox adding 7.211 g to be mixed, rear addition 29.400 to be mixed
G mass fraction is the manganese acetate solution of 20%, drips template triethylamine 9.110 g and diisopropylamine 9.110 after being sufficiently stirred for
g；
Carrying out crystallization at 210 DEG C by stirring during gel loads hydrothermal reaction kettle completely, crystallization time is 96 hours,
Then room temperature cooling, separates solid crystallized product with mother solution, and washing is to neutral, and 120 DEG C are dried 12 hours, in atmosphere with
1.5 DEG C/min is warmed up to 600 DEG C of roastings 9 hours, obtains the Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese；
In the method, the consumption controlling each reactant makes possess following quality proportion relation, i.e. Al in reaction system2O3、
P2O5、H2O、SiO2, the mol ratio of MnO, TEA, DIPA be 1:1:80:0.6:0.4:1.5:1.5.
Fig. 6 is the catalytic performance test figure of the catalyst that the present embodiment prepares, and this figure shows: change molecule in preparation process
The preparation conditions (in particular such as a liter high crystallization temperature) such as the crystallization time of sieve catalyst, crystallization temperature can significantly affect catalyst
Denitration activity, compared with the low-temperature denitration of the catalyst of embodiment 4 preparation, the low-temperature denitration of the catalyst that the present embodiment prepares is lived
Property is clearly worse.
The above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not to the present invention
The restriction of embodiment.For those of ordinary skill in the field, can also make on the basis of the above description
The change of other multi-form or variation.Here without also cannot all of embodiment be given exhaustive.All the present invention's
Any amendment, equivalent and the improvement etc. made within spirit and principle, should be included in the protection of the claims in the present invention
Within the scope of.
Claims (10)
1. the preparation method of the Mn-SAPO-34 molecular sieve catalyst of a rich manganese, it is characterised in that comprise the following steps:
(1) orthophosphoric acid is mixed with deionized water, is subsequently adding boehmite, to be mixed uniformly after add Ludox, wait to mix
Add manganese acetate solution after closing uniformly, after being sufficiently stirred for, drip organic amine template triethylamine and diisopropylamine；
(2) step (1) gained is stirred crystallization, then room temperature cooling in the hydrothermal reaction kettle of gel loading completely, solid is tied
Brilliant product separates with mother solution, and washing, to neutral, is dried, 500～600 DEG C of roastings in atmosphere, obtains the Mn-SAPO-of a kind of rich manganese
34 molecular sieve catalysts；In the method, the consumption controlling each reactant makes each material in reaction system possess following proportioning
Relation, i.e.
Al2O3、P2O5、H2O、SiO2, MnO, triethylamine, the mol ratio of diisopropylamine be 1:1:80:(0.2～1.0): (0.05～
0.6): (1.0～3.5): (0～1.5).
2. preparation method as claimed in claim 1, it is characterised in that in the method, the consumption controlling each reactant makes
In reaction system, each material possesses following proportion relation, i.e. Al2O3、P2O5、H2O、SiO2, MnO, TEA, DIPA be than for 1:1:80:
0.6:0.4:1.5:1.5.
3. preparation method as claimed in claim 1, it is characterised in that the temperature of step (2) described crystallization is 190～210
DEG C, the time of crystallization is 24～96 hours.
4. preparation method as claimed in claim 3, it is characterised in that the temperature of described crystallization is 200 DEG C, the time of crystallization
It it is 48 hours.
5. preparation method as claimed in claim 1, it is characterised in that the described dry temperature of step (2) is 90～110 DEG C,
The time being dried is 6～15 hours.
6. preparation method as claimed in claim 5, it is characterised in that described dry temperature is 110 DEG C, the time being dried
It it is 12 hours.
7. preparation method as claimed in claim 1, it is characterised in that step (2) described roasting is with 0.5～1.5 DEG C/min
It is warmed up to 500～600 DEG C of roastings 3～9 hours.
8. preparation method as claimed in claim 1, it is characterised in that described roasting is to be warmed up to 550 DEG C of roastings with 1 DEG C/min
6 hours.
9. the Mn-SAPO-34 molecular sieve catalytic of a kind of rich manganese prepared by the preparation method described in any one of claim 1-8
Agent.
10. the Mn-SAPO-34 molecular sieve catalyst of a kind of rich manganese described in claim 9 is applied to low temperature NH3In-SCR reaction.
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