CN108620123A - It is a kind of using Mn as active metal, using Nd as middle low-temperature denitration catalyst of auxiliary agent and preparation method thereof - Google Patents
It is a kind of using Mn as active metal, using Nd as middle low-temperature denitration catalyst of auxiliary agent and preparation method thereof Download PDFInfo
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- CN108620123A CN108620123A CN201810474249.4A CN201810474249A CN108620123A CN 108620123 A CN108620123 A CN 108620123A CN 201810474249 A CN201810474249 A CN 201810474249A CN 108620123 A CN108620123 A CN 108620123A
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- denitration catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010457 zeolite Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract 2
- 239000002808 molecular sieve Substances 0.000 claims abstract 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 claims description 18
- 229910016978 MnOx Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 229910003205 Nd(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 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 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 235000019441 ethanol Nutrition 0.000 abstract description 7
- 241000269350 Anura Species 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
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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
- B01D53/90—Injecting reactants
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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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
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Abstract
The invention discloses a kind of using Mn as active metal, using Nd as middle low-temperature denitration catalyst of auxiliary agent and preparation method thereof, the catalyst is prepared using ethyl alcohol dispersion method, it is carrier with zeolite molecular sieve SAPO 34, using the oxide of Mn as active component, using Nd as auxiliary agent, wherein on the basis of the quality of carrier, the load capacity of active component manganese is 20%, and the molar ratio of neodymium element and manganese element is respectively 0,0.1,0.2,0.3,0.4.The SCR catalyst of the invention compared with the catalyst of unsupported auxiliary agent, using Nd can improve Mn dispersion degree and can protection activity component the characteristics of, significantly improve the denitration efficiency of catalyst.When the molar ratio of Nd and Mn is 0.3, in 140~220 DEG C, the conversion ratio of NO can reach 99% or more.
Description
Technical field
The invention belongs to air contaminant treatment technologies and environment protection catalytic Material Field, are related to SCR (selective catalytic reduction)
Gas denitrifying technology, and in particular to it is a kind of using Mn as active metal, using Nd as the middle low-temperature denitration catalyst of auxiliary agent and its preparation
Method.
Background technology
Currently, mainstream denitration technology used by Industrial Boiler is with NH3For the selective catalytic reduction of reducing agent
(SCR), V is mostly used greatly2O5-WO3(MoO3)/TiO2Serial tradition SCR catalyst, in terms of major defect shows two, one
It is vanadium base SCR denitration running temperature at 350 DEG C or more, causes catalyst life short, engineering design is difficult, second is that real
Alkali metal, H in the application of border2O、SO2Equal impurity poison it so that catalyst performance declines to a great extent.Therefore, low temperature active is researched and developed
Good and high anti-sulfur poisonous performance Novel SCR catalyst has a very important significance.
In conclusion providing one kind having higher catalytic activity under low temperature environment (100~300 DEG C) and has more excellent
The SCR catalyst of anti-sulfur poisonous performance, so that it may to improve the denitration efficiency of Industrial Boiler, and realize under underrun
Denitration demand provides new direction for the development of Denitration in Boiler technology in future.
Invention content
In view of the deficiencies of the prior art, the present invention provide it is a kind of using Mn as active metal, it is de- as the middle low temperature of auxiliary agent using Nd
Denox catalyst and preparation method thereof, the catalyst are imitated by adding the low-temperature denitration for the dispersion degree raising catalyst that Nd improves Mn
Rate, and by Nd protection activity component Mn, to keep catalyst being passed through SO2Catalytic activity in flue gas.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows：
It is a kind of using Mn as active metal, using Nd as the middle low-temperature denitration catalyst of auxiliary agent, the catalyst is with zeolite molecules
Sieve SAPO-34 is carrier, and Supported Manganese metal oxide is as active component, wherein on the basis of the quality of carrier, Mn's is negative
The load capacity that carrying capacity is 20%, Nd, which is the addition of 10~40%, Nd of Mn moles, can improve the conversion ratio of NO, Er Qiesui
The increase of Nd contents, conversion takes the lead in reducing after increasing.
It is a kind of using Mn as active metal, using Nd as the preparation method of the middle low-temperature denitration catalyst of auxiliary agent, including following step
Suddenly：
Step 1) measures absolute ethyl alcohol, pours into container with spare；
Step 2) measures soluble-salt and the SAPO-34 powder of manganese, pours into the step 1) container, by container closure,
Then container is put into ultrasonic disperse in ultrasonic wave separating apparatus keeps solution uniform；
Into step 2) acquired solution, according to the molar ratio of Nd/Mn the soluble-salt of neodymium is added as auxiliary agent in step 3),
Magnetic stir bar is put into container again, container is then put into stirring in water bath in thermostat water bath, until most of in container
Liquid evaporation obtains colloid sample；
Step 3) the colloid sample is placed on drying box drying and dehydrating by step 4), then is taken out solid sample with spoon,
It is put into mortar to be ground, carrying out sieve with sieve takes, and collects sample；Finally, sample powder is put into Muffle furnace and is calcined, obtained
To NdOx-MnOx/ SAPO-34, the as described middle low-temperature denitration catalyst.
Further, the soluble-salt of the step 2) manganese is manganese nitrate, and the soluble-salt of the step 3) neodymium is Nd
(NO3)3·6H2O。
Further, the temperature of the step 4) drying is 105 DEG C, and the temperature of the calcining is 500 DEG C, dries and forges
The time of burning is 6h.
Further, the step 4) sieve takes the sieve using 100 mesh.
The device have the advantages that as follows：
The present invention using Mn as active metal, using Nd be the middle low-temperature denitration catalyst of auxiliary agent compared to only supported active
For the catalyst of metal, since the addition of Nd increases the dispersion degree of active metal Mn, effectively raise in middle low temperature ring
NO under borderxConversion ratio, and the presence of Nd protects active component Mn, to ensure that height of the catalyst after poisoning is urged
Change activity.Prepared catalyst carries out denitration performance test and sulfur resistive experiment, hair in fixed bed under the conditions of simulated flue gas
Now the catalyst has preferable low temperature active and stronger sulfur resistance.
Description of the drawings
Fig. 1 is the denitration performance test chart of catalyst prepared by Examples 1 to 5；
Fig. 2 is the sulfur resistance test chart of catalyst prepared by embodiment 1,4；
Fig. 3 is the XRD spectra of catalyst prepared by Examples 1 to 5.
Specific implementation mode
The present invention is described in further details with embodiment below in conjunction with the accompanying drawings.
It is of the present invention using Mn as active metal, by the middle low-temperature denitration catalyst of auxiliary agent of Nd be with zeolite molecules
Sieve SAPO-34 is carrier, and on the basis of the quality of carrier, the load capacity of active component Mn is 20%, neodymium element and manganese element
Molar ratio is respectively 0,0.1,0.2,0.3,0.4.
The preparation method of above-mentioned catalyst includes following key step：
(1) 100mL absolute ethyl alcohols are measured, pour into clean beaker with spare；
(2) manganese nitrate solution and SAPO-34 powder that mass fraction is 50wt.% are measured with precision electronic balance, poured into
In step (1) beaker, preservative film is used in combination to seal, beaker, which is then put into ultrasonic disperse in ultrasonic wave separating apparatus, keeps solution uniform；
(3) it into step (2) acquired solution, is separately added into not for 0,0.1,0.2,0.3,0.4 according to Nd/Mn molar ratios
Neodymium nitrate crystal (Nd (the NO of same amount3)3·6H2O), 5 parts of samples are obtained, magnetic agitation is put into the beaker of each sample
Son is put into stirring in water bath in thermostat water bath, until most of liquid evaporation in beaker, obtains colloid sample；
(4) five parts of samples of step (3) are placed on constant dry dehydration in drying box, spoon is used in combination to take solid sample
Go out, be put into mortar and be ground, carrying out sieve with sieve takes, and collects sample；Finally, sample powder is put into Muffle furnace and is calcined,
Finally obtain this catalyst prod.
Embodiment 1
(1) 100mL absolute ethyl alcohols are measured, pour into clean beaker with spare.
(2) manganese nitrate solution and 6.000 g that 7.8176g mass fractions are 50wt.% are measured with precision electronic balance
SAPO-34 powder pours into step (1) beaker, preservative film is used in combination to seal, and then beaker is put into ultrasonic wave separating apparatus and is surpassed
Sound dispersion 1h keeps solution uniform.
(3) into step (2) acquired solution beaker, it is put into magnetic stir bar, is put into water-bath in 60 DEG C of thermostat water bath
Stirring, until most of liquid evaporation in beaker, obtains colloid sample.
(4) sample of step (3) is placed on 105 DEG C of constant dry dehydration 6h in drying box, is used in combination spoon by solid sample
It takes out, is put into mortar and is ground, carrying out sieve with the sieve of 100 mesh takes, and collects sample.Finally, sample powder is put into 500
DEG C Muffle furnace in calcining 6h to get MnOx/SAPO-34。
Embodiment 2
(1) 100mL absolute ethyl alcohols are measured, pour into clean beaker with spare.
(2) manganese nitrate solution and 6.000 g that 7.8176g mass fractions are 50wt.% are measured with precision electronic balance
SAPO-34 powder pours into step (1) beaker, preservative film is used in combination to seal, and then beaker is put into ultrasonic wave separating apparatus and is surpassed
Sound dispersion 1h keeps solution uniform.
(3) into step (2) acquired solution, it is 0.1 addition neodymium nitrate crystal according to Nd/Mn molar ratios, that is, is added
The six nitric hydrate neodymiums of 0.9576g, obtain sample, magnetic stir bar are put into the beaker of sample, be put into 60 DEG C of thermostatted water
Stirring in water bath in bath, until most of liquid evaporation in beaker, obtains colloid sample.
(4) sample of step (3) is placed on 105 DEG C of constant dry dehydration 6h in drying box, is used in combination spoon by solid sample
It takes out, is put into mortar and is ground, carrying out sieve with the sieve of 100 mesh takes, and collects sample.Finally, sample powder is put into 500
DEG C Muffle furnace in calcining 6h to get NdOx(0.1)-MnOx/SAPO-34。
Embodiment 3
(1) 100mL absolute ethyl alcohols are measured, pour into clean beaker with spare.
(2) manganese nitrate solution and 6.000 g that 7.8176g mass fractions are 50wt.% are measured with precision electronic balance
SAPO-34 powder pours into step (1) beaker, preservative film is used in combination to seal, and then beaker is put into ultrasonic wave separating apparatus and is surpassed
Sound dispersion 1h keeps solution uniform.
(3) into step (2) acquired solution, it is 0.2 addition neodymium nitrate crystal according to Nd/Mn molar ratios, that is, is added
The six nitric hydrate neodymiums of 1.9152g, obtain sample, magnetic stir bar are put into the beaker of sample, be put into 60 DEG C of thermostatted water
Stirring in water bath in bath, until most of liquid evaporation in beaker, obtains colloid sample.
(4) sample of step (3) is placed on 105 DEG C of constant dry dehydration 6h in drying box, is used in combination spoon by solid sample
It takes out, is put into mortar and is ground, carrying out sieve with the sieve of 100 mesh takes, and collects sample.Finally, sample powder is put into 500
DEG C Muffle furnace in calcining 6h to get NdOx(0.2)-MnOx/SAPO-34。
Embodiment 4
(1) 100mL absolute ethyl alcohols are measured, pour into clean beaker with spare.
(2) manganese nitrate solution and 6.000 g that 7.8176g mass fractions are 50wt.% are measured with precision electronic balance
SAPO-34 powder pours into step (1) beaker, preservative film is used in combination to seal, and then beaker is put into ultrasonic wave separating apparatus and is surpassed
Sound dispersion 1h keeps solution uniform.
(3) into step (2) acquired solution, it is 0.3 addition neodymium nitrate crystal according to Nd/Mn molar ratios, that is, is added
The six nitric hydrate neodymiums of 2.8728g, obtain sample, magnetic stir bar are put into the beaker of sample, be put into 60 DEG C of thermostatted water
Stirring in water bath in bath, until most of liquid evaporation in beaker, obtains colloid sample.
(4) sample of step (3) is placed on 105 DEG C of constant dry dehydration 6h in drying box, is used in combination spoon by solid sample
It takes out, is put into mortar and is ground, carrying out sieve with the sieve of 100 mesh takes, and collects sample.Finally, sample powder is put into 500
DEG C Muffle furnace in calcining 6h to get NdOx(0.3)-MnOx/SAPO-34。
Embodiment 5
(1) 100mL absolute ethyl alcohols are measured, pour into clean beaker with spare.
(2) manganese nitrate solution and 6.000 g that 7.8176g mass fractions are 50wt.% are measured with precision electronic balance
SAPO-34 powder pours into step (1) beaker, preservative film is used in combination to seal, and then beaker is put into ultrasonic wave separating apparatus and is surpassed
Sound dispersion 1h keeps solution uniform.
(3) into step (2) acquired solution, it is 0.4 addition neodymium nitrate crystal according to Nd/Mn molar ratios, that is, is added
The six nitric hydrate neodymiums of 3.8304g, obtain sample, magnetic stir bar are put into the beaker of sample, be put into 60 DEG C of thermostatted water
Stirring in water bath in bath, until most of liquid evaporation in beaker, obtains colloid sample.
(4) sample of step (3) is placed on 105 DEG C of constant dry dehydration 6h in drying box, is used in combination spoon by solid sample
It takes out, is put into mortar and is ground, carrying out sieve with the sieve of 100 mesh takes, and collects sample.Finally, sample powder is put into 500
DEG C Muffle furnace in calcining 6h to get NdOx(0.4)-MnOx/SAPO-34。
Test case 1：Catalyst activity measures
Catalyst sample 1.000g prepared by Example 1~5 respectively is packed into fixed bed reactors and carries out catalyst
Active testing.Activity determination condition is as follows：Reaction system temperature is 100~300 DEG C, and reaction pressure is normal pressure, unstripped gas air speed
For 37500h-1, feed gas volume content：NO(400×10-6), NH3(400 ×10-6), O2(5%), carrier gas：N2.Gas is total
Flow is 500mL/min.Gradually mixing finally enters air pre-mixing device and is sufficiently mixed each road gas after mass flowmenter；
Reactor is the stainless steel tube of internal diameter 10mm, and three sections of heating vertical tubular furnaces with temperature control system provide reaction temperature condition；With
Airbag is analyzed after thief hatch acquires flue gas by 350 flue gas analyzers of Testo.
The activity of catalyst is evaluated with the conversion ratio of NO, and NO conversion ratio calculation formula are as follows：
Wherein, NOin、NOoutThe concentration of fixed bed reactors entrance and exit NO is indicated respectively, and all data are de-
It is read after nitre stable reaction.Active testing the result is shown in Figure 1.From figure 1 it appears that the addition of Nd can improve the conversion of NO
Rate, and with the increase of Nd contents, conversion takes the lead in reducing after increasing.Wherein, when the molar ratio of Nd and Mn is 0.3
Catalyst shows best catalytic activity, and at 140 DEG C, the conversion ratio of NO can reach 99% or more, just has until 220 DEG C
Declined.
Test case 2：Catalyst sulfur resistance measures
Catalyst sample 1.000g prepared by Example 1 and 4 respectively is packed into fixed bed reactors and carries out catalyst
Sulfur resistance is tested.Sulfur resistance testing conditions are as follows：Reaction system temperature is 220 DEG C, and reaction pressure is normal pressure, unstripped gas
Air speed is 37500h-1, feed gas volume content：NO(400×10-6), NH3 (400×10-6), O2(5%), carrier gas：N2.Gas
Body total flow is 500mL/min, and 140 × 10 are passed through after denitration reaction stabilization-6The SO of volume2, and SO is closed after 2h2
Channel.Gradually mixing finally enters air pre-mixing device and is sufficiently mixed each road gas after mass flowmenter；Reactor is internal diameter
The stainless steel tube of 10mm, three sections of heating vertical tubular furnaces with temperature control system provide reaction temperature condition；With airbag in thief hatch
It is analyzed by 350 flue gas analyzers of Testo after acquisition flue gas.
Likewise, sulfur resistance is evaluated with NO conversion ratios, calculation formula is shown in test case 1.
Sulfur resistance test result is shown in Fig. 2.From figure 2 it can be seen that working as SO2When being passed through, the NO of two samplesxConversion
Rate is begun to decline, NdOx(0.3)-MnOx/ SAPO-34 reaches stable required time ratio MnOx/ SAPO-34 is shorter.Stopping
Only it is passed through SO2Afterwards, NdOx(0.3)-MnOxThe catalytic activity of/SAPO-34 is significantly promoted, in 220min, NOxConversion ratio
Nearly 90% is increased to, opposite, MnOxThe catalytic activity of/SAPO-34 is without significant change.
Test case 3：X-ray diffraction analysis
Using X-ray diffraction analyzer, tube voltage 40kv, tube current 30mA, 0.02 °/s of step-length, X beam wavelengths are Cu
Target, 2 θ/θ couplings are continuously strafed, and sweep angle is 10~90 °, and catalyst sample is fully ground before testing, takes appropriate powder
Simultaneously tabletting, sample powder thickness about 1mm are filled on glass carrier.Fig. 3 is shown as the catalyst of Examples 1 to 5 preparation
XRD spectrum.Compared with the XRD diffraction maximums of SAPO-34, NdOx(y)-MnOxThe diffraction maximum position of/SAPO-34 and intensity are basic
It is identical, therefore, NdOx(y)-MnOx/ SAPO-34 has the crystal structure of complete SAPO-34.From figure 3, it can be seen that
NdOx(y)-MnOxIt is nearly no detectable MnO in/SAPO-34xDiffraction maximum, this shows that active component is with high dispersive, indefinite
Existing for form, opposite, MnOxIt is clear that Mn in/SAPO-342O3Diffraction maximum.
Test case 4：X-ray photoelectron spectroscopy XPS analysis
XPS is analyzed using x-ray photoelectron spectroscopy.The oxidation state and concentration of catalyst surface Mn, Nd and O
It can be obtained by XPS, result of calculation is shown on table 1.
The XPS result of calculations of 1 catalyst of table
From table 1 it follows that percentages of the Mn IV on catalyst surface is improved greatly in the addition of Nd
With the ratio of O α/O β, the addition that the promotion of the percentage of Mn IV and O α also explains Nd can improve MnOx/ SAPO-34 catalyst
SCR catalytic activity and resistance to SO_2.
The basic principles and main features and advantages of the present invention of the present invention of the present invention have been shown and described above.One's own profession
The technical staff of industry is it should be appreciated that the present invention is not limited to the above embodiments, described in the above embodiment and specification
It is to illustrate the principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various change and changes
Into these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended right
Claim and its equivalent thereof.
Claims (5)
1. it is a kind of using Mn as active metal, using Nd as the middle low-temperature denitration catalyst of auxiliary agent, which is characterized in that the catalyst with
Zeolite molecular sieve SAPO-34 is carrier, and Supported Manganese metal oxide is as active component, wherein on the basis of the quality of carrier,
The load capacity of Mn is that be the addition of 10~40%, Nd of Mn moles can improve the conversion ratio of NO to the load capacity of 20%, Nd, and
And with the increase of Nd contents, conversion takes the lead in reducing after increasing.
2. it is described in claim 1 it is a kind of using Mn as active metal, using Nd as the preparation side of the middle low-temperature denitration catalyst of auxiliary agent
Method, which is characterized in that include the following steps：
Step 1) measures absolute ethyl alcohol, pours into container with spare；
Step 2) measures the soluble-salt and SAPO-34 powder of manganese, pours into the step 1) container, by container closure, then
Container, which is put into ultrasonic disperse in ultrasonic wave separating apparatus, keeps solution uniform；
The soluble-salt of neodymium is added as auxiliary agent, then to appearance into step 2) acquired solution, according to the molar ratio of Nd/Mn in step 3)
It is put into magnetic stir bar in device, container is then put into stirring in water bath in thermostat water bath, until most of liquid steams in container
Hair, obtains colloid sample；
Step 3) the colloid sample is placed on drying box drying and dehydrating by step 4), then is taken out solid sample with spoon, is put into
Mortar is ground, and carrying out sieve with sieve takes, and collects sample；Finally, sample powder is put into Muffle furnace and is calcined, obtained
NdOx-MnOx/ SAPO-34, the as described middle low-temperature denitration catalyst.
3. it is according to claim 2 it is a kind of using Mn as active metal, using Nd as the system of the middle low-temperature denitration catalyst of auxiliary agent
Preparation Method, which is characterized in that the soluble-salt of the step 2) manganese is manganese nitrate, and the soluble-salt of the step 3) neodymium is Nd
(NO3)3·6H2O。
4. it is according to claim 2 it is a kind of using Mn as active metal, using Nd as the system of the middle low-temperature denitration catalyst of auxiliary agent
Preparation Method, which is characterized in that the temperature of the step 4) drying is 105 DEG C, and the temperature of the calcining is 500 DEG C, dries and forges
The time of burning is 6h.
5. it is according to claim 2 it is a kind of using Mn as active metal, using Nd as the system of the middle low-temperature denitration catalyst of auxiliary agent
Preparation Method, which is characterized in that the step 4) sieve takes the sieve using 100 mesh.
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| CN109876799A (en) * | 2019-04-08 | 2019-06-14 | 国电环境保护研究院有限公司 | Ultralow temperature SCR denitration and preparation method thereof |
| CN112973721A (en) * | 2021-02-24 | 2021-06-18 | 南京大学 | Low-temperature sulfur-resistant water-resistant denitration catalyst and preparation method and application thereof |
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