CN102019188A - Magnetic catalyst for denitration of NH3-SCR smoke and application thereof - Google Patents
Magnetic catalyst for denitration of NH3-SCR smoke and application thereof Download PDFInfo
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- CN102019188A CN102019188A CN201010596024XA CN201010596024A CN102019188A CN 102019188 A CN102019188 A CN 102019188A CN 201010596024X A CN201010596024X A CN 201010596024XA CN 201010596024 A CN201010596024 A CN 201010596024A CN 102019188 A CN102019188 A CN 102019188A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 239000000779 smoke Substances 0.000 title abstract description 4
- 239000011572 manganese Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 230000006698 induction Effects 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 23
- 239000003546 flue gas Substances 0.000 claims description 23
- 239000000696 magnetic material Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- AUFVVJFBLFWLJX-UHFFFAOYSA-N [Mn].[La] Chemical compound [Mn].[La] AUFVVJFBLFWLJX-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 230000004907 flux Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical group [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims 1
- 230000008878 coupling Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 7
- -1 lanthanum-manganese metal oxide Chemical class 0.000 abstract 1
- 239000011553 magnetic fluid Substances 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 229910001566 austenite Inorganic materials 0.000 description 24
- 238000003756 stirring Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a magnetic catalyst for denitration of NH3-SCR smoke. The NH3-SCR active component of the catalyst is magnetic iron oxide; and a carrier is perovskite type lanthanum-manganese metal oxide composite or lanthanum of which lanthanum and manganese are partially replaced by alkali metal and transition metal. The invention also discloses application of the catalyst in denitration of NH3-SCR smoke. A magnetic fluid bed reactor with coupling magnetic induction of 0.01-0.1 T is adopted to add the magnetic catalyst at an air speed of 4,000-6,000 h-1; and high NH3-SCR reaction activity is always shown under the conditions that the NH3/NO molar ratio is 1.0-1.3, the O2 content is 2-12% and a relatively wide range of reaction temperature is from 200 DEG C to 400 DEG C, and the denitration is over 80%. Due to relatively wide range of reaction temperature, various dedusting ways are available for the catalyst, and the method is NH3-SCR technology suitable for low and medium temperature.
Description
Technical field
The present invention relates to the Air Pollution Control field, be specifically related to be used for NH
3The magnetic material catalyst and the application thereof of-SCR denitrating flue gas.
Background technology
In the existing gas denitrifying technology, the most ripe and what obtain commercial applications is under middle high temperature (300~400 ℃) condition, be that reactor, ammonia are the selective catalytic reduction (NH of reducing agent with the fixed bed
3-SCR), this method can be expressed as
The gas-solid reaction pattern of reaction equation.NO in the flue gas more than 90%
xBe NO, if with flue gas NO
xMiddle NO
2/ (NO+NO
2) volume ratio (oxidizability) is increased to about 50% NH
3-SCR reaction rate will greatly be accelerated, and utilize the O that self contains in the flue gas about 5%
2With the NO partial oxidation is NO
2Be a good process route, but reaction rate is very slow under this temperature, needs mode by catalytic oxidation, that is, and with O
2Be oxidant, selective catalytic oxidation NO method (O
2-SCO) accelerate reaction rate.
As everyone knows, middle high temperature NH
3-SCR technology, catalyst are of paramount importance parts, and its initial cost accounts for 40%~60% of SCR system gross investment, NH
3The used catalyst activity composition of-SCR method is mainly WO
3And V
2O
5, this catalyst also is a catalytic oxidation NO catalyst preferably.Catalyst after the moulding is divided into three kinds of honeycomb fashion, board-like and corrugated plate dsts, and is wherein extensive with the honeycomb fashion Application of Catalyst, accounts for about 80% of global SCR catalyst supply of material total amount.NH
3-SCR catalyst both can be arranged in the preceding flue of dedusting, after also can being arranged in dedusting, commercial catalyst generally is applicable under the middle hot conditions, therefore be arranged in and satisfy required reaction temperature before the dedusting, after being arranged in dedusting, can reduce that ash-laden gas washes away catalyst and the poisoning effect of arsenic, increase the service life, but need electric heater unit.Generally speaking, commercial NH
3-SCR catalyst can be realized the denitration efficiency more than 80%, and the denitration product is harmless nitrogen, but its preparation and forming technique depend on abroad, and price is comparatively expensive, seriously hinders its application.
For reducing NH
3-SCR denitrating flue gas expense, people are to cheap NH
3-SCR catalyst is studied, and ferrum-based catalyst particularly studies show that ferrum-based catalyst particularly is that the catalyst of active component has denitration performance preferably with the iron oxide, even can also realize desulphurization denitration simultaneously.As: it is active component with the iron oxide that the Chinese patent of publication number CN 101279261A discloses a kind of, and flyash is carrier, adopts the catalyst of infusion process and temperature programming calcining preparation, and the denitration rate is more than 90%, and the desulfurization Sulfur capacity reaches 5~30wt%.
But be limited by technical bottlenecks such as shaping of catalyst, can predict above-mentioned catalyst and also have a segment distance from industrial applications.With NH in the fixed bed reactors of existing commercialization
3-SCR monoblock type preformed catalyst pattern is compared, Preparation of Catalyst is become the fine particle technology maturation, be easy to realize, be applied in the fluid bed, it is big to have a gas-solid contact-making surface, conducts heat, mass-transfer performance is good, even if catalyst is inactivation but be easy to plurality of advantages such as replacing easily, particularly be applied in the magnetically fluidized bed Armco magnetic iron is catalyst based, more may reach the reduction reaction activity, improve the effect of reactivity.As: literature research has been arranged magnetic iron-based γ-Fe
2O
3And Fe
3O
4NH in magnetically fluidized bed
3-SCR denitration performance is found γ-Fe
2O
3Catalytic performance is better, and in 200~250 ℃ under the low temperature, externally-applied magnetic field have remarkable invigoration effect (Qin Ye is etc. the experimental study [J] of cryomagnetism iron-based SCR denitrating flue gas for Yao Guihuan, Zhang Qi. environmental science, 2009,30 (10): 2852~2857).
Summary of the invention
The invention provides a kind of NH
3-SCR denitrating flue gas magnetic material catalyst, its cost of material is low, and is easy to prepare.
The present invention also provides the application of this catalyst in the magnetically fluidized bed reactor, and it is effective to carry out denitrating flue gas.
A kind of NH that is used for
3The magnetic material catalyst of-SCR denitrating flue gas, NH
3-SCR active component is magnetic oxide (γ-Fe
2O
3), the carrier of catalyst is LaMnO
3The lanthanum manganese burning compound La that the Ca-Ti ore type lanthanum manganese burning compound of structure or La, Mn are partly replaced by alkali metal, transition metal
1-xMa
xMb
yMn
1-yO
3, x=0~0.2, y=0~0.2, described Ma is an alkali metal, Mb is a transition metal.
La
1-xMa
xMb
yMn
1-yO
3Simultaneously also be that O takes place NO
2The active component of-SCO catalysts; La
1-xMa
xMb
yMn
1-yO
3Citric acid sol-gel process or coprecipitation, γ-Fe are adopted in preparation
2O
3/ La
1-xMa
xMb
yMn
1-yO
3Deposition-the precipitation method are adopted in preparation.
Preferably, described Ma is alkali metal K, and Mb is transition metal Cu.
Preparation of catalysts technology is specially:
(1) La
1-xMa
xMb
yMn
1-yO
3Preparation
The citric acid sol-gel process prepares La
1-xK
xCu
yMn
1-yO
3Carrier, be specially: the nitrate of lanthanum, alkali metal, transition metal, manganese is made into the aqueous solution by the catalyst chemical molecular formula atomic ratio for preparing, in 20~40 ℃ of water-baths, while stirring mixing salt solution is added drop-wise in the aqueous citric acid solution lanthanum molal quantity that the citric acid molal quantity equals to add in the solution.Dropwise the back and continue to stir, concentrated solution moves to 110~120 ℃ of baking oven inner dryings again to gluey then, the solid that must loosen, then in air 450~550 ℃ decompose 2~3h, at last under air atmosphere in 800~900 ℃ of calcining 6~8h, promptly make required catalyst carrier after the cooling.
Coprecipitation prepares La
1-xMa
xMb
yMn
1-yO
3Carrier is specially: the nitrate of lanthanum, alkali metal, transition metal, manganese is made into the aqueous solution by the catalyst chemical molecular formula atomic ratio for preparing, and is that precipitating reagent drips with ammoniacal liquor, and endpoint pH is controlled at about 10.Suction filtration behind the aging 8~10h of sediment, spend deionised water, and use absolute ethanol washing, at 110~120 ℃ of baking oven inner dryings, the gained sample is calcined 2~4h in 800~900 ℃ under air atmosphere, promptly make required catalyst carrier after the cooling.
(2) γ-Fe
2O
3/ La
1-xMa
xMb
yMn
1-yO
3Preparation
Deposition-the precipitation method prepare γ-Fe
2O
3/ La
1-xMa
xMb
yMn
1-yO
3Catalyst, be specially: ferric nitrate and ferrous nitrate are made into suspension solution together with the carrier that step (1) makes, in 60~80 ℃ of water-baths, to dropwise dropping ammonia while stirring, endpoint pH is controlled at about 9, continue to stir, aging 8~10h under the room temperature, filtering, spending deionised water to pH value is 7,100~120 ℃ of baking oven inner dryings, solidify about 12h, in 150~350 ℃ of calcining 6~8h, the graininess preformed catalyst γ-Fe that is prepared into required size is ground in cooling to the gained sample under air atmosphere
2O
3/ La
1-xMa
xMb
yMn
1-yO
3
Wherein by Fe
2+-Fe
3+Preparation γ-Fe
2O
3Chemical equation be:
Fe
2++2Fe
3++8OH
-→Fe
3O
4+4H
2O
Owing to there is Fe
2+~2Fe
3+~Fe
3O
4~2/3Fe
2O
3Quantitative relation, press γ-Fe in the catalyst
2O
3Load capacity can calculate the dosage of ferrous salt, molysite, carrier, γ-Fe
2O
3Load capacity between 5~15wt%.
The characteristic of catalyst of the present invention:
(1) iron oxide (γ-Fe
2O
3) mainly serve as Reduction of NO
xActive component, this material is cheap and easy to get and have a higher heat endurance; Because the Fe outermost layer has the d electron hole, strengthen chemisorbed NO, reduce NH
3With the activation energy of NO overall budget chemical reaction, possesses superior NH
3-SCR flue gas denitration catalyst reactivity; γ-Fe
2O
3Also be a kind of magnetic material simultaneously, its Curie temperature between 550~700 ℃, 440 ℃ of non-magnetic α-Fe of transformationization
2O
3Compare with nonmagnetic metal, the magnetic metal atomic energy with huge magnetic moment provides offers additional possibilities for the electronic interaction between NO and metal surface, promotes the chemisorbed of NO at magnetic surface.
(2) LaMnO
3The lanthanum manganese burning compound La that Ca-Ti ore type lanthanum manganese burning compound or La, Mn position are partly replaced
1-xMa
xMb
yMn
1-yO
3Not only served as the active component of catalytic oxidation NO but also served as the carrier of whole catalyst, this material has high thermal stability; Lanthanum manganese burning compound LaMnO wherein
3Ability with good catalytic oxidation NO, and LaMnO
3The ion of A position and B position is partly replaced by other ion and is not influenced its crystal structure in the crystal, by the principle of structures shape character as can be known, and the ABO after the ion of A position and B position is partly replaced by other ion
3Still have certain NO catalytic oxidation activity and heat endurance.As: partly replace LaMnO respectively with K and Cu simultaneously
3On La and Mn after because K
+With La
3+And Cu
2+With Mn
3+Between have ionic radius and valence state difference, cause more crystal defect and oxygen room to generate, this helps oxygen molecule and moves in lattice at the absorption on the catalyst and desorption and gas molecule, promotes the carrying out of whole catalytic reaction, improves catalyst performance; In addition, because Mn easily forms the body-centered structure cell, and Cu easily forms center of area structure cell, and various defectives there are differences itself in the two class structure cells, and Cu is incorporated into the Ca-Ti ore type crystal that contains Mn, and its inside can produce more crystal defect, has further improved catalyst performance.
(3) with γ-Fe
2O
3Load on La
1-xMa
xMb
yMn
1-yO
3On make γ-Fe
2O
3/ La
1-xMa
xMb
yMn
1-yO
3Catalyst, active component and carrier can produce cooperative effect, further improve NH
3-SCR denitrating flue gas reactivity; In addition, because catalyst has ferromagnetism, can be to its concentration and separation, recycling after using with magnet.
Described magnetic material catalyst is at NH
3Application in the-SCR denitrating flue gas, with ammonia be used for NH
3The magnetic material catalyst mix of-SCR denitrating flue gas contacts with flue gas, by air speed 4000~6000h
-1Add the magnetic material catalyst, NH
3/ NO mol ratio is 1.0~1.2, O
2Part NH takes place in concentration 2%~12%
3Behind-SCR the denitration reaction, enter the magnetically fluidized bed reaction zone that produces by Helmholtz coil after, be that flue gas and catalyst carry out NH under the invigoration effect of magnetic flux field of 0.01~0.1T at magnetic induction intensity
3It is complete that-SCR denitration reaction is tending towards.
γ-Fe of the present invention
2O
3/ La
1-xMa
xMb
yMn
1-yO
3When catalyst used at coupling magnetically fluidized bed reactor, bed adopted ferrimagnet, added steady magnetic field when being parallel to the axis of fluid bed, the easiest acquisition stabilization fluid of magnetically fluidized bed and magnetic-stability fluidized district maximum; Magnetically fluidized bed can successfully be realized the particulate fluidization of magnetic material fine particle (catalyst), have good adjusting and control characteristic, its good gas-solid contact has reduced the gas-solid reaction that contacts and has transmitted resistance, the surface of particle can strengthen relatively, reduce the activation energy of reaction, promote the carrying out of reaction.
Gained γ-Fe of the present invention
2O
3/ La
1-xMa
xMb
yMn
1-yO
3When catalyst coupling magnetically fluidized bed reactor uses, under comparatively wide mouthful reaction temperature (200~400 ℃), all show good NH
3-SCR reactivity (the denitration rate is more than 80%).Meanwhile, because the reaction temperature broad, dedusting method can have multiple choices, is the NH of low temperature in a kind of being applicable to
3-SCR technology.
Description of drawings
The flue gas NH that Fig. 1 uses for the catalyst of the present invention's preparation
3-SCR denitration reaction apparatus structure schematic diagram.
The specific embodiment
Embodiment 1:
The nitrate of lanthanum, manganese is pressed the catalyst chemical molecular formula LaMnO of preparation
3Atomic ratio is made into the aqueous solution, in 30 ℃ of water-baths, while stirring mixing salt solution is added drop-wise in the aqueous citric acid solution lanthanum molal quantity that the citric acid molal quantity equals to add in the solution.Dropwise the back and continue to stir 30min, concentrated solution moves to 110 ℃ of baking oven inner drying 12h again to gluey then, the solid that must loosen, then in air 500 ℃ decompose 2h, at last under air atmosphere in 800 ℃ of calcining 8h, promptly make required catalyst carrier after the cooling.With magnet prepared catalyst carrier is carried out preliminary magnetic test, find that there is magnetic in catalyst carrier.The element of ICP and EDX mensuration carrier is formed as shown in table 1, shows that carrier structure is LaMnO
3
Table 1 carrier ICP and EDX test report
Press γ-Fe
2O
3Load capacity 15wt% is with ferric nitrate and ferrous nitrate (Fe
3+: Fe
2+Mol ratio 2: 1) carrier that makes together with above-mentioned steps is made into suspension solution, in 70 ℃ of water-baths, to dropwise drip 28wt% ammoniacal liquor while stirring, endpoint pH is controlled at about 9, continues to stir 5h, aging 10h under the room temperature, filtering, spend deionised water to pH value is 7,110 ℃ of baking oven inner dryings, curing 12h, and the gained sample is calcined 6h in 350 ℃ under air atmosphere, cooling is ground and is prepared into the pellet type catalyst that average grain diameter is 55 μ m.With magnet prepared catalyst is carried out preliminary magnetic test, find that there is magnetic in catalyst.
As shown in Figure 1, enter gas-solid mixing chamber 2 by smoke inlet 1, and by the ammonia of distributor 3 ejections and by the concurrent first portion NH of ferrimagnet catalyst mix of feeder 4 ejections through the flue gas after bag-type dust or the cyclone dust removal
3-SCR denitration reaction.After entering the magnetically fluidized bed reaction zone that produces by Helmholtz coil 5, under the invigoration effect of magnetic flux field, NH
3It is complete that-SCR denitration reaction is tending towards.Gas and part catalyst granules enter cyclone separator 6 and carry out gas solid separation, and gas is through directly discharging of tail gas outlet 7.The solid particle of cyclone separator bottom is discharged through solid outlet 8, and the quality of looking catalytic reaction activity enters the magnetically fluidized bed reaction zone by feeder 4 again and participates in reaction or sublate.
With present embodiment gained γ-Fe
2O
3/ LaMnO
3The magnetically fluidized bed reactor that catalyst is 0.03T at above-mentioned coupling magnetic induction intensity uses, by air speed 4000h
-1Calculate catalyst amount, NO concentration 500ppm, NH
3/ NO mol ratio is 1.0, O
2Concentration 5%, under 400 ℃ reaction temperature, NH
3-SCR reaction denitration rate is about 80%.
Embodiment 2:
The nitrate of lanthanum, potassium, manganese is pressed the catalyst chemical molecular formula La of preparation
0.8K
0.2MnO
3Atomic ratio is made into the aqueous solution, in 30 ℃ of water-baths, while stirring mixing salt solution is added drop-wise in the aqueous citric acid solution lanthanum molal quantity that the citric acid molal quantity equals to add in the solution.Dropwise the back and continue to stir 30min, concentrated solution moves to 120 ℃ of baking oven inner drying 12h again to gluey then, the solid that must loosen, then in air 500 ℃ decompose 2h, at last under air atmosphere in 900 ℃ of calcining 6h, promptly make required catalyst carrier after the cooling.With magnet prepared catalyst carrier is carried out preliminary magnetic test, find that there is magnetic in catalyst carrier.The element of ICP and EDX mensuration carrier is formed as shown in table 2, shows that carrier structure is La
0.8K
0.2MnO
3
Table 2 carrier ICP and EDX test report
Press γ-Fe
2O
3Load capacity 10wt% is with ferric nitrate and ferrous nitrate (Fe
3+: Fe
2+Mol ratio 2: 1) carrier that makes together with above-mentioned steps is made into suspension solution, in 70 ℃ of water-baths, to dropwise drip 28wt% ammoniacal liquor while stirring, endpoint pH is controlled at about 9, continues to stir 5h, aging 10h under the room temperature, filtering, spend deionised water to pH value is 7,110 ℃ of baking oven inner dryings, curing 12h, and the gained sample is calcined 7h in 250 ℃ under air atmosphere, cooling is ground and is prepared into the pellet type catalyst that average grain diameter is 55 μ m.
Gained γ-Fe
2O
3/ La
0.8K
0.2MnO
3Catalyst is the magnetically fluidized bed reactor use of 0.05T at coupling magnetic induction intensity, by air speed 5000h
-1Calculate catalyst amount, NO concentration 500ppm, NH
3/ NO mol ratio is 1.2, O
2Concentration 5%, under 300 ℃ reaction temperature, NH
3-SCR reaction denitration rate is about 85%.
Embodiment 3:
The nitrate of lanthanum, copper, manganese is pressed the catalyst chemical molecular formula LaCu of preparation
0.2Mn
0.8O
3Atomic ratio is made into the aqueous solution, is that precipitating reagent drips with 28wt% ammoniacal liquor, and endpoint pH is controlled at about 10.Suction filtration behind the aging 10h of sediment, spend deionised water, and with absolute ethanol washing 3 times, 120 ℃ of baking oven inner drying 12h, gained sample calcine 4h in 800 ℃ under air atmosphere, promptly make required catalyst carrier after the cooling.With magnet prepared catalyst carrier is carried out preliminary magnetic test, find that there is magnetic in catalyst carrier.The element of ICP and EDX mensuration carrier is formed as shown in table 3, shows that carrier structure is LaCu
0.2Mn
0.8O
3
Table 3 carrier ICP and EDX test report
Press γ-Fe
2O
3Load capacity 10wt% is with ferric nitrate and ferrous nitrate (Fe
3+: Fe
2+Mol ratio 2: 1) carrier that makes together with above-mentioned steps is made into suspension solution, in 70 ℃ of water-baths, to dropwise drip 28wt% ammoniacal liquor while stirring, endpoint pH is controlled at about 9, continues to stir 5h, aging 10h under the room temperature, filtering, spend deionised water to pH value is 7,120 ℃ of baking oven inner dryings, curing 12h, and the gained sample is calcined 7h in 250 ℃ under air atmosphere, cooling is ground and is prepared into the pellet type catalyst that average grain diameter is 55 μ m.
Gained γ-Fe
2O
3/ LaCu
0.2Mn
0.8O
3Catalyst is the magnetically fluidized bed reactor use of 0.05T at coupling magnetic induction intensity, by air speed 5000h
-1Calculate catalyst amount, NO concentration 500ppm, NH
3/ NO mol ratio is 1.2, O
2Concentration 5%, under 300 ℃ reaction temperature, NH
3-SCR reaction denitration rate is about 90%.
Embodiment 4:
The nitrate of lanthanum, copper, manganese is pressed the catalyst chemical molecular formula La of preparation
0.8K
0.2Cu
0.2Mn
0.8O
3Atomic ratio is made into the aqueous solution, is that precipitating reagent drips with 28wt% ammoniacal liquor, and endpoint pH is controlled at about 10.Suction filtration behind the aging 10h of sediment, spend deionised water, and with absolute ethanol washing 3 times, 120 ℃ of baking oven inner drying 12h, gained sample calcine 2h in 900 ℃ under air atmosphere, promptly make required catalyst carrier after the cooling.With magnet prepared catalyst carrier is carried out preliminary magnetic test, find that there is magnetic in catalyst carrier.The element of ICP and EDX mensuration carrier is formed as shown in table 4, shows that carrier structure is La
0.8K
0.2Cu
0.2Mn
0.8O
3
Table 4 carrier ICP and EDX test report
Press γ-Fe
2O
3Load capacity 5wt% is with ferric nitrate and ferrous nitrate (Fe
3+: Fe
2+Mol ratio 2: 1) carrier that makes together with above-mentioned steps is made into suspension solution, in 70 ℃ of water-baths, to dropwise drip 28wt% ammoniacal liquor while stirring, endpoint pH is controlled at about 9, continues to stir 5h, aging 10h under the room temperature, filtering, spend deionised water to pH value is 7,120 ℃ of baking oven inner dryings, curing 12h, and the gained sample is calcined 6h in 150 ℃ under air atmosphere, cooling is ground and is prepared into the pellet type catalyst that average grain diameter is 55 μ m.
Gained γ-Fe
2O
3/ La
0.8K
0.2Cu
0.2Mn
0.8O
3Catalyst is the magnetically fluidized bed reactor use of 0.08T at coupling magnetic induction intensity, by air speed 6000h
-1Calculate catalyst amount, NO concentration 500ppm, NH
3/ NO mol ratio is 1.0, O
2Concentration 5%, under 200 ℃ reaction temperature, NH
3-SCR reaction denitration rate is about 90%.
Claims (7)
1. one kind is used for NH
3The magnetic material catalyst of-SCR denitrating flue gas is characterized in that: the NH of described catalyst
3-SCR active component is a magnetic oxide, and described carrier is Ca-Ti ore type lanthanum manganese burning compound: LaMnO
3Or the lanthanum manganese burning compound that partly replaced by alkali metal, transition metal of lanthanum, manganese: La
1-xMa
xMb
yMn
1-yO
3, x=0~0.2, y=0~0.2, described Ma is an alkali metal, Mb is a transition metal.
2. magnetic material catalyst as claimed in claim 1 is characterized in that: described Ma is K, and Mb is Cu.
3. magnetic material catalyst as claimed in claim 1 or 2 is characterized in that: described preparing carriers adopts citric acid sol-gel process or coprecipitation.
4. magnetic material catalyst as claimed in claim 1 or 2 is characterized in that: the deposition-precipitation method are adopted in the preparation of described carrier composite magnetic iron oxide.
As the described magnetic material catalyst of the arbitrary right of claim 1-4 at NH
3Application in the-SCR denitrating flue gas.
6. application as claimed in claim 5 is characterized in that: with ammonia be used for NH
3The magnetic material catalyst mix of-SCR denitrating flue gas contacts with flue gas, by air speed 4000~6000h
-1Add the magnetic material catalyst, NH
3/ NO mol ratio is 1.0~1.2, and part NH takes place
3Behind-SCR the denitration reaction, enter the magnetically fluidized bed reaction zone that is produced by Helmholtz coil, under the invigoration effect of magnetic flux field, flue gas and catalyst carry out NH
3-SCR denitration reaction is complete.
7. application as claimed in claim 6 is characterized in that: the magnetic induction intensity of described magnetic flux field is 0.01~0.1T.
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