CN109999895A - A kind of low-temperature catalyzed catalyst and preparation method thereof for removing denitrification - Google Patents
A kind of low-temperature catalyzed catalyst and preparation method thereof for removing denitrification Download PDFInfo
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- CN109999895A CN109999895A CN201910305219.5A CN201910305219A CN109999895A CN 109999895 A CN109999895 A CN 109999895A CN 201910305219 A CN201910305219 A CN 201910305219A CN 109999895 A CN109999895 A CN 109999895A
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- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 182
- 229910052742 iron Inorganic materials 0.000 claims abstract description 91
- 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 description 58
- 239000002808 molecular sieve Substances 0.000 claims abstract description 57
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000002161 passivation Methods 0.000 claims abstract description 18
- 150000001298 alcohols Chemical class 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000004202 carbamide Substances 0.000 claims description 22
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 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 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003125 aqueous solvent Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- -1 ZSM-5 Inorganic materials 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 239000012046 mixed solvent Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 7
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 238000012805 post-processing Methods 0.000 description 27
- 239000007789 gas Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- 238000010792 warming Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 239000005416 organic matter Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 239000003708 ampul Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 238000013480 data collection Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 238000004445 quantitative analysis Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- 239000012495 reaction gas Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 210000002268 wool Anatomy 0.000 description 7
- 239000012488 sample solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000006259 organic additive Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 238000013332 literature search Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7215—Zeolite Beta
-
- B01J35/40—
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
- F01N2570/14—Nitrogen oxides
Abstract
The present invention provides a kind of low-temperature catalyzed catalyst and preparation method thereof for removing denitrification.The catalyst is the iron-based molecular sieve of high Fe content；The preparation method includes: to be stirred molecular sieve and a kind of molysite substance and at least one organic compound under conditions of deionized water and at least one alcohols mixed solvent, then dries, calcines.After calcining removes the organic compound in mixture, pass through 350-800 DEG C under the atmosphere of reproducibility heating 2-6 hours, then the Passivation Treatment in air atmosphere.Compared with not with the iron content molecular sieve of heat treatment and air passivation under mixed solvent, organic compound, reducing atmosphere, this technology invention significantly increases the active site of iron over a molecular sieve, has widened active section, the NO in 125-500 DEG C of temperature rangexNH390% or more SCR conversion efficiency.
Description
Technical field
The invention belongs to environmental catalysis technical fields, and in particular, to a kind of low-temperature catalyzed catalysis for removing denitrification
Agent and preparation method thereof, more particularly, to one kind based on nitrogen oxygen in the improved low-temperature catalyzed removal diesel engine vent gas of molecular sieve
Catalyst of compound and preparation method thereof.
Background technique
With the development of modern industry and the increase of petrol and diesel oil locomotive stock, the discharge of nitrogen oxides are still main
One of environmental contaminants.These pollutions not only damage (ozone hole, acid rain and photochemical fog to atmospheric environment
Deng), more seriously endanger human health.Use nitrogenous reducing agent such as ammonia (NH3) or urea (CO (NH2)2) by the nitrogen in air-flow
Oxide (NOx) selective catalytic reduction is converted to nitrogen, it is that the main of nitrogen oxides is eliminated on current moving source and stationary source
Method.
Copper and the catalyst of iron modified molecular screen preparation are a kind of selective catalyst reduction of nitrogen oxides important at present
Catalyst.Copper zeolite catalyst realizes high NO at relative low temperature (about 180 DEG C-about 250 DEG C)xConversion ratio (90% or more
It is high), but it is effective to need to inject more urea at higher temperature (greater than about 450 DEG C), while some researches show that Cu-
Vapor of the ZSM-5 in reaction raw materials containing 2% just seriously affects catalytic activity, and contains up to 10% in diesel engine vent gas
~16% vapor, greatly affected NOxConversion ratio.On the other hand, the molecular sieves such as SSZ-13 and BETA are in the synthesis process
Need to introduce template and the crystallization period be long, thus this molecular sieve analog because cost it is high metal-modified to limit such
The application of molecular sieve.Some researches show that Fe-ZSM-5 catalyst is in SO2And H2In the presence of O, to NOxIt keeps higher
Conversion ratio, have good hydrothermal stability and sulfur resistance.Although Fe-ZSM-5 catalyst may be implemented higher than 350 DEG C
NOxHigh conversion (90% or higher), but at lower temperature (about 180 DEG C-about 250 DEG C), only reaching quick SCR's
Under the conditions of (the NO of 1:12: NO) obtain high conversion (up to 90%).
The synthesis main method of Fe-ZSM-5 catalyst is solid-liquid ion exchange and infusion process at present, but there are following
Problem: the first, the Fe-ZSM-5 catalyst iron content of current ion-exchange preparation is not high, generally 3% hereinafter, and general
The exchange times repeated calcination for needing twice or more can be just that Fe-ZSM-5 catalyst loads higher iron content, but repeatedly
Roasting be easy to cause the crystalline framework defect of Fe-ZSM-5 catalyst, influences the activity and stability of catalyst.The second, existing
Although infusion process can make the load of Fe-ZSM-5 catalyst, very high Fe content, its active site is mostly present in molecular sieve
Surface, and cluster together, causes the catalytic activity of molecular sieve not high in the form of the oxide.
Through the literature search of existing technologies, the Chinese invention patent of Publication No. 106029228A " has and improves
The SCR catalyst of cryogenic property and production and preparation method thereof ", by 600-900 DEG C of temperature, by molecular sieve non-oxide
Property atmosphere in do not use steam with steam or in reducing atmosphere, heat 5 minutes and manufacture to 2 hours.It is formed by iron point
It is 60% to the selective reduction efficiency of nitrogen oxides that son sieve, which shows 250 DEG C with ammonia or urea, it is contemplated that for bavin
Oily tail gas reduces the standard of discharge, and low temperature conversion rate does not reach requirement still.
Through the literature search of existing technologies, Chinese invention patent " a kind of high-speed rail of Publication No. 108217681A
The preparation method of the Fe-ZSM-5 molecular sieve of content " improves iron content in molecular sieve surface by primary ions exchange process, makes
It obtains ferro element inside and outside framework of molecular sieve to be evenly distributed, and remains the opposite crystallization of Fe-ZSM-5 molecular sieve to greatest extent
Degree.But the Fe-ZSM-5 molecular sieve of synthesis contains the Fe of high level (being greater than 6%)2O3, and active temperature windows are relatively narrow
(270-350℃)。
Through the literature search of existing technologies, the Chinese invention patent of Publication No. 106029227A " has and improves
The SCR catalyst of cryogenic property and production and preparation method thereof ", the patent is by molecular sieve and a kind of ion iron substance and one kind
Organic compound merges to form mixture, calcines the mixture then to remove organic compound.The method improves iron and exists
Dispersibility in molecular sieve has widened active temperature section, but since (iron content is general in the prior art for lower iron content
Below 5%) and bad dispersibility, cause active site insufficient, it is difficult to reach the requirement of low temperature emission reduction.
The application for a patent for invention of Publication No. CN 105709856A discloses what a kind of modulation metal was distributed over a molecular sieve
The preparation method of catalyst, this method block the pH value of molecular sieve pore passage and solution by control, or appropriate by selection
The metal complex of size and the pH value for adjusting deposition sedimentation procedure parameter and solution, catalytically-active metals element can be selected
The "outside" surface specific site for being deposited on molecular sieve or preferential deposition of selecting property are in molecular sieve "inner" surface specific site.But
Active metallic element, is deposited on "outside" or the "inner" surface specific site of molecular sieve by pH of this method due to adjusting solution, must
So cause a large amount of iron to exist in the form of iron oxide, catalytic activity and selectivity is caused to be deteriorated.
Summary of the invention
Present invention aims to overcome that above-mentioned the shortcomings of the prior art, it is relatively simple to propose a kind of at low cost and technique
Single low-temperature catalyzed catalyst and preparation method thereof for removing denitrification.Catalyst prepared by the present invention low-temperature catalyzed can be gone
Denitrification is applied to through ammine selectivity catalytic reduction, thus the nitrogen oxidation of low-temperature catalyzed removal exhaust gas from diesel vehicle discharge
Object field.
The purpose of the present invention is achieved through the following technical solutions:
In a first aspect, the present invention provides a kind of preparation method of low-temperature catalyzed catalyst for removing denitrification, including such as
Lower step: molecular sieve, source of iron, organic compound, aqueous solvent being mixed, mixed liquor is obtained, and the mixed liquor is dried
After calcine, obtain the catalyst；
In the catalyst, the mass percentage content of iron is 5%~15%.When iron content is lower than 5% in catalyst
When, since active component is on the low side, it is unable to reach excellent cryogenic property；When iron content is higher than 15% in catalyst, due to iron
Too high levels cause iron species to agglomerate into a large amount of oxide particle, reduce the activity of catalyst.
Preferably, the molecular sieve include BEA (beta-zeolite), MFI (ZSM-5), FER (ferrierite), SAPO-34,
One or more of SSZ-13.
Preferably, the source of iron includes one or more of ferric nitrate, oxalic acid ammonia iron, ferric acetate, ironic citrate.
Preferably, the organic compound includes one of citric acid, succinic acid, oxalic acid, sucrose, glucose, urea
Or it is several.
Preferably, the molar ratio of the organic compound and ferro element in source of iron is 1:1-9:1.
Preferably, the molar ratio of the organic compound and iron in source of iron is 3:1-7:1.
It is highly preferred that the molar ratio of iron is 5:1 in the organic compound and source of iron.
Preferably, the aqueous solvent is one or both of deionized water, alcohols；
The alcohols includes one or more of methanol, ethyl alcohol, ethylene glycol, n-butanol, isobutanol.
It is highly preferred that the aqueous solvent is the mixture of deionized water and alcohols.
Preferably, the step of mixing are as follows: molecular sieve is mixed with source of iron, aqueous solvent first, obtains intermediate blend,
Organic compound is added in the intermediate blend again.
Preferably, the condition of the calcining are as follows: 500-700 DEG C calcining .4-6. hours.
Preferably, after the calcining, further include the steps that heat treatment；
The step of heat treatment are as follows: under reducing atmosphere, 350-800 DEG C high-temperature calcination 2-6 hours.If temperature mistake
It is low to will lead to reduction not exclusively, big oxide particle can not be made to decompose；If the excessively high skeleton that can destroy molecular sieve of temperature
Structure causes the activity of denitrification to reduce.
It is highly preferred that the step of heat treatment are as follows: under reducing atmosphere, 500-700 DEG C high-temperature calcination 4-6 hours.
Preferably, the reducing atmosphere is hydrogen or ammonia.
Preferably, after the heat treatment, Passivation Treatment is carried out after further including the steps that cooling；
The step of Passivation Treatment is；In air atmosphere, 500-600 DEG C heat treatment 1-2 hours.If passivation
Temperature is too low, and the passivating process of catalyst is incomplete, then catalyst can continue to change during reaction, Wu Fabao
Confirm the reliability tested.If the temperature of passivation is excessively high, first is that the iron species excessive oxidation on catalyst may be made, two
It is that possible destroy the skeleton structure of molecular sieve to reduce catalytic performance.
Second aspect, the present invention provide a kind of low-temperature catalyzed catalysis for removing denitrification of method preparation according to
Agent exists, and in the catalyst, the mass percentage content of iron is 5%~15%.
The third aspect, the present invention provide a kind of nitrogen oxides in low-temperature catalyzed removal diesel engine of the catalyst according to
Application.
The present invention relates to a kind of methods of catalyst based on iron molecule sieve for producing SCR activity comprising by molecular sieve,
It is mixed at least one ion iron substance and at least one organic compound, it is mixed by deionized water and at least one alcohols solvent
It closes stirring and forms mixture；The mixture is calcined to remove at least one organic compound, the invention belongs to wet stain methods.Mixing
The presence of solvent and organic compound improves iron ion in the dispersion of molecular sieve surface, promotes ion exchange, thus improves
The cryogenic property of molecular sieve.This method further includes in reducing atmosphere, certain density hydrogen or ammonia being selected, about
4-6 hours time spans are heat-treated at a temperature of 500-700 DEG C to iron molecule sieve.Then it will be cooled to ring under reducing atmosphere
The catalyst of border temperature heats 500-600 DEG C of 1-2 hours time spans of Temperature Treatment in air atmosphere.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, catalyst prepared by the present invention is bright in the catalytic performance of low-temperature catalyzed removal nitrous oxides selectivity catalysis reduction
It is aobvious to be better than general iron-based molecular sieve catalyst.
2, preparation process economical and convenient of the present invention, it is raw materials used cheap, it is beneficial to the popularization and application in market.
3, the present invention can widen nitrous oxides selectivity catalytic reduction reaction compared to common iron-based molecular sieve catalyst
Temperature window promotes the stability of catalyst.
4, under the present invention uses mixed solvent, organic matter to add, be heat-treated under reducing atmosphere and air atmosphere at passivation
The means of reason obtain to be difficult to expect and stablize excellent low-temperature SCR performance, nitrogen oxidation within the temperature range of 125-500 DEG C
Object removal rate is higher than 90% effect.
5, the processing for passing through reducing atmosphere and air passivation in the present invention, is dispersed in so that the oxide particle of iron becomes smaller
Molecular sieve "outside" or "inner" surface, so without adjusting pH value.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is that iron-containing beta-zeolite catalyst uses water or methanol or both mixture as the NO of different solventsxConversion
Rate；
Fig. 2 is that iron-containing MFI molecular sieve catalyst uses water or methanol or both mixture as the NO of different solventsx
Conversion ratio；
Fig. 3 is that iron-containing beta-zeolite catalyst uses water and methanol as mixed solvent, uses citric acid or oxalic acid or urea
NO as organic additivexConversion ratio；
Fig. 4 is that iron-containing MFI molecular sieve catalyst uses water and methanol as mixed solvent, using citric acid or oxalic acid or
NO of the urea as organic additivexConversion ratio；
Fig. 5 is that iron-containing MFI molecular sieve uses water and methanol as mixed solvent, uses urea as organic additive,
It is post-processed without post-processing or by reducing atmosphere or by the NO after reducing atmosphere and air passivation post-processingxTurn
Rate；
Fig. 6 is that iron-containing MFI molecular sieve uses water and methanol as mixed solvent, uses urea as organic additive,
Diffusion-the reflection for post-processing without post-processing or by reducing atmosphere or being post-processed by reducing atmosphere and air passivation
Than (UV-Vis) map；
Fig. 7 be iron-containing MFI molecular sieve using mixed solvent and organic matter addition after, without post-processing or pass through reduction
Property atmosphere post-processing or pass through reducing atmosphere and air passivation post-processing diffusion-reflectivity x-ray photoelectron spectroscopy
Analyze (XPS) map.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Embodiment 1
The present embodiment is related to SCR of the different solvents for iron/beta-zeolite catalyst when oxalic acid is added as organic matter
Active influence, preparation method include the following steps:
1. using ferric acetate as source of iron, oxalic acid is as organic compound, mole of organic compound and ferro element in source of iron
Than being 1: 1.Comparison uses water or ethyl alcohol or both mixture as solvent.
2. different 90 DEG C of stirrings of sample solution are evaporated, it is placed in 110 DEG C of dry 12h in baking oven.
3. powder solid sample is put into the corundum crucible that volume is 200mL, the crucible for filling sample is then placed in Muffle furnace
In, 550 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 4h.It takes out to be placed in agate mortar after cooling and grind, obtain object.
In catalyst obtained, the mass percentage content of iron is 5%.
4. different solvents iron/beta-zeolite catalyst powder of acquisition is controlled catalyst particles by squeezing, being crushed and be sieved
Particle size is in 0.2-0.4mm.
5. weighing above-mentioned catalyst 0.15g, being placed in material is to be fixed with silica wool, instead in quartz ampoule fixed bed reactors
Answering atmosphere is 350ppmNO, 385ppmNH3And 15%O2, reaction gas flow speed 150ml/min.With the heating rate pair of 5 DEG C/min
Mixed powder heating keeps the constant 20min of temperature to guarantee the accuracy of data, generates after reaction in each data collection point
Gas, make quantitative analysis with Fourier Transform Infrared Spectrometer gas cell.
As shown in Figure 1, the mixed solvent of water and alcohols, compared with single water or alcohols solvent, hence it is evident that improve iron/β
The SCR activity of zeolite catalyst, active temperature windows of the NO conversion ratio greater than 90% are 200-500 DEG C.
Embodiment 2
The present embodiment is related to different solvents and adds situation as organic matter in citric acid for iron-based MFI molecular sieve catalyst
Under SCR activity influence, preparation method includes the following steps:
1. use ferric acetate as source of iron, as organic compound, organic compound rubs citric acid with ferro element in source of iron
, than being 9: 1, comparison uses water or methanol or both mixture as solvent for you.
2. different 90 DEG C of stirrings of sample solution are evaporated, it is placed in 110 DEG C of dry 12h in baking oven.
3. powder solid sample is put into the corundum crucible that volume is 200mL, the crucible for filling sample is then placed in Muffle furnace
In, 550 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 4h.It takes out to be placed in agate mortar after cooling and grind, obtain object.
In catalyst obtained, the mass percentage content of iron is 15%.
4. by the iron-based MFI molecular sieve catalyst powder of the different solvents of acquisition by squeezing, being crushed and be sieved, control catalysis
Agent particle size is in 0.2-0.4mm.
5. weighing above-mentioned catalyst 0.15g, being placed in material is to be fixed with silica wool, instead in quartz ampoule fixed bed reactors
Answering atmosphere is 350ppmNO, 385ppmNH3And 15%O2, reaction gas flow speed 150ml/min.With the heating rate pair of 5 DEG C/min
Mixed powder heating keeps the constant 20min of temperature to guarantee the accuracy of data, generates after reaction in each data collection point
Gas, make quantitative analysis with Fourier Transform Infrared Spectrometer gas cell.
As shown in Fig. 2, the mixed solvent of water and alcohols, compared with single water or alcohols solvent, hence it is evident that improve iron-based
The SCR activity of MFI molecular sieve catalyst, active temperature windows of the NO conversion ratio greater than 90% are 200-500 DEG C.
Embodiment 3
The present embodiment is related to influence of the different organic matters additions for iron/beta-zeolite catalyst SCR activity, preparation side
Method includes the following steps:
1. using ferric nitrate as source of iron, comparison uses both water and ethyl alcohol mixture as solvent.
2. the oxalic acid or citric acid or urea of addition 5 times of molar ratios of ferro element in the above solution, is dispersed with stirring, will be different
90 DEG C of stirrings of sample solution be evaporated, be placed in 110 DEG C of dry 12h in baking oven.
3. powder solid sample is put into the corundum crucible that volume is 200mL, the crucible for filling sample is then placed in Muffle furnace
In, 550 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 4h.It takes out to be placed in agate mortar after cooling and grind, obtain object.
In catalyst obtained, the mass percentage content of iron is 5%.
4. different solvents iron/beta-zeolite catalyst powder of acquisition is controlled catalyst particles by squeezing, being crushed and be sieved
Particle size is in 0.2-0.4mm.
5. weighing above-mentioned catalyst 0.15g, being placed in material is to be fixed with silica wool, instead in quartz ampoule fixed bed reactors
Answering atmosphere is 350ppmNO, 385ppmNH3And 15%O2, reaction gas flow speed 150ml/min.With the heating rate pair of 5 DEG C/min
Mixed powder heating keeps the constant 20min of temperature to guarantee the accuracy of data, generates after reaction in each data collection point
Gas, make quantitative analysis with Fourier Transform Infrared Spectrometer gas cell.
As shown in figure 3, using the organic matter of oxalic acid or citric acid or urea add, with not use organic matter add
Iron/beta-zeolite catalyst is compared, and has widened iron/beta-zeolite catalyst SCR activity window in various degree.The wherein addition effect of urea
Fruit is the most significant, and at 150 DEG C, when NO conversion ratio is close to 90%, 550 DEG C, NO conversion ratio is still more than 90%.
Embodiment 4
The present embodiment is related to influence of the different organic matter additions for the SCR activity of iron-based MFI molecular sieve catalyst, system
Preparation Method includes the following steps:
1. using ferric nitrate as source of iron, comparison uses both water and methanol mixture as solvent.
2. the oxalic acid or citric acid or urea of addition 5 times of molar ratios of ferro element in the above solution, is dispersed with stirring, will be different
90 DEG C of stirrings of sample solution be evaporated, be placed in 110 DEG C of dry 12h in baking oven.
3. powder solid sample is put into the corundum crucible that volume is 200mL, the crucible for filling sample is then placed in Muffle furnace
In, 550 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 4h.It takes out to be placed in agate mortar after cooling and grind, obtain object.
In catalyst obtained, the mass percentage content of iron is 12%.
4. by the iron-based MFI molecular sieve catalyst powder of the different solvents of acquisition by squeezing, being crushed and be sieved, control catalysis
Agent particle size is in 0.2-0.4mm.
5. weighing above-mentioned catalyst 0.15g, being placed in material is to be fixed with silica wool, instead in quartz ampoule fixed bed reactors
Answering atmosphere is 350ppmNO, 385ppmNH3And 15%O2, reaction gas flow speed 150ml/min.With the heating rate pair of 5 DEG C/min
Mixed powder heating keeps the constant 20min of temperature to guarantee the accuracy of data, generates after reaction in each data collection point
Gas, make quantitative analysis with Fourier Transform Infrared Spectrometer gas cell.
As shown in figure 4, being added using the organic matter of oxalic acid or citric acid or urea, with the iron for organic matter not being used to add
Base MFI molecular sieve catalyst is compared, and has widened the SCR activity window of iron-based MFI molecular sieve catalyst in various degree.Wherein urea
Additive effect it is the most significant, at 150-550 DEG C, NO conversion ratio is more than 85%.
Embodiment 5
The present embodiment is related to influence of the urea addition of different proportion for the SCR activity of iron-based MFI molecular sieve catalyst,
Preparation method includes the following steps:
1. using ferric nitrate as source of iron, use both water and methanol mixture as solvent.
2. the urea of 1,3,5,7 and 9 times of molar ratio of ferro element is added in the above solution, it is dispersed with stirring, by different samples
The 90 DEG C of stirrings of product solution are evaporated, and are placed in 110 DEG C of dry 12h in baking oven.
3. powder solid sample is put into the corundum crucible that volume is 200mL, the crucible for filling sample is then placed in Muffle furnace
In, 550 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 4h.It takes out to be placed in agate mortar after cooling and grind, obtain object.
In catalyst obtained, the mass percentage content of iron is 12%.
4. by the iron-based MFI molecular sieve catalyst powder of the different solvents of acquisition by squeezing, being crushed and be sieved, control catalysis
Agent particle size is in 0.2-0.4mm.
5. weighing above-mentioned catalyst 0.15g, being placed in material is to be fixed with silica wool, instead in quartz ampoule fixed bed reactors
Answering atmosphere is 350ppmNO, 385ppmNH3And 15%O2, reaction gas flow speed 150ml/min.With the heating rate pair of 5 DEG C/min
Mixed powder heating keeps the constant 20min of temperature to guarantee the accuracy of data, generates after reaction in each data collection point
Gas, make quantitative analysis with Fourier Transform Infrared Spectrometer gas cell.
The result shows that although the SCR of iron-based MFI molecular sieve catalyst has been widened in the urea addition of different proportion in various degree
Active window, but the iron-based MFI molecular sieve catalyst of 5 times of molar ratio urea of ferro element, best performance, in 150-550 is added
DEG C when, NO conversion ratio is more than 85%.
Embodiment 6
The present embodiment is related to post-processing without post-processing or by reducing atmosphere or by reducing atmosphere and air
It is passivated the influence of the SCR activity for iron-based MFI molecular sieve catalyst of post-processing, preparation method includes the following steps:
1. using ferric nitrate as source of iron, use both water and methanol mixture as solvent.
2. the urea of 5 times of molar ratios of ferro element is added in the above solution, it is dispersed with stirring, 90 DEG C of stirrings of sample solution is steamed
It is dry, it is placed in 110 DEG C of dry 12h in baking oven.
3. powder solid sample is put into the corundum crucible that volume is 200mL, the crucible for filling sample is then placed in Muffle furnace
In, 550 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 4h.It takes out to be placed in agate mortar after cooling and grind, obtain object.
Alternatively, by powder in 5%H after cooling2Under/Ar atmosphere, 350 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 5h,
In 5%H2It takes out to be placed in agate mortar after being cooled to room temperature under/Ar atmosphere and grind, obtain object.
Alternatively, by powder in 5%H after cooling2Under/Ar atmosphere, 350 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 5h,
In 5%H2After being cooled to room temperature under/Ar atmosphere, sample is taken to be warming up to 600 DEG C in air atmosphere with the speed of 5 DEG C/min, protected
Warm 1h takes out to be placed in agate mortar and grind, obtains object after cooling.
In catalyst obtained, the mass percentage content of iron is 12%.
4. the iron-based MFI molecular sieve catalyst powder of the different post-processings of acquisition is passed through extruding, broken and sieving, control
Catalyst particle size is in 0.2-0.4mm.
5. weighing above-mentioned catalyst 0.15g, being placed in material is to be fixed with silica wool, instead in quartz ampoule fixed bed reactors
Answering atmosphere is 350ppmNO, 385ppmNH3And 15%O2, reaction gas flow speed 150ml/min.With the heating rate pair of 5 DEG C/min
Mixed powder heating keeps the constant 20min of temperature to guarantee the accuracy of data, generates after reaction in each data collection point
Gas, make quantitative analysis with Fourier Transform Infrared Spectrometer gas cell.
The result shows that using at 350 DEG C reducing atmosphere post-process sample, use reducing atmosphere and 600 at 350 DEG C
The sample of DEG C air passivation post-processing, respectively compared with the sample for not using post-processing, the SCR performance of low temperature is obviously obtained
It is promoted.At 125 DEG C, the NO conversion ratio of the sample post-processed using reducing atmosphere is close to 90%, but after 400 DEG C,
Performance sharply declines.The sample post-processed using reducing atmosphere and air passivation, NO conversion ratio are greater than 90% temperature window
It is 125-450 DEG C.
Embodiment 7
The present embodiment is related to post-processing without post-processing or by reducing atmosphere or by reducing atmosphere and air
It is passivated the influence of the SCR activity for iron-based MFI molecular sieve catalyst of post-processing, preparation method includes the following steps:
1. using ferric nitrate as source of iron, use both water and methanol mixture as solvent.
2. the urea of 5 times of molar ratios of ferro element is added in the above solution, it is dispersed with stirring, 90 DEG C of stirrings of sample solution is steamed
It is dry, it is placed in 110 DEG C of dry 12h in baking oven.
3. powder solid sample is put into the corundum crucible that volume is 200mL, the crucible for filling sample is then placed in Muffle furnace
In, 550 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 4h.It takes out to be placed in agate mortar after cooling and grind, obtain object.
Alternatively, by powder in 5%H after cooling2Under/Ar atmosphere, 800 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 5h,
In 5%H2It takes out to be placed in agate mortar after being cooled to room temperature under/Ar atmosphere and grind, obtain object.
Alternatively, by powder in 5%H after cooling2Under/Ar atmosphere, 800 DEG C are warming up to the speed of 5 DEG C/min, keeps the temperature 5h,
In 5%H2After being cooled to room temperature under/Ar atmosphere, sample is taken to be warming up to 500 DEG C in air atmosphere with the speed of 5 DEG C/min, protected
Warm 1h takes out to be placed in agate mortar and grind, obtains object after cooling.
In catalyst obtained, the mass percentage content of iron is 12%.
4. the iron-based MFI molecular sieve catalyst powder of the different post-processings of acquisition is passed through extruding, broken and sieving, control
Catalyst particle size is in 0.2-0.4mm.
5. weighing above-mentioned catalyst 0.15g, being placed in material is to be fixed with silica wool, instead in quartz ampoule fixed bed reactors
Answering atmosphere is 350ppmNO, 385ppmNH3And 15%O2, reaction gas flow speed 150ml/min.With the heating rate pair of 5 DEG C/min
Mixed powder heating keeps the constant 20min of temperature to guarantee the accuracy of data, generates after reaction in each data collection point
Gas, make quantitative analysis with Fourier Transform Infrared Spectrometer gas cell.
As shown in figure 5, being post-processed using the sample of reducing atmosphere post-processing and using reducing atmosphere and air passivation
Sample, compared with the sample for not using post-processing, the SCR performance of low temperature obviously gets a promotion.At 125 DEG C, using also
Close to 90%, but after 400 DEG C, performance sharply declines the NO conversion ratio of the sample of originality atmosphere post-processing.Use reduction
Property atmosphere and air passivation post-processing sample, NO conversion ratio greater than 90% temperature window be 125-500 DEG C.
As shown in Figure 6 and Figure 7, it is compared with the sample of no post-processing, uses the trivalent iron ratio of reducing atmosphere post-processing sample
Example decline, while Fe2O3It is reduced with the oligomeric nuclear matter of iron, but isolated Fe3+Become more.Increased isolated Fe3+Exactly make
The reason of with reducing atmosphere post-processing sample cryogenic property enhancing, but because reducing atmosphere makes last point of molecular sieve
Iron restores, so that the active sites of molecular sieve surface are reduced, the high-temperature behavior of sample is caused sharply to decline.Use reproducibility gas
The sample of atmosphere and air passivation post-processing, compared with the sample for not using post-processing, trivalent iron ratio is obviously increased, simultaneously
Fe2O3It reduces, but the oligomeric nuclear matter of iron and isolated Fe3+Become more, to widen the active section of sample significantly.
Along with industrialized deep, atmospheric environment deteriorates increasingly, and various pollutants discharge beyond standards are commonplace, motor vehicle
The nitrogen oxides of tail gas and industrial discharge is one of the main reason for atmospheric environment is deteriorated, therefore country also enhances system and builds
If having worked out harsh motor vehicle and industrial discharge standard.In order to meet the requirement of emission regulation, motor vehicle and industrial discharge need
Install qualified after-treatment device additional.The core of after-treatment device is catalyst technology, the catalyst technology energy that the present invention develops
Ammine selectivity catalytic reduction is realized in wider temperature window, will bring biggish Social benefit and economic benefit.
In conclusion the present invention is combined by mixed solvent, urea and hydrogen post-processing, it is prepared for iron-based point of high Fe content
Sub- sieve catalyst；Preparation process of the invention is easy, and economy is preferable, is the catalyst skill of the following potential large-scale application
Art.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (11)
1. a kind of preparation method of the low-temperature catalyzed catalyst for removing denitrification, which comprises the steps of: will divide
Sub- sieve, source of iron, organic compound, aqueous solvent are mixed, and mixed liquor is obtained, and will be calcined, are obtained after mixed liquor drying
The catalyst；
In the catalyst, the mass percentage content of iron is 5%~15%.
2. the preparation method of the low-temperature catalyzed catalyst for removing denitrification according to claim 1, which is characterized in that institute
Stating molecular sieve includes one or more of beta-zeolite, ZSM-5, ferrierite, SAPO-34, SSZ-13.
3. the preparation method of the low-temperature catalyzed catalyst for removing denitrification according to claim 1, which is characterized in that institute
Stating source of iron includes one or more of ferric nitrate, oxalic acid ammonia iron, ferric acetate, ironic citrate.
4. the preparation method of the low-temperature catalyzed catalyst for removing denitrification according to claim 1, which is characterized in that institute
Stating organic compound includes one or more of citric acid, succinic acid, oxalic acid, sucrose, glucose, urea.
5. the preparation method of the low-temperature catalyzed catalyst for removing denitrification according to claim 1 or 4, feature exist
In the molar ratio of ferro element is 1:1-9:1 in the organic compound and source of iron.
6. the preparation method of the low-temperature catalyzed catalyst for removing denitrification according to claim 1, which is characterized in that institute
Stating aqueous solvent is one or both of deionized water, alcohols；
The alcohols includes one or more of methanol, ethyl alcohol, ethylene glycol, n-butanol, isobutanol.
7. the preparation method of the low-temperature catalyzed catalyst for removing denitrification according to claim 1, which is characterized in that institute
The step of stating mixing are as follows: molecular sieve is mixed with source of iron, aqueous solvent first, obtains intermediate blend, then organic compound is added
It adds in the intermediate blend；
The condition of the calcining are as follows: 500-700 DEG C calcining .4-6. hours.
8. the preparation method of the low-temperature catalyzed catalyst for removing denitrification according to claim 1, which is characterized in that
After the calcining, further include the steps that heat treatment；
The step of heat treatment are as follows: under reducing atmosphere, 350-800 DEG C high-temperature calcination 2-6 hours.
9. the preparation method of the low-temperature catalyzed catalyst for removing denitrification according to claim 8, which is characterized in that
After the heat treatment, Passivation Treatment is carried out after further including the steps that cooling；
The step of Passivation Treatment is；In air atmosphere, 500-600 DEG C heat treatment 1-2 hours.
10. a kind of low-temperature catalyzed catalyst for removing denitrification of method according to claim 11 preparation, is urged described
In agent, the mass percentage content of iron is 5%~15%.
11. a kind of application of catalyst according to claim 10 nitrogen oxides in low-temperature catalyzed removal diesel engine.
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| CN112973770B (en) * | 2021-01-27 | 2023-03-03 | 南开沧州渤海新区绿色化工研究有限公司 | Nitrogen oxide methane selective catalytic reduction catalyst and application method thereof |
| CN113000063A (en) * | 2021-02-23 | 2021-06-22 | 浙江浙能技术研究院有限公司 | Fe, Cu-SSZ-13 molecular sieve with Cu and Fe occupying different sites and preparation method thereof |
| CN113000063B (en) * | 2021-02-23 | 2022-06-07 | 浙江浙能技术研究院有限公司 | Fe, Cu-SSZ-13 molecular sieve with Cu and Fe occupying different sites and preparation method thereof |
| CN114345402A (en) * | 2021-08-30 | 2022-04-15 | 武汉科技大学 | Preparation method of iron-based molecular sieve catalyst |
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