CN101711991B - Fe molecular sieve composite catalyst and preparation method thereof - Google Patents
Fe molecular sieve composite catalyst and preparation method thereof Download PDFInfo
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- CN101711991B CN101711991B CN2009100243360A CN200910024336A CN101711991B CN 101711991 B CN101711991 B CN 101711991B CN 2009100243360 A CN2009100243360 A CN 2009100243360A CN 200910024336 A CN200910024336 A CN 200910024336A CN 101711991 B CN101711991 B CN 101711991B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 239000002808 molecular sieve Substances 0.000 title 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 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 239000012065 filter cake Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 11
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 11
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 20
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000003643 water by type Substances 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052680 mordenite Inorganic materials 0.000 abstract description 4
- 239000003502 gasoline Substances 0.000 abstract description 3
- 239000003345 natural gas Substances 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 3
- 210000002966 serum Anatomy 0.000 abstract 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 abstract 1
- 238000007664 blowing Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229960003753 nitric oxide Drugs 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a Fe molecular sieve composite catalyst, which comprises an active component Fe, a catalyst carrier Beta and a mordenite. A preparation method comprises the following steps of: 1, performing ion exchange on a Si/Al H-Beta molecular sieve and FeCl2; 2, removing Cl ions in the solution, and drying the obtained filter cake and roasting the filter cake in a muffle furnace to obtain the Fe/Beta molecular sieve catalyst; 3, placing the Fe/Beta molecular sieve catalyst in the water, adding the mordenite, and roasting the mixture to obtain the Fe/Beta/Mor molecular sieve composite catalyst; 4, dissolving the Fe/Beta/Mor molecular sieve into the de-ionized water, and adding concentrated nitric acid to obtain coating serum; and 5, dipping a Cordierite honeycomb ceramic carrier in the serum, blowing a residual liquid, and after drying the mixture in the shade, drying and roasting the mixture. The catalyst can efficiently purify NOx in the tail gas of a diesel vehicle, a lean-burning gasoline car and a lean-burning natural gas vehicle, and has the characteristics of environment protection and highly efficient catalytic activity.
Description
Technical field
The invention belongs to nitrogen oxide control technology field in the environmental protection, be specifically related to a kind of Fe molecular sieve composite catalyst and preparation method thereof.
Background technology
Along with progress of science and technology, productivity is greatly improved, but existent environment of people has also obtained very big destruction, acid rain, and the environmental problem in the global ranges such as photochemical fog, depletion of the ozone layer and greenhouse effects becomes increasingly conspicuous.The generation of these problems, closely related with hydro carbons and nitrogen oxide that the mankind are discharged in the atmosphere.According to estimating that not exclusively the annual whole world has 8.6 * 10 approximately because of the NOx that combustion of fossil fuels enters atmosphere
10Kg, NOx becomes one of major pollutants of atmospheric environment.Meanwhile; People are increasingly high to the cry of environmental protection; Various countries formulate and carry out strict emission control standards day by day in succession, and to strict day by day to the discharged nitrous oxides restriction of motor vehicle and stationary source discharging, the discharging of therefore controlling NOx receives the extensive attention of scientific and technological circle and industrial quarters.
NO
XEmission source comprises stationary source (burning of fossil fuels such as coal and oil and the exhaust that the factory of nitric acid is used in production in producing, living) and moving source (motor-vehicle tail-gas).Automobile engine adopts lean burn, promptly when fuel combustion, adds excess air, can significantly improve the utilization rate of fuel on the one hand, improves the economy of fuel; Can also greatly reduce carbon monoxide in the waste gas (CO), hydrocarbon harmful substance and greenhouse gases carbon dioxide (CO such as (HC) on the other hand
2) discharging.Such as petrolic air-fuel ratio is brought up to 22 by common 14.8, then capable of saving fuel 15%, thus reduce CO
2Discharge capacity.But the oxygen (generally being higher than 5%) that contains higher concentration in the lean burn makes can not be applicable to the purification of the NO of diesel engine and lean-burn type gasoline exhaust by the automobile three-way catalyst that generally uses at present.Meanwhile, people are increasingly high to the cry of environmental protection, and industrially developed country such as U.S.A, Japan and Korea S. and Europe work out and carry out new discharge standard in succession in recent years, and are strict day by day to the emission limit set of NO.Therefore, how to control nitrogen oxide and become a research focus both domestic and external.
NH
3Selective Catalytic Reduction of NO x (NH
3-SCR) be the NOx method that the most effectively purifies at present, this techniques make use reducing agent NH
3On catalyst with NO
XBe reduced to harmless N
2And H
2O.The core of SCR technology is the catalyst of high activity and stability, and noble metal, metal oxide etc. all is proved to be effective SCR catalyst, in all these catalyst, with TiO
2For the catalytic component based on vanadium of carrier has good active and anti-water sulfur resistance.With V
2O
5For active component catalytic component based on vanadium eighties of last century the seventies and eighties begun industrialization production abroad because such catalyst has good activity and anti-water and SO
2Performance has obtained using widely in the stationary source coal-fired flue gas denitration.In exhaust gas from diesel vehicle aspect the NOx purification; Correlative study has also been carried out in Europe a few years ago; And be applied to tail gas clean-up (Guido Busca, LucaLietti, the Gianguido Ramis of NOx in the heavy-duty diesel vehicle; Francesco Berti, Chemical andmechanistic aspects of the selective catalytic reduction of NOxby ammonia over oxide catalysts:A review.Appl.Catal.B 18 (1998) 1-36.).But this catalyst still has deficiency in motor-vehicle tail-gas control, the one, and active component V
2O
5Poisonous, behind the vaporization at high temperature atmospheric environment is worked the mischief, secondly be the SO in the tail gas on the catalyst
2Be oxidized to SO
3, further give off the sulphate particle thing.Even more serious is on the diesel vehicle that the particle trap is housed, and when trap regeneration, temperature surpasses 700 ℃ often, thereby makes catalyst carrier TiO
2Undergo phase transition, cause catalyst activity to decline to a great extent.
Molecular sieve catalyst has high catalytic activity to selective reduction NOx, and active temperature windows receives much concern in selecting the catalytic reduction of NOx technology than broad.Molecular sieve is used as catalyst and is based on its special microcellular structure, and the ionic species of its type, silica alumina ratio, exchange, reaction condition, exchange degree etc. all can influence its activity.The molecular sieve that is used for the SCR catalyst carrier mainly comprises ZSM series, Y type, mordenite (MOR), beta type etc., and the metallic element that is used for ion-exchange mainly comprises Fe, Cu, Mn, Ce, Co and Ni etc.The research of carrying out about Fe/ZSM-5 in recent years is more, and at NH
3Reductive NO
xReaction in obtained effect (1.Long, RQ preferably; Yang, RT.Reaction mechanism of selectivecatalytic reduction of NO with NH
3Over Fe-ZSM-5 catalyst.J.Catal., 207 (2002): 224-231.2.Qi, GS; Yang, RT.Ultra-activeFe/ZSM-5 catalyst for selective catalytic reduction of nitricoxide with ammonia, Appl.Catal.B, 60 (2005): 13-22.).The catalytic activity of Fe/ZSM-5 is relevant with the silica alumina ratio of Fe exchange degree and ZSM-5, and catalyst activity increases with the increase of Fe content under the cryogenic conditions, and active increase with Fe content reduces under the hot conditions.Purify to NOx in the motor-vehicle tail-gas; At present industrial quarters is relatively more good is to be active component with Cu, Fe; H-ZSM-5 and Beta are that the catalyst of carrier is found in practical application, and inevitable hydrocarbon emission in the tail gas can cause in various degree catalyst carbon deposition and inactivation.
At present domestic at the early-stage to NOx technical research in the molecular sieve catalyst purifying motor tail gas, the heat endurance of catalyst, HC compound are such catalyst needs solution in practical application key issues to the catalyst poisoning problem.
Summary of the invention
In order to overcome the deficiency of above-mentioned prior art; The object of the present invention is to provide a kind of Fe molecular sieve composite catalyst and preparation method thereof; Be used for the purification of efficient purification of diesel car, lean-burn gasoline motor car and lean burn natural gas tail gas Nox, have the characteristics of environmental protection and high-efficiency catalytic activity.
To achieve these goals, the technical scheme of the present invention's employing is: a kind of Fe molecular sieve composite catalyst comprises following component:
Active component Fe is 1～5wt.%; Catalyst carrier Beta is 55～89wt.%; Modenite is 10-40wt.%.
A kind of preparation method of Fe molecular sieve composite catalyst comprises the steps:
One, measure 200～500mL deionized water, adding 2～20g Si/Al mol ratio is 10～25 H-Beta molecular sieve, under 25～80 ℃ of room temperatures, stirs 30～60min, adds the FeCl of 1～5g again by stoichiometric proportion
2, stir 24～30h under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 5～6 times deionized waters, remove the Cl ion in the solution, avoid the interference of Cl ion, the filter cake that obtains is dry 10h～24h in 100～120 ℃ the baking oven in temperature earlier;
Three, filter cake 500～800 ℃ of following roasting 3～8h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst;
Four; The top Fe/Beta molecular sieve catalyst that obtains is put into the water of 50～100mL, add the modenite of anticipating of 1～5g, in Rotary Evaporators, dry; 500～800 ℃ of roasting 2～6h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, the Fe/Beta/Mor molecular sieve composite catalyst of 2～8g is dissolved in 20～80mL deionized water, stir that to add mass fraction concentration after 10～30 minutes be red fuming nitric acid (RFNA) 2～6mL of 66%, and stir after 30～60 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing to apply in the slurries; Flood after 1～5 minute and take out; Blow the raffinate in the most duct, 110～120 ℃ of drying 8～24h in back that in air, dry in the shade, roasting 2～5h under 500～650 ℃ of h air.
With compare under the prior art, the present invention has following advantage:
(1) adopting the Beta molecular sieve of Heat stability is good is catalyst carrier, and the Fe/Beta molecular sieve catalyst of preparation has extraordinary catalyst activity.
(2) adopting modenite is outer HC selective absorbent, can effectively suppress absorption and the carbon distribution of HC, thereby improves the anti-carbon performance of catalyst.
Description of drawings
Accompanying drawing has or not the NH of Fe-Beta and Fe-Beta/Mor honeycomb catalyst sample under the propylene for the present invention
3Selective Catalytic Reduction of NO x experimental result picture.
The specific embodiment
Below in conjunction with embodiment the present invention is done further explain.
Embodiment 1
A kind of Fe molecular sieve composite catalyst comprises following component:
The content of active component Fe is 2.5wt.%, and the content of catalyst carrier Beta is 82.5wt.%, and modenite is 15wt.%;
A kind of preparation method of Fe molecular sieve composite catalyst comprises the steps:
One, measure the 300mL deionized water, adding 5gSi/Al mol ratio is 12.5 H-Beta molecular sieve, under 30 ℃ of room temperatures, on magnetic stirring apparatus, stirs 30min, adds 5gFeCl by stoichiometric proportion again
2, stirred 24 hours under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 5 times deionized waters, remove the Cl ion in the solution, the filter cake that obtains is dry 15h in 110 ℃ of baking ovens earlier;
Three, the filter cake 600 ℃ of following roasting 5h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst, are designated as Fe/ZSM-5, Fe/Beta, Fe/ZSM-5, Fe/Mor, Fe/Y and Fe/Fer respectively;
Four, the top Fe/Beta molecular sieve catalyst that obtains is put into the water of 80mL, add the modenite that 2g anticipates, in Rotary Evaporators, dry, 600 ℃ of roasting 3h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, the 3gFe/Beta/Mor molecular sieve composite catalyst is dissolved in the 40mL deionized water, stir after 30 minutes that to add 2mL mass fraction concentration be 66% red fuming nitric acid (RFNA), and stir after 30 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing applies in the slurries, flood after 2 minutes and take out, blow the raffinate in the most duct; In air, dry in the shade back 110 ℃ and descend dry 2h, roasting 2h under 550 ℃ of h air.
Embodiment 2
A kind of Fe molecular sieve composite catalyst comprises that following component: active component Fe is 3wt.%; Catalyst carrier Beta is 77wt.%; Modenite is 20wt.%.
A kind of preparation method of Fe molecular sieve composite catalyst comprises the steps:
One, measure the 350mL deionized water, adding 8g Si/Al mol ratio is 15 H-Beta molecular sieve, under 30 ℃ of room temperatures, on magnetic stirring apparatus, stirs 40min, adds the FeCl of 4g again by stoichiometric proportion
2, stirred 28 hours under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 6 times deionized waters, remove the Cl ion in the solution, the filter cake that obtains is dry 15h in 110 ℃ of baking ovens earlier;
Three, the filter cake 600 ℃ of roasting 3h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst;
Four; The top Fe/Beta molecular sieve catalyst that obtains is put into the water of 80mL, add the modenite that 2.5g anticipates, in Rotary Evaporators, dry; 600 ℃ of roasting 3h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, the Fe/Beta/Mor molecular sieve composite catalyst of 5g is dissolved in the 70mL deionized water, stir that to add 3mL mass fraction concentration after 30 minutes be 66% red fuming nitric acid (RFNA), and stir after 50 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing applies in the slurries, flood after 3 minutes and take out, blow the raffinate in the most duct; The back 110 ℃ of dry 2h that in air, dry in the shade, roasting 2h under 600 ℃ of air.
Embodiment 3
A kind of Fe molecular sieve composite catalyst comprises following component:
Active component Fe is 5wt.%, and catalyst carrier Beta is 70wt.%, and modenite is 25wt.%.
A kind of preparation method of Fe molecular sieve composite catalyst comprises the steps:
One, measure the 250mL deionized water, adding 10g Si/Al mol ratio is 15 H-Beta molecular sieve, under 30 ℃ of room temperatures, on magnetic stirring apparatus, stirs 35min, adds 2gFeCl by stoichiometric proportion again
2, stirred 30 hours under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 5 times deionized waters, remove the Cl ion in the solution, the filter cake that obtains is dry 18h in 110 ℃ of baking ovens earlier;
Three, the filter cake 600 ℃ of roasting 4h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst;
Four, the top Fe/Beta molecular sieve catalyst that obtains is put into the water of 100mL, add the modenite that 3g anticipates, in Rotary Evaporators, dry, 600 ℃ of roasting 3h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, 5g Fe/Beta/Mor molecular sieve composite catalyst is dissolved in the 80mL deionized water, stir after 30 minutes that to add 2mL mass fraction concentration be 66% red fuming nitric acid (RFNA), and stir after 30 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing applies in the slurries, flood after 2 minutes and take out, blow the raffinate in the most duct; The back 110 ℃ of dry 3h that in air, dry in the shade, roasting 3h under 600 ℃ of h air.
Embodiment 4
A kind of Fe molecular sieve composite catalyst comprises following component:
Active component Fe is 2.5wt.%, and catalyst carrier Beta is 72.5wt.%, and modenite is 25wt.%.
A kind of preparation method of Fe molecular sieve composite catalyst comprises the steps:
One, measure the 500mL deionized water, adding 15g Si/Al mol ratio is 12.5 H-Beta molecular sieve, under 30 ℃ of room temperatures, on magnetic stirring apparatus, stirs 60min, adds the FeCl of 3g again by stoichiometric proportion
2, stirred 24 hours under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 5 times deionized waters, remove the Cl ion in the solution, the filter cake that obtains is dry 18h in 110 ℃ of baking ovens earlier;
Three, the filter cake 600 ℃ of roasting 3～8h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst;
Four, the top Fe/Beta molecular sieve catalyst that obtains is put into the water of 80mL, add the modenite that 5g anticipates, in Rotary Evaporators, dry, 600 ℃ of roasting 2h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, 5g Fe/Beta/Mor molecular sieve composite catalyst is dissolved in the 70mL deionized water, stir after 10 minutes that to add 3mL mass fraction concentration be 66% red fuming nitric acid (RFNA), and stir after 30 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing applies in the slurries, flood after 3 minutes and take out, blow the raffinate in the most duct; The back 110 ℃ of dry 5h that in air, dry in the shade, roasting 2h under 650 ℃ of h air.
Referring to accompanying drawing, accompanying drawing is the NH that has or not Fe-Beta catalyst and Fe-Beta/Mor honeycomb catalyst sample under the propylene
3Selective Catalytic Reduction of NO x result has the modification of the Fe/Beta catalyst of excellent activity and heat endurance through modenite, has also had good anti-HC poisoning capability.Reaction condition is: 1000ppm NH
3, or 1000ppm C
3H
6, 1000ppm NO, 5%O
2, balance gas is helium, air speed is 1.9 * 10
5h
-1
Claims (5)
1. the preparation method of a Fe molecular sieve composite catalyst is characterized in that, comprises the steps:
One, measure 200～500mL deionized water, adding 2～20g Si/Al mol ratio is 10～25 H-Beta molecular sieve, under 25～80 ℃ of room temperatures, stirs 30～60min, adds the FeCl of 1～5g again by stoichiometric proportion
2, stir 24～30h under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 5-6 deionized water doubly, remove the Cl ion in the solution, the filter cake that obtains is dry 10h～24h in 100～120 ℃ the baking oven in temperature earlier;
Three, filter cake 500～800 ℃ of following roasting 3～8h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst;
Four; The top Fe/Beta molecular sieve catalyst that obtains is put into the water of 50～100mL, add the modenite that 1～5g anticipates, in Rotary Evaporators, dry; 500～800 ℃ of roasting 2～6h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, the Fe/Beta/Mor molecular sieve composite catalyst of 2～8g is dissolved in 20～80mL deionized water, stir that to add 2～6mL mass fraction concentration after 10～30 minutes be 66% red fuming nitric acid (RFNA), and stir after 30～60 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing to apply in the slurries; Flood after 1～5 minute and take out; Blow the raffinate in the most duct, 110～120 ℃ of drying 8～24h in back that in air, dry in the shade, roasting 2～5h under 500～650 ℃ of air.
2. the preparation method of a Fe molecular sieve composite catalyst is characterized in that, comprises the steps:
One, measure the 300mL deionized water, adding 5g Si/Al mol ratio is 12.5 H-Beta molecular sieve, under 30 ℃ of room temperatures, on magnetic stirring apparatus, stirs 30min, adds 5gFeCl by stoichiometric proportion again
2, stirred 24 hours under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 5 times deionized waters, remove the Cl ion in the solution, the filter cake that obtains is dry 15h in 110 ℃ of baking ovens earlier;
Three, the filter cake 600 ℃ of following roasting 5h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst;
Four, the top Fe/Beta molecular sieve catalyst that obtains is put into the water of 80mL, add the modenite that 2g anticipates, in Rotary Evaporators, dry, 600 ℃ of roasting 3h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, the 3gFe/Beta/Mor molecular sieve composite catalyst is dissolved in the 40mL deionized water, stir after 30 minutes that to add 2mL mass fraction concentration be 66% red fuming nitric acid (RFNA), and stir after 30 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing applies in the slurries, flood after 2 minutes and take out, blow the raffinate in the most duct; In air, dry in the shade back 110 ℃ and descend dry 2h, roasting 2h under 550 ℃ of air.
3. the preparation method of a Fe molecular sieve composite catalyst is characterized in that, comprises the steps:
One, measure the 350mL deionized water, adding 8g Si/Al mol ratio is 15 H-Beta molecular sieve, under 30 ℃ of room temperatures, on magnetic stirring apparatus, stirs 40min, adds the FeCl of 4g again by stoichiometric proportion
2, stirred 28 hours under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 6 times deionized waters, remove the Cl ion in the solution, the filter cake that obtains is dry 15h in 110 ℃ of baking ovens earlier;
Three, the filter cake 600 ℃ of roasting 3h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst;
Four; The top Fe/Beta molecular sieve catalyst that obtains is put into the water of 80mL, add the modenite that 2.5g anticipates, in Rotary Evaporators, dry; 600 ℃ of roasting 3h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, the Fe/Beta/Mor molecular sieve composite catalyst of 5g is dissolved in the 70mL deionized water, stir that to add 3mL mass fraction concentration after 30 minutes be 66% red fuming nitric acid (RFNA), and stir after 50 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing applies in the slurries, flood after 3 minutes and take out, blow the raffinate in the most duct; The back 110 ℃ of dry 2h that in air, dry in the shade, roasting 2h under 600 ℃ of air.
4. the preparation method of a Fe molecular sieve composite catalyst is characterized in that, comprises the steps:
One, measure the 250mL deionized water, the Si/Al mol ratio that adds 10g is 15 H-Beta molecular sieve, under 30 ℃ of room temperatures, on magnetic stirring apparatus, stirs 35min, adds 2gFeCl by stoichiometric proportion again
2, stirred 30 hours under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 5 times deionized waters, remove the Cl ion in the solution, the filter cake that obtains is dry 18h in 110 ℃ of baking ovens earlier;
Three, the filter cake 600 ℃ of roasting 4h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst;
Four, the top Fe/Beta molecular sieve catalyst that obtains is put into the water of 100mL, add the modenite that 3g anticipates, in Rotary Evaporators, dry, 600 ℃ of roasting 3h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, 5g Fe/Beta/Mor molecular sieve composite catalyst is dissolved in the 80mL deionized water, stir after 30 minutes that to add 2mL mass fraction concentration be 66% red fuming nitric acid (RFNA), and stir after 30 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing applies in the slurries, flood after 2 minutes and take out, blow the raffinate in the most duct; The back 110 ℃ of dry 3h that in air, dry in the shade, roasting 3h under 600 ℃ of air.
5. the preparation method of a Fe molecular sieve composite catalyst is characterized in that, comprises the steps:
One, measure the 500mL deionized water, adding 15g Si/Al mol ratio is 12.5 H-Beta molecular sieve, under 30 ℃ of room temperatures, on magnetic stirring apparatus, stirs 60min, adds the FeCl of 3g again by stoichiometric proportion
2, stirred 24 hours under the room temperature, carry out ion-exchange;
Two, wash suction filtration with 5 times deionized waters, remove the Cl ion in the solution, the filter cake that obtains is dry 18h in 110 ℃ of baking ovens earlier;
Three, the filter cake 600 ℃ of roasting 3～8h in muffle furnace with drying is crossed obtain the Fe/Beta molecular sieve catalyst;
Four, the top Fe/Beta molecular sieve catalyst that obtains is put into the water of 80mL, add the modenite that 5g anticipates, in Rotary Evaporators, dry, 600 ℃ of roasting 2h in muffle furnace obtain the Fe/Beta/Mor molecular sieve composite catalyst at last;
Five, 5g Fe/Beta/Mor molecular sieve composite catalyst is dissolved in the 70mL deionized water, stir after 10 minutes that to add 3mL mass fraction concentration be 66% red fuming nitric acid (RFNA), and stir after 30 minutes and obtain applying slurries;
Six; The cordierite honeycomb ceramic carrier of anticipating is immersed in the Fe/Beta/Mor molecular sieve composite catalyst for preparing applies in the slurries, flood after 3 minutes and take out, blow the raffinate in the most duct; The back 110 ℃ of dry 5h that in air, dry in the shade, roasting 2h under 650 ℃ of air.
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| US9352277B2 (en) | 2010-06-02 | 2016-05-31 | Johnson Matthey Plc | Diesel particulate filter |
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