CN105413740A - High-efficiency Fe-SCR integrated catalyst preparation method - Google Patents
High-efficiency Fe-SCR integrated catalyst preparation method Download PDFInfo
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- CN105413740A CN105413740A CN201510753894.6A CN201510753894A CN105413740A CN 105413740 A CN105413740 A CN 105413740A CN 201510753894 A CN201510753894 A CN 201510753894A CN 105413740 A CN105413740 A CN 105413740A
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- molecular sieve
- boehmite
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 79
- 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 75
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 239000002002 slurry Substances 0.000 claims abstract description 40
- 238000005342 ion exchange Methods 0.000 claims abstract description 37
- 239000007767 bonding agent Substances 0.000 claims abstract description 27
- 230000032683 aging Effects 0.000 claims abstract description 25
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000003618 dip coating Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 57
- 239000008236 heating water Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- 229910001593 boehmite Inorganic materials 0.000 claims description 24
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 24
- 238000009413 insulation Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000001935 peptisation Methods 0.000 claims description 8
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- 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 group [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 description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 239000000243 solution Substances 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000003303 reheating Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- -1 stir Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010457 zeolite 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
- B01J29/70—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
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—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
- B01J29/40—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
- B01J29/76—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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a high-efficiency Fe-SCR integrated catalyst preparation method. The method includes: using a Fe source for preparation to obtain an exchange solution, adding a molecular sieve into the exchange solution to realize ion exchange, and drying and roasting to obtain a high-exchange-capacity molecular sieve; well mixing pseudo-boehmite in deionized water, slowly adding nitric acid, and adding nanometer SiO2 powder to regulate a pH value after the pseudo-boehmite is peptized completely; reheating in water bath and ageing to obtain an aluminum-silicon compound adhesive serving as a bonding agent, adding the exchanged Fe molecular sieve into an aqueous solution of the bonding agent to prepare a slurry solution, and stirring for 3h; loading the slurry solution to a carrier to obtain a Fe-SCR integrated catalyst according to a dip coating method. The high-efficiency Fe-SCR integrated catalyst preparation method is simple and easy to operate; since the bonding agent is prepared by mixture of the pseudo-boehmite and the nanometer SiO2 powder, adhesive power of the Fe-SCR integrated catalyst can be increased, and low-temperature catalytic performance of the catalyst can be improved.
Description
Technical field
The present invention relates to a kind of preparation method of efficient Fe-SCR integral catalyzer, belong to catalyst preparation technical field.
Background technology
Molecular sieve forms primarily of elements such as Si, Al, P, H and O, has uniform microcellular structure, these uniform holes can the inside of the ionic adsorption less than its diameter to vestibule, molecular sieve has the features such as heat endurance is high, acidity is strong due to it, and is widely used in PETROLEUM PROCESSING and chemical industry catalytic field.Suitable acidity and pore passage structure, be particularly suitable for motor-vehicle tail-gas nitrous oxides selectivity catalytic reduction (NOx-SCR) reaction.Industrial normal selection molecular sieve, as carrier, adopts ion exchange technique to have the copper (Cu) of catalytic action, iron (Fe) isoreactivity Metal Supported on framework of molecular sieve.Wherein, Y, ZSM-5, Beta equimolecular sieve of load Fe shows good catalytic activity in motor-vehicle tail-gas NOx eliminates, and can be used as the catalyst meeting state V and above diesel vehicle NOx emission standard.The molecular sieve coating technology and the paint-on technique that comprise bonding agent are the key points realizing the overall reducing property of its efficient NOx.
Industrial normal selection molecular sieve, as carrier, adopts ion exchange technique comparatively to have the ion-exchange of catalytic action on framework of molecular sieve.In molecular sieve exchange process, depositing the key point limiting its large-scale application in the application is at present that its ion exchange capacity is not high, and the not high decline directly causing catalytic performance of ion exchange capacity, also can cause the raising of NOx-SCR holistic cost simultaneously.
Catalytic field is eliminated, normal employing integral catalyzer form at motor vehicle NOx.In the preparation of Fe based molecular sieve SCR integral catalyzer, the poor and molecular sieve poor performance at low temperatures of the adhesive force of coating limits the application of Fe-SCR always.Coating adhesion difference not only directly causes the sharply decline of catalytic performance, also can cause the increase of diesel vehicle particle (PM) simultaneously; Bonding agent not only affects the adhesive force of coating, also affects the low-temperature catalytic activity of catalyst simultaneously; Although the bonding agent of high-adhesion energy improves adhesive force, to sacrifice catalyst low-temperature catalytic activity for cost.Therefore, raising Fe-SCR integral catalyzer adhesive force and low-temperature catalytic activity have very great meaning.
The object of this invention is to provide one and there is comparatively high adhesion force, there is the Fe-SCR integral catalyzer of excellent catalysts catalytic performance.
Summary of the invention
The object of the invention is to solve in prior art the coating problem when the preparation of Fe based molecular sieve SCR integral catalyzer, provide the preparation method that a kind of preparation method is simple, step is easy to a kind of efficient Fe-SCR integral catalyzer operated, the Fe-SCR integral catalyzer adhesive force prepared improves, excellent catalytic effect.
The present invention adopts following technical scheme: a kind of preparation method of efficient Fe-SCR integral catalyzer, comprises the steps:
(1) molecular sieve ion-exchange:
A. Fe source is added to deionized water for stirring even, heating water bath to 30 ~ 50 DEG C, treat that Fe source is dissolved completely and make exchange liquid, be 0.1 ~ 0.8 according to Fe source and molecular sieve mass ratio, in exchange liquid, add molecular sieve, continue to be heated to 60 ~ 90 DEG C, stir 1 ~ 5h and carry out ion-exchange;
B. after ion-exchange terminates, exchange liquid cooling is but passed in filter press and washs, after eluate is colourless, molecular sieve is put into baking oven stand-by in 100 ~ 120 DEG C of oven dry 1 ~ 5h;
C. dried molecular sieve is put into roasting kiln roasting, after roasting terminates, be cooled to room temperature, obtain Fe molecular sieve;
(2) boehmite is added in deionized water fully stirs, according to H
+/ boehmite mol ratio is 0.1 ~ 0.8, slowly adds the HNO that mass concentration is 1 ~ 5%
3solution, after the complete peptization of boehmite, heating water bath to 65 ~ 90 DEG C, insulation 2 ~ 6h, ageing 10 ~ 20h, obtains Pseudo-boehmite;
(3) by same for the Pseudo-boehmite after ageing Nano-meter SiO_2
2powder mixes, and at the uniform velocity stirs, and adopts mass concentration to be the HNO of 1 ~ 5%
3solution adjust ph to 3 ~ 5, heating water bath to 65 ~ 90 DEG C, insulation 2 ~ 5h, after ageing 2 ~ 8h, obtains bonding agent;
(4) bonding agent is mixed with the slurries that mass fraction is 30 ~ 50%, be added to by Fe molecular sieve in slurries and stir 1 ~ 3h, being milled to grain graininess size through ball mill is 2 ~ 20 μm;
(5) by carrier impregnation in slurries, dip time is 2 ~ 10s, then lifts with the speed of 2 ~ 10cm/min, is got by unnecessary slurries, after carrier drying, is warming up to 400 ~ 600 DEG C of roasting 1 ~ 3h.
Further, described source of iron is FeCl
3, Fe (NO
3)
3or Fe
2(SO
4)
3one or several.
Further, described carrier is cordierite or stainless steel carrier.
Further, described colloidal sol heating water bath adopts Temperature Programmed Processes, and heating rate scope is 2 ~ 10 DEG C/min, and bath temperature is 70 ~ 85 DEG C.
Further, the mol ratio of the Al/Si in described bonding agent is 0.1 ~ 0.5.
Further, in described slurries, bonding agent solid content accounts for 5 ~ 15% of Fe molecular sieve quality.
Further, described molecular sieve is one or more in Y, ZSM-5, Beta, SSZ-13 or SAPO-34.
Further, can repeatedly in dip-coating procedure in described step (6), until be coated to targeted coating amount.
Further, during the roasting of described step (1) Middle molecule sieve, roaster is warming up to 450 ~ 650 DEG C with the speed of 1 ~ 6 DEG C/min, insulation 1 ~ 5h.
Preparation method of the present invention is simple, and step is easy to operation, adopts the same Nano-meter SiO_2 of Pseudo-boehmite
2powder two kinds of materials are mixed with out bonding agent, can improve the adhesive force of Fe-SCR integral catalyzer, improve catalyst catalytic performance at low temperatures.
Accompanying drawing explanation
Fig. 1 is Fe-SCR integral catalyzer catalytic effect figure prepared by the embodiment of the present invention one.
Fig. 2 is the embodiment of the present invention one gained Fe molecular sieve ion exchange capacity experimental result.
Fig. 3 is the embodiment of the present invention one gained Fe-SCR integral catalyzer expulsion rate experimental result.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment one: a kind of preparation method of efficient Fe-SCR integral catalyzer, comprises the steps:
(1) Fe molecular sieve ion exchange technique
A. by FeCl
3be added in deionized water and mix, heating water bath to 50 DEG C, treat FeCl
3dissolving completely and obtain exchanging liquid, is 0.5 according to Fe source/beta-molecular sieve mass ratio, and in exchange liquid, add beta-molecular sieve, continue to be warming up to 90 DEG C, uniform stirring 5h carries out ion-exchange;
B. after ion-exchange completes, exchange liquid cooling is but passed in filter press afterwards and washs, after eluate is colourless, molecular sieve is placed in baking oven stand-by in 120 DEG C of oven dry 5h.
C. dried molecular sieve is put into roaster, be warming up to 450 DEG C with the speed of 2 DEG C/min, insulation 1h, stand-by with stove cooling, obtain Fe molecular sieve.
(2) boehmite is fully stirred in deionized water, according to H
+/ boehmite mol ratio is 0.6, slowly adds the HNO that mass concentration is 4%
3solution, after the complete peptization of boehmite, heating water bath to 80 DEG C, insulation 4h, ageing 15h, obtains Pseudo-boehmite;
(3) by same for the Pseudo-boehmite after ageing Nano-meter SiO_2
2powder mixes, and make the mol ratio of Al/Si be 9, adjust ph is 3, at the uniform velocity stirs, heating water bath to 80 DEG C, and insulation 2h, obtains bonding agent after ageing 3h
(4) bonding agent is mixed with the slurries that mass fraction is 35%, is added in slurries by Fe molecular sieve and stirs 2h, being milled to grain graininess size through ball mill is 10 μm;
(5) get carrier impregnation in slurries, dip time is 10s, then lifts with the speed of 10cm/min, gets by unnecessary slurries, after the carrier flooded is carried out drying, is warming up to 600 DEG C of roasting 3h.
(6) can repeatedly in Fe-SCR integral catalyzer dip-coating procedure, until be coated to targeted coating amount.
Comparative example: a kind of preparation method of Fe-SCR integral catalyzer, comprises the steps:
(1) molecular sieve ion-exchange:
A. according to mass percent FeCl
35%, beta-molecular sieve 30%, water 65% are mixed with exchange liquid, 80 DEG C of heating water baths, stir 2h and carry out ion-exchange;
B. after ion-exchange terminates, liquid washing will be exchanged, after washing out unnecessary Fe ion, molecular sieve be put into baking oven stand-by in 120 DEG C of oven dry 2h, Fe molecular sieve;
C. dried molecular sieve is put into roasting kiln roasting, after roasting terminates, be cooled to room temperature;
(2) conventional Al glue is mixed with the slurries that mass fraction is 35%, is added in slurries by Fe molecular sieve and stirs 2h, being milled to grain graininess size through ball mill is 10 μm;
(5) by carrier impregnation in slurries, dip time is 10s, then lifts with the speed of 10cm/min, is got by unnecessary slurries, after carrier drying, is warming up to 450 DEG C of roasting 2h;
(6) can repeatedly in Fe-SCR integral catalyzer dip-coating procedure, until be coated to targeted coating amount.
Fig. 1 is Fe-SCR integral catalyzer catalytic effect figure, and detect and adopt AVL experiment instrument to detect, air speed is 35000, NOx350ppm, NH
3350ppm, the T80 temperature of Fe-SCR integral catalyzer prepared by embodiment one is about 200 DEG C, and in comparative example, adopt traditional preparation methods, T80 appears at 260 DEG C, the low-temperature catalyzed performance optimization about 60 DEG C of the Fe-SCR integral catalyzer that embodiment one is prepared compared with comparative example, and catalytic efficiency is very stable.
Fig. 2 is the contrast of comparative example intermediate ion exchange and embodiment one ion exchange capacity adopting ICP to detect, and the Fe ion exchange capacity of result display embodiment one is obviously greater than comparative example.
Fig. 3 is Fe-SCR integral catalyzer expulsion rate experimental result, integral catalyzer expulsion rate prepared by result display embodiment one is 0.5%, and the integral catalyzer expulsion rate of comparative example is 5.8%, obviously can finds out and adopt preparation method's adhesive force of the present invention to have great lifting.
Embodiment two: a kind of preparation method of efficient Fe-SCR integral catalyzer, comprises the steps:
(1) molecular sieve ion-exchange:
A. by FeCl
3be added in deionized water, stir, heating water bath to 50 DEG C, treating that Fe source is dissolved completely and make exchange liquid, is 0.6 according to Fe source/beta-molecular sieve mass ratio, adds beta-molecular sieve, continue to be heated to 80 DEG C in exchange liquid, stirs 5h and carries out ion-exchange;
B. after ion-exchange terminates, exchange liquid cooling but passed in filter press and wash, after eluate is colourless, molecular sieve is put into baking oven, 120 DEG C of oven dry 5h are stand-by;
C. dried molecular sieve is put into roasting kiln roasting, after roasting terminates, be cooled to room temperature, obtain Fe molecular sieve;
(2) boehmite is added in deionized water fully stirs, according to H
+/ boehmite mol ratio is 0.6, slowly adds the HNO that mass concentration is 3%
3solution, after the complete peptization of boehmite, heating water bath to 80 DEG C, insulation 4h, ageing 15h, obtains Pseudo-boehmite;
(3) by same for the Pseudo-boehmite after ageing Nano-meter SiO_2
2powder mixes, and at the uniform velocity stirs, and employing mass concentration is the HNO3 solution adjust ph to 3 of 3%, heating water bath to 80 DEG C, and insulation 3h, after ageing 8h, obtains bonding agent;
(4) bonding agent is mixed with the slurries that mass fraction is 35%, is added in slurries by Fe molecular sieve and stirs 2h, being milled to grain graininess size through ball mill is 10 μm;
(5) by carrier impregnation in slurries, dip time is 10s, then lifts with the speed of 10cm/min, is got by unnecessary slurries, after carrier drying, is warming up to 450 DEG C of roasting 2h;
(6) can repeatedly in Fe-SCR integral catalyzer dip-coating procedure, until be coated to targeted coating amount.
Embodiment three: a kind of preparation method of efficient Fe-SCR integral catalyzer, comprises the steps:
(1) molecular sieve ion-exchange:
A. by Fe (NO
3)
3be added in deionized water, stir, heating water bath to 50 DEG C, treat Fe (NO
3)
3dissolving completely and make exchange liquid, is 0.7 according to Fe source/SSZ-13 molecular sieve mass ratio, adds molecular sieve, continue to be heated to 90 DEG C in exchange liquid, stirs 5h and carries out ion-exchange;
B. after ion-exchange terminates, exchange liquid cooling is but passed in filter press and washs, after eluate is colourless, molecular sieve is put into baking oven stand-by in 120 DEG C of oven dry 6h;
C. dried molecular sieve is put into roasting kiln roasting, after roasting terminates, be cooled to room temperature, obtain Fe molecular sieve;
(2) boehmite is added in deionized water fully stirs, according to H
+/ boehmite mol ratio is 0.6, slowly adds the HNO that mass concentration is 4%
3solution, after the complete peptization of boehmite, heating water bath to 90 DEG C, insulation 4h, ageing 15h, obtains Pseudo-boehmite;
(3) by same for the Pseudo-boehmite after ageing Nano-meter SiO_2
2powder mixes, and at the uniform velocity stirs, and adopts mass concentration to be the HNO of 4%
3solution adjust ph to 3, heating water bath to 80 DEG C, insulation 3h, after ageing 8h, obtains bonding agent;
(4) bonding agent is mixed with the slurries that mass fraction is 35%, is added in slurries by Fe molecular sieve and stirs 2h, being milled to grain graininess size through ball mill is 10 μm;
(5) by carrier impregnation in slurries, dip time is 10s, then lifts with the speed of 10cm/min, is got by unnecessary slurries, after carrier drying, is warming up to 550 DEG C of roasting 2h;
(6) can repeatedly in Fe-SCR integral catalyzer dip-coating procedure, until be coated to targeted coating amount.
Embodiment four: a kind of preparation method of efficient Fe-SCR integral catalyzer, comprises the steps:
(1) molecular sieve ion-exchange:
A. by Fe (NO
3)
3be added in deionized water, stir, heating water bath to 60 DEG C, treat Fe (NO
3)
3dissolving completely and make exchange liquid, is 0.5 according to Fe source/ZSM-5 molecular sieve mass ratio, adds molecular sieve, continue to be heated to 90 DEG C in exchange liquid, stirs 4h and carries out ion-exchange;
B. after ion-exchange terminates, exchange liquid cooling but passed in filter press and wash, after eluate is colourless, molecular sieve is put into baking oven, 110 DEG C of oven dry 6h are stand-by;
C. dried molecular sieve is put into roasting kiln roasting, after roasting terminates, be cooled to room temperature, obtain Fe molecular sieve;
(2) boehmite is added in deionized water fully stirs, according to H
+/ boehmite mol ratio is 0.8, slowly adds the HNO that mass concentration is 5%
3solution, after the complete peptization of boehmite, heating water bath to 80 DEG C, insulation 4h, ageing 15h, obtains Pseudo-boehmite;
(3) by same for the Pseudo-boehmite after ageing Nano-meter SiO_2
2powder mixes, and at the uniform velocity stirs, and adopts mass concentration to be the HNO of 4%
3solution adjust ph to 4, heating water bath to 80 DEG C, insulation 3h, after ageing 8h, obtains bonding agent;
(4) bonding agent is mixed with the slurries that mass fraction is 35%, is added in slurries by Fe molecular sieve and stirs 2h, being milled to grain graininess size through ball mill is 20 μm;
(5) by carrier impregnation in slurries, dip time is 8s, then lifts with the speed of 6cm/min, is got by unnecessary slurries, after carrier drying, is warming up to 600 DEG C of roasting 2h;
(6) can repeatedly in Fe-SCR integral catalyzer dip-coating procedure, until be coated to targeted coating amount.
Embodiment five: a kind of preparation method of efficient Fe-SCR integral catalyzer, comprises the steps:
(1) molecular sieve ion-exchange:
A. by Fe (NO
3)
3be added in deionized water, stir, heating water bath to 40 DEG C, treat Fe (NO
3)
3dissolving completely and make exchange liquid, is 0.65 according to Fe source/SAPO-34 molecular sieve mass ratio, adds molecular sieve, continue to be heated to 65 DEG C in exchange liquid, stirs 1h and carries out ion-exchange;
B. after ion-exchange terminates, exchange liquid cooling but passed in filter press and wash, after eluate is colourless, molecular sieve is put into baking oven, 100 DEG C of oven dry 1h are stand-by;
C. dried molecular sieve is put into roasting kiln roasting, after roasting terminates, be cooled to room temperature, obtain Fe molecular sieve;
(2) boehmite is added in deionized water fully stirs, according to H
+/ boehmite mol ratio is 0.2, slowly adds the HNO that mass concentration is 5%
3solution, after the complete peptization of boehmite, heating water bath to 65 DEG C, insulation 2h, ageing 10h, obtains Pseudo-boehmite;
(3) by same for the Pseudo-boehmite after ageing Nano-meter SiO_2
2powder mixes, and at the uniform velocity stirs, and adopts mass concentration to be the HNO of 5%
3solution adjust ph to 5, heating water bath to 75 DEG C, insulation 2h, after ageing 2h, obtains bonding agent;
(4) bonding agent is mixed with the slurries that mass fraction is 30%, is added in slurries by Fe molecular sieve and stirs 1h, being milled to grain graininess size through ball mill is 2 μm;
(5) by carrier impregnation in slurries, dip time is 5s, then lifts with the speed of 5cm/min, is got by unnecessary slurries, after carrier drying, is warming up to 500 DEG C of roasting 2h;
(6) can repeatedly in Fe-SCR integral catalyzer dip-coating procedure, until be coated to targeted coating amount.
Embodiment six: a kind of preparation method of efficient Fe-SCR integral catalyzer, comprises the steps:
(1) molecular sieve ion-exchange:
A. by Fe
2(SO
4)
3be added in deionized water, stir, heating water bath to 35 DEG C, treat Fe
2(SO
4)
3dissolving completely and make exchange liquid, is 0.8 according to Fe source/y-zeolite mass ratio, adds molecular sieve, continue to be heated to 60 DEG C in exchange liquid, stirs 3h and carries out ion-exchange;
B. after ion-exchange terminates, exchange liquid cooling but passed in filter press and wash, after eluate is colourless, molecular sieve is put into baking oven, 120 DEG C of oven dry 2h are stand-by;
C. dried molecular sieve is put into roasting kiln roasting, after roasting terminates, be cooled to room temperature, obtain Fe molecular sieve;
(2) boehmite is added in deionized water fully stirs, according to H
+/ boehmite mol ratio is 0.6, slowly adds the HNO that mass concentration is 5%
3solution, after the complete peptization of boehmite, heating water bath to 75 DEG C, insulation 4h, ageing 15h, obtains Pseudo-boehmite;
(3) by same for the Pseudo-boehmite after ageing Nano-meter SiO_2
2powder mixes, and at the uniform velocity stirs, and adopts mass concentration to be the HNO of 5%
3solution adjust ph to 4, heating water bath to 65 DEG C, insulation 2h, after ageing 8h, obtains bonding agent;
(4) bonding agent is mixed with the slurries that mass fraction is 50%, is added in slurries by Fe molecular sieve and stirs 3h, being milled to grain graininess size through ball mill is 20 μm;
(5) by carrier impregnation in slurries, dip time is 10s, then lifts with the speed of 10cm/min, is got by unnecessary slurries, after carrier drying, is warming up to 600 DEG C of roasting 3h;
(6) can repeatedly in Fe-SCR integral catalyzer dip-coating procedure, until be coated to targeted coating amount.
Claims (9)
1. a preparation method for efficient Fe-SCR integral catalyzer, is characterized in that: comprise the steps: (1) molecular sieve ion-exchange:
A. Fe source is added to deionized water for stirring even, heating water bath to 30 ~ 50 DEG C, treat that Fe source is dissolved completely and make exchange liquid, are 0.1 ~ 0.8 add molecular sieve exchanging in liquid according to Fe source and molecular sieve mass ratio, continue to be heated to 60 ~ 90 DEG C, stir 1 ~ 5h and carry out ion-exchange;
B. after ion-exchange terminates, exchange liquid cooling is but passed in filter press afterwards and washs, after eluate is colourless, molecular sieve is put into baking oven stand-by in 100 ~ 120 DEG C of oven dry 1 ~ 5h;
C. dried molecular sieve is put into roasting kiln roasting, after roasting terminates, be cooled to room temperature, obtain Fe molecular sieve;
(2) boehmite is added in deionized water fully stirs, according to H
+/ boehmite mol ratio is 0.1 ~ 0.8, slowly adds the HNO that mass concentration is 1 ~ 5%
3solution, after the complete peptization of boehmite, heating water bath to 65 ~ 90 DEG C, insulation 2 ~ 6h, ageing 10 ~ 20h, obtains Pseudo-boehmite;
(3) by same for the Pseudo-boehmite after ageing Nano-meter SiO_2
2powder mixes, and at the uniform velocity stirs, and adopts mass concentration to be the HNO of 1 ~ 5%
3solution adjust ph to 3 ~ 5, heating water bath to 65 ~ 90 DEG C, insulation 2 ~ 5h, after ageing 2 ~ 8h, obtains bonding agent;
(4) bonding agent is mixed with the slurries that mass fraction is 30 ~ 50%, be added to by Fe molecular sieve in slurries and stir 1 ~ 3h, being milled to grain graininess size through ball mill is 2 ~ 20 μm;
(5) by carrier impregnation in slurries, dip time is 2 ~ 10s, then lifts with the speed of 2 ~ 10cm/min, is got by unnecessary slurries, after carrier drying, is warming up to 400 ~ 600 DEG C of roasting 1 ~ 3h.
2. the preparation method of efficient Fe-SCR integral catalyzer as claimed in claim 1, is characterized in that: described source of iron is FeCl
3, Fe (NO
3)
3or Fe
2(SO
4)
3one or several.
3. the preparation method of efficient Fe-SCR integral catalyzer as claimed in claim 1, is characterized in that: described carrier is cordierite or stainless steel carrier.
4. the preparation method of efficient Fe-SCR integral catalyzer as claimed in claim 1, is characterized in that: in described step (3), heating water bath adopts Temperature Programmed Processes, and heating rate scope is 2 ~ 10 DEG C/min, and bath temperature is 70 ~ 85 DEG C.
5. the preparation method of efficient Fe-SCR integral catalyzer as claimed in claim 1, is characterized in that: the mol ratio of the Al/Si in described bonding agent is 0.1 ~ 0.5.
6. the preparation method of efficient Fe-SCR integral catalyzer as claimed in claim 1, is characterized in that: in described slurries, bonding agent solid content accounts for 5 ~ 15% of Fe molecular sieve quality.
7. the preparation method of efficient Fe-SCR integral catalyzer as claimed in claim 1, is characterized in that: described molecular sieve is one or more in Y, ZSM-5, Beta, SSZ-13 or SAPO-34.
8. the preparation method of efficient Fe-SCR integral catalyzer as claimed in claim 1, is characterized in that: can repeatedly in dip-coating procedure in described step (6), until be coated to targeted coating amount.
9. the preparation method of efficient Fe-SCR integral catalyzer as claimed in claim 1, is characterized in that: during the roasting of described step (1) Middle molecule sieve, roaster is warming up to 450 ~ 650 DEG C with the speed of 1 ~ 6 DEG C/min, insulation 1 ~ 5h.
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