CN112717991A - Preparation method and application of Fe and Cu composite molecular sieve catalyst - Google Patents
Preparation method and application of Fe and Cu composite molecular sieve catalyst Download PDFInfo
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- CN112717991A CN112717991A CN202011603112.8A CN202011603112A CN112717991A CN 112717991 A CN112717991 A CN 112717991A CN 202011603112 A CN202011603112 A CN 202011603112A CN 112717991 A CN112717991 A CN 112717991A
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- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 43
- 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 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 65
- 238000000576 coating method Methods 0.000 claims abstract description 65
- 239000002002 slurry Substances 0.000 claims abstract description 46
- 239000003365 glass fiber Substances 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 238000007598 dipping method Methods 0.000 claims abstract description 10
- 238000007654 immersion Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 20
- 238000005342 ion exchange Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000007664 blowing Methods 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001771 vacuum deposition Methods 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 15
- 239000010949 copper Substances 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000002518 antifoaming agent Substances 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000005357 flat glass Substances 0.000 description 6
- 238000003892 spreading Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 210000004911 serous fluid Anatomy 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000712 assembly Effects 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
Images
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
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
-
- B01J35/58—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/402—Dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Abstract
The invention provides a preparation method and application of a Fe and Cu composite molecular sieve catalyst, wherein the preparation method comprises the following steps: s1: manufacturing a glass fiber substrate into a carrier with a preset shape and size; s2: preparing a Fe molecular sieve catalyst; s3, preparing a Cu molecular sieve catalyst; s4, coating and drying the carrier with the preset shape and size by using the slurry in the step S2 by adopting a dipping method, and then coating and drying the carrier with the preset shape and size for the second time by using the slurry in the step S3, and roasting after the coating amount reaches 150g/L and 120-; or, coating and drying the carrier with the preset shape and size by using the slurry in the step S3 by adopting an immersion method, and then coating and drying the carrier with the preset shape and size for the second time by using the slurry in the step S2 until the coating amount reaches 120 g/L and 150g/L, and then roasting to obtain the catalyst finished product. The method widens the activity window of the catalyst, has simpler process and reduces energy consumption.
Description
Technical Field
The invention relates to the technical field of environmental materials for controlling air pollution, in particular to a preparation method and application of a Fe and Cu composite molecular sieve catalyst.
Background
At present, the window of the denitration catalyst is mostly 250-280 ℃, the low-temperature and high-temperature catalytic performance is difficult to achieve basically, the application range of a single catalyst is narrow, the treatment difficulty is high under the working conditions of complex working conditions and large fluctuation of the flue gas temperature, and the standard exceeding emission is easy to cause.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method and application of a Fe and Cu composite molecular sieve catalyst, which broadens the activity window of the catalyst. In order to achieve the purpose, the technical scheme of the invention is as follows:
the preparation method of the Fe and Cu composite molecular sieve catalyst comprises the following steps:
s1: manufacturing a glass fiber substrate into a carrier with a preset shape and size;
s2: preparation of Fe molecular sieve catalyst
Measuring deionized water, adding FeCl according to stoichiometric ratio2Stirring and dissolving at room temperature; adding a molecular sieve, stirring for 4 hours at 70 ℃, carrying out ion exchange, adding an auxiliary agent, and carrying out ball milling to obtain Fe molecular sieve catalyst slurry for later use;
s3 preparation of Cu molecular sieve catalyst
Measuring deionized water, Adding Cu (AC) according to stoichiometric ratio2Stirring and dissolving at room temperature; adding a molecular sieve, stirring for 4 hours at 70 ℃, carrying out ion exchange, adding an auxiliary agent, and carrying out ball milling to obtain Cu molecular sieve catalyst slurry for later use;
s4, coating and drying the carrier with the preset shape and size by using the slurry in the step S2 by adopting a dipping method, and then coating and drying the carrier with the preset shape and size for the second time by using the slurry in the step S3, and roasting after the coating amount reaches 150g/L and 120-;
or, coating and drying the carrier with the preset shape and size by using the slurry in the step S3 by adopting an immersion method, and then coating and drying the carrier with the preset shape and size for the second time by using the slurry in the step S2 until the coating amount reaches 120 g/L and 150g/L, and then roasting to obtain the catalyst finished product.
In the above technical solution, the auxiliary agent in step S2 and step S3 is one or more of resin, ethylene glycol, polyethylene glycol, glycerol, butanol, isobutanol, acetylenes, ethers, silicone, mineral oil, polyethers, polycarboxylates, and polyacrylic acid, and the content is 0.1-10%.
In the technical scheme, the solid content of the slurry in the step S2 and the step S3 is 10-40%, and the content of Fe/Cu is 0.1-10%.
In the technical scheme, the molecular sieve in the step S2 and the step S3 is at least one of ZSM-5, SSZ-13, SAPO-34, MOR and Beta; SiO of the molecular sieve2/Al2O3Is 10-50.
In the technical scheme, the step S4 adopts dipping vacuum coating or dipping dip-coating, and the coating time is 3-30 min.
In the above technical solution, when drying in step S4, at least one of drying in the shade, drying by blowing, drying by hot air, and drying by microwave is selected.
In the above technical scheme, when the step S4 is carried out, the roasting temperature is 300-500 ℃, and the roasting time is 2-24 h.
In the technical scheme, the carrier comprises a plurality of glass fiber paper components which are stacked, each glass fiber paper component comprises a glass fiber paper body and a glass fiber paper substrate which is bonded with the glass fiber paper body, the longitudinal section of each glass fiber paper body is corrugated, each glass fiber paper substrate is flat, and each glass fiber paper body is arranged above the corresponding glass fiber paper substrate.
In the above technical scheme, the length, width, height and size of the carrier are 500mm x 500 mm.
The catalyst prepared by the method is used for selectively catalyzing and reducing nitrogen oxides, and comprises the following steps:
loading a Fe and Cu composite molecular sieve catalyst in a fixed bed reactor, and controlling the reaction temperature to be 150-500 ℃;
step two, ammonia is taken as a reducing agent, the concentration of NOx is 100-1000ppm, the ratio of NH3/NOx is within the range of 1.0-1.1, and the airspeed of gas is controlled to be 10000h-1。
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a nontoxic molecular sieve based catalyst, thereby being green and environment-friendly;
(2) the volume density of the catalyst is reduced by adopting a glass fiber carrier;
(3) the method adopts a mode of directly coating the slurry after the ion exchange of the molecular sieve in one step, and compared with the process of firstly preparing the catalyst powder and then coating, the process is simpler, and the energy consumption is reduced;
(4) and a multi-layer coating mode is adopted, and two layers of active components are different, so that the activity window of the catalyst is widened.
Drawings
FIG. 1 is a schematic perspective view of a catalyst support according to an embodiment of the present invention;
FIG. 2 is a graph showing activity curves of catalysts of examples 1, 2, 3 and 4 of the present invention and comparative examples 1 and 2.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The preparation method of the Fe and Cu composite molecular sieve catalyst provided by the embodiment of the invention comprises the following steps:
step S1: manufacturing a glass fiber substrate into a carrier with a preset shape and size;
step S2: preparation of Fe molecular sieve catalyst
Measuring deionized water, adding FeCl according to stoichiometric ratio2Stirring and dissolving at room temperature; adding a molecular sieve, stirring for 4 hours at 70 ℃, carrying out ion exchange, adding an auxiliary agent, and carrying out ball milling to obtain Fe molecular sieve catalyst slurry for later use;
step S3 preparation of Cu molecular sieve catalyst
Measuring deionized water, Adding Cu (AC) according to stoichiometric ratio2Stirring and dissolving at room temperature; adding a molecular sieve, stirring for 4 hours at 70 ℃, carrying out ion exchange, adding an auxiliary agent, and carrying out ball milling to obtain Cu molecular sieve catalyst slurry for later use;
step S4, coating and drying the carrier with the preset shape and size by using the slurry in the step S2 by adopting a dipping method, and then coating and drying the carrier with the preset shape and size for the second time by using the slurry in the step S3, and roasting after the coating amount reaches 120-150g/L to obtain a catalyst finished product;
or, coating and drying the carrier with the preset shape and size by using the slurry in the step S3 by adopting an immersion method, and then coating and drying the carrier with the preset shape and size for the second time by using the slurry in the step S2 until the coating amount reaches 120 g/L and 150g/L, and then roasting to obtain the catalyst finished product.
In a preferable mode, the auxiliary agent in step S2 and step S3 is one or more of resin, glycol, polyethylene glycol, glycerol, butanol, isobutanol, alkynes, ethers, organic silicon, mineral oil, polyethers, polycarboxylates, and polyacrylic acid, and the content is 0.1-10%.
Preferably, the slurry solids content in step S2 and step S3 is 10-40%, and the Fe/Cu content is 0.1-10%.
Preferably, the molecular sieve in step S2 and step S3 is at least one of ZSM-5, SSZ-13, SAPO-34, MOR and Beta; SiO of the molecular sieve2/Al2O3Is 10-50.
Preferably, the step S4 adopts dipping vacuum coating or dipping dip-coating, and the coating time is 3-30 min.
Preferably, in the step S4, at least one of drying in the shade, drying by blowing, drying by hot air, and drying by microwave is selected.
Preferably, the calcination temperature in the step S4 is 300-.
Preferably, as shown in fig. 1, the carrier includes a plurality of glass fiber paper assemblies 100 arranged in a stacked manner, the glass fiber paper assemblies 100 include a glass fiber paper body 101 and a glass fiber paper substrate 102 bonded to the glass fiber paper body 101, a longitudinal section of the glass fiber paper body 101 is corrugated, the glass fiber paper substrate 102 is flat, and the glass fiber paper body 101 is disposed above the glass fiber paper substrate 102. The length, width and height dimensions of the carrier are 500 mm. The plurality of stacked cellophane assemblies 100 may be integrally connected by bonding.
Example 1
S1 preparation of catalyst carrier
S11, adhering and combining the corrugated glass fiber paper sheet and the flat glass fiber paper substrate together;
s12, spreading and cutting the glass fiber paper into a 500mm cube carrier (figure 1), and placing the carrier in a die for convenient coating;
s2 catalytic module coating
S21, 8.88kg of ferrous chloride and 150kg of water are uniformly stirred, 50kg of ZSM-5 serous fluid is added, and stirring is carried out at 70 ℃ for ion exchange for 4 hours;
s22, adding 25kg of silica sol, 9kg of ammonia water, 0.15kg of 780 dispersing agent and 0.25kg of 670 antifoaming agent into the S21 slurry to increase the coatability of the slurry.
S23, soaking the carrier for 60-120S, taking out, blowing by air, and drying by hot air;
s24, 3.12kg of copper acetate and 150kg of water are evenly stirred, 50kg of SSZ-13 slurry is added, and ion exchange is carried out for 4h under stirring at 70 ℃;
s25, adding 25kg of silica sol, 3kg of ammonia water, 0.15kg of 780 dispersing agent and 0.25kg of 670 antifoaming agent into the S21 slurry to increase the coatability of the slurry.
S26, soaking the carrier for 60-120S, taking out, blowing by air, and drying by hot air;
s27, roasting: roasting at 480 deg.C for 4.0h, and flat-roasting at 5 deg.C/min (100, 200, 300 deg.C, respectively, and holding for 1.0 h).
The total coating amount of the catalyst active coating of the catalytic module prepared by the steps is 157g/L, and the coating effect is better.
Example 2
S1 preparation of catalyst carrier
S11, adhering and combining the corrugated glass fiber paper sheet and the flat glass fiber paper substrate together;
s12, spreading and cutting the glass fiber paper into a 500mm cube carrier (figure 1), and placing the carrier in a die for convenient coating;
s2 catalytic module coating
S21, 3.12kg of copper acetate and 150kg of water are evenly stirred, 50kg of SSZ-13 slurry is added, and ion exchange is carried out for 4h under stirring at 70 ℃;
s22, adding 25kg of silica sol, 3kg of ammonia water, 0.15kg of 780 dispersing agent and 0.25kg of 670 antifoaming agent into the S21 slurry to increase the coatability of the slurry.
S23, soaking the carrier for 60-120S, taking out, blowing by air, and drying by hot air;
s24, 8.88kg of ferrous chloride and 150kg of water are uniformly stirred, 50kg of ZSM-5 serous fluid is added, and stirring is carried out at 70 ℃ for ion exchange for 4 hours;
s25, adding 25kg of silica sol, 9kg of ammonia water, 0.15kg of 780 dispersing agent and 0.25kg of 670 antifoaming agent into the S21 slurry to increase the coatability of the slurry.
S26, soaking the carrier for 60-120S, taking out, blowing by air, and drying by hot air;
s27, roasting: roasting at 480 deg.C for 4.0h, and flat-roasting at 5 deg.C/min (100, 200, 300 deg.C, respectively, and holding for 1.0 h).
The total coating amount of the catalyst active coating of the catalytic module prepared by the steps is 148g/L, and the coating effect is good.
Example 3
S1 preparation of catalyst carrier
S11, adhering and combining the corrugated glass fiber paper sheet and the flat glass fiber paper substrate together;
s12, spreading and cutting the glass fiber paper into a 500mm cube carrier (figure 1), and placing the carrier in a die for convenient coating;
s2 catalytic module coating
S21, 8.88kg of ferrous chloride and 110kg of water are uniformly stirred, 50kg of ZSM-5 serous fluid is added, and stirring is carried out at 70 ℃ for ion exchange for 4 hours;
s22, adding 25kg of silica sol, 9kg of ammonia water, 0.15kg of 780 dispersing agent and 0.25kg of 670 antifoaming agent into the S21 slurry to increase the coatability of the slurry.
S23, soaking the carrier for 60-120S, taking out, blowing by air, and drying by hot air;
s24, roasting: roasting at 480 deg.C for 4.0h, and flat-roasting at 5 deg.C/min (100, 200, 300 deg.C, respectively, and holding for 1.0 h).
The total coating amount of the catalyst active coating of the catalytic module prepared by the steps is 138g/L, and the coating effect is general.
Example 4
S1 preparation of catalyst carrier
S11, adhering and combining the corrugated glass fiber paper sheet and the flat glass fiber paper substrate together;
s12, spreading and cutting the glass fiber paper into a 500mm cube carrier (figure 1), and placing the carrier in a die for convenient coating;
s2 catalytic module coating
S21, 3.12kg of copper acetate and 150kg of water are evenly stirred, 50kg of SSZ-13 slurry is added, and ion exchange is carried out for 4h under stirring at 70 ℃;
s22, adding 25kg of silica sol, 3kg of ammonia water, 0.15kg of 780 dispersing agent and 0.25kg of 670 antifoaming agent into the S21 slurry to increase the coatability of the slurry.
S23, soaking the carrier for 60-120S, taking out, blowing by air, and drying by hot air;
s24, roasting: roasting at 480 deg.C for 4.0h, and flat-roasting at 5 deg.C/min (100, 200, 300 deg.C, respectively, and holding for 1.0 h).
The total coating amount of the catalyst active coating of the catalytic module prepared by the steps is 131g/L, and the coating effect is general.
Comparative example 1
S1 preparation of catalyst carrier
S11, adhering and combining the corrugated glass fiber paper sheet and the flat glass fiber paper substrate together;
s12, spreading and cutting the glass fiber paper into a 500mm cube carrier (figure 1), and placing the carrier in a die for convenient coating;
s2 catalytic module coating
S21, 8.88kg of ferrous chloride and 150kg of water are uniformly stirred, 50kg of ZSM-5 serous fluid is added, and stirring is carried out at 70 ℃ for ion exchange for 4 hours;
s22, adding 25kg of silica sol, 9kg of ammonia water, 0.15kg of 780 dispersing agent and 0.25kg of 670 antifoaming agent into the S21 slurry to increase the coatability of the slurry.
S23, soaking the carrier for 60-120S, taking out, blowing by air, and drying by hot air;
s24, repeating the process of S23, and coating twice to meet the coating requirement;
s25, roasting: roasting at 480 deg.C for 4.0h, and flat-roasting at 5 deg.C/min (100, 200, 300 deg.C, respectively, and holding for 1.0 h).
The total coating amount of the catalyst active coating of the catalytic module prepared by the steps is 152g/L, and the coating effect is good.
Comparative example 2
S1 preparation of catalyst carrier
S11, adhering and combining the corrugated glass fiber paper sheet and the flat glass fiber paper substrate together;
s12, spreading and cutting the glass fiber paper into a 500mm cube carrier (figure 1), and placing the carrier in a die for convenient coating;
s2 catalytic module coating
S21, 3.12kg of copper acetate and 150kg of water are evenly stirred, 50kg of SSZ-13 slurry is added, and ion exchange is carried out for 4h under stirring at 70 ℃;
s22, adding 25kg of silica sol, 3kg of ammonia water, 0.15kg of 780 dispersing agent and 0.25kg of 670 antifoaming agent into the S21 slurry to increase the coatability of the slurry.
S23, soaking the carrier for 60-120S, taking out, blowing by air, and drying by hot air;
s24, repeating the process of S23, and coating twice to meet the coating requirement;
s25, roasting: roasting at 480 deg.C for 4.0h, and flat-roasting at 5 deg.C/min (100 deg.C, 200 deg.C, 300 deg.C, respectively for 1.0 h).
The total coating amount of the catalyst active coating of the catalytic module prepared by the steps is 145g/L, and the coating effect is good.
Test example
And (4) taking a small sample for testing the low-temperature SCR catalyst sample. Sample size: at the program temperature, the inlet and outlet concentrations of the catalyst before and after the reaction were measured by a flue gas analyzer, and the catalytic activity of the low-temperature SCR catalyst was calculated as shown in fig. 2.
And (3) testing conditions are as follows: NOx 1000mg/m3Ammonia nitrogen molar ratio is 1:1, O2vol% 6%, space velocity SV 10000h-1。
The catalytic modules of examples 1-4 and comparative examples 1-2 were tested for NOx conversion efficiency under the test conditions shown in table 1.
TABLE 1
It should be noted that the features of the above embodiments and examples may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
- A preparation method of a Fe and Cu composite molecular sieve catalyst is characterized by comprising the following steps:s1: manufacturing a glass fiber substrate into a carrier with a preset shape and size;s2: preparation of Fe molecular sieve catalystMeasuring deionized water, adding FeCl according to stoichiometric ratio2Stirring and dissolving at room temperature; adding a molecular sieve, stirring for 4 hours at 70 ℃, carrying out ion exchange, adding an auxiliary agent, and carrying out ball milling to obtain Fe molecular sieve catalyst slurry for later use;s3 preparation of Cu molecular sieve catalystMeasuring deionized water, Adding Cu (AC) according to stoichiometric ratio2Stirring and dissolving at room temperature; adding a molecular sieve, stirring for 4 hours at 70 ℃, carrying out ion exchange, adding an auxiliary agent, and carrying out ball milling to obtain Cu molecular sieve catalyst slurry for later use;s4, coating and drying the carrier with the preset shape and size by using the slurry in the step S2 by adopting a dipping method, and then coating and drying the carrier with the preset shape and size for the second time by using the slurry in the step S3, and roasting after the coating amount reaches 150g/L and 120-;or, coating and drying the carrier with the preset shape and size by using the slurry in the step S3 by adopting an immersion method, and then coating and drying the carrier with the preset shape and size for the second time by using the slurry in the step S2 until the coating amount reaches 120 g/L and 150g/L, and then roasting to obtain the catalyst finished product.
- 2. The method for preparing the Fe and Cu composite molecular sieve catalyst according to claim 1, wherein the auxiliary agent in the step S2 and the step S3 is one or more of resin, glycol, polyethylene glycol, glycerol, butanol, isobutanol, alkynes, ethers, organic silicon, mineral oil, polyethers, polycarboxylates and polyacrylic acid, and the content of the auxiliary agent is 0.1-10%.
- 3. The method of claim 1, wherein the slurry has a solid content of 10-40% and a Fe/Cu content of 0.1-10% in steps S2 and S3.
- 4. The method of preparing a Fe and Cu composite molecular sieve catalyst according to claim 1, wherein the molecular sieve in step S2 and step S3 is at least one of ZSM-5, SSZ-13, SAPO-34, MOR and Beta; SiO of the molecular sieve2/Al2O3Is 10-50.
- 5. The method for preparing the Fe and Cu composite molecular sieve catalyst according to claim 1, wherein the step S4 coating is a dipping vacuum coating or a dipping dip-coating, and the coating time is 3-30 min.
- 6. The method of claim 1, wherein the drying in step S4 is performed by at least one of drying in the shade, drying by blowing air, drying by hot air, and drying by microwave.
- 7. The method for preparing the Fe and Cu composite molecular sieve catalyst according to claim 1, wherein the calcination temperature is 300-500 ℃ and the calcination time is 2-24 h in the calcination step S4.
- 8. The preparation method of the Fe and Cu composite molecular sieve catalyst according to any one of claims 1 to 7, wherein the carrier comprises a plurality of glass fiber paper components which are stacked, each glass fiber paper component comprises a glass fiber paper body and a glass fiber paper substrate which is bonded with the glass fiber paper body, the longitudinal section of each glass fiber paper body is corrugated, each glass fiber paper substrate is flat, and each glass fiber paper body is arranged above the corresponding glass fiber paper substrate.
- 9. The method of claim 8, wherein the length, width, and height dimensions of the support are 500 mm.
- 10. The catalyst prepared according to the method of claim 1 for selective catalytic reduction of nitrogen oxides, comprising the steps of:loading a Fe and Cu composite molecular sieve catalyst in a fixed bed reactor, and controlling the reaction temperature to be 150-500 ℃;step two, ammonia is taken as a reducing agent, the concentration of NOx is 100-1000ppm, the ratio of NH3/NOx is within the range of 1.0-1.1, and the airspeed of gas is controlled to be 10000h-1。
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