CN111375445A - Preparation method and application of molecular sieve-loaded manganese-based denitration catalyst - Google Patents
Preparation method and application of molecular sieve-loaded manganese-based denitration catalyst Download PDFInfo
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- CN111375445A CN111375445A CN201811637619.8A CN201811637619A CN111375445A CN 111375445 A CN111375445 A CN 111375445A CN 201811637619 A CN201811637619 A CN 201811637619A CN 111375445 A CN111375445 A CN 111375445A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 239000011572 manganese Substances 0.000 title claims abstract description 99
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 73
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 71
- 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 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003446 ligand Substances 0.000 claims abstract description 30
- 150000002696 manganese Chemical class 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
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- 238000011068 loading method Methods 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
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- 229910021529 ammonia Inorganic materials 0.000 claims description 4
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
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- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical compound C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 claims description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- ZQHKAIDDHTYINE-UHFFFAOYSA-J disodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;manganese(2+) Chemical compound [Na+].[Na+].[Mn+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O ZQHKAIDDHTYINE-UHFFFAOYSA-J 0.000 claims 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 241000894007 species Species 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- VHBSECWYEFJRNV-UHFFFAOYSA-N 2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1O.OC(=O)C1=CC=CC=C1O VHBSECWYEFJRNV-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISTIEXLDUGQAAO-UHFFFAOYSA-J [Mn+4].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O Chemical compound [Mn+4].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O ISTIEXLDUGQAAO-UHFFFAOYSA-J 0.000 description 1
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 description 1
- RIPZIAOLXVVULW-UHFFFAOYSA-N pentane-2,4-dione Chemical compound CC(=O)CC(C)=O.CC(=O)CC(C)=O RIPZIAOLXVVULW-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
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- 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]
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention discloses a preparation method of a molecular sieve-supported manganese-based denitration catalyst, which comprises the steps of mixing a molecular sieve, a soluble aqueous solution of manganese salt and a ligand to form a mixed solution, enabling the electric properties of a complex formed by the molecular sieve, the manganese salt and the ligand to be opposite, and carrying out electrostatic adsorption on the mixed solution to obtain the molecular sieve-supported manganese-based denitration catalyst. The molecular sieve loaded manganese-based denitration catalyst prepared by the invention has uniform particle size of active components and uniform distribution of the active components on the surface of a carrier, and is particularly suitable for removing nitric oxides.
Description
Technical Field
The invention relates to a molecular sieve catalyst, in particular to a preparation method and application of a molecular sieve-loaded manganese-based denitration catalyst.
Background
With the increase of the consumption of Chinese coal and the keeping quantity of motor vehicles, NOxThe amount of emissions of (a) rapidly rises, and environmental problems caused thereby are increasing. NOxGreat harm to human body and environment: can cause harm to the respiratory system of human body, form acid rain and photochemical smog, and participate in destroying the ozone layer. At present, NO is removedxMainly comprising NOxDirect catalytic decomposition of NOxStorage-reduction catalytic purification (NSR), plasma technology, non-catalytic selective reduction (SNCR), and Selective Catalytic Reduction (SCR), among others.
Selective catalytic reduction for removal of NOxCan remove NO betterxIs a mainstream technology which has been successfully used in recent years and is based on NH3Selective addition of NO as a reducing agentxReduction to N2. According to NOxFrom different sources, can remove NO by selective catalytic reductionxThe technology of (1) is divided into a fixed source and a mobile source. The stationary source is primarily a coal-fired power plant, and the catalyst currently in commercial use is V2O5+WO3/TiO2The active temperature window of the catalyst is within 300-400 ℃, and the temperature of ash and SO2The SCR device is easy to inactivate in high environmental property, and if the SCR device is placed in a dust removal and desulfurization device, the temperature of flue gas is reduced to below 200 ℃, so that the catalyst is difficult to play a role. The mobile source mainly refers to a motor vehicle, and along with the gradual upgrade of the emission regulations of the motor vehicle, the emission of the engine under the working conditions of low speed and low load is more severe, which means that higher requirements are put on the low-temperature performance of the SCR catalyst.
Removal of NO for enhanced catalytic reductionxThe catalyst performance and the production cost are reduced, Chinese patents CN103157505B and CN103601211B report Cu-SSZ-13 molecular sieves,the ignition temperature of the catalyst is higher than 150 ℃, the temperature range of NOx conversion rate higher than 80% is up to 225-400 ℃, and the requirement of increasingly severe national emission standard can not be completely met.
Therefore, it is necessary to remove NO by selective catalytic reductionxThe catalyst of (3) is subjected to further technical improvements.
Disclosure of Invention
The present inventors removed NO in selective catalytic reductionxThe research of the catalyst creatively discovers that the size and the distribution form of the active components in the molecular sieve loaded manganese-based denitration catalyst have a crucial influence on the ignition temperature, and if the particle size of the active components is uneven, the distribution of the active components on the surface of the carrier is uneven, the activity and the ignition temperature of the molecular sieve loaded manganese-based denitration catalyst are influenced.
The application aims to provide a preparation method of a molecular sieve-loaded manganese-based denitration catalyst, which comprises the following steps:
(1) mixing a soluble aqueous solution of a molecular sieve and a manganese salt with a ligand to form a mixed solution, and enabling the electric property of a complex formed by the molecular sieve, the manganese salt and the ligand to be opposite;
(2) and (3) carrying out electrostatic adsorption on the mixed solution, and washing, drying and roasting to obtain the molecular sieve-loaded manganese-based denitration catalyst.
The invention also provides application of the molecular sieve loaded manganese-based denitration catalyst, which is used for removing nitrogen oxides.
The molecular sieve-loaded manganese-based denitration catalyst prepared by the preparation method provided by the invention has the following advantages:
(1) the electrostatic adsorption effect is utilized to control the electrification of the surface of the carrier and the coordination state in the manganese salt solution, and the directional adsorption of the synthesized manganese salt on the reducible oxide is designed, so that the single control of an acid site and an oxidation-reduction active site in the manganese-based catalyst is realized;
(2) the structure matching and the function cooperation matching of an acid site and an oxidation-reduction active site in the manganese-based catalyst are realized, and the use temperature of the molecular sieve loaded manganese-based denitration catalyst can be reduced;
(3) by utilizing the specific isoelectric point of the oxide, a specific ligand is selected to be combined with manganese salt through a coordination bond, and the high-stability and high-dispersion low-temperature molecular sieve loaded manganese-based denitration catalyst can be prepared by utilizing an electrostatic adsorption mode;
(4) in the molecular sieve-loaded manganese-based denitration catalyst, the particle size distribution of an active component manganese-containing compound is uniform, and the size distribution can be 0.5-1000 nm;
(5) when the molecular sieve loaded manganese-based denitration catalyst is used for removing nitrogen oxides, the using temperature can be lower than 100 ℃, the NOx conversion rate can reach over 80% when the reaction temperature is 95-465 ℃, and the NOx conversion rate can reach 100% when the reaction temperature is 150-465 ℃.
Drawings
FIG. 1 is a TEM spectrum of the finished catalyst Mn/SSZ-13(5) -EA (en) prepared in example 1
FIG. 2 is a plot of the particle size distribution of the manganese species for the finished catalyst Mn/SSZ-13(5) -EA (en) prepared in example 1.
Fig. 3 is an XRD spectrum of the molecular sieve-supported manganese-based catalyst prepared in examples 1 to 5.
Fig. 4 is a graph showing the denitration performance of the molecular sieve-supported manganese-based catalyst prepared in examples 1 to 5.
Fig. 5 is a graph showing the denitration performance of the molecular sieve-supported manganese-based catalysts prepared in examples 6 to 8.
FIG. 6 shows the denitration performance of the hydrothermal aged catalyst Mn/SSZ-13(10) -EA (en) in example 10.
FIG. 7 is a graph showing the denitration performance of the hydrothermally aged catalysts Mn/SSZ-13(10) -EA (en) in example 11
Fig. 8 is a graph showing the denitration performance of the catalyst prepared in example 2 and the catalysts prepared in comparative examples 1 and 2.
FIG. 9 is H for the catalyst prepared in example 2 and the catalysts prepared in comparative examples 1 and 22TPR contrast plot.
Detailed Description
The invention provides a preparation method of a molecular sieve-loaded manganese-based denitration catalyst, which is characterized in that when a molecular sieve, a soluble aqueous solution of manganese salt and a ligand are mixed to prepare a mixed solution, the electric properties of a complex formed by the molecular sieve, the manganese salt and the ligand are opposite. In order to make the electric property of the molecular sieve opposite to that of the complex formed by the manganese salt and the ligand, the pH value of the mixed solution can be adjusted. In one embodiment, the pH of the mixture is adjusted to be below the isoelectric point of the molecular sieve, thereby making the complex formed by the manganese salt and the ligand positively charged. In another embodiment, the pH of the mixed liquor is adjusted to be above the isoelectric point of the molecular sieve, thereby making the complex formed by the manganese salt and the ligand negatively charged.
The pH value of the mixed solution can be 1-14. Preferably, the pH value of the mixed solution is 1-9.
The invention provides a preparation method of a molecular sieve supported manganese-based denitration catalyst, wherein the framework configuration of the molecular sieve used in the preparation method can be at least one of AEI, AFT, AFX, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, WEN and ZSM.
In a preferred mode, the molecular sieve has a framework configuration selected from at least one of AEI, CHA, FAU and ZSM.
As another preferred mode, the molecular sieve has a framework configuration selected from CHA.
When the framework configuration of the molecular sieve is CHA, the CHA-configured molecular sieve may be at least one selected from SAPO-34, SAPO-44, SAPO-47, LZ-218, LZ-235, LZ-236, SSZ-13, SSZ-62, ZK-14, ZYT-6, Linde D and Linde R.
In a preferred mode, the CHA-configured molecular sieve is selected from at least one of SSZ-13 molecular sieves and SAPO-34 molecular sieves.
In another preferable mode, in the CHA-configuration molecular sieve, the silicon-aluminum ratio is 5-60.
The invention provides a preparation method of a molecular sieve loaded manganese-based denitration catalyst, and the used manganese salt can be soluble manganese salt commonly used in the field. In a preferred mode, the manganese salt is at least one selected from the group consisting of manganese nitrate, manganese chloride, manganese carbonate, manganese sulfate, manganese oxalate and disodium salt of manganese ethylenediaminetetraacetate.
The invention provides a preparation method of a molecular sieve-loaded manganese-based denitration catalyst, and the ligand used can be a ligand capable of forming a complex with manganese salt. In a preferred embodiment, the ligand is at least one selected from the group consisting of diethylamine, triethylamine, diphenylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pyridine, 2-methyl-8-hydroxyquinoline, salicylic acid, sulfosalicylic acid, glycine, oxalic acid, acetic acid, disodium ethylenediaminetetraacetate, tartaric acid, succinic acid, lactic acid, acetylacetone, and ammonia. In a further preferred embodiment, the ligand is at least one selected from the group consisting of ammonia, ethylenediamine, acetic acid, oxalic acid, salicylic acid, and acetylacetone.
The ratio between the manganese salt and the ligand should be such that the manganese salt and the ligand form a complex and the molecular sieve is electrically opposite to the complex formed by the manganese salt and the ligand in the mixed solution. Preferably, the molar ratio of the manganese salt to the ligand is 1: 0.5-20.
The invention provides a preparation method of a molecular sieve-loaded manganese-based denitration catalyst, which comprises the step (2) of drying a mixed solution after electrostatic adsorption and washing. The drying temperature may be a temperature commonly used in the art. Preferably, the drying temperature is 80-200 ℃.
The invention provides a preparation method of a molecular sieve-loaded manganese-based denitration catalyst, which comprises the step (2) of roasting after carrying out electrostatic adsorption, washing and drying on a mixed solution. The firing temperature may be a temperature commonly used in the art. Preferably, the roasting temperature is 300-800 ℃.
According to the molecular sieve loaded manganese-based denitration catalyst prepared by the preparation method provided by the invention, the loading amount of manganese is preferably 1-10 wt%, and the particle size distribution of a manganese-containing compound is preferably 0.5-1000 nm.
The molecular sieve loaded manganese-based denitration catalyst prepared by the preparation method provided by the invention is suitable for removing nitrogen oxides, and is particularly suitable for removing nitrogen oxides in tail gas discharged by diesel vehicles and/or low-temperature flue gas discharged by coal-fired power plants.
When the molecular sieve loaded manganese-based denitration catalyst prepared by the invention is used for removing nitrogen oxides, the reaction temperature can be over 95 ℃. Preferably, the reaction temperature is 95-465 ℃. Further preferably, the reaction temperature is 150-465 ℃.
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1: catalyst preparation
1g of SSZ-13 molecular sieve with the silicon-aluminum ratio of 5 is taken and dispersed in 100mL of water, manganese nitrate and a ligand ethylenediamine are sequentially added under vigorous stirring, the molar weight ratio of ethylenediamine to manganese nitrate is 2:1, stirring is carried out for 1h, then dilute nitric acid is slowly dripped, and the pH is controlled to be about 7. After electrostatic adsorption for 24h, the solution was filtered and the solid powder was washed with deionized water. Three washes were performed using 100mL of deionized water each time. And after washing, drying the product in a blast oven at 110 ℃ for 12h, transferring the product to a muffle furnace, raising the temperature to 550 ℃ at 1 ℃/min, and keeping the temperature for 6h to obtain a catalyst finished product, which is marked as Mn/SSZ-13(5) -EA (en).
In the catalyst finished product Mn/SSZ-13(5) -EA (en), SSZ-13(5) represents an SSZ-13 molecular sieve with a silicon-aluminum ratio of 5, and the suffix en represents that a ligand complexed with manganese in the electrostatic adsorption process is ethylenediamine (ethylene diamine)
Mn was supported by ICP at 1.3 wt% in the final catalyst Mn/SSZ-13(5) -EA (en) by ICP analysis.
The prepared catalyst finished product Mn/SSZ-13(5) -EA (en) has a TEM pattern as shown in figure 1, and has a manganese species particle size distribution as shown in figure 2. As can be seen from FIGS. 1 and 2, the particle size distribution of the manganese species is relatively narrow, with particles in the range of 3 to 5nm accounting for about 95%.
The prepared finished catalyst product Mn/SSZ-13(5) -EA (en) has an XRD spectrum shown in figure 3. As can be seen from fig. 3, no diffraction peak of the manganese species appears in the XRD spectrum of the catalyst after loading manganese, indicating that the manganese species is in a highly dispersed state.
Example 2: preparation of the catalyst
The catalyst obtained by adjusting the silica/alumina ratio of the SSZ-13 molecular sieve to 10 and otherwise preparing the catalyst under the same operating conditions as in claim 1 is designated as Mn/SSZ-13(10) -EA (en).
The prepared finished catalyst product Mn/SSZ-13(10) -EA (en) has an XRD spectrum shown in figure 3. As can be seen from fig. 3, no diffraction peak of the manganese species appears in the XRD spectrum of the catalyst after loading manganese, indicating that the manganese species is in a highly dispersed state.
Example 3: preparation of the catalyst
The catalyst obtained by adjusting the silica/alumina ratio of the SSZ-13 molecular sieve to 20 and otherwise preparing the catalyst under the same operating conditions as in claim 1 is designated as Mn/SSZ-13(20) -EA (en).
The prepared finished catalyst product Mn/SSZ-13(20) -EA (en) has an XRD spectrum shown in figure 3. As can be seen from fig. 3, no diffraction peak of the manganese species appears in the XRD spectrum of the catalyst after loading manganese, indicating that the manganese species is in a highly dispersed state.
Example 4: preparation of the catalyst
The catalyst obtained by adjusting the silica/alumina ratio of the SSZ-13 molecular sieve to 30 and otherwise preparing the catalyst under the same operating conditions as in claim 1 is designated as Mn/SSZ-13(30) -EA (en).
The prepared finished catalyst Mn/SSZ-13(30) -EA (en) has an XRD spectrum shown in figure 3. As can be seen from fig. 3, no diffraction peak of the manganese species appears in the XRD spectrum of the catalyst after loading manganese, indicating that the manganese species is in a highly dispersed state.
Example 5: preparation of the catalyst
The SSZ-13 molecular sieve is changed into a SAPO-34 molecular sieve with the Si/Al ratio of 40, and the rest of the SSZ-13 molecular sieve is used for preparing the catalyst according to the operating conditions of the claim 1, and the obtained catalyst is marked as Mn/SAPO-34(40) -EA (en).
The prepared finished catalyst Mn/SAPO-34(40) -EA (en) has an XRD spectrum shown in figure 3. As can be seen from fig. 3, no diffraction peak of the manganese species appears in the XRD spectrum of the catalyst after loading manganese, indicating that the manganese species is in a highly dispersed state.
Example 6: preparation of the catalyst
The catalyst obtained by changing the ligand from ethylenediamine to oxalic acid (oxalic acid) and otherwise operating under the same conditions as in claim 2 is designated Mn/SSZ-13(10) -EA (oa).
Example 7: preparation of the catalyst
The catalyst obtained by changing the ligand from ethylenediamine to acetylacetone (acetyl acetone) and otherwise following the same operating conditions as in claim 2 is designated Mn/SSZ-13(10) -EA (acac).
Example 8: preparation of the catalyst
The catalyst obtained by changing the ligand from ethylenediamine to salicylic acid (salicylic acid) and preparing the rest of the catalyst under the same operating conditions as in claim 2 is designated as Mn/SSZ-13(10) -EA (sa).
Example 9: test of denitration Performance
The catalysts prepared in examples 1 to 8 were subjected to SCR activity evaluation. The evaluation method is as follows:
and (3) taking a 100mg catalyst sample, loading the catalyst sample into a fixed bed reactor, and testing the denitration activity of the catalyst within the range of 65-465 ℃. The denitration performance test conditions of the molecular sieve-loaded manganese-based SCR low-temperature denitration catalyst are as follows: space velocity of 40000h-1Simulating smoke components: 500ppm NO, 500ppm NH3,、5%H2O,5%O2Ar is balance gas.
The denitration performance of the catalysts prepared in examples 1 to 8 is shown in fig. 1 and fig. 2.
Example 10: water vapor resistance test
The catalyst Mn/SSZ-13(10) -EA (en) prepared in example 2 was hydrothermally aged and NH added3-SCR activity evaluation.
Hydrothermal aging conditions: space velocity of 30000h-1The temperature is 670 ℃, the water vapor concentration is 10 percent, air is balance gas, and the aging time is 64 hours.
After the hydrothermal aging, the denitration performance of the hydrothermally aged catalyst Mn/SSZ-13(10) -EA (en) was tested according to the conditions of example 9, as shown in FIG. 6.
Example 11: test for Sulfur resistance
The catalyst prepared in example 2 was subjected to sulfur aging and then to NH3-evaluation of SCR activity:
and (3) sulfur aging conditions: space velocity of 30000h-1At a temperature of 250 ℃ SO2The concentration is 112ppm, the water vapor concentration is 10 percent, air is balance gas, and the aging time is 16 hours.
After the completion of the sulfur aging, the hydrothermally aged catalysts Mn/SSZ-13(10) -EA (en) were tested for denitration performance under the conditions of example 9, as shown in FIG. 7.
Comparative example 1 preparation of catalyst by impregnation
For comparison, 1g of the SSZ-13 molecular sieve in example 2 was immersed in an equal volume of aqueous solution of manganese nitrate by an equivalent immersion method for 24h at room temperature, the solvent was removed by a rotary evaporator and dried at 110 ℃ for 12h, and then the resulting solution was placed in a muffle furnace, heated to 550 ℃ at 1 ℃/min and kept at the temperature for 6h to obtain the final catalyst, which was designated as Mn/SSZ-13(10) -Imp.
Comparative example 2 preparation of catalyst by ion exchange
For comparison, 1g of the SSZ-13 molecular sieve of example 2 was taken, added to 100mL of a 0.1mol/L manganese nitrate solution, stirred for 4h, and washed three times with 100mL of deionized water. And (3) drying in a blast oven for 12h after washing, then placing in a muffle furnace, heating to 550 ℃ at the speed of 1 ℃/min, and keeping the temperature for 6h to obtain a catalyst finished product, which is marked as Mn/SSZ-13(10) -IE.
The catalyst of example 2 was tested for denitration performance with the catalysts prepared in comparative examples 1 and 2, as shown in fig. 8.
H of catalyst prepared in example 2 and catalysts prepared in comparative examples 1 and 22TPR contrast graph, FIG. 9.
As can be seen from the above examples and comparative examples, the molecular sieve supported manganese-based catalyst prepared by the preparation method provided by the invention comprises the following steps:
(1) the catalyst has narrow particle size distribution and high dispersity, and has higher denitration activity compared with catalysts prepared by an impregnation method and an ion exchange method;
(2) the reduction temperature is lower than that of an impregnation method and an ion exchange method, which shows that the reducibility is higher, and the NH3-SCR reaction is more favorably carried out, so that the denitration activity of the catalyst is improved.
Claims (16)
1. A preparation method of a molecular sieve-loaded manganese-based denitration catalyst is characterized by comprising the following steps:
(1) mixing a soluble aqueous solution of a molecular sieve and a manganese salt with a ligand to form a mixed solution, and enabling the electric property of a complex formed by the molecular sieve, the manganese salt and the ligand to be opposite;
(2) and (3) carrying out electrostatic adsorption on the mixed solution, and washing, drying and roasting to obtain the molecular sieve-loaded manganese-based denitration catalyst.
2. The preparation method of the molecular sieve-supported manganese-based denitration catalyst according to claim 1, characterized in that in the step (1) of the method, a soluble aqueous solution of the molecular sieve and the manganese salt and a ligand are mixed to form a mixed solution, the pH value of the mixed solution is adjusted to 1-9, and the electric properties of a complex formed by the molecular sieve, the manganese salt and the ligand are opposite.
3. The method for preparing a molecular sieve-supported manganese-based denitration catalyst according to claim 2, wherein the molecular sieve has a framework configuration selected from at least one of AEI, AFT, AFX, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, WEN, and ZSM.
4. The method for preparing a molecular sieve-supported manganese-based denitration catalyst according to claim 3, wherein said molecular sieve has a framework configuration selected from at least one of AEI, CHA, FAU and ZSM.
5. The method for preparing a molecular sieve-supported manganese-based denitration catalyst according to claim 4, wherein said molecular sieve has a framework configuration selected from CHA.
6. The method for preparing a molecular sieve-supported manganese-based denitration catalyst according to claim 5, wherein the CHA-configured molecular sieve is selected from at least one of SAPO-34, SAPO-44, SAPO-47, LZ-218, LZ-235, LZ-236, SSZ-13, SSZ-62, ZK-14, ZYT-6, Linde D and Linde R.
7. The method for preparing a molecular sieve-supported manganese-based denitration catalyst according to claim 6, characterized in that said CHA-configured molecular sieve is selected from at least one of SSZ-13 molecular sieves and SAPO-34 molecular sieves.
8. The preparation method of the molecular sieve-supported manganese-based denitration catalyst according to claim 7, characterized in that in the CHA-configured molecular sieve, the silica-alumina ratio is 5-60.
9. The preparation method of the molecular sieve-supported manganese-based denitration catalyst according to claim 1, characterized in that:
the manganese salt is selected from at least one of manganese nitrate, manganese chloride, manganese carbonate, manganese sulfate, manganese oxalate and ethylenediaminetetraacetic acid manganese disodium salt;
the ligand is at least one selected from diethylamine, triethylamine, diphenylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pyridine, 2-methyl-8-hydroxyquinoline, salicylic acid, sulfosalicylic acid, glycine, oxalic acid, acetic acid, disodium ethylenediamine tetraacetate, tartaric acid, succinic acid, lactic acid, acetylacetone and ammonia;
the molar ratio of the manganese salt to the ligand is 1: 0.5-20.
10. The method for preparing a molecular sieve-supported manganese-based denitration catalyst according to claim 1, wherein the ligand is at least one selected from the group consisting of ammonia, ethylenediamine, acetic acid, oxalic acid, salicylic acid, and acetylacetone.
11. The preparation method of the molecular sieve-supported manganese-based denitration catalyst according to claim 1, wherein in the step (2), the drying temperature is 80-200 ℃ and the roasting temperature is 300-800 ℃.
12. The preparation method of the molecular sieve-supported manganese-based denitration catalyst according to claim 1, characterized in that:
in the molecular sieve-loaded manganese-based denitration catalyst, the loading amount of manganese is 1-10 wt%, and the particle size distribution of a manganese-containing compound is 0.5-1000 nm.
13. Use of the molecular sieve-supported manganese-based denitration catalyst of claim 1, wherein the molecular sieve-supported manganese-based denitration catalyst is used for removal of nitrogen oxides.
14. Use of the molecular sieve-supported manganese-based denitration catalyst according to claim 13, wherein the molecular sieve-supported manganese-based denitration catalyst is used for removing nitrogen oxides from diesel vehicle exhaust and/or low-temperature flue gas discharged from a coal-fired power plant.
15. The use of the molecular sieve-supported manganese-based denitration catalyst of claim 13, wherein the reaction temperature is 95-465 ℃ when the molecular sieve-supported manganese-based denitration catalyst is used for removing nitrogen oxides.
16. The use of the molecular sieve-supported manganese-based denitration catalyst of claim 15, wherein the reaction temperature is 150-465 ℃ when the molecular sieve-supported manganese-based denitration catalyst is used for removing nitrogen oxides.
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