CN111542389A - Catalyst activation method and method for selectively removing nitrogen oxide by using same - Google Patents
Catalyst activation method and method for selectively removing nitrogen oxide by using same Download PDFInfo
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- CN111542389A CN111542389A CN201880077243.1A CN201880077243A CN111542389A CN 111542389 A CN111542389 A CN 111542389A CN 201880077243 A CN201880077243 A CN 201880077243A CN 111542389 A CN111542389 A CN 111542389A
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- catalyst
- conductive
- temperature
- conductive substrate
- activation method
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- 239000003054 catalyst Substances 0.000 title claims abstract description 324
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 238000000034 method Methods 0.000 title claims abstract description 66
- 230000004913 activation Effects 0.000 title claims abstract description 37
- 239000000758 substrate Substances 0.000 claims description 80
- 239000000203 mixture Substances 0.000 claims description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 52
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000010936 titanium Substances 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 22
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 21
- 239000004917 carbon fiber Substances 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000011941 photocatalyst Substances 0.000 claims description 5
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000001994 activation Methods 0.000 description 24
- -1 alcohol compound Chemical class 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 239000004408 titanium dioxide Substances 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 11
- 239000008199 coating composition Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
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- 235000012239 silicon dioxide Nutrition 0.000 description 8
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- 238000003786 synthesis reaction Methods 0.000 description 7
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
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- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
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- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- 238000005520 cutting process Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003858 2-ethylbutoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])O*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
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- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
- B01J31/124—Silicones or siloxanes or comprising such units
- B01J31/127—Silicones or siloxanes or comprising such units the siloxane units, e.g. silsesquioxane units, being grafted onto other polymers or inorganic supports, e.g. via an organic linker
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- B01J35/39—
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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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
Abstract
The present invention relates to a catalyst activation method capable of maximizing the activity of a catalyst at a low temperature for a short time to exhibit high catalytic reaction efficiency at low energy and enabling the catalyst to have excellent durability, and a method for selectively removing nitrogen oxides using the same.
Description
Technical Field
The invention relates to a catalyst activation method and a method for selectively removing nitrogen oxides by using the method. And more particularly, to a catalyst activation method capable of maximizing the activity of a catalyst at a low temperature for a short time, thereby exhibiting high catalytic reaction efficiency at low energy, and enabling the catalyst to have excellent durability, and a method of selectively removing nitrogen oxides using the same.
Background
Boilers for power generation, gas turbines, industrial boilers, incinerators, diesel engines, diesel vehicles, marine engines, and the like, which discharge a large amount of Nitrogen Oxides (NO)x) This is a cause of pollution.
Low NO is used as a method for inhibiting or reducing the formation of nitrogen oxidesxA burner, a Selective Non-Catalytic Reduction method (SNCR), a Selective Catalytic Reduction method (SCR), and the like.
Among them, the selective catalytic reduction method is a method of converting nitrogen oxides in exhaust gas into pollution-free water and nitrogen by injecting ammonia or urea at the front end of a denitrification catalyst and causing the nitrogen oxides and ammonia to flow through the catalyst together through the following chemical reaction.
4NO+4NH3+O2→4N2+6H2O
The reaction is called a standard Selective Catalytic Reduction (SCR) method and shows the highest reaction efficiency at a reaction temperature of about 300 to 400 ℃.
Therefore, in a thermal power plant using coal or oil as fuel, the thermal power plant is operated so that a catalyst is installed in a temperature range of 300 to 400 ℃ at the rear end of a boiler to achieve an optimum denitrification efficiency, thereby removing NO generated from the boilerx. When the exhaust gas temperature is lower than these temperatures, the temperature is raised by using a burner or the likeThe temperature of the exhaust gas. In particular, when the boiler is started, the exhaust gas temperature is lower than the catalyst activation temperature, and an auxiliary heating device such as a burner is required to be operated to adjust the temperature, and therefore, a large amount of energy is consumed.
In an incinerator or a boiler for Liquefied Natural Gas (LNG), it is often difficult to optimally operate SCR because the exhaust gas temperature is reduced to 230 ℃. In particular, in a hybrid thermal power plant using LNG, NO discharged when the exhaust gas temperature is 200 ℃ or lower cannot be removed when the gas turbine is initially started.
When the temperature of the exhaust gas is low, there is a method of increasing the amount of the catalyst to increase the denitrification efficiency in the SCR, in addition to the method of heating using the burner described above, but there is a technical limitation in that the denitrification efficiency is rapidly decreased with a decrease in temperature and the amount of the catalyst required is greatly increased. In addition, the increase in the amount of the denitrification catalyst increases the pressure loss of the gas turbine or the boiler, and thus, there is a disadvantage that the combustion efficiency is drastically reduced.
Even in a denitrification facility for a light oil vehicle or a ship, it is difficult to effectively remove NO at the initial stage of operation because of a low exhaust gas temperaturexAnd the like. In order to solve these problems, a method of using an auxiliary heating apparatus such as a burner in a plurality of apparatuses to heat the discharged exhaust gas to a catalyst activation temperature is being attempted.
In particular, in the denitrification catalyst for ships, when low-sulfur fuel is used, the optimum temperature is 250 ℃ or higher, but the exhaust gas temperature is about 230 ℃, and therefore, a burner is also provided as an auxiliary heating means to achieve the optimum temperature of the catalyst.
Similarly, in the denitrification facility of the sintering furnace of the steel mill, SO is contained in the by-product gas due to the use as fuelxThe catalyst operating temperature should be 250 ℃ or higher, but the exhaust gas temperature is about 230 ℃, and a large amount of extra fuel is consumed when auxiliary heating equipment such as a burner is installed and operated in order to achieve the proper temperature of the catalyst.
In addition to the above-described auxiliary burner heating method, korean patent No. 1541743 proposes a method of catalytically heating low-temperature exhaust gas to the activation temperature of a catalyst at the initial start-up of a light oil vehicle using a self-heating catalyst.
This type of catalyst is a catalyst (EHC) that is Electrically heated when the exhaust gas temperature is low, and is a method of heating the exhaust gas to a suitable temperature by heat energy by applying electricity to a metal catalyst. The EHC is formed of a sintered metal or metal foil as a resistance factor, and the resistance material is an alloy made of iron and chromium, aluminum, and rare earth metals.
Raising the temperature of the catalyst as quickly as possible is key to minimizing harmful components discharged at the initial start of a light oil automobile. Therefore, the EHC has disadvantages in that a large amount of energy (150 to 250A, 20 seconds) is required during cold start, the energy consumption is large, and the conventional automotive battery has insufficient capacity, and thus, it is difficult to use.
Prior art documents
Patent document 1: korean granted patent No. 1541743 (granted date: 2015, 7 and 29)
Disclosure of Invention
Technical problem
The present invention is directed to provide a catalyst activation method capable of maximizing the activity of a catalyst at a low temperature for a short time to exhibit high catalytic reaction efficiency at low energy and enabling the catalyst to have excellent durability, and a method for selectively removing nitrogen oxides using the same.
Technical scheme
In the present specification, there is provided a catalyst activation method comprising the steps of coating a conductive catalyst composition on a conductive substrate, and applying 1.00 × 10 at a temperature of 20 ℃ to 200 ℃ to the conductive substrate coated with the conductive catalyst composition-4V/mm2The above voltages.
In this specification, there is also provided a method of selectively removing nitrogen oxides, comprising the steps of: coating a denitrification catalyst composition for Selective Catalytic Reduction (SCR) on a conductive substrate; and in the presence of a mixed gas containing nitrogen oxides and having a temperature of 20 ℃ to 200 ℃Conductive substrate application 1.00 × 10 coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR)-4V/mm2The above voltages.
Hereinafter, a catalyst activation method and a method for selectively removing nitrogen oxides according to an embodiment of the present invention will be described in more detail.
According to an embodiment of the invention, there can be provided a catalyst activation method including the steps of coating a conductive catalyst composition on a conductive substrate, and applying 1.00 × 10 to the conductive substrate coated with the conductive catalyst composition at a temperature of 20 to 200 ℃-4V/mm2The above voltages.
The inventors of the present invention confirmed through experiments that when the above-described catalyst activation method is used, a specific voltage is applied to a conductive substrate coated with a conductive catalyst composition, so that as the movement of remaining electrons inside the conductive catalyst becomes active by supplying electrical energy, the catalyst can be rapidly activated at a relatively low temperature, and high reaction efficiency is achieved, and thus completed the present invention.
Therefore, the catalyst activity can be improved even at a lower catalyst surface temperature than in the conventional art, thereby achieving excellent reaction efficiency, and particularly, when carbon fibers are used as a conductive substrate for supplying electric energy, the initial temperature rise rate of the catalyst surface can be increased by supplying electric energy, and the temperature can be rapidly raised to the catalyst activation temperature by supplying the minimum electric energy, thereby improving energy consumption efficiency.
Specifically, the method comprises coating a conductive catalyst composition on a conductive substrate, and applying 1.00 × 10 to the conductive substrate coated with the conductive catalyst composition at 20-200 deg.C-4V/mm2The above voltages.
Hereinafter, a catalyst activation method according to one embodiment of the present invention will be described in detail with reference to the respective steps.
Step of coating conductive catalyst composition on conductive substrate
The conductive substrate may include at least one selected from a carbon fiber plate, a nickel chromium plate, and a quartz plate. That is, the conductive substrate may include a mixture of at least two selected from a carbon fiber plate, a nickel chromium plate, a quartz plate, and the like.
However, carbon fiber plates may be preferably used. This is because the carbon fiber sheet has a small resistance value, and therefore, the initial temperature rise rate is very high at the time of energization as compared with a nichrome wire or the like, and the temperature rises instantaneously.
For example, when a voltage of 9V is applied to a carbon fiber sheet having a width of 5mm and a length of 50mm, a current of about 1,680mA flows and reaches 300 ℃ within 1 second and nearly 360 ℃ within 10 seconds. When a voltage of 9V was applied to a carbon fiber sheet having a width of 5mm and a length of 100mm, a current of about 720mA flowed, and reached 160 ℃ in 7 seconds and nearly 180 ℃ in 30 seconds.
As shown in fig. 1 below, the carbon fiber sheet can be produced in a ribbon-like form or a plate-like form by weaving carbon fibers.
Specifically, the resistance of the conductive substrate may be 10 Ω to 15 Ω, or 11 Ω to 14 Ω.
The conductive catalyst composition may include a conductive catalyst and a binder compound. Examples of the conductive catalyst are not particularly limited, and may include, for example, at least one selected from a denitrification catalyst for Selective Catalytic Reduction (SCR), an oxidation catalyst, a VOC removal catalyst, and a photocatalyst. That is, the conductive catalyst may include a denitrification catalyst for Selective Catalytic Reduction (SCR), an oxidation catalyst, a VOC removal catalyst, a photocatalyst, and a mixture of at least two thereof.
A conventional proposal has been made to use various catalysts ranging from noble metal catalysts to alkali metal catalysts as denitrification catalysts for selective catalytic reduction technology, and it is known that the role of carriers supporting these active substances is large. In connection with this, most of recent selective catalytic reduction catalysts have been studied centering on vanadium as an active component, and it is known that vanadium pentoxide (V) is produced by2O5) Precipitated on or supported on titanium dioxide (TiO)2) Alumina (Al)2O3) Or silicon dioxide (SiO)2) After the use, an excellent selective catalytic reduction reaction can be performed. In particular, the most important criterion for selecting the carrier is durability to the sulfur component, and for this reason, most of the commercial catalysts mainly use titania as the carrier. In addition, as a method for reducing sulfur trioxide produced by the following reaction formula, catalysts to which tungsten, molybdenum, or the like is added are being actively developed.
The reaction formula is as follows: 2SO2+O2→2SO3
In the denitrification catalyst for Selective Catalytic Reduction (SCR), 0.1 to 10 wt% of vanadium in the form of an oxide is supported on a titania carrier based on the catalyst. The amount of vanadium supported on the titania support is usually preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight.
The vanadium used in the present invention is not particularly limited, but is preferably selected from the group consisting of ammonium metavanadate (NH)4VO3) Or vanadium oxytrichloride (VOCl)3) And the like.
In addition, the titania support changes the kind and surface distribution ratio of the supported vanadium oxide according to the degree of reduction of titania used as a support, and thus determines nitrogen oxide removal activity at low temperatures. Although the remaining characteristics of the titania used as a carrier, i.e., specific surface area, pore volume, average pore size, etc., are not decisive factors for achieving the characteristics of the present invention, it is preferable to have about 30m in order to achieve the basic characteristics of the catalyst2/g～350m2A specific surface area per gram, a pore volume of about 0.1 cc/gram to about 0.8 cc/gram, and
average pore size of (a).
A decisive factor for achieving the features of the invention is titanium dioxide which can successfully supply lattice oxygen to vanadium and this property can be derived by a hydrogen-based reduction reaction of titanium dioxide.
The atomic ratio of oxygen to titanium (O/Ti) falls within the range of 1.47 to 2.0. It was confirmed that the catalyst prepared by using the titania having the above range as a carrier has high low-temperature denitrification efficiency.
When the molar ratio of O/Ti falls within the range of 1.47 to 2.0, the activity increases, and particularly, as the molar ratio of O/Ti increases to 2.0, oxygen contained in titanium dioxide increases, and therefore, oxygen that can be supplied in the reduction reaction also increases, and the activity increases. Therefore, the amount of hydrogen consumed can be increased when the titanium oxide is subjected to a reduction reaction, and the supported vanadium precursor can smoothly obtain oxygen of the titanium oxide during firing, thereby forming a vanadium oxide having high activity. Thus, the maximum activity is exhibited around a molar O/Ti ratio of about 2.0, and therefore, the closer the titanium dioxide is to the stoichiometric TiO2The higher its activity. However, when the molar ratio of O/Ti is increased to 2.0 or more, electrons excited by external energy are transferred to the peroxidized oxygen, resulting in consumption of electrons in the titanium dioxide and the catalyst supporting vanadium, and thus, the electron acceptance actually proceeding with the reactant is reduced. Therefore, the titanium oxide cannot be reduced smoothly, and oxygen cannot be supplied smoothly during firing after the vanadium precursor is supported. In addition, the lattice oxygen of titanium dioxide can be increased by high-temperature firing when titanium dioxide is produced. Therefore, the specific surface area is reduced due to the heat treatment at high temperature, resulting in a reduction in the chance of the titanium dioxide to contact with vanadium, and thus, is disadvantageous for the formation of vanadium oxide.
The ratio of the number of moles of oxygen bound to the titanium to the number of moles of titanium (O/Ti) can be determined by XPS (X-ray photoelectron spectroscopy, under the trade name ESCALB 201 from VG Scientific). Oxygen bonded to titanium was determined by O1s, and was generally composed of O-Ti bonded to titanium, -OH contained in physically adsorbed moisture or hydroxyl group, and C-O bonded to carbon, and was 529.9eV, 530.2eV, and 531.6eV, respectively. The molar ratio of oxygen to titanium in titania can be determined by analyzing Ti 2p and O1s, and as described above, the molar ratio has a very high correlation with the nitrogen oxide removal activity.
The binder compound enables the conductive catalyst to be effectively coated on the conductive substrate, and can be applied to various organic binders or inorganic binders widely used in the coating field without limitation, and the binder compound may include not only compounds but also polymers or copolymers thereof. The binder compound may be, for example, an organic silicon polymer compound or an alcohol compound. The organic silicon polymer compound may be, for example, specifically, silica crosslinked by siloxane bonds.
Specifically, the silica crosslinked by siloxane bonds is chemically bonded to each other by a plurality of silica particles through siloxane bonds represented by the following chemical formula 1.
Chemical formula 1:
in the chemical formula 1, R1And R2The groups may be the same or different and are each independently an ether bond, hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. In the chemical formula 1, when R1And R2When both are ether bonds, it may be a tetravalent crosslinking unit represented by the following chemical formula 1-1.
Chemical formula 1-1:
that is, silicon atoms (Si) present in the silica particles may be bonded to a bonding point (—) located at one end of the siloxane bond represented by the chemical formula 1, and silicon atoms (Si) present in the other silica particles may be bonded to a bonding point (—) located at the other end opposite to the one end of the siloxane bond.
In the context of the present specification,
represents a bond to other substituents.
In the present specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. According to one embodiment, the alkyl group has 1 to 5 carbon atoms. According to another embodiment, the alkyl group has 1 to 3 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, and, Isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.
In the present specification, the alkoxy group may be a straight chain, a branched chain or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 10. Specifically, there are methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, sec-butoxy group, n-pentoxy group, neopentoxy group, isopentoxy group, n-hexoxy group, 3-dimethylbutoxy group, 2-ethylbutoxy group, n-octoxy group, n-nonoxy group, n-decoxy group, benzyloxy group, p-methylbenzyloxy group and the like, but not limited thereto.
Examples of the method for producing the silica crosslinked by the siloxane bond are not particularly limited, and for example, a hydrolytic condensation reaction of alkoxysilane (alkoxysilane) with water-dispersible silica having a hydroxyl group on the surface may be used. The alkoxysilane may be, for example, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and the like.
On the other hand, specific examples of the alcohol compound may be methanol, ethanol, or the like.
Preferably, the binder compound may have a boiling point of 100 ℃ to 300 ℃. Therefore, when heat treatment is performed at a temperature of more than 100 ℃, the binder compound included in the conductive catalyst composition is removed in a volatile manner. Specifically, in the drying and firing step of the catalyst described later, the binder compound can be removed in a volatile manner by performing heat treatment at a temperature of 100 ℃ or higher, so that the conductivity of the conductive catalyst can be improved, and the temperature can be rapidly raised to the catalyst activation temperature by supplying the minimum electric energy, and the energy use efficiency can be improved.
The conductive catalyst composition may be coated on a conductive substrate, and examples of the coating method are not particularly limited, and various coating methods widely used in the coating field may be used, but a dip coating method may be preferably used.
In another aspect, the method may further comprise: a step of volatilizing a binder compound contained in the coated conductive catalyst composition after the step of coating the conductive catalyst composition on the conductive substrate; and a step of firing the conductive catalyst contained in the coated conductive catalyst composition.
In the step of volatilizing the binder compound contained in the coated conductive catalyst composition, the binder compound can be removed in a volatilized manner, so that the conductivity of the conductive catalyst can be improved, and the temperature is rapidly raised to a catalyst activation temperature by supplying a minimum amount of electric energy, thereby improving energy consumption efficiency.
Specifically, the step of volatilizing the binder compound contained in the coated conductive catalyst composition may be performed at 100 to 200 ℃.
In addition, the step of firing the conductive catalyst contained in the coated conductive catalyst composition may be performed at 300 to 400 ℃.
Step of applying voltage to conductive substrate coated with conductive catalyst composition
On the other hand, in the step of applying a voltage to the conductive substrate coated with the conductive catalyst composition, by applying a voltage to the conductive substrate coated with the conductive catalyst composition, movement of remaining electrons inside the conductive catalyst becomes active with supply of electric energy, so that the catalyst can be rapidly activated even at a relatively low temperature, thereby achieving high reaction efficiency.
In the step of applying a voltage to the conductive substrate coated with the conductive catalyst composition, the applied voltage may be 5V to 25V, or 5V to 8V, or 10V to 22V.
More specifically, 1.00 × 10 can be applied-4V/mm2Above, or 1.00 × 10-4V/mm2～1.00×10-2V/mm2Or 1.00 × 10-4V/mm2～1.00×10-3V/mm2Or 1.00 × 10-4V/mm2～5.00×10-4V/mm2The voltage of (c). At the stated V/mm2The voltage expressed in units represents the voltage per unit area (mm) to the conductive substrate2) The applied voltage can be calculated by dividing the voltage applied to the conductive substrate by the area of the conductive substrate (width × length).
When less than 1.00 × 10 is applied to a conductive substrate coated with the conductive catalyst composition-4V/mm2At a low driving voltage of (2), it is difficult to activate the movement of surplus electrons in the conductive catalyst by the supply of electric energy, and activation of the catalyst is delayed, and thus it is difficult to achieve high reaction efficiency in a short time.
In addition, the step of applying a voltage to the conductive substrate coated with the conductive catalyst composition may be performed at a temperature of 20 to 200 ℃ or 20 to 150 ℃. That is, in the step of applying a voltage to the conductive substrate coated with the conductive catalyst composition, the temperature of the external gas contacting the conductive substrate coated with the conductive catalyst composition may be 20 to 200 ℃ or 20 to 150 ℃.
In order to rapidly raise the surface of the conductive catalyst to an active temperature, it has been necessary to consume an excessive amount of energy by contact with a gas under a high temperature condition of 300 ℃ or higher, but in the above-described embodiment, by applying a voltage in a specific range, the catalyst can exhibit a high activity even under a condition of a low external temperature.
Specifically, the initial temperature increase rate of the surface of the conductive catalyst may be 5 ℃/sec to 14 ℃/sec. The initial temperature increase rate of the surface of the conductive catalyst means an average temperature increase rate of the surface of the conductive catalyst in the first second of applying a voltage to the conductive substrate coated with the conductive catalyst composition, and when the initial temperature increase rate of the surface of the catalyst is too small, the catalyst activity cannot be sufficiently improved in a short time, and thus, the catalyst efficiency may be reduced.
As a more specific example, a voltage of 10V to 22V may be applied to a circular catalyst manufactured by rolling one conductive substrate coated with the conductive catalyst composition into a circular shape as shown in fig. 7 below, and a voltage of 5V to 8V may be applied to a plate catalyst manufactured by stacking four conductive substrates coated with the conductive catalyst composition into a plate shape as shown in fig. 8 below.
On the other hand, the initial temperature rise rate of the conductive substrate may be 7 ℃/sec to 23 ℃/sec. The initial temperature increase rate of the conductive substrate means an average temperature increase rate of the conductive substrate within the first second of applying a voltage to the conductive substrate coated with the conductive catalyst composition, and when the initial temperature increase rate of the substrate is excessively low, the temperature increase of the substrate becomes slow, and thus, the catalyst can be activated at a high temperature only by supplying a large amount of electric energy, and thus, the energy efficiency may be reduced.
In the step of applying a voltage to the conductive substrate coated with the conductive catalyst composition, the temperature of the catalyst surface may be 60 ℃ or more, or 60 to 200 ℃, or 60 to 180 ℃, or 90 to 150 ℃.
The step of applying a voltage to the conductive substrate coated with the conductive catalyst composition is preceded by a step of applying a voltage thereto at an ordinary temperature, and thus, the catalyst surface is at an ordinary temperature, having a temperature of about 20 ℃ to 30 ℃.
In the step of applying a voltage to the conductive substrate coated with the conductive catalyst composition, as the temperature of the catalyst surface satisfies 60 ℃ or more, or 60 to 200 ℃, or 90 to 200 ℃, the voltage is applied to the conductive catalyst composition, the movement of the surplus electrons inside the conductive catalyst due to the supply of electric energy is more active than the movement of the surplus electrons inside the conductive catalyst due to the temperature rise of the catalyst surface, and therefore the catalyst can be rapidly activated even at a relatively low temperature, thereby achieving high reaction efficiency.
In the step of applying a voltage to the conductive substrate coated with the conductive catalyst composition, when the temperature of the catalyst surface is reduced to less than 60 ℃, the temperature of the catalyst is not sufficiently increased, and thus, the catalyst activity may be greatly reduced.
In another aspect, the method may further comprise: and cutting off the voltage when the temperature of the surface of the catalyst reaches more than 200 ℃ or 200-400 ℃. When the temperature of the surface of the catalyst reaches 200 ℃ or more or 200 to 400 ℃, the catalyst can reach an activation temperature at which the catalyst can be sufficiently activated without external power supply, thereby achieving high reaction efficiency. Therefore, when falling within the above temperature range, the supply of external electric energy can be cut off, thereby minimizing a reduction in energy efficiency due to the supply of excessive energy.
Alternatively, the method may further comprise applying 1.00 × 10 to the conductive substrate coated with the conductive catalyst composition at a temperature of 20 ℃ to 200 ℃-4V/mm2For example, when the method further comprises applying 1.00 × 10 to the conductive substrate coated with the conductive catalyst composition at the temperature of 20 ℃ to 200 ℃-4V/mm2Applying greater than 1.00 × 10 to the conductive substrate after the step of applying the voltage above-2V/mm2The temperature of the catalyst surface may be increased to 300 ℃ or more as an overcurrent flows in the conductive substrate.
As described above, the catalyst regeneration step of raising the temperature of the surface of the catalyst to 300 ℃ or more can be performed for 3 to 10 hours, thereby effectively removing the contaminants (e.g., ammonium sulfate, etc.) bound to the surface of the catalyst. Thus, it is possible to easily regenerate the catalyst by using the existing catalyst activation process without providing additional equipment such as a catalyst regeneration device or an air duct burner, and in this regard, the efficiency of the regeneration process is remarkably improved.
Method for activating catalyst
On the other hand, the catalyst activation method of the above-described embodiment can be applied to equipment and the like for various purposes using a catalyst. The equipment may be, for example, a boiler, a gas turbine, an engine, etc., and the catalyst may include, for example, at least one selected from a denitrification catalyst for Selective Catalytic Reduction (SCR), an oxidation catalyst, a VOC removal catalyst, and a photocatalyst. That is, the conductive catalyst may include a denitrification catalyst for Selective Catalytic Reduction (SCR), an oxidation catalyst, a VOC removal catalyst, a photocatalyst, and a mixture of at least two thereof.
The denitrification catalyst for Selective Catalytic Reduction (SCR) can be used as a denitrification catalyst for automobiles, a denitrification catalyst for ships or diesel engines, a denitrification catalyst for boilers or incinerators, etc., and the VOC removing catalyst can be used as a VOC removing catalyst for air purifiers or air conditioning equipment, etc.
More specifically, as shown in fig. 9 below, when used in an SCR denitrification apparatus for an automobile or a ship, the voltage applied to the catalyst is not supplied in accordance with the exhaust gas temperature conditions at the rear end of the SCR reactor in the same manner as the operation of the conventional denitrification apparatus, but NO is provided at the rear end thereofxAn analyzer, etc., according to the measured denitrification efficiency. This is because the catalyst reaction temperature in the present invention is considerably lower than that of the conventional catalyst, and low energy should be consumed by operating the catalyst based on the denitrification efficiency rather than the exhaust gas temperature.
On the other hand, in the rear end of the boiler or the incinerator, etc., it can be arranged and operated as shown in fig. 10 below, in which case a control device is provided which also measures the denitrification efficiency instead of the exhaust gas and appropriately adjusts the power supply to achieve the desired denitrification efficiency.
On the other hand, according to another embodiment of the invention, there can be provided a method of selectively removing nitrogen oxides, which includes the steps of coating a denitrification catalyst composition for Selective Catalytic Reduction (SCR) on a conductive substrate, and applying 1.00 × 10 to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR) in the presence of a mixed gas containing nitrogen oxides and having a temperature of 20 to 200 ℃-4V/mm2The above voltages.
Specifically, in the step of applying a voltage to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR), an initial temperature rise rate of the surface of the denitrification catalyst for Selective Catalytic Reduction (SCR) may be 5 ℃/sec to 14 ℃/sec.
In the step of applying a voltage to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR), 1.00 × 10 may be applied-4V/mm2～1.00×10-2V/mm2The voltage of (c).
In the step of applying a voltage to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR), the applied voltage may be 5V to 25V.
The conductive substrate may include at least one selected from a carbon fiber plate, a nickel chromium plate, and a quartz plate.
In the step of applying a voltage to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR), an initial temperature increase rate of the conductive substrate may be 7 ℃/sec to 23 ℃/sec.
The resistance of the conductive substrate may be 10 Ω to 15 Ω or 11 Ω to 14 Ω.
The denitrification catalyst composition for Selective Catalytic Reduction (SCR) may include a denitrification catalyst for Selective Catalytic Reduction (SCR) and a binder compound.
In the denitrification catalyst for Selective Catalytic Reduction (SCR), 0.1 to 10 wt% of vanadium in the form of an oxide is supported on a titania carrier based on the catalyst.
In the titania support, the atomic ratio of oxygen to titanium (O/Ti) may be 1.47 to 2.0.
The binder compound may have a boiling point of less than 100 ℃.
May further comprise: a step of volatilizing a binder compound contained in the coated denitrification catalyst composition for Selective Catalytic Reduction (SCR) after the step of coating the denitrification catalyst composition for Selective Catalytic Reduction (SCR) on the conductive substrate; and a step of firing a denitrification catalyst for Selective Catalytic Reduction (SCR) included in the coated denitrification catalyst composition for Selective Catalytic Reduction (SCR).
The step of volatilizing the binder compound included in the coated denitrification catalyst composition for Selective Catalytic Reduction (SCR) may be performed at 100 to 200 ℃, and the step of firing the denitrification catalyst for Selective Catalytic Reduction (SCR) included in the coated denitrification catalyst composition for Selective Catalytic Reduction (SCR) may be performed at 300 to 400 ℃.
May further comprise: a step of cutting off a voltage when a temperature of a surface of the catalyst reaches 300 ℃ or more after the step of applying a voltage to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR).
That is, the contents of the conductive substrate, the denitrification catalyst composition for Selective Catalytic Reduction (SCR), and the applied voltage may include those described in the above embodiment.
On the other hand, the step of applying a voltage to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR) may be performed in the presence of a mixed gas containing nitrogen oxide and having a temperature of 20 to 200 ℃.
The step of performing the reaction in the presence of a mixed gas containing nitrogen oxide and having a temperature of 20 to 200 ℃ means that a voltage is applied to a conductive substrate in an environment where the mixed gas containing nitrogen oxide and having a temperature of 20 to 200 ℃ can come into contact with the surface of the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR).
From this, it is found that, by applying a voltage to the denitrification catalyst composition for Selective Catalytic Reduction (SCR), the movement of the surplus electrons in the catalyst due to the supply of electric energy is more active than the movement of the surplus electrons in the catalyst due to the temperature rise on the surface of the catalyst, and thus the catalyst can be rapidly activated at a relatively low temperature, thereby achieving a high reaction efficiency.
In the step of applying a voltage to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR), the temperature of the surface of the denitrification catalyst for Selective Catalytic Reduction (SCR) may be 60 ℃ or more, or 60 to 300 ℃, or 60 to 200 ℃, or 90 to 150 ℃.
The mixed gas may include ammonia, nitrogen, oxygen, nitrogen oxides, and sulfur oxides.
The denitrification catalyst for Selective Catalytic Reduction (SCR) can be used as an automobile denitrification catalyst, a marine denitrification catalyst, a diesel engine denitrification catalyst, a boiler or incinerator denitrification catalyst, and the like, and more specifically, can be applied to an automobile or marine SCR denitrification facility as shown in fig. 9, or to a boiler rear end, an incinerator, and the like as shown in fig. 10.
May further comprise applying 1.00 × 10 to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR) in the presence of a mixed gas comprising the nitrogen oxide and having a temperature of 20 ℃ to 200 ℃-4V/mm2For example, when the method further comprises applying 1.00 × 10 to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR) in the presence of a mixed gas containing the nitrogen oxide and having a temperature of 20 to 200 ℃-4V/mm2Applying greater than 1.00 × 10 to the conductive substrate after the step of applying the voltage above-2V/mm2The temperature of the catalyst surface can be increased to 300 ℃ or more as an overcurrent flows in the conductive substrate.
As described above, the catalyst regeneration step of raising the temperature of the surface of the catalyst to 300 ℃ or more can be performed for 3 to 10 hours, thereby effectively removing the contaminants (e.g., ammonium sulfate, etc.) bound to the surface of the catalyst. Thus, it is possible to easily regenerate the catalyst by using the existing catalyst activation process without providing additional equipment such as a catalyst regeneration device or an air duct burner, and in this regard, the efficiency of the regeneration process is remarkably improved.
Advantageous effects
The present invention provides a catalyst activation method capable of maximizing the activity of a catalyst at a low temperature for a short time to exhibit high catalytic reaction efficiency at low energy and enabling the catalyst to have excellent durability, and a method for selectively removing nitrogen oxides using the same.
Drawings
Fig. 1 shows the shape of a carbon fiber sheet.
FIG. 2 shows a state in which electrodes are adhered to both ends of a carbon fiber sheet having a width of 75mm and a length of 1,600mm, and then a denitrification catalyst is coated and wound in a round shape to make a round catalyst.
Fig. 3 shows a state after a round catalyst was put into a quartz tube.
FIG. 4 shows a state in which a denitrification catalyst is coated on carbon fibers having a width of 70mm and a length of 300 mm.
Fig. 5 is a sectional view showing a reactor in which 4 catalyst plates of fig. 4 are arranged to measure denitrification efficiency.
FIG. 6 shows a state where denitrification efficiency is measured.
Fig. 7 shows a state where the electrically-driven carbon fiber sheet catalyst is made circular.
Fig. 8 shows a state where the electrically-driven carbon fiber sheet catalyst is formed in a quadrangular shape.
Fig. 9 is a side view showing an installation state when the catalyst is applied to an SCR denitrification apparatus for an automobile or a ship.
Fig. 10 is a side view showing an installation state of a catalyst in an SCR denitrification apparatus such as a boiler rear end or an incinerator.
Detailed Description
In the following examples, the invention will be explained in more detail. However, the following examples are provided to illustrate the present invention, and the contents of the present invention are not limited to the following examples.
< synthesis example: synthesis of catalyst powder >
Titanium dioxide having a ratio of the number of moles of oxygen bonded to titanium to the number of moles of titanium (O/Ti) of 1.92 was prepared at 200 ℃. The ratio of the number of moles of oxygen bound to the titanium to the number of moles of titanium (O/Ti) was measured by XPS (X-ray photoelectron spectroscopy, a product name of VG Scientific Inc. is ESCALB 201).
0.91g of ammonium metavanadate (NH)4VO3(ii) a Trade name 20555-9 from Aldrich Chemical co.) was dissolved in 30mL of distilled water, and after 1.4g of oxalic acid was added and dissolved in the aqueous solution, 20g of the titanium dioxide was put into the aqueous solution to prepare a slurry form, which was then heated at 70 ℃ with stirring using a vacuum evaporator and dried at 100 ℃ for 24 hours. Thereafter, the catalyst powder was fired at a temperature of 400 ℃ for 6 hours in an air atmosphere and analyzed using an element analyzer (product name of Perkin Elmer is Optima 3000XL), and as a result, a catalyst powder supporting 2.0 wt% of vanadium based on the weight of the titanium dioxide used was prepared.
< preparation example: preparation of electrically driven catalyst >
Preparation example 1
50 to 80g of the catalyst powder of the synthesis example is mixed with 1 to 20g of an organosilicon polymer compound (a hydrolysis-condensation reaction product of alkoxysilane and water-dispersible silica having a hydroxyl group on the surface) to prepare a coating composition. Thereafter, a carbon fiber sheet having a width of 75mm and a length of 1,600mm was impregnated (nipping) with 30 wt% of the coating composition, and then dried at normal temperature to prepare an electrically driven catalyst.
Preparation example 2
50 to 80g of the catalyst powder of the synthesis example is mixed with 1 to 20g of an organosilicon polymer compound (a hydrolysis-condensation reaction product of alkoxysilane and water-dispersible silica having a hydroxyl group on the surface) to prepare a coating composition. Thereafter, a carbon fiber sheet having a width of 75mm and a length of 1,600mm was impregnated (nipping) with 30 wt% of the coating composition, and then dried at a temperature of 110 ℃ for 5 hours after being heated at 70 ℃ with stirring using a vacuum evaporator to prepare an electrically driven catalyst.
Preparation example 3
50 to 80g of the catalyst powder of the synthesis example is mixed with 1 to 20g of an organosilicon polymer compound (a hydrolysis-condensation reaction product of alkoxysilane and water-dispersible silica having a hydroxyl group on the surface) to prepare a coating composition. Thereafter, a carbon fiber sheet having a width of 75mm and a length of 1,600mm was impregnated (compacting) with 30 wt% of the coating composition, heated at 70 ℃ with stirring using a vacuum evaporator, dried at 110 ℃ for 5 hours, and then fired at 300 ℃ for 5 hours in an air atmosphere to prepare an electrically driven catalyst.
Preparation example 4
50 to 80g of the catalyst powder of the synthesis example is mixed with 1 to 20g of an organosilicon polymer compound (a hydrolysis-condensation reaction product of alkoxysilane and water-dispersible silica having a hydroxyl group on the surface) to prepare a coating composition. Thereafter, a carbon fiber sheet having a width of 75mm and a length of 1,600mm was impregnated (compacting) with 35 wt% of the coating composition, heated at 70 ℃ with stirring using a vacuum evaporator, dried at 110 ℃ for 5 hours, and then fired at 300 ℃ in an air atmosphere for 5 hours to prepare an electrically driven catalyst.
Preparation example 5
50 to 80g of the catalyst powder of the synthesis example is mixed with 1 to 20g of an organosilicon polymer compound (a hydrolysis-condensation reaction product of alkoxysilane and water-dispersible silica having a hydroxyl group on the surface) to prepare a coating composition. Thereafter, a carbon fiber sheet having a width of 70mm and a length of 300mm was impregnated (compacting) with 30 wt% of the coating composition, heated at 70 ℃ under stirring using a vacuum evaporator, dried at 110 ℃ for 5 hours, and then fired at 300 ℃ under an air atmosphere for 5 hours to prepare an electrically driven catalyst.
< examples and comparative examples: method for activating catalyst >
(1) Examples 1 to 8/comparative examples 1 to 8: measurement of denitrification efficiency with respect to round catalyst
1) Activation of the catalyst
As shown in table 1 below, the electrically-driven catalysts obtained in the preparation examples 1 to 4 were placed in a quartz tube after being wound in a round shape as shown in fig. 4 below after electrodes were attached to both ends thereof as shown in fig. 5 below. Then, NO and NH are added3、N2、O2、SOxThe mixed gas was introduced into the quartz tube at a flow rate of 6,609L/min, and a voltage was applied through the electrodes to activate the catalyst, thereby selectively reducing and removing Nitrogen Oxides (NO).
At this time, Nitrogen Oxide (NO) concentrations at the inlet (inlet) and outlet (outlet) of the quartz tube of each of the examples and comparative examples were measured using a Testo 350K flue gas analyzer (Tesco, germany), thereby measuring denitrification efficiency, and the results thereof are described in table 1 below.
Further, the temperature of the mixed gas at the outlet (outlet) and the temperature of the surface of the catalyst layer were measured using a K-type thermocouple thermometer and an infrared thermometer, and the results thereof are described in table 1 below.
2) Regeneration of catalyst
After the selective reduction removal of the Nitrogen Oxides (NO), an overvoltage of 25V or more is applied to the electrically driven catalyst to raise the catalyst surface temperature to 300 ℃ or more, and then the catalyst is maintained for 5 hours or more to remove catalyst contaminants, thereby regenerating the catalyst.
TABLE 1
Measurement results of denitrification efficiency with respect to round catalyst
As shown in table 1 above, it can be confirmed that when the catalyst is a circular catalyst, the denitrification efficiency is significantly increased in the embodiment in which the voltage applied to the catalyst is increased to 15V or more, as compared to the comparative example in which the voltage less than 15V is applied. In addition, in examples 1 to 8, the measured surface temperatures of the catalyst layers were all higher than the outlet gas temperature at the rear end of the reactor, and therefore it is considered that in the selective reduction removal reaction of nitrogen oxides by the catalyst, the movement of the remaining electrons inside the catalyst due to the electrical load is more active than the movement of the remaining electrons inside the catalyst due to the rise in the exhaust gas temperature due to the electrical heating and the thermal energy generated thereby, contributing more to the improvement of the catalytic efficiency.
(2) Examples 9 to 12: measurement of denitrification efficiency of plate catalyst
1) Activation of the catalyst
As shown in Table 2 below, 4 electrically-driven catalysts obtained in the preparation example 5 were installed after a quadrangular catalyst reactor as shown in FIG. 7 below, and NO, NH3、N2、O2、SOxThe mixed gas was introduced at a flow rate of 6,609L/min, and a voltage was applied to activate the catalyst, thereby selectively reducing and removing nitrogen oxides.
At this time, the Nitrogen Oxide (NO) concentrations at the inlet (let) and outlet (outlet) of the quadrangular catalyst reactor of each example were measured, and thus the denitrification efficiency was measured, and the results thereof are described in table 2 below.
In addition, the temperature of the surface of the catalyst layer was measured, and the results thereof are described in table 2 below.
2) Regeneration of catalyst
After the selective reduction removal of the Nitrogen Oxides (NO), an overvoltage of 25V or more is applied to the electrically driven catalyst to raise the catalyst surface temperature to 300 ℃ or more, and then the catalyst is maintained for 5 hours or more to remove catalyst contaminants, thereby regenerating the catalyst.
TABLE 2
Measurement result of denitrification efficiency of plate-type catalyst
As shown in table 2 above, it was confirmed that the denitrification efficiency significantly increased as the voltage applied to the catalyst increased in the case of the plate catalyst. In addition, in examples 9 to 12, the measured surface temperatures of the catalyst layers were all higher than the outlet gas temperature at the rear end of the reactor, and in the selective reduction removal reaction of nitrogen oxides by the catalyst, the movement of the remaining electrons inside the catalyst caused by the electrical load was more active than the movement of the remaining electrons inside the catalyst caused by the temperature rise of the exhaust gas due to electrical heating and the thermal energy generated thereby, contributing more to the improvement of the catalytic efficiency.
< test example >
With the electrically driven catalyst of preparation example 5 used in the nitrogen oxide selective reduction removal method performed in said example 9 as an object, a durability test was performed in the following manner, and the results thereof are described in table 3 below.
In said example 9, the outlet nitrogen oxide concentration (N1) after applying a voltage of 9.5V to the catalyst and maintaining the catalyst temperature at 200 ℃ for 1 hour and the outlet nitrogen oxide concentration (N2) after applying a voltage of 9.5V to the catalyst and maintaining the catalyst temperature at 200 ℃ for 2 hours were measured, respectively, to thereby obtain the denitrification efficiency.
TABLE 3
Durability measurement results for plate catalyst
As shown in table 3 above, the nitrogen oxide concentration at the outlet immediately after the temperature was raised to 200 ℃ was 6ppm, but the nitrogen oxide concentration at the outlet after the temperature was maintained at 200 ℃ for 1 hour was 2ppm, and the nitrogen oxide concentration at the outlet after the temperature was maintained at 200 ℃ for 2 hours was still 2ppm, and therefore, it was confirmed that the nitrogen removal efficiency was maintained at 90% or more.
Detailed description of the preferred embodiments
The catalyst activation method according to an embodiment of the present invention includes the steps of coating a conductive catalyst composition on a conductive substrate, and applying 1.00 × 10 to the conductive substrate coated with the conductive catalyst composition at a temperature of 20 to 200 deg.C-4V/mm2The above voltages.
The method for selectively removing nitrogen oxides according to an embodiment of the present invention includes the steps of coating a denitrification catalyst composition for Selective Catalytic Reduction (SCR) on a conductive substrate, and applying 1.00 × 10 to the conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR) in the presence of a mixed gas containing nitrogen oxides and having a temperature of 20 to 200 DEG C-4V/mm2The above voltages.
Claims (16)
1. A method of activating a catalyst, comprising the steps of:
coating a conductive catalyst composition on a conductive substrate; and
applying 1.00 × 10 to a conductive substrate coated with the conductive catalyst composition at a temperature of 20 ℃ to 200 ℃-4V/mm2The above voltages.
2. The catalyst activation method according to claim 1,
in the step of applying a voltage to the conductive substrate coated with the conductive catalyst composition, 1.00 × 10 was applied-4V/mm2～1.00×10-2V/mm2The voltage of (c).
3. The catalyst activation method according to claim 1,
in the step of applying a voltage to the conductive substrate coated with the conductive catalyst composition, the initial temperature rise rate of the conductive substrate is 5 ℃/sec to 14 ℃/sec.
4. The catalyst activation method according to claim 1,
the conductive substrate includes at least one selected from a carbon fiber plate, a nickel chromium plate, and a quartz plate.
5. The catalyst activation method according to claim 1,
the resistance of the conductive substrate is 10-15 omega.
6. The catalyst activation method according to claim 1,
the conductive catalyst composition includes a conductive catalyst and a binder compound.
7. The catalyst activation method according to claim 6,
the conductive catalyst includes at least one selected from a denitrification catalyst for Selective Catalytic Reduction (SCR), an oxidation catalyst, a VOC removal catalyst, and a photocatalyst.
8. The catalyst activation method according to claim 7,
in the denitrification catalyst for Selective Catalytic Reduction (SCR), 0.1 to 10 wt% of vanadium in the form of an oxide is supported on a titania carrier based on the catalyst.
9. The catalyst activation method according to claim 8,
in the titania carrier, the atomic ratio of oxygen to titanium (O/Ti) is in the range of 1.47 to 2.0.
10. The catalyst activation method according to claim 6,
the boiling point of the binder compound is 100-300 ℃.
11. The catalyst activation method according to claim 6,
the binder compound includes silica crosslinked by siloxane bonds represented by the following chemical formula 1,
chemical formula 1:
in the chemical formula 1, R1And R2The same or different, and each independently is an ether bond, hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
12. The catalyst activation method according to claim 1, characterized by further comprising:
a step of volatilizing a binder compound contained in the coated conductive catalyst composition after coating the conductive catalyst composition on the conductive substrate; and a step of firing the conductive catalyst contained in the coated conductive catalyst composition.
13. The catalyst activation method according to claim 12,
the step of volatilizing the binder compound contained in the coated conductive catalyst composition is performed at 100 to 200 c,
the step of firing the conductive catalyst contained in the coated conductive catalyst composition is performed at 300 to 400 ℃.
14. The catalyst activation method according to claim 1, characterized by further comprising:
applying 1.00 × 10 to the conductive substrate coated with the conductive catalyst composition at a temperature of 20 ℃ to 200 DEG C-4V/mm2After the step of applying the above voltage, the surface temperature of the catalyst is increased toAnd (3) regenerating the catalyst at a temperature of 300 ℃ or higher.
15. A method for selectively removing nitrogen oxides, comprising the steps of:
coating a denitrification catalyst composition for Selective Catalytic Reduction (SCR) on a conductive substrate; and
applying 1.00 × 10 to a conductive substrate coated with the denitrification catalyst composition for Selective Catalytic Reduction (SCR) in the presence of a mixed gas containing nitrogen oxide and having a temperature of 20-200 DEG C-4V/mm2The above voltages.
16. The method for selectively removing nitrogen oxides according to claim 15,
the mixed gas includes ammonia, nitrogen, oxygen, nitrogen oxides, and sulfur oxides.
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| KR102146304B1 (en) * | 2018-06-15 | 2020-08-20 | 재단법인 포항산업과학연구원 | Catalyst for exhaust gas purification and exhaust gas purifying method |
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| KR100549778B1 (en) * | 2003-09-27 | 2006-02-08 | 한국전력기술 주식회사 | Vanadium/titania-based catalyst for the removal of nitrogen oxide at low temperature, its uses and method of removing nitrogen oxide using the same |
| BR112014001813A2 (en) * | 2011-07-25 | 2017-02-21 | H2 Catalyst Llc | method and system of producing a catalyst for hydrogen production |
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| KR101629483B1 (en) * | 2015-02-27 | 2016-06-13 | 주식회사 에코프로 | Vanadium-based denitration catalyst and preparing method of the same |
| KR101566505B1 (en) * | 2015-05-12 | 2015-11-05 | 주식회사 지스코 | Method for regenerating scr catalyst |
| KR101860777B1 (en) * | 2017-12-11 | 2018-05-25 | 주식회사 지스코 | Method for activating catalyst, and method for selective removing of nitrogen oxide using the same |
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