CN113996289A - Hollow carbon sphere denitration catalyst for low-temperature flue gas and preparation method thereof - Google Patents
Hollow carbon sphere denitration catalyst for low-temperature flue gas and preparation method thereof Download PDFInfo
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- CN113996289A CN113996289A CN202111338740.2A CN202111338740A CN113996289A CN 113996289 A CN113996289 A CN 113996289A CN 202111338740 A CN202111338740 A CN 202111338740A CN 113996289 A CN113996289 A CN 113996289A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000003546 flue gas Substances 0.000 title claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 239000003112 inhibitor Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 20
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 11
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 9
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 244000282866 Euchlaena mexicana Species 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 abstract description 17
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 239000001272 nitrous oxide Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 102000029749 Microtubule Human genes 0.000 description 2
- 108091022875 Microtubule Proteins 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 210000004688 microtubule Anatomy 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
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- B01D2258/0283—Flue gases
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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
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Abstract
The invention relates to the technical field of catalysts containing metal or metal oxide or hydroxide, and discloses a hollow carbon sphere denitration catalyst for low-temperature flue gas and a preparation method thereof, wherein the hollow carbon sphere denitration catalyst comprises a hollow carbon sphere serving as a carrier, manganese dioxide serving as an active component loaded on the inner surface and the outer surface of the hollow carbon sphere, and a cocatalyst loaded on the inner surface and the outer surface of the hollow carbon sphere together with the active component; the hollow carbon spheres are carbon oxide spheres, holes for gas to enter and exit are formed in the spherical shell, and the catalyst promoter is an inhibitor for reducing the oxidizability of manganese dioxide. In the invention, the hollow carbon spheres are carbon oxide spheres with oxidizing groups capable of adsorbing ammonia on the inner and outer surfaces, and the inner and outer surfaces can play a role in catalysis, which is equivalent to a micro tube with uniform aperture, short length and difficult blockage, thereby greatly improving the adsorption capacity and catalytic reaction efficiency of the catalyst; the original strong oxidizing property of manganese dioxide is adjusted through load modification, and the catalytic action on the side reaction for generating nitrous oxide is reduced.
Description
Technical Field
The invention relates to the technical field of catalysts containing metal or metal oxide or hydroxide, in particular to a hollow carbon sphere denitration catalyst for low-temperature flue gas and a preparation method thereof.
Background
With the development of human social productivity, the demand for energy is increasing, and the use of energy is accompanied by the generation of nitrogen oxides, including nitrogen oxides released from nitrogen elements in fossil fuels, nitrogen oxides generated by the reaction of nitrogen and oxygen in the air in a high-temperature environment, and nitrogen oxides generated by the reaction of nitrogen and oxygen in the air broken down during discharge. These nitrogen oxides cause acid rain, photochemical smog, and are seriously harmful to human health.
At present, the mature denitration method is to adopt ammonia gas or urea to catalyze and reduce nitrogen oxide, and the most common denitration catalyst is a vanadium-based catalyst, namely V2O5As an active ingredient, WO3As an auxiliary agent, TiO2The catalyst is a carrier and is widely applied to the electric power industry and the automobile exhaust treatment. The working temperature of the vanadium-based catalyst is 300-400 ℃, which is suitable for the smoke temperature of the conventional coal-fired boiler before entering the economizer (a tubular heat exchanger for smoke heat recovery).
In order to reduce haze, coal-to-gas conversion is generally carried out on various boilers such as heating boilers and the like in various cities including Beijing at present, namely, coal-fired boilers are converted into natural gas boilers. For a natural gas boiler, because natural gas is subjected to desulfurization treatment before entering the boiler, the sulfur content in boiler flue gas is low, and SO does not need to be considered in flue gasXThe temperature of the flue gas can be reduced to be very low, and is usually about 120-180 ℃. And because the whole combustion process of the natural gas boiler is carried out in a gas phase, the common natural gas boiler is structurally a large-size tubular heat exchanger, the combustion and the heat recovery of the flue gas are carried out simultaneously, which is equivalent to two-in-one of a coal-fired boiler and an economizer, high-temperature flue gas which is positioned in front of the economizer like the coal-fired boiler does not exist, and the existing vanadium-based catalyst cannot be used.
The vanadium-based catalyst is not the only available denitration catalyst, and the active component can play a catalytic role as long as the active component has a plurality of valence states which are easy to be mutually converted. Various transition metal oxides such as Mn, Co, Ce, Fe, Cu and the like can play a catalytic role, the required reaction temperature is lower, and the catalyst is called as a low-temperature SCR catalyst. The manganese-based catalyst has strong oxidation-reduction performance, can keep higher denitration activity at low temperature, and is a research hotspot in the field of low-temperature denitration catalysts at present. Of manganese-based catalysts of the several classes, MnO2The activity was the highest.
But existing MnO2The catalyst has two problems, one is that in low-temperature flue gas such as a natural gas boiler, denitration efficiency cannot meet the demand, and the other is that it also has a catalytic effect on parallel side reactions for generating nitrous oxide (Liu C, Gao G, Shi J W, et al, MnOx-CeO)2 shell-in-shell microspheres for NH3-SCR de-NOx at low temperature[J]. Catalysis Communications, 2016. Tangchangjin, Sun Jing Fang, Dong Lin, ultra-low temperature (ultra-low temperature) ((A))<Research progress of 150 ℃) SCR denitration technology [ J]In the chemical report, 71(11): 12), nitrous oxide is very stable in low-temperature flue gas and cannot be reduced, and the nitrous oxide is discharged into the atmosphere to cause serious greenhouse effect.
For MnO2In the case of the catalyst, because the reaction activity is very high, the rate determining step is adsorption in seven steps (external diffusion, internal diffusion, adsorption, reaction, desorption, internal diffusion and external diffusion) of the heterogeneous catalytic reaction in the catalytic denitration process.
Note that, unlike CN108906074A, a low-temperature SCR catalyst using carbon spheres as a template and a preparation method thereof, the carbon spheres in CN108906074A are a template agent, and are burned off during the preparation process, and the finished catalyst does not contain carbon.
Disclosure of Invention
The invention provides a hollow carbon sphere denitration catalyst for low-temperature flue gas and a preparation method thereof.
The technical problem to be solved is that: existing MnO2The catalyst has two problems, one is that in low-temperature flue gas such as a natural gas boiler, denitration efficiency cannot meet the demand, and the other is that it is easy to catalytically generate nitrous oxide.
In order to solve the technical problems, the invention adopts the following technical scheme: a hollow carbon sphere denitration catalyst for low-temperature flue gas is used for a denitration device using ammonia or urea as a reducing agent; the manganese dioxide catalyst comprises hollow carbon spheres serving as a carrier, manganese dioxide serving as an active component and loaded on the inner and outer surfaces of the hollow carbon spheres, and a cocatalyst loaded on the inner and outer surfaces of the hollow carbon spheres together with the active component;
the hollow carbon spheres are carbon oxide spheres, holes for gas to enter and exit are formed in the spherical shells of the hollow carbon spheres, and the catalyst promoter is an inhibitor for reducing the oxidizability of manganese dioxide.
Further, the catalyst promoter is an oxide of cobalt, and the oxide of cobalt is one or a mixture of two of cobaltous oxide and cobalt monoxide.
Further, the outer diameter of the hollow carbon sphere is 200-400 nm.
Further, in the catalyst, the mass ratio of manganese dioxide to hollow carbon spheres is 1: 0.1 to 5; the mass ratio of the cobalt oxide to the hollow carbon spheres is 0.05-0.1: 1.
a preparation method of a hollow carbon sphere denitration catalyst for low-temperature flue gas is used for preparing the hollow carbon sphere denitration catalyst for low-temperature flue gas, and comprises the following steps:
the method comprises the following steps: preparing hollow carbon spheres by a template method;
step two: oxidizing the surface of the hollow carbon sphere with an oxidant solution;
step three: manganese dioxide is loaded on the surface of the hollow carbon sphere by a hydrothermal method,
step four: and putting the hollow carbon spheres into a cobalt salt solution, then evaporating the cobalt salt solution to dryness, and carrying out anaerobic roasting to obtain a catalyst finished product.
Further, the step one specifically comprises the following sub-steps:
step 1.1: uniformly mixing the hollow carbon sphere raw materials, and filtering to obtain filter residues; the hollow carbon sphere raw materials comprise ammonia water, TEOS, formaldehyde, resorcinol and ethanol; the detailed process of uniformly mixing the hollow carbon sphere raw materials is as follows: adding TEOS into the mixed solution of ethanol and ammonia water, slowly stirring uniformly, then adding formaldehyde and resorcinol, and continuously stirring;
step 1.2: washing the filter residue to be neutral, and then, carrying out anaerobic roasting on the filter residue;
step 1.3: and removing the template agent by using hydrofluoric acid, then filtering, and washing filter residues to be neutral to obtain the hollow carbon spheres.
Further, in the hollow carbon sphere raw material in the step 1.1, the concentration of ethanol is 75-95% vt, and the molar ratio of resorcinol to formaldehyde is 1: 0.5-1, wherein in the mixed solution of ethanol and ammonia water, the volume ratio of the ammonia water to the ethanol is 1: 20-50.
Further, in the step 1.2, the filter residue is roasted in argon gas, the roasting temperature is 500-800 ℃, and the roasting time is 3-8 h; and in the fourth step, the hollow carbon spheres are roasted in argon at the roasting temperature of 300-500 ℃ for 5-10 h.
Further, in the cobalt salt solution in the fourth step, the cobalt ions are divalent cobalt ions and/or trivalent cobalt ions, and the acid ions are carbonate and/or nitrate.
Compared with the prior art, the hollow carbon sphere denitration catalyst for low-temperature flue gas and the preparation method thereof have the following beneficial effects:
in the invention, the hollow carbon spheres with the outer diameter of 200-400nm are used as the carrier of the catalyst, the sphere shell of each hollow carbon sphere is provided with holes, and the inner surface and the outer surface of each hollow carbon sphere can play a role in catalysis, so that the catalyst has a great specific surface area, and the catalytic reaction efficiency is greatly improved;
in the invention, the hollow carbon spheres are equivalent to microtubules with uniform aperture, short length and difficult blockage, and a large amount of gas-phase reactants are adsorbed in the spherical shell due to micropore filling and capillary condensation, including NO which is difficult to be adsorbed, so that the adsorption capacity and catalytic reaction efficiency of the catalyst are further improved, and the microtubules are difficult to be blocked like carbon nanotubes, and the time required by internal diffusion is also obviously reduced;
in the invention, the hollow carbon spheres are carbon oxide spheres with oxidizing groups on the inner and outer surfaces, can provide more active acid sites (L acid), and selectively increase the NH of the catalyst as a reducing agent3The adsorption of (2) further improves the catalytic reaction efficiency of the catalyst;
according to the invention, the manganese dioxide is subjected to load modification by adopting the cobalt oxide, the acidity of the surface of the catalyst is adjusted, the original strong oxidizing property of the manganese dioxide is changed, and the catalytic action on the side reaction generating the nitrous oxide is reduced, so that the selectivity of the catalyst is improved, and the nitrous oxide in the product is reduced.
Drawings
FIG. 1 is an SEM image of a catalyst in the present invention, in which the electron microscope is a scanning electron microscope of Hitachi SU8010, in which the outer diameter of each hollow carbon sphere is 200-400 nm;
FIG. 2 is a TEM image of the catalyst of the present invention, wherein the electron microscope is a TALOS F200 transmission electron microscope, and the outer diameter of each hollow carbon sphere is 200-400 nm.
Detailed Description
Note that, in the present application, the surface treatment of the hollow carbon sphere refers to the simultaneous treatment of the inner and outer surfaces.
As shown in fig. 1-2, a hollow carbon sphere denitration catalyst for low-temperature flue gas is used in a denitration device using ammonia or urea as a reducing agent; the manganese dioxide catalyst comprises hollow carbon spheres serving as a carrier, manganese dioxide serving as an active component and loaded on the inner and outer surfaces of the hollow carbon spheres, and a cocatalyst loaded on the inner and outer surfaces of the hollow carbon spheres together with the active component;
the low-temperature flue gas in the present application generally refers to flue gas at 120-. The catalyst in the present application was found to work normally at operating temperatures of 120 ℃ to 160 ℃. The catalyst may in particular be loaded in a fixed bed/fluidized bed/slurry bed reactor.
The hollow carbon spheres are carbon oxide spheres, and as can be seen from fig. 1, holes for gas to enter and exit are formed in the spherical shells of the hollow carbon spheres, and the catalyst promoter is an inhibitor for reducing the oxidizability of manganese dioxide. The holes for gas to enter and exit are not closed on the hollow carbon sphere in nature, and hydrofluoric acid enters the sphere along the holes in the process of removing the template agent.
In this embodiment, the promoter is cobalt oxide, and the cobalt oxide is one or a mixture of two of cobalt oxide and cobalt monoxide. It has been found that the addition of cobalt oxide is effective in increasing the selectivity, and that after the addition of cobalt oxide the nitrous oxide concentration in the treated exhaust gas is reduced to trace levels.
The outer diameter of the hollow carbon sphere is 200-400 nm. Hollow carbon spheres of this size have a specific surface area that is sufficiently large so as not to adversely affect internal diffusion. In the catalyst, the mass ratio of manganese dioxide to hollow carbon spheres is 1: 0.1 to 5; the mass ratio of the cobalt oxide to the hollow carbon spheres is 0.05-0.1: 1.
a preparation method of a hollow carbon sphere denitration catalyst for low-temperature flue gas is used for preparing the hollow carbon sphere denitration catalyst for low-temperature flue gas, and comprises the following steps:
the method comprises the following steps: preparing hollow carbon spheres by a template method;
step two: oxidizing the surface of the hollow carbon sphere with an oxidant solution; the oxidant solution is 20mM-40mM potassium permanganate solution; dispersing the hollow carbon spheres synthesized in the step one in a potassium permanganate aqueous solution and carrying out ultrasonic treatment; thus, the potassium permanganate plays the role of an oxidant and the role of a reactant of a hydrothermal reaction at the same time, and weak parts on the hollow carbon spheres are expanded into regular holes;
step three: transferring the potassium permanganate aqueous solution in the second step into a hydrothermal reaction kettle for reaction, and loading manganese dioxide on the surface of the hollow carbon spheres by a hydrothermal method, wherein the hydrothermal reaction temperature is 2-3 hours and is 120-150 ℃; finally, collecting the hollow carbon spheres loaded with manganese dioxide through centrifugation;
step four: and putting the hollow carbon spheres into a cobalt salt solution, then evaporating the cobalt salt solution to dryness, and carrying out anaerobic roasting to obtain a catalyst finished product.
The first step specifically comprises the following sub-steps:
step 1.1: uniformly mixing the hollow carbon sphere raw materials, and filtering to obtain filter residues; the hollow carbon sphere raw materials comprise ammonia water, TEOS, formaldehyde, resorcinol and ethanol; the detailed process of uniformly mixing the hollow carbon sphere raw materials is as follows: adding TEOS into the mixed solution of ethanol and ammonia water, slowly stirring uniformly, adding formaldehyde and resorcinol, and continuously stirring for 10-20 h;
step 1.2: washing the filter residue to be neutral, and then, carrying out anaerobic roasting on the filter residue;
step 1.3: removing the template agent by using hydrofluoric acid, then filtering, and washing filter residue to be neutral to obtain hollow carbon spheres;
step 1.1, in the hollow carbon sphere raw material, the concentration of ethanol is 75-95% vt, and the molar ratio of resorcinol to formaldehyde is 1: 0.5-1, wherein in the mixed solution of ethanol and ammonia water, the volume ratio of the ammonia water to the ethanol is 1: 20-50, the preferable formula of the mixed solution of ethanol and ammonia water is ammonia water: deionized water: ethanol = 3: 10: 70;
in step 1.2, the filter residue is roasted in argon at 500-800 deg.C, preferably 650-750 deg.C for 3-8 h.
In the fourth step, the hollow carbon spheres are roasted in argon at the temperature of 300-500 ℃, preferably at the temperature of 300-350 ℃ for 5-10 h.
In the cobalt salt solution in the fourth step, cobalt ions are divalent cobalt ions and/or trivalent cobalt ions, acid radical ions are carbonate and/or nitrate, and the preferable formula is that the ratio of cobalt nitrate to cobalt carbonate is 1: 1-1.2 preparing solution.
In the process of practical use, only the cobalt nitrate and the cobalt carbonate have good loading effect, and the cobalt nitrate and the cobalt carbonate are mixed for use to improve the effect to a certain extent, but the effect is not obvious. From the xrf results we hypothesize that cobalt nitrate favors the formation of cobaltous oxide, whereas cobalt carbonate favors the formation of cobaltous oxide.
We formulated two groups of catalysts for testing, as follows:
example 1:
firstly, uniformly mixing 600mL of 80% ethanol and 20mL of ammonia water, then adding 25mL of ethyl orthosilicate into the mixed solution, stirring for one hour at room temperature, adding 4mL of 40% formaldehyde solution and 3g of resorcinol, stirring overnight, carrying out suction filtration and washing to neutrality, then transferring the material into a tubular furnace, carbonizing for 4 hours at 800 ℃ under argon atmosphere, cooling to room temperature, washing a silicon-based template by using hydrofluoric acid with the concentration of 10%, and washing with deionized water to neutrality to obtain the hollow carbon sphere.
The hollow carbon spheres obtained above were dispersed in 80mL of 0.1M acidic KMnO4In the solution, the mixed solution is subjected to ultrasonic treatment for 15min, then is subjected to hydrothermal synthesis for 10h at 150 ℃, and then is filtered and washed to be neutral, so that the manganese dioxide-loaded hollow carbon spheres are obtained.
30 mmol of cobalt salt was dissolved in 30mL of 0.2M diluted HNO3And then putting the hollow carbon spheres loaded with manganese dioxide into the catalyst, fully mixing, evaporating to dryness, and roasting at 300 ℃ for 10 hours under an argon atmosphere to obtain a catalyst finished product.
Example 2:
firstly, uniformly mixing 800mL of 75% ethanol and 30mL of ammonia water, then adding 30mL of ethyl orthosilicate into the mixed solution, stirring for one hour at room temperature, then adding 6mL of 30% formaldehyde solution and 2.5g of resorcinol, stirring overnight, then carrying out suction filtration and washing to neutrality, then transferring the material into a tubular furnace, carbonizing at 600 ℃ for 4 hours under argon atmosphere, cooling to room temperature, washing a silicon-based template by using hydrofluoric acid with the concentration of 8%, and washing with deionized water to neutrality to obtain the hollow carbon sphere.
The hollow carbon spheres obtained above were dispersed in 60mL of 0.2M acidic KMnO4And in the solution, carrying out ultrasonic treatment on the mixed solution for 40min, carrying out hydrothermal synthesis at 180 ℃ for 6h, filtering and washing to be neutral to obtain the manganese dioxide-loaded hollow carbon spheres.
Dissolving 20 millimole of cobalt salt in 30mL of deionized water, then putting the hollow carbon spheres loaded with manganese dioxide into the deionized water, fully mixing, evaporating to dryness, and roasting at 330 ℃ for 6 hours under an argon atmosphere to obtain a catalyst finished product.
The performance of the catalysts in both examples is shown in table 1:
TABLE 1 specific surface area and reaction conversion ratio of two catalysts
As can be seen from table 1, the specific surface area and catalytic activity of the catalyst prepared in the present application are significantly improved compared to the existing catalysts.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A hollow carbon sphere denitration catalyst for low-temperature flue gas is used for a denitration device using ammonia or urea as a reducing agent; the method is characterized in that: the manganese dioxide catalyst comprises hollow carbon spheres serving as a carrier, manganese dioxide serving as an active component and loaded on the inner and outer surfaces of the hollow carbon spheres, and a cocatalyst loaded on the inner and outer surfaces of the hollow carbon spheres together with the active component;
the hollow carbon spheres are carbon oxide spheres, holes for gas to enter and exit are formed in the spherical shells of the hollow carbon spheres, and the catalyst promoter is an inhibitor for reducing the oxidizability of manganese dioxide.
2. The hollow carbon sphere denitration catalyst for low-temperature flue gas according to claim 1, characterized in that: the catalyst promoter is cobalt oxide, and the cobalt oxide is one or a mixture of cobaltous oxide and cobaltous oxide.
3. The hollow carbon sphere denitration catalyst for low-temperature flue gas according to claim 1, characterized in that: the outer diameter of the hollow carbon sphere is 200-400 nm.
4. The hollow carbon sphere denitration catalyst for low-temperature flue gas according to claim 1, characterized in that: in the catalyst, the mass ratio of manganese dioxide to hollow carbon spheres is 1: 0.1 to 5; the mass ratio of the cobalt oxide to the hollow carbon spheres is 0.05-0.1: 1.
5. a preparation method of a hollow carbon sphere denitration catalyst for low-temperature flue gas is characterized by comprising the following steps: the preparation method of the hollow carbon sphere denitration catalyst for low-temperature flue gas, which is disclosed by claim 2, comprises the following steps:
the method comprises the following steps: preparing hollow carbon spheres by a template method;
step two: oxidizing the surface of the hollow carbon sphere with an oxidant solution;
step three: manganese dioxide is loaded on the surface of the hollow carbon sphere by a hydrothermal method,
step four: and putting the hollow carbon spheres into a cobalt salt solution, then evaporating the cobalt salt solution to dryness, and carrying out anaerobic roasting to obtain a catalyst finished product.
6. The preparation method of the hollow carbon sphere denitration catalyst for low-temperature flue gas according to claim 5, wherein the preparation method comprises the following steps: the first step specifically comprises the following sub-steps:
step 1.1: uniformly mixing the hollow carbon sphere raw materials, and filtering to obtain filter residues; the hollow carbon sphere raw materials comprise ammonia water, TEOS, formaldehyde, resorcinol and ethanol; the detailed process of uniformly mixing the hollow carbon sphere raw materials is as follows: adding TEOS into the mixed solution of ethanol and ammonia water, slowly stirring uniformly, then adding formaldehyde and resorcinol, and continuously stirring;
step 1.2: washing the filter residue to be neutral, and then, carrying out anaerobic roasting on the filter residue;
step 1.3: and removing the template agent by using hydrofluoric acid, then filtering, and washing filter residues to be neutral to obtain the hollow carbon spheres.
7. The preparation method of the hollow carbon sphere denitration catalyst for low-temperature flue gas according to claim 6, characterized by comprising the following steps: in the hollow carbon sphere raw material in the step 1.1, the concentration of ethanol is 75-95% vt, and the molar ratio of resorcinol to formaldehyde is 1: 0.5-1, wherein in the mixed solution of ethanol and ammonia water, the volume ratio of the ammonia water to the ethanol is 1: 20-50.
8. The preparation method of the hollow carbon sphere denitration catalyst for low-temperature flue gas according to claim 6, characterized by comprising the following steps: in the step 1.2, the filter residue is roasted in argon gas, the roasting temperature is 500-800 ℃, and the roasting time is 3-8 h; and in the fourth step, the hollow carbon spheres are roasted in argon at the roasting temperature of 300-500 ℃ for 5-10 h.
9. The preparation method of the hollow carbon sphere denitration catalyst for low-temperature flue gas according to claim 5, wherein the preparation method comprises the following steps: in the second step, the oxidant solution is a potassium permanganate solution;
the second step is as follows: dispersing the hollow carbon spheres synthesized in the step one in a potassium permanganate aqueous solution and carrying out ultrasonic treatment;
the third step is as follows: and transferring the potassium permanganate aqueous solution in the second step into a hydrothermal reaction kettle for reaction, wherein the hydrothermal reaction temperature is 2-3 hours and 120-150 ℃, and finally, collecting the hollow carbon spheres loaded with manganese dioxide through centrifugation.
10. The preparation method of the hollow carbon sphere denitration catalyst for low-temperature flue gas according to claim 5, wherein the preparation method comprises the following steps: in the cobalt salt solution in the fourth step, the cobalt ions are divalent cobalt ions and/or trivalent cobalt ions, and the acid ions are carbonate and/or nitrate.
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|---|---|---|---|---|
| CN115920900A (en) * | 2022-11-24 | 2023-04-07 | 大唐南京环保科技有限责任公司 | Supermolecule low-temperature honeycomb denitration catalyst with ball-like structure and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003340282A (en) * | 2002-05-22 | 2003-12-02 | Osaka Gas Co Ltd | Low temperature denitration catalyst, and low temperature denitration method for exhaust gas |
| WO2010083247A1 (en) * | 2009-01-16 | 2010-07-22 | Intematix Corporation | PROCESS FOR SYNTHESIZING LixFeMZO4 / CARBON AND LixMZO4 / CARBON COMPOSITE MATERIALS |
| CN104324729A (en) * | 2014-10-08 | 2015-02-04 | 重庆大学 | Flue gas low temperature denitration cobalt manganese oxide catalyst and preparation method thereof |
| WO2016150406A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere, and preparation and application thereof |
| CN106409522A (en) * | 2016-10-10 | 2017-02-15 | 华南师范大学 | Manganese dioxide-coated hollow carbon spheres and preparation method and application thereof |
| CN107126955A (en) * | 2017-06-01 | 2017-09-05 | 重庆大学 | A kind of base low-temperature sintered catalyst for denitrating flue gas of charcoal and preparation method |
| CN108906074A (en) * | 2018-07-18 | 2018-11-30 | 江苏新沃催化剂有限公司 | It is a kind of using carbon ball as low-temperature SCR catalyst of template and preparation method thereof |
-
2021
- 2021-11-12 CN CN202111338740.2A patent/CN113996289B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003340282A (en) * | 2002-05-22 | 2003-12-02 | Osaka Gas Co Ltd | Low temperature denitration catalyst, and low temperature denitration method for exhaust gas |
| WO2010083247A1 (en) * | 2009-01-16 | 2010-07-22 | Intematix Corporation | PROCESS FOR SYNTHESIZING LixFeMZO4 / CARBON AND LixMZO4 / CARBON COMPOSITE MATERIALS |
| CN104324729A (en) * | 2014-10-08 | 2015-02-04 | 重庆大学 | Flue gas low temperature denitration cobalt manganese oxide catalyst and preparation method thereof |
| WO2016150406A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere, and preparation and application thereof |
| CN106409522A (en) * | 2016-10-10 | 2017-02-15 | 华南师范大学 | Manganese dioxide-coated hollow carbon spheres and preparation method and application thereof |
| CN107126955A (en) * | 2017-06-01 | 2017-09-05 | 重庆大学 | A kind of base low-temperature sintered catalyst for denitrating flue gas of charcoal and preparation method |
| CN108906074A (en) * | 2018-07-18 | 2018-11-30 | 江苏新沃催化剂有限公司 | It is a kind of using carbon ball as low-temperature SCR catalyst of template and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| FENGYU GAO 等: "Co- or Ni-modified Sn-MnOx low-dimensional multi-oxides for high-efficient NH3-SCR De-NOx: Performance optimization and reaction mechanism", 《JOURNAL OF ENVIRONMENTAL SCIENCES》, vol. 113, pages 204 - 218 * |
| LIN CHEN 等: "Low-temperature NH3-SCR activity of M (M = Zr, Ni and Co) doped MnOx supported biochar catalysts", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》, vol. 9, no. 6, pages 1 - 12 * |
| 姚小江 等: "非钒基脱硝催化剂上副产物N2O的控制研究", 《第二十五届大气污染防治技术研讨会论文集》, pages 453 * |
| 邹浩 等: "N2O在锰系低温催化剂上的生成途径", 《燃烧科学与技术》, vol. 21, no. 4, pages 293 - 296 * |
| 郑德洲: "二氧化锰及其复合物的制备和电化学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 1, pages 46 - 47 * |
| 陈丙义 等: "《物理化学》", 徐州：中国矿业大学出版社, pages: 184 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115920900A (en) * | 2022-11-24 | 2023-04-07 | 大唐南京环保科技有限责任公司 | Supermolecule low-temperature honeycomb denitration catalyst with ball-like structure and preparation method thereof |
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