CN114225972A - Sulfur poisoning resistant presulfurization SCR denitration catalyst and preparation method thereof - Google Patents
Sulfur poisoning resistant presulfurization SCR denitration catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 16
- 239000011593 sulfur Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 11
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000011261 inert gas Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000010926 purge Methods 0.000 claims abstract description 8
- 230000005587 bubbling Effects 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 10
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical group [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 5
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- XYWDPYKBIRQXQS-UHFFFAOYSA-N di-isopropyl sulphide Natural products CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 claims description 3
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 3
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 21
- 239000010453 quartz Substances 0.000 abstract description 11
- 238000005520 cutting process Methods 0.000 abstract description 5
- 238000005303 weighing Methods 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000003546 flue gas Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 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
- B01J37/20—Sulfiding
-
- 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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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- 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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- B01D2251/2062—Ammonia
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Abstract
The invention discloses a pre-vulcanized SCR denitration catalyst with sulfur poisoning resistance and a preparation method thereof, belonging to the field of catalyst preparation. The presulfurization SCR denitration catalyst with sulfur poisoning resistance and the preparation method thereof are characterized by comprising the following specific steps: (1) weighing a certain volume of prepared SCR denitration catalyst, and filling the prepared SCR denitration catalyst into a quartz glass tube; (2) continuously introducing inert gas into the quartz tube in the step (1), and heating the catalyst in the quartz tube by utilizing a heating furnace; (3) after the temperature of the catalyst in the step (2) is stable, continuously introducing a vulcanizing agent into the quartz glass tube by using another path of inert gas in a bubbling or gas distribution mode, and simultaneously stopping introducing the inert gas in the step (2); (4) and (3) cutting off one path of gas containing the vulcanizing agent after the vulcanizing is carried out for a period of time, closing heating, and simultaneously opening the inert gas in the step (2) for purging until the temperature of the catalyst is reduced to room temperature to obtain the pre-vulcanized SCR denitration catalyst.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a sulfur poisoning resistant pre-vulcanized SCR denitration catalyst and a preparation method thereof.
Background
The core of the SCR denitration technology is a denitration catalyst, the current commercial SCR denitration catalyst mainly comprises vanadium-titanium catalysts and manganese catalysts, and the denitration requirements of industrial flue gas of different types of kilns can be met by adjusting the content of main components of the catalysts. Most industrial flue gas generated by the kiln contains a certain amount of SO2In NH3SO in SCR denitration Process2Will react with O under the action of the denitration catalyst2Reaction to form SO3. Further, SO3Will react with water vapor and NH3Reaction to produce ammonium hydrogen sulfate (NH)4HSO4)，NH4HSO4Can adhere to the surface of the catalyst and cause the catalyst to be deactivated. Therefore, the sulfur poisoning resistance is an important index for measuring the performance of the SCR denitration catalyst.
For a denitration catalyst which is poisoned by sulfur in the practical application process, an on-line heating regeneration method is generally adopted to heat the denitration catalyst to more than 360 ℃ so as to enable NH attached to the surface of the catalyst4HSO4And (4) thermal decomposition. The method for post-treatment regeneration not only brings higher energy consumption to the use unit of the denitration catalyst, but also brings NH4HSO4The products after thermal decomposition can regenerate NH due to temperature reduction in subsequent environment-friendly treatment equipment4HSO4And cause corrosion of the equipment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a pre-vulcanized SCR denitration catalyst with sulfur poisoning resistance and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of an SCR denitration catalyst comprises the following steps:
loading a denitration catalyst into a container, and introducing inert gas for heating;
and adding a vulcanizing agent into the container to vulcanize the denitration catalyst.
Optionally, the inert gas is nitrogen, helium or argon.
Optionally, the vulcanizing agent is one or more of methyl mercaptan, ethyl mercaptan, ethylene glycol mercaptan, 1-propyl mercaptan, 1, 3-propanedithiol, 2-mercaptoethanol, thiophene, ethyl sulfide, methyl ethyl sulfide, thioanisole, thiophenol.
Optionally, the vulcanizing agent is introduced for 2-6 h.
Optionally, the denitration catalyst is a vanadium-titanium based denitration catalyst, a manganese based denitration catalyst, or a rare earth based denitration catalyst.
Optionally, the sulfiding agent is passed into the vessel with an inert gas.
Optionally, the sulfiding agent is bubbled or gassed into the vessel with an inert gas.
Optionally, introducing inert gas to purge and reduce the temperature after the vulcanization is finished.
Optionally, the container is a quartz tube.
In another aspect, the invention also includes an SCR denitration catalyst prepared by the above method.
A method for preventing sulfur poisoning of a denitration catalyst, comprising the steps of:
heating and vulcanizing the denitration catalyst under the protection of inert gas to generate O-M-S on the surface;
in the denitration process, water is introduced to react with O-M-S to generate hydrogen sulfide, and the hydrogen sulfide reacts with sulfur dioxide to generate elemental sulfur and water.
The invention has the beneficial effects that:
after the pre-vulcanization treatment is carried out on the SCR denitration catalyst by taking the organic sulfur compound as the vulcanizing agent, on one hand, SO in flue gas in the application process of the catalyst can be avoided2Conversion to SO3Thereby leading to the deactivation of the catalyst, and on the other hand, sulfur species on the surface of the catalyst after the pre-vulcanization treatment can be mixed with SO in the flue gas2The elemental sulfur which is easy to sublimate is generated by the reaction, the catalyst does not need to be heated and regenerated, and the corrosion to equipment such as a reactor and the like is avoided.
Drawings
The invention will be further described with reference to the accompanying drawings.
Fig. 1 is a schematic view of an SCR denitration catalyst presulfiding device according to the present application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In some examples of the invention, a preparation method of a pre-vulcanized SCR denitration catalyst with sulfur poisoning resistance is disclosed, which is characterized by comprising the following specific steps:
(1) weighing a certain volume of prepared SCR denitration catalyst, and filling the prepared SCR denitration catalyst into a quartz glass tube;
(2) continuously introducing inert gas into the quartz tube in the step (1), and heating the catalyst in the quartz tube by utilizing a heating furnace;
(3) after the temperature of the catalyst in the step (2) is stable, continuously introducing a vulcanizing agent into the quartz glass tube by using another path of inert gas in a bubbling or gas distribution mode, and simultaneously stopping introducing the inert gas in the step (2);
(4) and (3) cutting off one path of gas containing the vulcanizing agent after the vulcanizing is carried out for a period of time, closing heating, and simultaneously opening the inert gas in the step (2) for purging until the temperature of the catalyst is reduced to room temperature to obtain the pre-vulcanized SCR denitration catalyst.
In some examples, the SCR denitration catalyst in the step (1) is a vanadium-titanium-based denitration catalyst, a manganese-based denitration catalyst, a rare earth-based denitration catalyst;
in some examples, the inert gas in step (2) may be nitrogen (N)2) Helium (He), argon (Ar), gas purity>99.5 percent and the gas space velocity is 10000--1；
In some examples, the heating temperature in the step (2) is 200-500 ℃;
in some examples, the sulfurizing agent in step (2) may be, but is not limited to, one or more of methyl mercaptan, ethyl mercaptan, ethylene dithiol, 1-propyl mercaptan, 1, 3-propanedithiol, 2-mercaptoethanol, thiophene, ethyl sulfide, methyl ethyl sulfide, anisole, phenylene sulfide, and thiophenol;
in some examples, the type and flow rate of the other inert gas in the step (3) are consistent with the flow rate of the inert gas in the step (2); when the bubbling method is adopted, the temperature of the vulcanizing agent is room temperature;
in some examples, the vulcanizing agent in the step (3) is introduced for 2-6 h;
in some examples, the inert gas purge flow in step (4) is consistent with step (2).
The invention has the advantages that: after the pre-vulcanization treatment is carried out on the SCR denitration catalyst by taking the organic sulfur compound as the vulcanizing agent, on one hand, SO in flue gas in the application process of the catalyst can be avoided2Conversion to SO3Thereby leading to the deactivation of the catalyst, and on the other hand, sulfur species on the surface of the catalyst after the pre-vulcanization treatment can be mixed with SO in the flue gas2The elemental sulfur which is easy to sublimate is generated by the reaction, the catalyst does not need to be heated and regenerated, and the corrosion to equipment such as a reactor and the like is avoided.
Specifically, in the above process, the sulfur species on the surface of the pre-sulfided catalyst can be represented as O-M-S, which can be hydrolyzed with water in the flue gas or water generated in the denitration reaction to generate H during the reaction process2S，H2S is continuously reacted with SO under the action of catalyst2The neutralization reaction is carried out to generate the elemental sulfur (S) which is easy to sublimate. The reaction principle is expressed by the following chemical equation:
O-M-S+H2O→O-M-O+H2S
2H2S+SO2→3S+2H2O
wherein M represents a metal (V, Mn, rare earth metal) in the metal oxide of the active component of the catalyst, and O-M-S represents that an oxygen atom O is connected with a metal atom M and a sulfur atom S in turn by a chemical bond.
For example, the chemical formula or specific structural formula of O-M-S can be:
wherein Mn-Mn, V-V and Re-rare earth metal atom.
Specific examples of the preparation method of the SCR denitration catalyst are further disclosed below.
Example 1
(1) Weighing prepared V in a volume of 10mL2O5-WO3/TiO2The denitration catalyst is filled in a quartz glass tube with the inner diameter of 2 cm;
(2) continuously introducing common nitrogen with the flow rate of 1.67L/min into the quartz tube in the step (1), and then heating the catalyst in the quartz tube to 500 ℃ from room temperature by using a heating furnace;
(3) after the heating is stable, introducing nitrogen into a reagent bottle filled with ethanethiol liquid through another pipeline according to the flow of 1.67L/min, carrying ethanethiol into a quartz glass tube filled with a catalyst in a bubbling manner, stopping introducing the nitrogen in the step (2) at the same time;
(4) and (3) vulcanizing at 500 ℃ for 2h, cutting off the introduction of ethanethiol and nitrogen, closing heating, and opening the nitrogen in the step (2) for purging until the temperature of the catalyst is reduced to room temperature, thus obtaining the pre-vulcanized SCR denitration catalyst.
The performance evaluation of the denitration catalyst before and after pre-vulcanization is carried out under the following reaction conditions:
reaction conditions are as follows: NO concentration 2000ppm, NH3Concentration 2000ppm, 5 vol.% H2O，10vol.％O2The others are Ar, and the space velocity is 20000h-1The reaction temperature was 150 ℃. The denitration performance is shown in Table 1.
Reaction conditions 2: NO concentration 2000ppm, NH3Concentration 2000ppm, SO2Concentration 1000ppm, 5 vol.% H2O，10vol.％O2The others are Ar, and the space velocity is 20000h-1The reaction temperature was 150 ℃. The denitration performance is shown in Table 1.
Example 2
(1) Weighing prepared MnO of 10mL volume2-Fe2O3-CeO2/TiO2The denitration catalyst is filled in a quartz glass tube with the inner diameter of 2 cm;
(2) continuously introducing common argon with the flow rate of 3.3L/min into the quartz tube in the step (1), and then heating the catalyst in the quartz tube to 200 ℃ from room temperature by using a heating furnace;
(3) after the heating is stable, introducing argon into a reagent bottle filled with ethyl sulfide liquid through another pipeline according to the flow of 3.3L/min, carrying the ethyl sulfide into a quartz glass tube filled with a catalyst in a bubbling mode, stopping simultaneously, and stopping introducing the argon in the step (2);
(4) and (3) vulcanizing at 200 ℃ for 6h, cutting off the introduction of the ethyl sulfide and argon, closing heating, and simultaneously opening the argon in the step (2) for purging until the temperature of the catalyst is reduced to room temperature, thus obtaining the pre-vulcanized SCR denitration catalyst.
The performance evaluation of the denitration catalyst before and after pre-vulcanization is carried out under the following reaction conditions:
reaction conditions are as follows: NO concentration 2000ppm, NH3Concentration 2000ppm, 5 vol.% H2O，10vol.％O2The others are Ar, and the space velocity is 20000h-1The reaction temperature was 150 ℃. The denitration performance is shown in Table 1.
Reaction conditions 2: NO concentration 2000ppm, NH3Concentration 2000ppm, SO2Concentration 1000ppm, 5 vol.% H2O，10vol.％O2The others are Ar, and the space velocity is 20000h-1The reaction temperature was 150 ℃. The denitration performance is shown in Table 1.
Example 3
(1) Weighing prepared La in 10mL volume2O3-WO3/TiO2The denitration catalyst is filled in a quartz glass tube with the inner diameter of 2 cm;
(2) continuously introducing common nitrogen with the flow rate of 2.5L/min into the quartz tube in the step (1), and then heating the catalyst in the quartz tube to 400 ℃ from room temperature by using a heating furnace;
(3) after the heating is stable, introducing nitrogen into a reagent bottle filled with thiophene liquid through another pipeline according to the flow of 2.5L/min, carrying thiophene into a quartz glass tube filled with a catalyst in a bubbling mode, stopping simultaneously, and stopping introducing the nitrogen in the step (2);
(4) and (3) vulcanizing at 400 ℃ for 4h, cutting off the introduction of thiophene and nitrogen, closing heating, and opening the nitrogen in the step (2) for purging at the same time until the temperature of the catalyst is reduced to room temperature to obtain the pre-vulcanized SCR denitration catalyst.
The performance evaluation of the denitration catalyst before and after pre-vulcanization is carried out under the following reaction conditions:
reaction conditions are as follows: NO concentration 2000ppm, NH3Concentration 2000ppm, 5 vol.% H2O，10vol.％O2The others are Ar, and the space velocity is 20000h-1The reaction temperature was 150 ℃. The denitration performance is shown in Table 1.
Reaction conditions 2: NO concentration 2000ppm, NH3Concentration 2000ppm, SO2Concentration 1000ppm, 5 vol.% H2O，10vol.％O2The others are Ar, and the space velocity is 20000h-1The reaction temperature was 150 ℃. The denitration performance is shown in Table 1.
TABLE 1 denitration Performance of catalyst
The test results show that the SCR denitration catalysts obtained by high-temperature pre-sulfurization with organic sulfur obtained in the embodiments 1, 2 and 3 have denitration efficiency without SO2Under the working condition, the catalyst is close to an unvulcanized catalyst, but contains SO2Under the working condition, the catalyst is obviously higher than the denitration catalyst which is not subjected to presulfurization treatment. The above results show that the denitration catalyst obtained after high-temperature pre-vulcanization with organic sulfur has excellent sulfur poisoning resistance and excellent denitration activity.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing embodiments illustrate and describe the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the SCR denitration catalyst is characterized by comprising the following steps of:
loading a denitration catalyst into a container, and introducing inert gas for heating;
adding a vulcanizing agent into the container to vulcanize the denitration catalyst to generate O-M-S species.
2. The SCR denitration catalyst of claim 1, wherein the inert gas is nitrogen, helium or argon.
3. The method for preparing an SCR denitration catalyst according to claim 1, wherein the sulfiding agent is one or more of methyl mercaptan, ethyl mercaptan, ethylene glycol mercaptan, 1-propyl mercaptan, 1, 3-propanedithiol, 2-mercaptoethanol, thiophene, ethyl sulfide, methyl ethyl sulfide, anisole, diphenyl sulfide, and thiophenol.
4. The preparation method of the SCR denitration catalyst according to claim 1, wherein the continuous adding time of the vulcanizing agent is 2-6 h.
5. The method of preparing an SCR denitration catalyst according to claim 1, wherein the denitration catalyst is a vanadium-titanium-based denitration catalyst, a manganese-based denitration catalyst, or a rare earth-based denitration catalyst.
6. The method for preparing an SCR denitration catalyst according to claim 1, wherein the sulfiding agent is introduced into the vessel with an inert gas by bubbling or gas distribution.
7. The preparation method of the SCR denitration catalyst according to claim 1, wherein an inert gas is introduced to purge and reduce the temperature after the vulcanization is finished.
8. An SCR denitration catalyst, O-M-S is formed on the surface.
9. A method for preventing sulfur poisoning of a denitration catalyst is characterized by comprising the following steps:
heating and vulcanizing the denitration catalyst under the protection of inert gas to generate O-M-S on the surface;
in the denitration process, water is introduced to react with O-M-S to generate hydrogen sulfide, and the hydrogen sulfide reacts with sulfur dioxide to generate elemental sulfur and water.
10. The method of claim 1, wherein the denitration catalyst is a vanadium-titanium-based denitration catalyst, a manganese-based denitration catalyst, or a rare earth-based denitration catalyst.
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