CN114984944B - Preparation method of high-sulfur-resistance low-temperature SCR catalyst - Google Patents
Preparation method of high-sulfur-resistance low-temperature SCR catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004005 microsphere Substances 0.000 claims abstract description 38
- 239000006104 solid solution Substances 0.000 claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000008103 glucose Substances 0.000 claims abstract description 12
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000002149 hierarchical pore Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 231100000572 poisoning Toxicity 0.000 abstract description 7
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000019635 sulfation Effects 0.000 abstract description 3
- 238000005670 sulfation reaction Methods 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 27
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 16
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 16
- 229910044991 metal oxide Inorganic materials 0.000 description 13
- 150000004706 metal oxides Chemical class 0.000 description 13
- 239000011229 interlayer Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 230000002950 deficient Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion 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
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
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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
- B01J23/83—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 rare earths or actinides
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- B01J35/396—
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- B01J35/51—
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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 invention provides a preparation method of a high sulfur-resistant low-temperature SCR catalyst, which comprises the following steps: mixing cerium nitrate hexahydrate a with manganese nitrate solution, adding glycol for hydrothermal reaction, cooling, centrifuging, drying and roasting to obtain MnCeOx solid solution microspheres; dissolving glucose and p-phenylenediamine in deionized water, adding MnCeOx solid solution microspheres for hydrothermal carbonization reaction, cooling, washing and drying to obtain an N-doped porous carbon coated MnCeOx@C material; mixing metal salt and cerium nitrate hexahydrate b, dissolving in deionized water, adding N-doped porous carbon coated MnCeOx@C material, performing ultrasonic dispersion, and N 2 Calcining for 3h to obtain the high sulfur resistance low temperature SCR catalyst. The catalyst of the invention utilizes a multishell structure to sequentially limit denitration active sites and SO 2 Adsorption site and catalytic decomposition of metal active site of ABS, solving the problem of NH 3 And SO 2 ABS deposition and metal sulfation problems caused by co-adsorption at the denitrating active site, and has high SO concentration resistance 2 Poisoning and heightAnd the low-temperature denitration performance is effectively stabilized.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a high-sulfur-resistance low-temperature SCR catalyst.
Background
In recent years, the non-electric industry has gradually become a major area of coal-fired flue gas remediation, with NOx emission control being an important issue. Low temperature NH 3 SCR denitration technology<The catalyst can be arranged after dedusting or desulfurization at 300 ℃, so that the influence of dust erosion on the catalyst is reduced, and the catalyst has the advantages of simple smoke composition, low energy consumption, low transformation cost and the like, so that the denitration process is paid attention to. However, under the condition of low temperature<300 ℃ and SO in the flue gas 2 Has strong poisoning effect on SCR catalyst, and limits the industrial application thereof. The sulfur poisoning of the SCR catalyst is caused by two reasons, firstly, the generated Ammonium Bisulfate (ABS) is difficult to decompose below 300 ℃, so that the blocking of catalytic active sites and the corrosion of equipment are caused, and the service lives of the catalyst and the equipment are reduced. Secondly, SO 2 React with the metal active component to generate metal sulfate, resulting in reduced catalyst activity. The development of the high-efficiency sulfur poisoning resistant low-temperature SCR catalyst has important practical significance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a high sulfur-resistant low-temperature SCR catalyst aiming at the defects of the prior art, wherein the catalyst utilizes a multi-shell structure to sequentially limit denitration active sites and SO 2 Adsorption site and catalytic decomposition of metal active site of ABS, solving the problem of NH 3 And SO 2 ABS deposition and metal sulfation problems caused by co-adsorption at the denitrating active site, and has high SO concentration resistance 2 Poisoning and high-efficiency stable low-temperature denitration performance.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a high sulfur-resistant low-temperature SCR catalyst comprises the following steps:
s1, mixing cerium nitrate hexahydrate a and 50% manganese nitrate solution by mass fraction, adding into ethylene glycol, uniformly stirring, carrying out hydrothermal reaction for 15h at 180 ℃, cooling, centrifuging, drying a precipitate at 80 ℃ for 5h, and roasting at 550 ℃ for 6h to obtain MnCeOx solid solution microspheres;
s2, dissolving glucose and p-phenylenediamine in deionized water to obtain a mixed solution, dispersing the MnCeOx solid solution microspheres obtained in the S1 in the mixed solution uniformly by ultrasonic assistance, carrying out hydrothermal carbonization reaction at 160 ℃ for 16 hours, cooling, washing and drying to obtain an N-doped porous carbon coated MnCeOx@C material;
according to the invention, glucose provides a carbon source and is used as an interlayer of the finally prepared high-sulfur-resistance low-temperature SCR catalyst, and the thickness of the interlayer can be regulated and controlled by regulating the addition amount of glucose; the phenylenediamine is used as a nitrogen source, and the N doping amount of the interlayer of the finally prepared high-sulfur-resistance low-temperature SCR catalyst can be adjusted by adjusting the addition amount of the p-phenylenediamine;
s3, mixing metal salt and cerium nitrate hexahydrate b, then dissolving in deionized water, uniformly dispersing and mixing by utilizing ultrasonic assistance to obtain metal salt mixed solution, adding the N-doped porous carbon coated MnCeOx@C material obtained in S2 into the metal salt mixed solution, performing ultrasonic dispersion, uniformly stirring, and then N 2 Calcining for 3 hours at the temperature of 500 ℃ under the protection to obtain a multi-shell core MnCeOx@C@MCeox catalyst coated by oxygen-enriched defective metal oxide, namely a high sulfur-resistant low-temperature SCR catalyst;
the metal ion (M) in the metal salt is W 6+ 、Fe 3+ Or Sb (Sb) 3+ 。
The inner core of the high sulfur-resistant low-temperature SCR catalyst prepared by the invention is MnCeOx solid solution microspheres, and the N-doped porous carbon material is used as an interlayer and an oxygen-enriched defect metal oxide shell. The core solid solution metal oxide is an oxide of two elements of Mn and Ce with a molar ratio of 2:1; the thickness of the interlayer N-doped porous carbon material is 3-10 mu m; the shell metal oxide is an oxide of two elements of M (W, mo or Fe) and Ce in a molar ratio of (1-2) 1. The invention successfully realizes the spatial separation of multiple active sites by utilizing the space-time ordered effect of the multi-shell structure, isolates the denitration sites in the MnCeOx solid solution microspheres of the inner core, and further absorbs the interlayer N-doped porous carbon material with high selectivityAttached SO 2 And simultaneously inhibit SO 2 Diffuse to the inner core and expose the ABS catalytic site to the oxygen-enriched defect metal oxide of the outer shell to solve the problem of NH 3 And SO 2 ABS deposition and metal sulfation problems caused by co-adsorption at the denitration active site.
Preferably, the molar ratio of Mn element to Ce element in the MnCeOx solid solution microsphere in S1 is 2:1, and the MnCeOx solid solution microsphere provides a denitration active site.
Preferably, the particle size of the MnCeOx solid solution microspheres in S1 is 10-20 μm.
Preferably, the thickness of the interlayer N-doped porous carbon material coated on the outer side of the MnCeOx solid solution microsphere in the N-doped hierarchical pore carbon coated MnCeOx@C material in S2 is 3-10 μm, and the N-doped porous carbon material adsorbs SO 2 。
Preferably, the particle size of the high sulfur-resistant low temperature SCR catalyst in S3 is 30-80 μm.
Preferably, the dosage ratio of the glucose, the p-phenylenediamine, the deionized water and the MnCeOx solid solution microspheres in the S2 is (2.5 g-3.75 g): 0.27g:50mL:3.6g.
Preferably, the molar ratio of the metal salt in S3 to the metal atom and Ce atom in cerium nitrate hexahydrate b is (1-2): 1, and the oxygen-enriched defective metal oxide is obtained to catalyze the decomposition of ABS.
The denitration rate of the high sulfur-resistant low-temperature SCR catalyst of the invention is close to 100 percent at 240-280 ℃, the temperature is kept at 240 ℃, and 400ppm SO is introduced 2 After the reaction is carried out for 10 hours, the denitration rate is 93 to 96 percent, and the denitration rate is stabilized to 86 to 91 percent after 50 hours.
Compared with the prior art, the invention has the following advantages:
the invention utilizes a multi-shell core structure to sequentially limit denitration active sites and SO 2 Adsorption site and catalytic decomposition of metal active site of ABS to solve NH 3 And SO 2 Co-adsorption at the denitrification site. Firstly, constructing a multi-shell structure dual-function low-temperature catalyst, and utilizing the space-time ordering of the multi-shell structure to enable an ABS catalytic site to expose the outer surface and a denitration site to be isolated in an inner core so as to realize the space separation of dual active sites; secondly, the first step of the method comprises the steps of,the oxygen-enriched defect metal oxide is used for fast catalytic decomposition of ABS through cooperation of oxygen vacancies and metal sites; the interlayer N-doped hierarchical pore carbon material has high-efficiency SO 2 Selectively adsorb and further inhibit SO 2 And the ABS is diffused to the inner shell, so that the ABS is generated to stay on the surface of the catalyst outer shell, and the denitration active site of the inner core is protected. The synergistic effect of the multi-shell structure is effective on the high-efficiency denitration reaction characteristic and the long-acting sulfur-resistant action mechanism, so that the low-temperature high-efficiency denitration long-acting sulfur-resistant performance of the SCR catalyst is realized. Finally, the preparation of the multi-shell structure is realized by a sequential hydrothermal method and an impregnation method, and the microsphere, the N-doped porous carbon material interlayer and the shell metal oxide coating structure are sequentially synthesized in situ in one step, so that the method is simple and easy to operate, does not need to use solutions such as strong acid, strong alkali and the like, and does not generate secondary pollution and the like.
The invention is described in further detail below with reference to the drawings and examples.
Drawings
Fig. 1 is a TEM image of MnCeOx solid solution microspheres prepared in step S1 of example 1 of the present invention.
Fig. 2 is a TEM image of an N-doped hierarchical pore carbon coated mnceox@c material agent prepared by step S2 of example 1 of the present invention.
Fig. 3 is a TEM image of the high sulfur tolerant low temperature SCR catalyst of example 1 of the present invention.
FIG. 4 is a graph of pore size distribution of a multiple shell core catalyst of the present invention.
FIG. 5 is a thermogravimetric analysis multishell core MnCeOx@C@SbCoOx catalyst of comparative example 1 of the present invention versus ABS catalytic decomposition.
Detailed Description
Example 1
The preparation method of the high sulfur-resistant low-temperature SCR catalyst comprises the following steps:
s1, mixing 2.17g of cerium nitrate hexahydrate a and 2.33mL of 50% manganese nitrate solution, adding the mixture into 60mL of ethylene glycol, stirring the mixture uniformly for 30min, transferring the mixture into a polytetrafluoroethylene lining stainless steel autoclave, carrying out hydrothermal reaction for 15h at the temperature of 180 ℃, naturally cooling the mixture to room temperature, washing a precipitate with absolute ethyl alcohol, centrifugally collecting the precipitate, drying the centrifuged precipitate at the temperature of 80 ℃ for 5h, and roasting the dried precipitate at the temperature of 550 ℃ for 6h to obtain MnCeOx solid solution microspheres with the particle size of 10-20 mu m (TEM image is shown in figure 1), wherein the MnCeOx material is spherical and has a smooth surface and the particle size of 10-20 mu m as shown in figure 1; the mol ratio of Mn element to Ce element in the MnCeOx solid solution microspheres is 2:1;
s2, 2.5g of glucose (carbon source) and 0.27g of p-phenylenediamine (nitrogen source) are dissolved in 50mL of deionized water to obtain a mixed solution, 3.6g of MnCeOx solid solution microspheres obtained in S1 are dispersed in the mixed solution, ultrasonic assisted dispersion is uniform, hydrothermal carbonization reaction is carried out for 16 hours at 160 ℃, cooling, washing and drying are carried out to obtain an N-doped hierarchical pore carbon coated MnCeOx@C material, which is marked as MnCeOx@C-1 (TEM image is shown in figure 2), and compared with the MnCeOx microspheres before carbon coating, the particle size of the coated MnCeOx C material is slightly increased, the spherical structure of the coated MnCeOx C material is maintained, the thickness of a carbon coating layer is uniform, and the coated carbon coating layer has an obvious shell structure;
the thickness of the interlayer N-doped porous carbon material coated on the outer side of the MnCeOx solid solution microsphere in the N-doped hierarchical pore carbon coated MnCeOx@C material is 3-8 mu m;
s3, mixing 9.44g of metal salt (ammonium tungstate hexahydrate) and 2.17g of cerium nitrate hexahydrate b, dissolving in deionized water, uniformly dispersing and mixing by ultrasonic assistance to obtain a metal salt mixed solution, adding 4g of the N-doped porous carbon coated MnCeOx@C material obtained in S2 into the metal salt mixed solution, performing ultrasonic dispersion, uniformly stirring, and then N 2 Calcining for 3 hours at 500 ℃ under the protection condition to obtain a multi-shell core MnCeOx@C@WCeox catalyst coated by oxygen-enriched defective metal oxide, namely a high sulfur-resistant low-temperature SCR catalyst (TEM image is shown as figure 3), wherein the obtained high sulfur-resistant low-temperature SCR catalyst has a spherical structure with dispersed size and a particle size range of 30-80 mu m; w in the ammonium tungstate hexahydrate b 6+ And Ce in ammonium tungstate hexahydrate b 3+ The molar ratio of (2) is 1:1;
and testing the denitration dynamic sulfur-resistant activity research of the catalyst under the simulated flue gas condition, wherein the test flue gas condition is as follows: n (N) 2 、O 2 (6vol.％)、NO(500ppm)、NH 3 (500ppm)、SO 2 (400 ppm) and the like, the reaction temperature is 80-280 ℃, the gas flow is 1.2L/min, and the airspeed is 75,000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Reaction time (-50 h).
Firstly, a denitration activity test is carried out on a high sulfur-resistant low-temperature SCR catalyst (multi-shell core MnCeOx@C@WCeox catalyst), and SO is not introduced 2 When the reaction temperature is 80-240 ℃, the denitration rate of the multi-shell core MnCeOx@C@WCeOx catalyst is increased along with the increase of the reaction temperature, the denitration performance is optimal at 240-280 ℃, the denitration rate is close to 100%, and the result shows that the multi-shell core MnCeOx@C@WCeOx catalyst has high denitration activity at low temperature. Maintaining the temperature at 240 ℃, introducing 400ppm SO 2 After the reaction is carried out for 10 hours, the denitration rate is 96%, and the denitration rate is stabilized to about 89% after 50 hours; the multi-shell core MnCeOx@C@WCeox catalyst has good SO resistance 2 Performance.
Under the same condition, the denitration performance of the MnCeOx microsphere catalyst (MnCeOx solid solution microsphere prepared in S1) is tested without introducing SO 2 When the denitration performance reaches the optimum at 240 ℃, the denitration rate reaches 96%, and the denitration rate is stable at 240-280 ℃.240 ℃ and 400ppm SO 2 The denitration rate is 87% after 10 hours of reaction, and the denitration rate is stabilized to about 68% after 50 hours;
meanwhile, the denitration performance of MnCeOx@C-2 (N-doped hierarchical pore carbon coated MnCeOx@C material prepared in S2) is tested, and SO is not introduced 2 When the denitration performance reaches the optimum at 240 ℃, the denitration rate reaches 98%, and the denitration rate is stable at 240-280 ℃.240 ℃ and 400ppm SO 2 After 10 hours of reaction, the denitration rate is 91%, and after 50 hours, the denitration rate is stabilized to about 83%; compared with MnCeOx microsphere catalyst (MnCeOx solid solution microsphere prepared in S1), the addition of the carbon layer improves SO resistance of the catalyst 2 Performance.
Example 2
The preparation method of the high sulfur-resistant low-temperature SCR catalyst comprises the following steps:
s1, mixing 2.17g of cerium nitrate hexahydrate a with 2.33mL of 50% manganese nitrate solution, adding the mixture into 60mL of ethylene glycol, stirring the mixture uniformly for 30min, transferring the mixture into a polytetrafluoroethylene lining stainless steel autoclave, carrying out hydrothermal reaction for 15h at the temperature of 180 ℃, naturally cooling the mixture to room temperature, washing a precipitate with absolute ethyl alcohol, centrifugally collecting the precipitate, drying the centrifuged precipitate at the temperature of 80 ℃ for 5h, and roasting the dried precipitate at the temperature of 550 ℃ for 6h to obtain MnCeOx solid solution microspheres with the particle size of 10-20 mu m; the mol ratio of Mn element to Ce element in the MnCeOx solid solution microspheres is 2:1;
s2, dissolving 2.5g of glucose and 0.27g of p-phenylenediamine in 50mL of deionized water to obtain a mixed solution, dispersing 3.6g of MnCeOx solid solution microspheres obtained in S1 in the mixed solution, uniformly dispersing by ultrasonic assistance, performing hydrothermal carbonization reaction at 160 ℃ for 16 hours, and cooling, washing and drying to obtain an N-doped hierarchical pore carbon coated MnCeOx@C material agent;
the thickness of the interlayer N-doped porous carbon material coated on the outer side of the MnCeOx solid solution microsphere in the N-doped hierarchical pore carbon coated MnCeOx@C material is 3-8 mu m;
s3, mixing 4.04g of metal salt (ferric nitrate nonahydrate) and 2.17g of cerium nitrate hexahydrate b, dissolving in deionized water, uniformly dispersing and mixing by using ultrasonic assistance to obtain a metal salt mixed solution, adding 4g of the N-doped porous carbon coated MnCeOx@C material obtained in S2 into the metal salt mixed solution, performing ultrasonic dispersion, uniformly stirring, and then N 2 Calcining for 3 hours at 500 ℃ under the protection to obtain a multi-shell core MnCeOx@C@FeCeOx catalyst coated by oxygen-enriched defective metal oxide with the particle size of 30-80 μm, namely the high sulfur-resistant low-temperature SCR catalyst; fe in the ferric nitrate nonahydrate 3+ And ammonium tungstate hexahydrate b in a molar ratio of 2:1;
denitration activity test is carried out on the multi-shell core MnCeOx@C@FeCeOx catalyst coated by oxygen-enriched defective metal oxide, and SO is not introduced 2 The denitration performance reaches the optimum at 240-280 ℃ and the denitration rate is about 99%. Maintaining the temperature at 240 ℃, introducing 400ppm SO 2 After the reaction is carried out for 10 hours, the denitration rate is 93 percent, and the efficiency is reduced and stabilized to about 86 percent after 50 hours; the multi-shell core MnCeOx@C@FeCeOx catalyst has good SO resistance 2 Performance of。
Example 3
The preparation method of the high sulfur-resistant low-temperature SCR catalyst comprises the following steps:
s1, mixing 2.17g of cerium nitrate hexahydrate a with 2.33mL of 50% manganese nitrate solution, adding the mixture into 60mL of ethylene glycol, stirring the mixture uniformly for 30min, transferring the mixture into a polytetrafluoroethylene lining stainless steel autoclave, carrying out hydrothermal reaction for 15h at the temperature of 180 ℃, naturally cooling the mixture to room temperature, washing a precipitate with absolute ethyl alcohol, centrifugally collecting the precipitate, drying the centrifuged precipitate at the temperature of 80 ℃ for 5h, and roasting the dried precipitate at the temperature of 550 ℃ for 6h to obtain MnCeOx solid solution microspheres with the particle size of 10-20 mu m; the mol ratio of Mn element to Ce element in the MnCeOx solid solution microspheres is 2:1;
s2, dissolving 3.75g of glucose and 0.27g of p-phenylenediamine in 50mL of deionized water to obtain a mixed solution, dispersing 3.6g of MnCeOx solid solution microspheres obtained in S1 in the mixed solution uniformly by ultrasonic assistance, carrying out hydrothermal carbonization reaction at 160 ℃ for 16 hours, cooling, washing and drying to obtain an N-doped hierarchical pore carbon coated MnCeOx@C material agent which is marked as MnCeOx@C-2;
the thickness of the interlayer N-doped porous carbon material coated on the outer side of the MnCeOx solid solution microsphere in the N-doped hierarchical pore carbon coated MnCeOx@C material is 5-10 mu m;
as shown in FIG. 4, 3.75g of glucose is added in the embodiment to regulate the thickness of the carbon layer, so that the MnCeOx@C-2 microsphere catalyst is prepared, and the result shows that the catalyst has good sphericity, smooth outer surface and mainly distributed sphere diameters of micropores and mesopores, and the sphere diameters are mainly concentrated between 0.8 and 13 nm. The MnCeOx@C-1 microsphere catalyst prepared by adding 2.5g of glucose in example 1 has wide sphere diameter distribution, mainly comprises micropores and mesopores, and mainly concentrates between 1.0 and 15nm, and the multi-shell core MnCeOx@C@WCeox catalyst prepared in example 1 can be found to have a hierarchical pore structure in a pore size distribution curve, and a large number of micropores exist, SO that the SO (sulfur oxide) improvement is facilitated 2 Adsorption performance.
S3, 2.99g of a metal salt (acetic acidAntimony) and 2.17g cerium nitrate hexahydrate b are mixed and then dissolved in deionized water, ultrasonic-assisted dispersion and uniform mixing are utilized to obtain metal salt mixed solution, then 4g of N-doped porous carbon coated MnCeOx@C material obtained in S2 is added into the metal salt mixed solution, ultrasonic dispersion and uniform stirring are carried out, and then N is obtained 2 Calcining for 3 hours at 500 ℃ under the protection to obtain a multi-shell core MnCeOx@C@SbCoOx catalyst coated by oxygen-enriched defective metal oxide with the particle size of 30-80 μm, namely a high sulfur-resistant low-temperature SCR catalyst; sb in the ammonium tungstate hexahydrate 3+ And ammonium tungstate hexahydrate b in a molar ratio of 2:1;
the denitration activity test of the catalyst shows that when SO is not introduced 2 The denitration performance reaches the best at 200-280 ℃ and the denitration rate reaches 100%. Maintaining the temperature at 240 ℃, introducing 400ppm SO 2 After the reaction is carried out for 10 hours, the denitration rate exceeds 95%, and the denitration efficiency is stabilized to about 91% after 50 hours; the multi-shell core MnCeOx@C@SbCEOx catalyst has good SO resistance 2 Performance.
Comparative example 1
The embodiment is a preparation method of an ammonium bisulfate poisoning catalyst with a load mass fraction of 5%, which comprises the following steps:
and (3) weighing 0.05g of ammonium bisulfate reagent, dissolving the ammonium bisulfate reagent in deionized water, immersing 1g of the multi-shell core MnCeOx@C@SbCEOx catalyst coated by the oxygen-enriched defective metal oxide prepared in the embodiment 3 into the ammonium bisulfate solution, uniformly mixing, stirring in a water bath at 80 ℃ for 6 hours, drying in an oven at 105 ℃ for 6 hours, and preparing the Ammonium Bisulfate (ABS) poisoning catalyst with the load mass fraction of 5 wt%, namely 5 wt% ABS-MnCeOx@C@SbCEOx.
The denitration performance of the MnCeOx@C@SbCoOx catalyst poisoned by ABS is researched, and the denitration rate is maintained to be more than 96 percent at 240-280 ℃. Maintaining the temperature at 240 ℃, introducing 400ppm SO 2 After the reaction is carried out for 10 hours, the denitration rate exceeds 91 percent, and the denitration efficiency is stabilized to about 85 percent after 50 hours; the multi-shell core MnCeOx@C@SbCEOx catalyst has high-efficiency SO resistance 2 Performance.
Meanwhile, as shown in fig. 5, the thermogravimetric analysis is carried out on pure ammonium bisulfate and an ammonium bisulfate poisoning catalyst ABS-MnCeOx@C@SbCoOx, and the pure ABS is found to be decomposed at the decomposition temperature of 290-600 ℃ and is completely decomposed at the temperature of nearly 600 ℃; the ABS decomposition temperature of the ABS-MnCeOx@C@SbCoOx is obviously shifted to low temperature, and the decomposition is started when the temperature is reduced to 240 ℃, so that the decomposition is complete when the temperature is 480 ℃, which shows that the multi-shell MnCeOx@C@SbCoOx catalyst can reduce the ABS decomposition temperature for ABS and has good ABS catalytic decomposition capability.
TABLE 1 denitration sulfur resistance Properties of the respective catalysts of examples 1 to 3 and comparative example 1
Note that: a, no SO 2 Adding; b: 400ppm SO is added into the flue gas 2 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature was 240 ℃.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (7)
1. The preparation method of the high sulfur-resistant low-temperature SCR catalyst is characterized by comprising the following steps:
s1, mixing cerium nitrate hexahydrate a and 50% manganese nitrate solution by mass fraction, adding into ethylene glycol, uniformly stirring, carrying out hydrothermal reaction for 15h at 180 ℃, cooling, centrifuging, drying a precipitate at 80 ℃ for 5h, and roasting at 550 ℃ for 6h to obtain MnCeOx solid solution microspheres;
s2, dissolving glucose and p-phenylenediamine in deionized water to obtain a mixed solution, dispersing the MnCeOx solid solution microspheres obtained in the S1 in the mixed solution uniformly by ultrasonic assistance, carrying out hydrothermal carbonization reaction at 160 ℃ for 16 hours, cooling, washing and drying to obtain an N-doped porous carbon coated MnCeOx@C material;
s3, mixing the metal salt and cerium nitrate hexahydrate b, then dissolving the mixture in deionized water, uniformly dispersing and mixing the mixture by utilizing ultrasonic assistance to obtain a metal salt mixed solution, and then mixing the metal salt mixed solutionAdding the N-doped porous carbon coated MnCeOx@C material obtained in S2 into the metal salt mixed solution, performing ultrasonic dispersion, uniformly stirring, and then N 2 Calcining for 3 hours at the temperature of 500 ℃ under the protection to obtain the high sulfur-resistant low-temperature SCR catalyst;
the metal ion in the metal salt is W 6+ 、Fe 3+ Or Sb (Sb) 3+ 。
2. The method for preparing the high sulfur-resistant low-temperature SCR catalyst according to claim 1, wherein the molar ratio of Mn element to Ce element in the MnCeOx solid solution microspheres in S1 is 2:1.
3. The method for preparing the high sulfur-resistant low-temperature SCR catalyst according to claim 1, wherein the particle size of the MnCeOx solid solution microspheres in S1 is 10-20 μm.
4. The preparation method of the high sulfur resistance low temperature SCR catalyst according to claim 1, wherein the thickness of the N-doped porous carbon material coated on the outer side of the MnCeOx solid solution microspheres in the N-doped hierarchical pore carbon coated MnCeOx@C material in S2 is 3-10 μm.
5. The method for preparing a high sulfur-resistant low temperature SCR catalyst according to claim 1, wherein the particle size of the high sulfur-resistant low temperature SCR catalyst in S3 is 30 μm to 80 μm.
6. The preparation method of the high sulfur-resistant low-temperature SCR catalyst according to claim 1, wherein the dosage ratio of glucose, p-phenylenediamine, deionized water and MnCeOx solid solution microspheres in S2 is (2.5 g-3.75 g): 0.27g:50mL:3.6g.
7. The method for preparing a high sulfur-resistant low temperature SCR catalyst according to claim 1, wherein the molar ratio of metal ions to Ce atoms in the metal salt in S3 and cerium nitrate hexahydrate b is (1-2): 1.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335604A (en) * | 2011-07-21 | 2012-02-01 | 上海大学 | SCR (selective catalyctic reduction) low-temperature denitrification catalyst with nano core-shell structure and preparation method thereof |
| CN104857950A (en) * | 2015-03-27 | 2015-08-26 | 西安交通大学 | Manganese-cerium composite oxide low-temperature denitration catalyst with hollow multi-shell microsphere structure |
| CN105289644A (en) * | 2015-11-13 | 2016-02-03 | 华北电力大学 | Flat-plate type sulfur-resistant low-temperature SCR denitration catalyst and preparation method thereof |
| WO2019144572A1 (en) * | 2018-01-24 | 2019-08-01 | 清华大学 | Manganese-based catalyst, preparation method therefor and application thereof |
| CN111001416A (en) * | 2019-12-25 | 2020-04-14 | 佛山科学技术学院 | Preparation method of composite manganese-based low-temperature sulfur-resistant denitration catalyst and catalyst |
| CN111250078A (en) * | 2020-04-10 | 2020-06-09 | 江西农业大学 | MnOx @ Eu-CeOx low-temperature SCR flue gas denitration catalyst and preparation method and application thereof |
| CN112403488A (en) * | 2020-12-16 | 2021-02-26 | 南京师范大学 | Low-sulfur-resistant low-temperature carbon-based denitration catalyst and preparation method and application thereof |
| US11247197B1 (en) * | 2020-11-11 | 2022-02-15 | Kunming University Of Science And Technology | Core-shell structured catalyst, preparation method thereof and method for treating industrial tail gas |
| CN114293223A (en) * | 2021-11-22 | 2022-04-08 | 江西师范大学 | Method for preparing superfine cerium dioxide supported metal single-atom catalyst from cluster-based framework material |
| CN114433074A (en) * | 2022-01-20 | 2022-05-06 | 大连海事大学 | Petal-shaped manganese-cerium composite oxide denitration catalyst and preparation method thereof |
-
2022
- 2022-06-24 CN CN202210729708.5A patent/CN114984944B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335604A (en) * | 2011-07-21 | 2012-02-01 | 上海大学 | SCR (selective catalyctic reduction) low-temperature denitrification catalyst with nano core-shell structure and preparation method thereof |
| CN104857950A (en) * | 2015-03-27 | 2015-08-26 | 西安交通大学 | Manganese-cerium composite oxide low-temperature denitration catalyst with hollow multi-shell microsphere structure |
| CN105289644A (en) * | 2015-11-13 | 2016-02-03 | 华北电力大学 | Flat-plate type sulfur-resistant low-temperature SCR denitration catalyst and preparation method thereof |
| WO2019144572A1 (en) * | 2018-01-24 | 2019-08-01 | 清华大学 | Manganese-based catalyst, preparation method therefor and application thereof |
| CN111001416A (en) * | 2019-12-25 | 2020-04-14 | 佛山科学技术学院 | Preparation method of composite manganese-based low-temperature sulfur-resistant denitration catalyst and catalyst |
| CN111250078A (en) * | 2020-04-10 | 2020-06-09 | 江西农业大学 | MnOx @ Eu-CeOx low-temperature SCR flue gas denitration catalyst and preparation method and application thereof |
| US11247197B1 (en) * | 2020-11-11 | 2022-02-15 | Kunming University Of Science And Technology | Core-shell structured catalyst, preparation method thereof and method for treating industrial tail gas |
| CN112403488A (en) * | 2020-12-16 | 2021-02-26 | 南京师范大学 | Low-sulfur-resistant low-temperature carbon-based denitration catalyst and preparation method and application thereof |
| CN114293223A (en) * | 2021-11-22 | 2022-04-08 | 江西师范大学 | Method for preparing superfine cerium dioxide supported metal single-atom catalyst from cluster-based framework material |
| CN114433074A (en) * | 2022-01-20 | 2022-05-06 | 大连海事大学 | Petal-shaped manganese-cerium composite oxide denitration catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| A hollow structure WO3@CeO2 catalyst for NH3-SCR of NOx;Xiaoping Chen等;《Catalysis Communications》;第149卷;第1-3页 * |
| An overview of the deactivation mechanism and modification methods of the SCR catalysts for denitration from marine engine exhaust;Shuo Feng等;《Journal ofEnvironmentalManagement》;第1-23页 * |
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