CN113634254B - Non-road field denitration catalyst coating material and application thereof - Google Patents
Non-road field denitration catalyst coating material and application thereof Download PDFInfo
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- CN113634254B CN113634254B CN202110930938.3A CN202110930938A CN113634254B CN 113634254 B CN113634254 B CN 113634254B CN 202110930938 A CN202110930938 A CN 202110930938A CN 113634254 B CN113634254 B CN 113634254B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000000576 coating method Methods 0.000 title claims abstract description 48
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008213 purified water Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 7
- 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 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 239000006255 coating slurry Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 7
- 150000004706 metal oxides Chemical class 0.000 abstract description 7
- 231100000614 poison Toxicity 0.000 abstract description 5
- 239000003440 toxic substance Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 230000001934 delay Effects 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 4
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing 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
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/70—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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8875—Germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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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
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Materials Engineering (AREA)
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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a denitration catalyst coating material in the non-road field, which comprises the following components in percentage by mass: silicon dioxide: 40% -85%, titanium dioxide: 10-50%, alumina: 0 to 20%, metal oxide providing an acid site: 0.5 to 20 percent. The invention also discloses a method for preparing the non-road field modified denitration catalyst by adopting the coating material, which comprises the following steps: firstly), ball-milling precursors of various components of the coating material and purified water to obtain slurry with the solid content of the coating material of 20-45%; secondly), coating a layer of slurry on the surface of the denitration catalyst; thirdly), drying; and IV) roasting. The invention is an improvement of the existing denitration catalyst, considers the chemical action between the toxic substances and the coating while considering the physical barrier of the toxic substances, effectively delays the inactivation process of the catalyst at the bottom layer, and can improve the application economy of the catalyst.
Description
Technical Field
The invention relates to a preparation method of a denitration catalyst, in particular to a coating material of the denitration catalyst in the non-road field and a method for preparing a modified denitration catalyst in the non-road field by adopting the coating material.
Background
Selective Catalytic Reduction (SCR) is a process in which a reducing agent reacts with nitrogen oxides (NOx) over a catalyst under oxygen-containing conditions to reduce the NOx to N2. The commonly used reducing agent is liquid ammonia or urea aqueous solution, and ammonia generated by the decomposition of the reducing agent is used for selective catalytic reduction reaction, NH3-SCR for short. The NH3-SCR technology is widely applied to the control of NOx emission concentration in tail gas in the fields of coal-fired power plants, motor vehicles, steel smelting, coking, ship engines and the like.
With the improvement of fuel quality in the field of motor vehicles, the emission requirements of related NOx regulations can be met by using a single-coating vanadium-titanium catalyst or a molecular sieve SCR catalyst. In recent years, with the maturity of denitration technology of power plants, the emission of domestic coal-fired units has gradually reached the level of 'ultra-low emission' (50 mg/m < 3 >). The current interest in denitration technology has shifted to non-electric industries such as steel making, coking, glass, cement, and ship engine. For example, aiming at the high-ash and high-sulfur component tail gas generated by heavy oil fuel used by ocean-going ships, the vanadium-titanium catalyst is difficult to guarantee due to the erosion of fly ash, arsenic, sulfate and other harmful substances, and the service life of the vanadium-titanium catalyst is difficult to guarantee, so that the development of a denitration catalyst capable of resisting the scouring of fly ash and delaying the poisoning is an urgent application requirement.
Patent CN200910024785.5 increases the wear resistance of the end of the catalyst module in the reactor through the edge hardening of the catalyst module, and has less influence on the overall performance of the catalyst due to the addition of active components in the hardening liquid. Patent CN 20161005636.8 provides a hardening liquid and a hardening method for a denitration catalyst module, which solves the problem of abrasion of the denitration catalyst module. The method mainly aims at the scouring of high-concentration fly ash on a catalytic coating, has little influence on catalyst poisoning caused by elements such as arsenic, K/Ca and the like in the fly ash, and is easy to generate aluminum sulfate in the application process to cause volume expansion and block an SCR reaction channel by taking the aluminum oxide as a main hardening component.
Disclosure of Invention
The invention provides a non-road field denitration catalyst coating material and a method for preparing a non-road field modified denitration catalyst by adopting the material for solving the technical problems in the known technology, and the catalyst using the coating material has better tolerance capability to toxic substances such As As, K, ca, SO2 and the like.
The invention adopts a technical scheme for solving the technical problems in the prior art, which is as follows: a non-road field denitration catalyst coating material comprises the following components in percentage by mass: silica: 40% -85%, titanium dioxide: 10-50%, alumina: 0 to 20%, metal oxide providing an acid site: 0.5 to 20 percent.
The metal oxide providing the acidic site includes at least one of metal oxides of Fe, mo, co, W, sn.
The content of the metal oxide providing the acid sites is 4-15%.
The invention adopts another technical scheme for solving the technical problems in the prior art, which is as follows: a method for preparing a non-road field modified denitration catalyst by adopting the coating material comprises the following steps: firstly), performing ball milling on precursors of various components of the coating material and purified water to obtain slurry with the solid content of the coating material being 20-45%, and then adding a regulator to adjust the viscosity of the slurry to be 100-3000 cp; secondly), coating a layer of slurry on the surface of the denitration catalyst by adopting a quantitative slurry feeding or soaking and pulling method; thirdly), drying; and IV) roasting.
The coating amount of the slurry in the second step) is 10-120 g/L.
The coating amount of the slurry in the second step is 40-70 g/L.
The denitration catalyst in the second step is a coating type denitration catalyst or an extrusion type denitration catalyst.
And when the denitration catalyst in the step two) is a coating type denitration catalyst, continuously coating the two coatings, and then drying and roasting.
Supporting a precursor of the metal oxide providing an acidic site on a material of at least one of the components of the silica, the titania and the alumina.
The regulator adopts any one of silica sol, boehmite or hydroxymethyl cellulose.
The invention has the advantages and positive effects that: the coating made of the coating material is added on the denitration catalyst, so that the improvement of the existing denitration catalyst is realized, the physical blocking of toxic substances is considered, and the chemical action between the toxic substances and the coating is considered, the inactivation process of the catalyst at the bottom layer is effectively delayed, and the application economy of the catalyst can be improved in application.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the present invention are described below in conjunction with the following examples, which are included merely to further illustrate features and advantages of the present invention, and are not intended to limit the claims of the present invention.
Example 1:
(1) 1050g of acidic silica sol with the mass fraction of 40.0%, 500g of titanium dioxide, 150g of aluminum sol with the mass fraction of 20.0%, 202.0g of ferric nitrate nonahydrate, 39.2g of cobalt nitrate and 500g of purified water are subjected to ball milling, slurry with the solid content of 31% is obtained after ball milling, and the slurry is converted into slurry with the solid content of 42% of silicon dioxide, 50% of titanium dioxide, 3% of aluminum oxide and 4% and 1% of Fe and Co metal oxide components respectively. Then adding hydroxymethyl cellulose with the solid content of 0.8 percent to adjust the viscosity of the pulp to 1700cp;
(2) Coating slurry on the original coating by a quantitative slurry feeding method by taking a coating type square honeycomb catalyst with the pore size of 50 meshes and the size of 150mm, wherein the coating amount is 50g/L;
(3) Drying the coated slurry catalyst for 4 hours in an air atmosphere at 120 ℃;
(4) And roasting the dried catalyst for 2 hours in an air atmosphere at 500 ℃ to obtain a modified denitration catalyst finished product.
Example 2:
(1) 1000g of acid silica sol with the mass fraction of 40.0%, 500g of titanium dioxide, 150g of aluminum sol with the mass fraction of 20.0%, 202.0g of ferric nitrate nonahydrate, 24.5g of ammonium molybdate, 14.2g of stannous sulfate and 500g of purified water are ball-milled to obtain slurry with the solid content of 42%, and the slurry is converted into slurry with the solid content of 40%, the titanium dioxide content of 50%, the aluminum oxide content of 3% and the oxide components of Fe, mo and Sn of 4%, 2% and 1% respectively. Then adding hydroxymethyl cellulose with the solid content of 0.8 percent to adjust the viscosity of the slurry to 3000cp;
(2) Coating slurry on the original coating by using a coating type square honeycomb catalyst with the pore size of 50 meshes and the size of 150mm, wherein the coating amount is 120g/L;
(3) Drying the catalyst coated with the slurry for 4 hours in an air atmosphere at 120 ℃;
(4) And roasting the dried catalyst for 2 hours in an air atmosphere at 500 ℃ to obtain a modified denitration catalyst finished product.
Example 3:
(1) 850g of porous silica, 1000g of titanium sol with the content of 10%, 43.6g of ammonium tungstate, 14.2g of stannous sulfate and 3100g of purified water are subjected to ball milling to obtain slurry with the solid content of 20%, the slurry is converted into slurry with the solid content of 85%, the solid content of 10%, the content of Sn and W oxide components of 1% and 4%, and hydroxymethyl cellulose with the solid content of 1.1% is added to adjust the viscosity of the slurry to about 1900cp;
(2) Coating slurry on the original coating by using a coating type square honeycomb catalyst with the pore size of 50 meshes and the size of 150mm, wherein the coating amount is 10g/L;
(3) Drying the catalyst coated with the slurry in an air atmosphere at 120 ℃ for 4 hours;
(4) And roasting the dried catalyst for 2 hours in an air atmosphere at 500 ℃ to obtain a modified denitration catalyst finished product.
Example 4:
(1) 680g of gas phase silicon, 300g of titanium dioxide, 20.3g of boehmite, 6.8g of ammonium molybdate and 2400g of purified water are ball-milled to obtain slurry with the solid content of 29 percent, the slurry is converted into slurry with the silicon dioxide content of 68 percent, the titanium dioxide content of 30 percent, the alumina content of 1.5 percent and the Mo oxide component content of 0.5 percent, and the viscosity of the slurry is adjusted to 100cp;
(2) Taking an extruded square honeycomb catalyst with the pore size of 50 meshes and the size of 150mm, soaking the extruded square honeycomb catalyst in the slurry for about 20s, taking out the catalyst, and pumping out the excess slurry under negative pressure, wherein the coating amount is 83g/L;
(3) Drying the catalyst coated with the slurry for 4 hours in an air atmosphere at 120 ℃;
(4) And roasting the dried catalyst in an air atmosphere at 500 ℃ for 2 hours to obtain a modified denitration catalyst finished product.
Example 5:
(1) Loading 120.0g of ferric nitrate nonahydrate to 200g of titanium dioxide material by an isometric immersion method, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 2 hours in an air atmosphere to obtain iron-loaded titanium dioxide;
(2) Ball-milling 400g of iron-loaded titanium dioxide, 400g of gas-phase silicon, 200g of alumina, 355g of ferric nitrate nonahydrate, 54.4g of ammonium molybdate, 39.2g of cobalt nitrate hexahydrate, 22.2g of ammonium tungstate, 42.8g of stannous sulfate and 950g of purified water, and obtaining slurry with the solid content of 44.0% after ball-milling, wherein the slurry is converted into slurry with the solid content of 40% of silicon dioxide, 20% of titanium dioxide, 20% of alumina and 10%, 4%, 1%, 2% and 3% of Fe, mo, co, W and Sn oxide components. Then, 60g of 40% silica sol is added to adjust the viscosity of the slurry to 600cp;
(3) Taking an extruded square honeycomb catalyst with the pore size of 50 meshes and the size of 150mm, and coating slurry by adopting quantitative negative pressure, wherein the coating amount is about 40g/L;
(4) Drying the catalyst coated with the slurry for 4 hours in an air atmosphere at 120 ℃;
(5) And roasting the dried catalyst for 2 hours in an air atmosphere at 500 ℃ to obtain a modified denitration catalyst finished product.
Example 6:
(1) 560g of gas phase silicon, 300g of titanium dioxide, 135g of Beta molecular sieve with silicon-aluminum atomic ratio of 7, 6.1g of ammonium molybdate and 1200g of pure water are ball milled to obtain slurry with solid content of 45 percent, the slurry is converted into slurry with silicon dioxide content of 67.8 percent, titanium dioxide content of 30 percent, aluminum oxide content of 1.7 percent and Mo oxide component content of 0.5 percent, and the viscosity of the slurry is adjusted to 1400cp;
(2) Taking an extruded square honeycomb catalyst with the pore size of 50 meshes and the size of 150mm, and coating the slurry by adopting quantitative negative pressure, wherein the coating amount is 80g/L;
(3) Drying the catalyst coated with the slurry in an air atmosphere at 120 ℃ for 4 hours;
(4) And roasting the dried catalyst for 2 hours in an air atmosphere at 500 ℃ to obtain a modified denitration catalyst finished product.
The modified catalysts obtained in examples 1 to 6 and the denitration catalyst of the same batch as a comparative example, which had no coating added, were subjected to a coating firmness test, a denitration performance test and a sulfur resistance test, respectively, under the following test conditions:
(1) Testing the firmness of the coating: and (3) carrying out coating firmness inspection by adopting a compressed air end face blowing method, wherein the firmness is measured by the quality of falling objects, and the smaller the quality of the falling objects is, the better the washing resistance of the coating is. The amount of the exfoliated material was the mass (g/g) of each catalyst purged under the same conditions.
(2) And (3) performance testing: the samples aged at 500 ℃ and 10% H2O for 100h were subjected to SCR reaction in a gas atmosphere: 1000ppm NO,1000ppm NH3,5% CO2,5% H2O,13% O2, 100ppm SO2, N2 is balance gas. The space velocity is GHSV =20000h-1. Conversion was calculated by measuring the NO concentration after passing the catalyst at 300 ℃, NO conversion = (1000-NO outlet concentration)/1000 x 100%.
(3) And (3) sulfur resistance test: passing 500ppm SO2, GHSV =20000h-1 in 250 ℃ air atmosphere for 100h, taking out the sample, and carrying out SCR reaction under the same gas atmosphere conditions as the performance test conditions.
The results of the test are shown in table 1:
table 1 comparative table of performance test results
Referring to table 1, the sulfur tolerance test results show that, compared with the comparative ratio, the sulfur tolerance of the catalyst modified by the coating material is improved to different degrees, except for example 3.
The above-mentioned embodiments are only for illustrating the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and to carry out the same, and the present invention shall not be limited to the embodiments, i.e. the equivalent changes or modifications made within the spirit of the present invention shall fall within the scope of the present invention.
Claims (1)
1. A preparation method of a modified denitration catalyst in the non-road field is characterized by comprising the following steps:
(1) Loading 120.0g of ferric nitrate nonahydrate to 200g of titanium dioxide material by an isometric immersion method, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 2 hours in an air atmosphere to obtain iron-loaded titanium dioxide;
(2) Ball-milling the iron-loaded titanium dioxide, 400g of gas-phase silicon, 200g of alumina, 355g of ferric nitrate nonahydrate, 54.4g of ammonium molybdate, 39.2g of cobalt nitrate hexahydrate, 22.2g of ammonium tungstate, 42.8g of stannous sulfate and 950g of purified water to obtain slurry with the solid content of 44.0% after ball milling, wherein the slurry is converted into slurry with the solid content of 40% of silicon dioxide, 20% of titanium dioxide, 20% of alumina and the contents of oxides of Fe, mo, co, W and Sn of 10%, 4%, 1%, 2% and 3% respectively; then, 60g of 40% silica sol is added to adjust the viscosity of the slurry to 600cp;
(3) Taking an extruded square honeycomb catalyst with the pore size of 50 meshes and the size of 150mm, and coating slurry by adopting quantitative negative pressure, wherein the coating amount is 40g/L;
(4) Drying the catalyst coated with the slurry in an air atmosphere at 120 ℃ for 4 hours;
(5) And roasting the dried catalyst for 2 hours in an air atmosphere at 500 ℃ to obtain a modified denitration catalyst finished product.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019187A (en) * | 2010-11-25 | 2011-04-20 | 浙江工业大学 | Low-temperature flue gas SCR (Selective Catalytic Reduction) denitrating catalyst and preparation method and application thereof |
| CN103240078A (en) * | 2013-05-22 | 2013-08-14 | 重庆远达催化剂制造有限公司 | Wear-resistant SCR (Selective Catalytic Reduction) denitration catalyst and preparation method thereof |
| CN103877990A (en) * | 2014-04-14 | 2014-06-25 | 重庆大学 | Polynary metallic oxide denitration catalyst |
| CN104245135A (en) * | 2012-02-22 | 2014-12-24 | 日立造船株式会社 | End-treating method for catalyst-carrying honeycomb structure in exhaust gas denitration system |
| CN110354843A (en) * | 2019-08-28 | 2019-10-22 | 华北电力大学 | A kind of thin-walled honeycomb formula low temperature sulfur resistive SCR denitration and preparation method thereof |
| CN111151241A (en) * | 2018-11-08 | 2020-05-15 | 中国科学院大连化学物理研究所 | Integral honeycomb coating catalyst and preparation method and application thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4852475B2 (en) * | 2007-05-30 | 2012-01-11 | 日立造船株式会社 | Slurry for denitration catalyst production |
| CN103316717A (en) * | 2013-06-18 | 2013-09-25 | 浙江德创环保科技股份有限公司 | SCR (Selective Catalytic Reduction) denitration catalyst module hardening liquid |
| CN104841420A (en) * | 2015-05-05 | 2015-08-19 | 广州迪森热能技术股份有限公司 | Denitration catalyst activity mother liquor preparation method and application of denitration catalyst activity mother liquor |
| CN105126827B (en) * | 2015-09-10 | 2018-01-26 | 西南化工研究设计院有限公司 | A kind of coating type low-temperature denitration of flue gas catalyst and its preparation method and application |
| CN105057005B (en) * | 2015-09-18 | 2017-06-30 | 西南化工研究设计院有限公司 | A kind of denitrating catalyst end gardening liquid and its preparation method and application |
| CN105665032B (en) * | 2016-01-27 | 2018-09-04 | 龙净科杰环保技术（上海）有限公司 | Denitrification catalyst module hardening bath and method for curing |
| CN112439423B (en) * | 2019-08-30 | 2023-11-21 | 大连海事大学 | Sulfur-resistant NO oxidation structured catalyst and preparation method and application thereof |
| CN113634254B (en) * | 2021-08-13 | 2023-02-14 | 交通运输部天津水运工程科学研究所 | Non-road field denitration catalyst coating material and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019187A (en) * | 2010-11-25 | 2011-04-20 | 浙江工业大学 | Low-temperature flue gas SCR (Selective Catalytic Reduction) denitrating catalyst and preparation method and application thereof |
| CN104245135A (en) * | 2012-02-22 | 2014-12-24 | 日立造船株式会社 | End-treating method for catalyst-carrying honeycomb structure in exhaust gas denitration system |
| CN103240078A (en) * | 2013-05-22 | 2013-08-14 | 重庆远达催化剂制造有限公司 | Wear-resistant SCR (Selective Catalytic Reduction) denitration catalyst and preparation method thereof |
| CN103877990A (en) * | 2014-04-14 | 2014-06-25 | 重庆大学 | Polynary metallic oxide denitration catalyst |
| CN111151241A (en) * | 2018-11-08 | 2020-05-15 | 中国科学院大连化学物理研究所 | Integral honeycomb coating catalyst and preparation method and application thereof |
| CN110354843A (en) * | 2019-08-28 | 2019-10-22 | 华北电力大学 | A kind of thin-walled honeycomb formula low temperature sulfur resistive SCR denitration and preparation method thereof |
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