WO2023015890A1 - 一种非道路领域脱硝催化剂涂覆材料及其应用 - Google Patents
一种非道路领域脱硝催化剂涂覆材料及其应用 Download PDFInfo
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- Prior art keywords
- denitration catalyst
- slurry
- coating material
- catalyst
- road field
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000000576 coating method Methods 0.000 title claims abstract description 46
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 5
- 229940031574 hydroxymethyl cellulose Drugs 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
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000000498 ball milling Methods 0.000 abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003440 toxic substance Substances 0.000 abstract description 5
- 231100000167 toxic agent Toxicity 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000008213 purified water Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract description 2
- 230000001934 delay Effects 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 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 4
- 238000011056 performance test Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000446 fuel 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
- 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
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 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
- 230000032683 aging Effects 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
- 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
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004202 carbamide Substances 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
- 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 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the invention relates to a preparation method of a denitration catalyst, in particular to a non-road field denitration catalyst coating material and a method for preparing a non-road field modified denitration catalyst using the material.
- Selective Catalytic Reduction is a method of reducing NOx to N2 by reacting a reducing agent with nitrogen oxides (NOx) on a catalyst under oxygen-containing conditions.
- the commonly used reducing agent is liquid ammonia or urea aqueous solution, and the ammonia gas generated by the decomposition of the reducing agent is used for selective catalytic reduction reaction, referred to as NH3-SCR.
- NH3-SCR technology is widely used in the control of NOx emission concentration in the tail gas of coal-fired power plants, motor vehicles, iron and steel smelting, coking and marine machinery and other fields.
- the vanadium-titanium catalyst is eroded by harmful substances such as fly ash, arsenic, and sulfate, and its service life is difficult to guarantee. It is necessary to develop a catalyst that can resist fly ash erosion and delay poisoning. High-quality denitration catalysts have become an urgent demand for applications.
- Patent CN200910024785.5 increases the wear resistance of the end of the catalyst module in the reactor by hardening the edge of the catalyst module. Since the active components are added to the hardening solution, the overall performance of the catalyst is less affected.
- Patent CN201610056313.8 provides a denitration catalyst module hardening solution and a hardening method to solve the problem of denitration catalyst module wear. This type of method is mainly aimed at the erosion of catalytic coatings by high-concentration fly ash, and has little effect on catalyst poisoning caused by elements such as arsenic and K/Ca in fly ash, and alumina is the main hardening component, which is easy to form in the application process. Aluminum sulfate causes volume expansion to block the SCR reaction channel.
- the present invention provides a non-road field denitrification catalyst coating material and a method for preparing a non-road field modified denitration catalyst using the material.
- the catalyst using the coating material has better resistance to Tolerance of toxic substances such as As, K, Ca and SO2.
- a technical solution adopted by the present invention to solve the technical problems existing in the known technology is: a non-road field denitration catalyst coating material, including the following components in mass fractions: silicon dioxide: 40% to 85%, titanium dioxide: 10% to 50%, alumina: 0 to 20%, metal oxides providing acidic sites: 0.5% to 20%.
- the metal oxides providing acidic sites include at least one of Fe, Mo, Co, W, and Sn metal oxides.
- the content of the metal oxide providing acid sites is 4%-15%.
- Another technical solution adopted by the present invention to solve the technical problems existing in the known technology is: a method for preparing a modified denitrification catalyst in the non-road field by using the above-mentioned coating material. After ball milling the precursors of the components and pure water, a slurry with a solid content of 20% to 45% of the coating material is obtained, and then a regulator is added to adjust the viscosity of the slurry to 100 to 3000cp; Coating a layer of slurry on the surface of the denitration catalyst; 3) drying; 4) roasting.
- the coating amount of the slurry in the step 2) is 10g/L-120g/L.
- the coating amount of the slurry in the step 2) is 40g/L-70g/L.
- the denitration catalyst in the step 2) is a coating-type denitration catalyst or an extrusion-type denitration catalyst.
- the denitration catalyst in the step 2) is a coated denitration catalyst, two coatings are coated continuously, and then dried and roasted.
- the acid site-providing metal oxide precursor is supported on at least one component material of the silicon dioxide, the titanium dioxide and the aluminum oxide.
- the regulator is any one of silica sol, boehmite or hydroxymethyl cellulose.
- the advantages and positive effects of the present invention are: by adding a coating using the coating material on the denitration catalyst, the improvement of the existing denitration catalyst is realized, and the toxic substance and the coating are considered while considering the physical barrier of the toxic substance.
- the chemical interaction between them effectively delays the deactivation process of the underlying catalyst, and can improve the economy of catalyst application in the application.
- Figure 1 is a comparison chart of performance test results.
- (1) 850g of porous silica, 1000g of 10% titanium sol, 43.6g of ammonium tungstate, 14.2g of stannous sulfate and 3100g of pure water are ball milled to obtain a slurry with a solid content of 20% after ball milling, which is converted into two
- the content of silicon oxide is 85%
- the content of titanium dioxide is 10%
- the content of Sn and W oxide components is 1% and 4% respectively
- hydroxymethyl cellulose with a solid content of 1.1% is added to adjust the viscosity of the slurry to about 1900cp;
- (1) 680g of fumed silicon, 300g of titanium dioxide, 20.3g of boehmite, 6.8g of ammonium molybdate and 2400g of purified water are ball milled to obtain a slurry with a solid content of 29% after ball milling, which is converted into a solid with a silicon dioxide content of 68%.
- the content of titanium dioxide is 30%
- the content of aluminum oxide is 1.5%
- the content of Mo oxide component is 0.5%
- the viscosity of the slurry is adjusted to 100cp;
- Titanium dioxide, fumed silicon 400g, alumina 200g, ferric nitrate nonahydrate 355g, ammonium molybdate 54.4g, cobalt nitrate hexahydrate 39.2g, ammonium tungstate 22.2g, stannous sulfate 42.8g and pure 950g of water is ball milled, and after ball milling, a slurry with a solid content of 44.0% is obtained, which is converted into a solid with a silicon dioxide content of 40%, a titanium dioxide content of 20%, an aluminum oxide content of 20%, and Fe, Mo, Co, W and Sn oxides
- the component contents are 10%, 4%, 1%, 2% and 3%, respectively. Then by adding 60g of 40% silica sol, adjust the slurry viscosity to 600cp;
- Embodiment 6 is a diagrammatic representation of Embodiment 6
- the silicon content is 67.8%
- the titanium dioxide content is 30%
- the alumina content is 1.7%
- the Mo oxide component content is 0.5%
- the slurry viscosity is adjusted to 1400cp;
- the modified catalysts obtained in Examples 1 to 6 and the same batch of denitration catalysts without coating added as a comparative example were respectively subjected to coating firmness test, denitration performance test and sulfur resistance test.
- the test conditions are as follows:
- Coating firmness test The compressed air end face blowing method is used to test the coating firmness. The firmness is measured by the amount of falling off matter. The less the falling off matter, the better the erosion resistance of the coating. The amount of exfoliated matter is the mass (g/piece) of the exfoliated matter purged by each catalyst under the same conditions.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- 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)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
本发明公开了一种非道路领域脱硝催化剂涂覆材料，包括以下质量分数的组分：二氧化硅：40％～85％，二氧化钛：10％～50％，氧化铝：0～20％，提供酸性位点的金属氧化物：0.5％～20％。本发明还公开了一种采用上述涂覆材料制备非道路领域改性脱硝催化剂的方法，采用以下步骤：一)将涂覆材料各种组分的前驱体和纯净水球磨后得到涂覆材料固含量为20％～45％的浆液；二)在脱硝催化剂表面涂覆一层浆液；三)烘干；四)焙烧。本发明是对现有脱硝催化剂的改进，在考虑对毒性物质物理阻挡的同时考虑了毒性物质与涂层之间的化学作用，有效延缓了底层催化剂失活过程，可以提高催化剂应用的经济性。
Description
本发明涉及一种脱硝催化剂的制备方法，特别是一种非道路领域脱硝催化剂涂覆材料以及采用该材料制备非道路领域改性脱硝催化剂的方法。
选择性催化还原(Selective Catalytic Reduction，SCR)是在含氧条件下还原剂与氮氧化物(NOx)在催化剂上发生反应，将NOx还原为N2的方法。常用的还原剂是液氨或尿素水溶液，还原剂分解产生的氨气用于选择性催化还原反应，简称NH3-SCR。NH3-SCR技术广泛用于燃煤电厂、机动车、钢铁冶炼、焦化和船机等领域尾气中NOx排放浓度控制。
随着机动车领域燃油品质的提升，使用单涂层的钒钛催化剂或分子筛SCR催化剂即可满足相关NOx法规排放要求。近年来，随着电厂脱硝技术的成熟，国内燃煤机组排放已经逐步达到了“超低排放”水平(50mg/m3)。目前脱硝技术的关注点已经转移到炼钢、焦化、玻璃、水泥和船机等非电行业。如针对远洋船舶使用重油燃料产生的高灰、高硫组分尾气，钒钛催化剂面临飞灰、砷、硫酸盐等有害物质的侵蚀，寿命难以保证，开发一种能够抵抗飞灰冲刷、延缓中毒的脱硝催化剂成为应用迫切需求。
专利CN200910024785.5通过催化剂模块边缘硬化增加了催化剂模块端部在反应器中的耐磨损性能，由于硬化液中增加了活性组分，对催化剂的整体性能影响较小。专利CN201610056313.8提供了一种脱硝催化剂模块硬化液及硬化方法，解决脱硝催化剂模块磨损问题。此类方法主要针对高浓度飞灰对催化涂层的冲刷，对砷、飞灰中K/Ca等元素造成的催化剂中毒影响不大，且以氧化铝为主要硬化成分，容易在应用过程中生成硫酸铝造成体积膨胀堵塞SCR反应通道。
本发明为解决公知技术中存在的技术问题而提供一种非道路领域脱硝催化剂涂覆材料以及采用该材料制备非道路领域改性脱硝催化剂的方法，应用该涂覆材料的催化剂具有较好的对As、K、Ca和SO2等有毒物质的耐受能力。
本发明为解决公知技术中存在的技术问题所采取的一个技术方案是：一种非道路领域脱硝催化剂涂覆材料，包括以下质量分数的组分：二氧化硅：40％～85％，二氧化钛：10％～50％，氧化铝：0～20％，提供酸性位点的金属氧化物：0.5％～20％。
所述提供酸性位点的金属氧化物包括Fe、Mo、Co、W、Sn金属氧化物中的至少一种。
所述提供酸性位点的金属氧化物含量为4％～15％。
本发明为解决公知技术中存在的技术问题所采取的另一个技术方案是：一种采用上述涂覆材料制备非道路领域改性脱硝催化剂的方法，采用以下步骤：一)将涂覆材料各种组分的前驱体和纯净水球磨后得到涂覆材料固含量为20％～45％的浆液，然后加入调节剂调整浆液粘度为100～3000cp；二)采用定量给浆或浸泡提拉的方法在脱硝催化剂表面涂覆一层浆液；三)烘干；四)焙烧。
所述步骤二)中浆液的涂覆量为10g/L～120g/L。
所述步骤二)中浆液的涂覆量为40g/L～70g/L。
所述步骤二)中的脱硝催化剂为涂覆式脱硝催化剂或挤出式脱硝催化剂。
当所述步骤二)中的脱硝催化剂为涂覆式脱硝催化剂时，两个涂层连续涂覆，然后进行烘干和焙烧。
将所述提供酸性位点的金属氧化物的前驱体负载在所述二氧化硅、所述二氧化钛和所述氧化铝至少一种组分的材料上。
所述调节剂采用硅溶胶、勃姆石或羟甲基纤维素中的任意一种。
本发明具有的优点和积极效果是：通过在脱硝催化剂上增加采用该涂覆材料的涂层，实现对现有脱硝催化剂的改进，在考虑对毒性物质物理阻挡的同时考虑了毒性物质与涂层之间的化学作用，有效延缓了底层催化剂失活过程，在应用中可以提高催化剂应用的经济性。
图1是性能测试结果对比图。
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
实施例1：
(1)将质量分数40.0％的酸性硅溶胶1050g、二氧化钛500g、质量分数20.0％的铝溶胶150g，九水硝酸铁202.0g、硝酸钴39.2g和纯净水500g球磨，球磨后得到固含量为31％的浆液，折算成固体中二氧化硅含量为42％，二氧化钛含量为50％，氧化铝含量3％，Fe、Co金属氧化物组分含量分别为4％和1％。然后加入固体含量为0.8％的羟甲基纤维素调节浆液粘度至约1700cp；
(2)取孔大小为50目，尺寸为150mm*150mm*150mm的涂覆式方形蜂窝催化剂，采用定量给浆的方法在原有涂层上涂覆浆液，涂覆量为50g/L；
(3)将涂覆浆液催化剂在120℃空气气氛中烘干4小时；
(4)将烘干后的催化剂在500℃空气气氛中焙烧2小时，得到改性脱硝催化剂成品。
实施例2：
(1)将质量分数40.0％的酸性硅溶胶1000g、二氧化钛500g、质量分数20.0％的铝溶胶150g，九水硝酸铁202.0g、钼酸铵24.5g、硫酸亚锡14.2g和纯净水500g球磨，球磨后得到固含量为42％的浆液，折算成固体中二氧化硅含量为40％，二氧化钛含量为50％，氧化铝含量3％，Fe、Mo和Sn氧化物组分含量分别为4％、2％和1％。然后加入固体含量为0.8％的羟甲基纤维素调节浆液粘度至3000cp；
(2)取孔大小50目，尺寸为150mm*150mm*150mm的涂覆式方形蜂窝催化剂，的方法在原有涂层上涂覆浆液，涂覆量为120g/L；
(3)将涂覆浆液的催化剂在120℃空气气氛中烘干4小时；
(4)将烘干后的催化剂在500℃空气气氛中焙烧2小时，得到改性脱硝催化剂成品。
实施例3：
(1)将多孔二氧化硅850g、10％含量钛溶胶1000g、钨酸铵43.6g、硫酸亚锡14.2g和纯净水3100g球磨，球磨后得到固含量为20％的浆液，折算成固体中二氧化硅含量为85％，二氧化钛含量为10％，Sn和W氧化物组分含量分别为1％和4％，加入固体含量为1.1％的羟甲基纤维素调节浆液粘度至约1900cp；
(2)取孔大小50目，尺寸为150mm*150mm*150mm的涂覆式方形蜂窝催化剂，的方法在原有涂层上涂覆浆液，涂覆量为10g/L；
(3)将涂覆浆液的催化剂在120℃空气气氛中烘干4小时；
(4)将烘干后的催化剂在500℃空气气氛中焙烧2小时，得到改性脱硝催化剂成品。
实施例4：
(1)将气相硅680g、二氧化钛300g、勃姆石20.3g、钼酸铵6.8g和纯净水2400g球磨，球磨后得到固含量为29％的浆液，折算成固体中二氧化硅含量为68％，二氧化钛含量为30％，氧化铝含量1.5％，Mo氧化物组分含量0.5％，调节浆液粘度至100cp；
(2)取孔大小50目，尺寸为150mm*150mm*150mm的挤出式方形蜂窝催化剂，将其浸泡没入上述浆液约20s后提出，负压将多余浆液抽出，涂覆量为83g/L；
(3)将涂覆浆液的催化剂在120℃空气气氛中烘干4小时；
(4)将烘干后的催化剂在500℃空气气氛中焙烧2小时，得到改性脱硝催化剂成品。
实施例5：
(1)将120.0g九水硝酸铁通过等体积浸渍法负载到200g二氧化钛材料，经120℃干燥4小时、550℃空气气氛中焙烧2小时后得到负载铁的二氧化钛；
(2)将上述负载铁的二氧化钛、气相硅400g、氧化铝200g、九水硝酸铁355g、钼酸铵54.4g、六水合硝酸钴39.2g、钨酸铵22.2g、硫酸亚锡42.8g和纯净水950g球磨，球磨后得到固含量为44.0％的浆液，折算成固体中二氧化硅含量为40％，二氧化钛含量为20％，氧化铝含量20％，Fe、Mo、Co、W和Sn氧化物组分含量分别为10％、4％、1％、2％和3％。然后通过加入40％的硅溶胶60g，调节浆液粘度至600cp；
(3)取孔大小50目，尺寸为150mm*150mm*150mm的挤出式方形蜂窝催化剂，采用定量负压涂覆浆液，涂覆量约为40g/L；
(4)将涂覆浆液的催化剂在120℃空气气氛中烘干4小时；
(5)将烘干后的催化剂在500℃空气气氛中焙烧2小时，得到改性脱硝催化剂成品。
实施例6：
(1)将气相硅560g、二氧化钛300g、硅铝原子比为7的Beta分子筛135g、钼酸铵6.1g和纯净水1200g球磨，球磨后得到固含量为45％的浆液，折算成固体中二氧化硅含量为67.8％，二氧化钛含量为30％，氧化铝含量1.7％，Mo氧化物组分含量0.5％，调节浆液粘度至1400cp；
(2)取孔大小50目，尺寸为150mm*150mm*150mm的挤出式方形蜂窝催化剂，采用定量负压涂覆浆液，涂覆量为80g/L；
(3)将涂覆浆液的催化剂在120℃空气气氛中烘干4小时；
(4)将烘干后的催化剂在500℃空气气氛中焙烧2小时，得到改性脱硝催化剂成品。
对实施例1～6所得改性催化剂以及作为对比例未增加涂层的同批次脱硝催化剂分别进行涂层牢固度测试、脱硝性能测试和耐硫测试，测试条件如下：
(1)涂层牢固度测试：采用压缩空气端面吹扫法进行涂层牢固度检验，牢固度用脱落物质量来衡量，脱落物质量越少，表明涂层耐冲刷性能越好。脱落物质量为各催化剂在同样条件下吹扫脱落物的质量(g/只)。
(2)性能测试：经500℃、10％H2O、100h老化后的样品进行SCR反应，气体气氛：1000ppm NO，1000ppm NH3，5％CO2，5％H2O，13％O2，100ppm SO2,N2为平衡气。空速为GHSV＝20000h-1。通过检测300℃下经过催化剂后的NO浓度计算转化率，NO转化率＝(1000-NO出口浓度)/1000*100％。
(3)耐硫测试：在250℃空气气氛中通过500ppm SO2,GHSV＝20000h-1,持续100h，样品取出后进行SCR反应，气体气氛条件同上述性能测试条件。
测试所得结果如图1所示。
请参见表1，耐硫测试结果表明，除实施例3外，相比对比例，应用涂覆材料改性后的催化剂耐硫性能有不同程度提高。
以上所述的实施例仅用于说明本发明的技术思想及特点，其目的在于使本领域内的技术人员能够理解本发明的内容并据以实施，不能仅以本实施例来限定本发明的专利范围，即凡本发明所揭示的精神所作的同等变化或修饰，仍落在本发明的专利范围内。
Claims (10)
- 一种非道路领域脱硝催化剂涂覆材料，其特征在于，包括以下质量分数的组分：二氧化硅：40％～85％，二氧化钛：10％～50％，氧化铝：0～20％，提供酸性位点的金属氧化物：0.5％～20％。
- 根据权利要求1所述的非道路领域脱硝催化剂涂覆材料，其特征在于，所述提供酸性位点的金属氧化物包括Fe、Mo、Co、W、Sn金属氧化物中的至少一种。
- 根据权利要求2所述的非道路领域脱硝催化剂涂覆材料，其特征在于，所述提供酸性位点的金属氧化物含量为4％～15％。
- 一种采用权利要求1所述涂覆材料制备非道路领域改性脱硝催化剂的方法，其特征在于，采用以下步骤：一)将涂覆材料各种组分的前驱体和纯净水球磨后得到涂覆材料固含量为20％～45％的浆液，然后加入调节剂调整浆液粘度为100～3000cp；二)采用定量给浆或浸泡提拉的方法在脱硝催化剂表面涂覆一层浆液；三)烘干；四)焙烧。
- 根据权利要求4所述的制备非道路领域改性脱硝催化剂的方法，其特征在于，所述步骤二)中浆液的涂覆量为10g/L～120g/L。
- 根据权利要求5所述的制备非道路领域改性脱硝催化剂的方法，其特征在于，所述步骤二)中浆液的涂覆量为40g/L～70g/L。
- 根据权利要求5所述的制备非道路领域改性脱硝催化剂的方法，其特征在于，所述步骤二)中的脱硝催化剂为涂覆式脱硝催化剂或挤出式脱硝催化剂。
- 根据权利要求7所述的制备非道路领域改性脱硝催化剂的方法，其特征在于，当所述步骤二)中的脱硝催化剂为涂覆式脱硝催化剂时，两个涂层连续涂覆，然后进行烘干和焙烧。
- 根据权利要求1所述的制备非道路领域改性脱硝催化剂的方法，其特征在于，将所述提供酸性位点的金属氧化物的前驱体负载在所述二氧化硅、所述二氧化钛和所述氧化铝至少一种组分的材料上。
- 根据权利要求6所述的制备非道路领域改性脱硝催化剂的方法，其特征在于，所述调节剂采用硅溶胶、勃姆石或羟甲基纤维素中的任意一种。
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