WO2011099492A1 - バイオマス燃焼排ガス用脱硝触媒及び脱硝方法 - Google Patents
バイオマス燃焼排ガス用脱硝触媒及び脱硝方法 Download PDFInfo
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- WO2011099492A1 WO2011099492A1 PCT/JP2011/052688 JP2011052688W WO2011099492A1 WO 2011099492 A1 WO2011099492 A1 WO 2011099492A1 JP 2011052688 W JP2011052688 W JP 2011052688W WO 2011099492 A1 WO2011099492 A1 WO 2011099492A1
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- exhaust gas
- catalyst
- titanium oxide
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- nox reduction
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000002028 Biomass Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002485 combustion reaction Methods 0.000 title abstract description 19
- 230000009467 reduction Effects 0.000 title abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- -1 oxo acid salt Chemical class 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 150000004715 keto acids Chemical class 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 125000005287 vanadyl group Chemical group 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 26
- 239000002803 fossil fuel Substances 0.000 claims description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052700 potassium Inorganic materials 0.000 abstract description 5
- 239000011591 potassium Substances 0.000 abstract description 5
- 238000009937 brining Methods 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 7
- 150000003112 potassium compounds Chemical class 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LRDAUUGUXQIHED-UHFFFAOYSA-N N.[N]=O Chemical compound N.[N]=O LRDAUUGUXQIHED-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002023 wood Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- 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
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- 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
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20769—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
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- B01D2255/20776—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2255/70—Non-metallic catalysts, additives or dopants
- B01D2255/707—Additives or dopants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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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
- B01J35/58—Fabrics or filaments
Definitions
- the present invention relates to an exhaust gas purification catalyst and an exhaust gas purification method using the same, and in particular, a nitrogen oxide ammonia (NH 3 ) reduction catalyst which prevents deterioration due to a potassium compound contained in combustion exhaust gas of biomass.
- the present invention relates to a denitration method for biomass combustion exhaust gas using the same.
- CO 2 emission reduction measures include reducing fossil fuel usage through energy conservation, measures for using fossil fuels such as CO 2 capture and sequestration in combustion exhaust gas, and the use of natural energy such as solar cells and wind power generation. It is being advanced. In addition to these, power generation using biomass as fuel instead of fossil fuel is attracting attention as a method that does not lead to an increase in CO 2 , and has begun to be actively adopted especially in the form of biomass burning or co-firing with fossil fuel, especially in Europe. .
- biomass combustion exhaust gases have the advantage of containing less sulfur than fossil fuels, but the combustion ash of plant-derived materials such as wood chips and peat contains a large amount of deliquescent potassium carbonate, which is useful for denitration of exhaust gases. It is known that the catalyst used causes a phenomenon of rapid deterioration.
- Patent Document 1 describes a method of supporting vanadium after adsorbing phosphoric acid on the surface of a titania carrier and calcining it in order to prevent sintering of the titania carrier by vanadium in a denitration catalyst for catalytic catalytic reduction.
- exhaust gas treatment containing a high concentration of potassium components such as biomass fuel exhaust gas, and catalyst poisoning by this.
- An object of the present invention is to provide a method capable of realizing a denitration catalyst that hardly deteriorates even when used for treatment, and using this to denitrate biomass combustion exhaust gas with high efficiency for a long period of time.
- Titanium oxide is brought into contact with titanium oxide in excess of 1 as H 3 PO 4 in an amount of 15% by weight or less in the presence of water to adsorb phosphate ions on the surface.
- molybdenum (Mo) and / or tungsten (W) oxoacids or oxoacid salts and vanadium (V) oxoacid salts or vanadyl salts were supported in excess of 0 at 8 atomic% or less.
- An exhaust gas purifying catalyst characterized by the above.
- the catalyst according to (1) characterized in that the amount of phosphoric acid or ammonium phosphate to titanium oxide is more than 1 and not more than 10% by weight as H 3 PO 4 .
- a method for purifying exhaust gas comprising reducing and removing the exhaust gas.
- the present inventors have found that most of the potassium exists as carbonate, which is deliquescent when it is highly humid at the start and stop. Incorporated into the catalyst, the ammonia present on the titanium oxide (TiO 2 ) was found to adsorb at the NH 3 adsorption point to inhibit the adsorption of NH 3 and thereby deactivate the catalyst, completing the present invention.
- the catalyst deactivation by potassium carbonate and the mechanism of the catalyst of the present invention for improving this will be schematically described as follows.
- NH 3 which is a reducing agent used in the denitration reaction, is adsorbed as shown in Formula 1 to an OH group that is an acid point on titanium oxide.
- potassium ions in potassium carbonate that have entered the catalyst are also adsorbed to the OH group as shown in Formula 2, and their adsorption power is stronger than that of NH 3 , thereby inhibiting the adsorption of NH 3 .
- This is the cause of deactivation of the denitration catalyst due to potassium, and the denitration catalyst in the biomass combustion exhaust gas causes a rapid decrease in the denitration rate.
- the catalyst of the present invention by preliminarily adsorbing phosphate ions to a part of the active sites of TiO 2 as shown in formula 3, most of the potassium ions that entered are acids stronger than the NH 3 adsorption points. First, it reacts with a certain phosphate ion (Equation 3). As a result, an OH group is created on TiO 2 and this OH becomes the NH 3 adsorption point, which compensates for the reduced NH 3 adsorption point in Equation 2. Can be drastically reduced.
- the present invention it is possible to greatly reduce the deterioration of the catalyst due to the potassium compound contained in the exhaust gas, thereby maintaining high performance of the denitration device of the combustion exhaust gas of biomass fuel, and reducing the frequency of catalyst replacement. For example, the operating cost of the denitration apparatus can be greatly reduced.
- the catalyst of the present invention uses TiO 2 on which phosphate ions that react with potassium ions to form NH 3 adsorption points are adsorbed, and Mo or W oxoacids or oxoacid salts as active components, and V
- the oxo acid salt or vanadyl salt is supported by more than 0 and 8 atomic% or less. In carrying out the present invention, it is necessary to consider the following points.
- the amount of H 3 PO 4 added is 15% by weight or less, preferably 10% by weight or less of TiO 2. It is easy to obtain. Further, there is no restriction on the addition amount, but it is desirable to select 1% by weight or more with respect to TiO 2 in order to show remarkable K-toxicity.
- Active ingredients added to TiO 2 adsorbed with phosphate ions include molybdenum (Mo) and / or tungsten (W) oxoacids or oxoacid salts and vanadium (V) oxoacid salts or vanadyl salts. Can be used.
- the addition amount is not particularly limited, but is preferably more than 0 and less than 8 atomic% with respect to TiO 2 . Selecting a high value when the specific surface area of the TiO 2 raw material is large, and selecting a small addition amount when the TiO 2 raw material is low is advantageous because the denitration performance can be kept high and the oxidation performance of SO 2 can be lowered.
- any method for adding these active ingredients may be used, but a method of kneading or heating and kneading in the presence of water is economical and excellent.
- the catalyst component after supporting the active component is used after being formed into a honeycomb shape by a known method, and after being applied to fill a mesh on a metal substrate or ceramic fiber network processed into a net shape, Further, it is possible to stack a wave shape or the like having a spacer portion formed thereon and use it as a catalyst structure in a catalyst device. In particular, the latter tends to give good results because ash containing a potassium compound hardly accumulates between the catalysts.
- the catalyst of the present invention can be added with a binder such as silica sol, which is a binder for molding, and inorganic fibers for the purpose of reinforcement.
- a binder such as silica sol, which is a binder for molding, and inorganic fibers for the purpose of reinforcement.
- the catalyst thus obtained is also the present invention. Needless to say, this is the range.
- Example 1 Titanium oxide (Ishihara Sangyo Co., Ltd., specific surface area 290m 2 / g) 900g, 85% phosphoric acid 84.5g, silica sol (Nissan Chemical Co., OS sol) 219g and water 5568g were put into a kneader and kneaded for 45 minutes, phosphoric acid Was adsorbed on the TiO 2 surface. To this, 113 g of ammonium molybdate and 105 g of ammonium metavanadate were added and further kneaded for 1 hour, and Mo and V compounds were supported on the surface of TiO 2 adsorbed with phosphoric acid.
- silica-alumina ceramic fiber manufactured by Toshiba Fineflex
- 151 g of silica-alumina ceramic fiber manufactured by Toshiba Fineflex
- the obtained paste is placed on a 0.7 mm thick base material obtained by metallizing a SUS430 steel plate having a thickness of 0.2 mm, sandwiched between two polyethylene sheets, and passed through a pair of pressure rollers. It was applied to fill the mesh. This was air-dried and then calcined at 500 ° C. for 2 hours to obtain the catalyst of the present invention.
- Example 2 In Example 1, a catalyst was prepared in the same manner except that the amount of phosphoric acid added was changed from 84.5 g to 10.6 g and 42.4 g, respectively.
- Example 4 A catalyst was prepared in the same manner as in Example 1 except that the addition amount of phosphoric acid was changed to 159 g and the addition amount of ammonium metavanadate was changed to 121 g.
- Example 5 The titanium oxide used in Example 1 was changed to titanium oxide having a specific surface area of 90 m 2 / g, the addition amount of phosphoric acid was changed to 4% by weight with respect to TiO 2 , and ammonium metavanadate and ammonium molybdate were changed to 6.8.
- a catalyst was prepared in the same manner as in Example 1 except that g was changed to 61.8 g, and 27.7 g and 62.7 g, respectively.
- Example 7 A catalyst was prepared in the same manner as in Example 1 except that 113 g of ammonium molybdate used in the catalyst of Example 1 was changed to 162 g of ammonium metatungstate.
- catalysts were prepared in the same manner except that phosphoric acid addition and adsorption treatment were not performed.
- the catalysts of Examples 1 to 7 and Comparative Examples 1 to 4 were cut into 20 mm width ⁇ 100 mm length, and in order to simulate deterioration due to potassium compounds contained in the biomass combustion ash, an aqueous solution of potassium carbonate was added to the catalyst components. After impregnation so as to give an addition amount of 0.5% by weight as K 2 O, it was dried at 150 ° C.
- the catalyst of the example shows a small decrease in the denitration performance before and after the simulation test, whereas the catalyst of the comparative example shows a large decrease.
- the catalyst of the present invention can greatly reduce the deterioration caused by the potassium compound, whereby the performance of the biomass combustion exhaust gas denitration apparatus can be maintained high over a long period of time. As a result, the frequency of frequent catalyst replacement can be significantly reduced, and the operating cost of the denitration apparatus can be greatly reduced.
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- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
(1)酸化チタンと、酸化チタンに対しH3PO4として1を越えて15重量%以下のリン酸またはリン酸アンモニウム塩とを水の存在下で接触させ、表面にリン酸イオンを吸着させた酸化チタンに、モリブデン(Mo)及び/またはタングステン(W)のオキソ酸もしくはオキソ酸塩と、バナジウム(V)のオキソ酸塩もしくはバナジル塩とを、0を越えて8原子%以下で担持したことを特徴とする排ガスの浄化用触媒。
(2)前記酸化チタンに対するリン酸またはリン酸アンモニウム塩の量がH3PO4として1を越えて10重量%以下であることを特徴とする(1)記載の触媒。
(3)バイオマス専焼、またはこれと化石燃料とを混焼した排ガスに、還元剤としてNH3を吹き込み後、(1)または(2)記載の触媒と接触させ、排ガス中に含まれる窒素酸化物を還元除去することを特徴とする排ガスの浄化方法。
NH3+HO-Ti-(TiO2上の活性点) → NH4-O-Ti- (式1)
1/2K2CO3+HO-Ti-(TiO2上の活性点) → K-O-Ti- +1/2H2O+1/2CO2(式2)
H3PO4+3(HO-Ti-) → PO4(-Ti-)3+3/2H2O (式3)
3/2K2CO3+PO4(-Ti-)3+3/2H2O → K3PO4+3(HO-Ti-) (式4)
本願発明の触媒において、これら活性成分の添加方法はどのような方法でもあってもよいが、水の存在下で混練または加熱混練する方法が経済的であり、優れている。さらに活性成分担持後の触媒成分は、公知の方法によりハニカム状に成形して用いられる他、網状に加工した金属基板やセラミック繊維の網状物に目を埋めるように塗布して板状化した後、波型などにスペーサ部を成形したものを積層し、触媒構造体として触媒装置に用いることができる。特に後者はカリウム化合物を含む灰が触媒間に堆積しにくいので好結果を与え易い。
[実施例1]
酸化チタン(石原産業社製、比表面積290m2/g)900g、85%リン酸84.5g、シリカゾル(日産化学社製,OSゾル)219g及び水5568gをニーダに入れて45分間混練し、リン酸をTiO2表面に吸着させた。これにモリブデン酸アンモニウム113g及びメタバナジン酸アンモニウム105gを添加して更に1時間混練し、リン酸を吸着したTiO2表面にMoとVの化合物を担持させた。その後、シリカアルミナ系セラミック繊維(東芝ファインフレックス社製)を151gを徐々に添加しながら、30分間混練して均一なペースト状物を得た。得られたペーストを、厚さ0.2mmのSUS430製鋼板をメタルラス加工した厚さ0.7mmの基材の上にき、これを二枚のポリエチレンシートに挟んで一対の加圧ローラを通して、メタルラス基材の網目を埋めるように塗布した。これを風乾後、500℃で2時間焼成して本願発明の触媒を得た。この触媒の組成はTi/Mo/V=88/5/7原子比であり、H3PO4添加量はTiO2に対し8重量%である。
実施例1において、リン酸添加量をそれぞれ84.5gを10.6g及び42.4gに変える以外は同様にして触媒を調製した。
[実施例4]
実施例1において、リン酸の添加量を159g、メタバナジン酸アンモニウムの添加量を121gにそれぞれ変更する以外は同様にして触媒を調製した。本触媒の組成はTi/Mo/V=88/5/8原子比でありH3PO4添加量はTiO2に対し15重量%である。
実施例1に用いた酸化チタンを比表面積90m2/gの酸化チタンに変更し、リン酸の添加量をTiO2に対し4重量%に変え、さらにメタバナジン酸アンモニウムとモリブデン酸アンモニウムとを、6.8gと61.8g、及び27.7gと62.7gとにそれぞれ変更する以外は実施例1と同様にして触媒を調製した。本触媒の組成はTi/Mo/V=96.5/3/0.5原子比、及び95/3/2原子比、H3PO4添加量はTiO2に対し4重量%である。
[実施例7]
実施例1の触媒に用いたモリブデン酸アンモニウム113gをメタタングステン酸アンモニウム162gに変える以外は実施例1と同様にして触媒を調製した。本触媒の組成はTi/W/V=88/5/7原子比であり、H3PO4添加量はTiO2に対し8重量%である。
実施例1、5~7において、リン酸の添加及び吸着処理を行わない以外は同様にして触媒を調製した。
[試験例]
実施例1~7及び比較例1~4の触媒を20mm幅×100mm長さに切り出し、バイオマス燃焼灰中に含まれるカリウム化合物による劣化を模擬するため、これに炭酸カリウムの水溶液を触媒成分に対しK2Oとして0.5重量%の添加量になるように含浸後、150℃で乾燥した。
Claims (3)
- 酸化チタンと、酸化チタンに対しH3PO4として1を越えて15重量%以下のリン酸またはリン酸アンモニウム塩とを水の存在下で接触させ、表面にリン酸イオンを吸着させた酸化チタンに、モリブデン(Mo)及び/またはタングステン(W)のオキソ酸もしくはオキソ酸塩と、バナジウム(V)のオキソ酸塩もしくはバナジル塩とを、0を越えて8原子%以下で担持したことを特徴とする排ガスの浄化用触媒。
- 前記酸化チタンに対するリン酸またはリン酸アンモニウム塩の量がH3PO4として1を越えて10重量%以下であることを特徴とする請求項1記載の触媒。
- バイオマス専焼、またはこれと化石燃料とを混焼した排ガスに、還元剤としてNH3を吹き込み後、請求項1または2記載の触媒と接触させ、排ガス中に含まれる窒素酸化物を還元除去することを特徴とする排ガスの浄化方法。
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CN2011800122145A CN102781581A (zh) | 2010-02-09 | 2011-02-09 | 生物质燃烧排气用脱硝催化剂及脱硝方法 |
KR1020127020907A KR101717319B1 (ko) | 2010-02-09 | 2011-02-09 | 바이오매스 연소 배기 가스용 탈질 촉매 및 탈질 방법 |
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JP5916527B2 (ja) * | 2012-06-19 | 2016-05-11 | 三菱日立パワーシステムズ株式会社 | 排ガスの脱硝方法 |
CN105879879B (zh) * | 2016-05-23 | 2018-09-21 | 东南大学 | 一种高抗硫超低温scr脱硝催化剂及其制备方法 |
WO2022067440A1 (en) * | 2020-10-01 | 2022-04-07 | Anaergia Inc. | Volatilization and oxidation of organic waste |
CN114768601A (zh) * | 2020-12-22 | 2022-07-22 | 浙江德创环保科技股份有限公司 | 一种用于制备低温脱硝催化剂的搅拌装置 |
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