JP2011083714A - Activated alumina catalyst and method for removing nitrous oxide - Google Patents
Activated alumina catalyst and method for removing nitrous oxide Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000001272 nitrous oxide Substances 0.000 title claims abstract description 18
- 239000000567 combustion gas Substances 0.000 claims abstract description 15
- 238000002485 combustion reaction Methods 0.000 claims description 34
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 26
- 239000011734 sodium Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000446 fuel Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 6
- 239000012494 Quartz wool Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum alkoxide Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、活性アルミナ触媒及び亜酸化窒素の除去方法に関する。 The present invention relates to an activated alumina catalyst and a method for removing nitrous oxide.
石油、重油、石油コークス、バイオマス、産業廃棄物等を燃料とする流動層燃焼は、８００〜８５０℃程度の低温のため、公害性のガスである一酸化窒素（ＮＯ）、二酸化窒素（ＮＯ２）等の窒素酸化物の放出が少ないが、地球温暖化の原因である温暖化係数が高い亜酸化窒素（以下、「Ｎ２Ｏ」と略記する場合がある）の発生量が多くなり、その低減策の開発が望まれている。
例えば、Ｎ２Ｏの低減策には、これまで活性コークスによるＮ２Ｏ吸着、補助燃料ガスの燃焼装置への吹込みによる部分高温化、燃焼炉の外部の排ガス経路中にアルミナを配置して燃焼ガスに含まれるＮ２Ｏを除去するＮ２Ｏ除去などの方法が知られている（例えば特許文献１参照）。しかしながら、燃焼炉外にアルミナを配置してＮ２Ｏを除去する方法では、既存の燃焼装置を大幅に改良する必要があり、多額の費用が必要となる場合がある。
一方、燃焼炉内にアルミナを配置して燃焼ガスに含まれるＮ２Ｏを除去するＮ２Ｏ除去などの方法も知られている（例えば、特許文献２，３参照）。
Fluidized bed combustion using petroleum, heavy oil, petroleum coke, biomass, industrial waste, etc. as the fuel is a low temperature of about 800 to 850 ° C. Therefore, pollutant gases such as nitric oxide (NO) and nitrogen dioxide (NO 2 ). ) And the like, but the amount of nitrous oxide (hereinafter sometimes abbreviated as “N 2 O”), which has a high global warming potential, is a cause of global warming. Development of reduction measures is desired.
For example, N 2 O reduction measures include N 2 O adsorption by activated coke, partial temperature increase by blowing auxiliary fuel gas into the combustion device, and alumina in the exhaust gas path outside the combustion furnace. A method such as N 2 O removal for removing N 2 O contained in the combustion gas is known (see, for example, Patent Document 1). However, in the method of removing N 2 O by arranging alumina outside the combustion furnace, it is necessary to significantly improve the existing combustion apparatus, which may require a large amount of cost.
On the other hand, methods such as N 2 O removal in which alumina is disposed in a combustion furnace to remove N 2 O contained in the combustion gas are also known (see, for example, Patent Documents 2 and 3).
しかしながら、特許文献１に記載のアルミナは、ランタニド元素の酸化物と混合することで活性化が図られているため、アルミナ単体ではＮ２Ｏを十分に除去することができない可能性がある。
また、特許文献２に記載のアルミナは、７００℃で約２０％しかＮ２Ｏを除去することができない。一般にアルミナは不純物を複数種、トータルで１％近く含んでおり、より最適なＮ２Ｏ除去性能を有するアルミナがどのようなものかは開示されていない。
さらに、特許文献３に記載の多孔質アルミナ粒子は、Ｎ２Ｏの除去性能について具体的に開示されていないため、十分にＮ２Ｏを除去できない可能性がある。
However, since the alumina described in Patent Document 1 is activated by mixing with an oxide of a lanthanide element, there is a possibility that N 2 O cannot be sufficiently removed with alumina alone.
Further, the alumina described in Patent Document 2 can remove N 2 O only at about 20% at 700 ° C. In general, alumina contains a plurality of impurities and a total of nearly 1%, and it is not disclosed what kind of alumina has more optimal N 2 O removal performance.
Furthermore, since the porous alumina particles described in Patent Document 3 are not specifically disclosed with respect to N 2 O removal performance, there is a possibility that N 2 O cannot be sufficiently removed.
本発明は、燃焼ガスに含まれるＮ２Ｏを良好に除去することができる活性アルミナ触媒、及び、亜酸化窒素の除去方法を提供することを目的とする。 The present invention, activated alumina catalyst can be effectively removed the N 2 O contained in the combustion gas, and aims to provide a method of removing nitrous oxide.
（１）本発明の活性アルミナ触媒は、燃焼ガスに含有される亜酸化窒素を除去する活性アルミナ触媒であって、下記（ａ）及び（ｂ）を満たすことを特徴とする活性アルミナ触媒。
（ａ）酸化ナトリウム（Ｎａ２Ｏ）の含有量が０．０１質量％以上０．０５質量％以下
（ｂ）三酸化硫黄（ＳＯ３）の含有量が１質量％以下
（２）（１）に記載の活性アルミナ触媒において、前記三酸化硫黄（ＳＯ３）の含有量が０．０１質量％以下であることが好ましい。
（３）（１）又は（２）に記載の活性アルミナ触媒において、γ、χ、η、ρ、δ、ベーマイト型のいずれか一種、又はそれらの混合物であることが好ましい。
（４）本発明の亜酸化窒素の除去方法は、流動層燃焼炉内で（１）から（３）までのいずれか一つに記載の活性アルミナ触媒と亜酸化窒素を含む燃焼ガスを接触させることにより前記亜酸化窒素を除去することを特徴とする。
(1) The activated alumina catalyst of the present invention is an activated alumina catalyst that removes nitrous oxide contained in combustion gas, and satisfies the following (a) and (b):
(A) Content of sodium oxide (Na 2 O) is 0.01 mass% or more and 0.05 mass% or less (b) Content of sulfur trioxide (SO 3 ) is 1 mass% or less (2) (1) In the activated alumina catalyst described in 1 ), the content of the sulfur trioxide (SO 3 ) is preferably 0.01% by mass or less.
(3) In the activated alumina catalyst described in (1) or (2), any one of γ, χ, η, ρ, δ, boehmite type, or a mixture thereof is preferable.
(4) The method for removing nitrous oxide according to the present invention comprises contacting the activated alumina catalyst according to any one of (1) to (3) and a combustion gas containing nitrous oxide in a fluidized bed combustion furnace. The nitrous oxide is thereby removed.
本発明の活性アルミナ触媒は、不純物としての酸化ナトリウム（Ｎａ２Ｏ）の含有量が特定の範囲であり、不純物としての三酸化硫黄（ＳＯ３）の含有量が特定値以下であるため、Ｎ２Ｏの除去性能が高い。したがって、特に流動層燃焼炉内において、燃焼ガス中に含まれるＮ２Ｏを良好に除去することができる。 In the activated alumina catalyst of the present invention, the content of sodium oxide (Na 2 O) as an impurity is in a specific range, and the content of sulfur trioxide (SO 3 ) as an impurity is below a specific value. 2 O removal performance is high. Therefore, particularly in a fluidized bed combustion furnace, N 2 O contained in the combustion gas can be removed well.
以下、本発明を実施するための形態について詳述する。
［活性アルミナ触媒の構成］
本実施形態の活性アルミナ触媒は、流動層燃焼炉で発生した燃焼ガス中に含まれるＮ２Ｏに接触して燃焼ガスからＮ２Ｏを除去する。
活性アルミナ触媒は、純度が９５％以上であることが好ましい。純度が９５％未満であると、Ｎ２Ｏの除去性能が低下する場合がある。そのため、活性アルミナ触媒の純度は、９８％以上であることがより好ましい。活性アルミナ触媒は、不純物として、酸化ナトリウム（以下、「Ｎａ２Ｏ」と略記する）、三酸化硫黄（以下、「ＳＯ３」と略記する）、二酸化ケイ素、二酸化チタン、三酸化鉄（Ｆｅ２Ｏ３）、酸化カルシウム、酸化マグネシウム、塩素などを含んでいる。
Hereinafter, embodiments for carrying out the present invention will be described in detail.
[Configuration of activated alumina catalyst]
The activated alumina catalyst of the present embodiment contacts N 2 O contained in the combustion gas generated in the fluidized bed combustion furnace to remove N 2 O from the combustion gas.
The activated alumina catalyst preferably has a purity of 95% or more. If the purity is less than 95%, N 2 O removal performance may be reduced. Therefore, the purity of the activated alumina catalyst is more preferably 98% or more. The activated alumina catalyst contains, as impurities, sodium oxide (hereinafter abbreviated as “Na 2 O”), sulfur trioxide (hereinafter abbreviated as “SO 3 ”), silicon dioxide, titanium dioxide, iron trioxide (Fe 2). O 3 ), calcium oxide, magnesium oxide, chlorine and the like are included.
ここで、Ｎａ２Ｏの含有量は、０．０１質量％以上０．０５質量％以下である。Ｎａ２Ｏの含有量を０．０１質量％未満とするには、活性アルミナ触媒の洗浄に手間がかかり、効率的な活性アルミナ触媒の製造が困難になる可能性がある。また、Ｎａ２Ｏの含有量が０．０１質量％未満であっても、Ｎ２Ｏの除去性能が向上しない可能性がある。一方、Ｎａ２Ｏの含有量が０．０５質量％を超える場合には、Ｎ２Ｏの除去性能が低下する。 Here, the Na 2 O content is 0.05 mass% or less than 0.01 mass%. If the Na 2 O content is less than 0.01% by mass, it takes time to clean the activated alumina catalyst, which may make it difficult to produce an activated alumina catalyst efficiently. Moreover, even if the content of Na 2 O is less than 0.01% by mass, the N 2 O removal performance may not be improved. On the other hand, when the content of Na 2 O exceeds 0.05 mass%, the removal performance of N 2 O decreases.
不純物としてのＮａ２Ｏは、ボーキサイト、ボーキサイトからアルミナを得る過程で経由するアルミン酸ナトリム、及びアルミナ自体などのアルミニウム含有金属を酸（塩酸、硫酸、硝酸）などにより酸洗浄する方法により、得られるアルミナ中のＮａ２Ｏを減少させることができる。
例えば、攪拌機付き容器にアルミナ触媒と希塩酸を混合したアルミナ含有スラリー（スラリー濃度が５０質量％以下）を入れて、１〜２４時間攪拌し、ろ過などで固液分離して得られる固体分を十分な水で洗浄する。水洗後の水のｐＨが、水洗に使う前の水と略同じｐＨに収まった時点で洗浄をやめる。
Na 2 O as an impurity can be obtained by a method of acid cleaning an aluminum-containing metal such as bauxite, sodium aluminate in the process of obtaining alumina from bauxite, and alumina itself with an acid (hydrochloric acid, sulfuric acid, nitric acid) or the like. Na 2 O in alumina can be reduced.
For example, an alumina-containing slurry (a slurry concentration of 50% by mass or less) in which an alumina catalyst and dilute hydrochloric acid are mixed is placed in a container equipped with a stirrer and stirred for 1 to 24 hours. Wash with fresh water. Washing is stopped when the pH of the water after washing is approximately the same as that of water before washing.
又、ボーキサイトを水酸化ナトリウム以外の強アルカリ、例えば水酸化カルシウムなどを使用して処理すれば、アルミン酸カルシウムが得られ、Ｎａ２Ｏの含有量が極めて少ない活性アルミナ触媒を得ることもできる。
さらに、ほぼ完全にＮａ２Ｏを含有しない活性アルミナ触媒を製造する方法として、アルミニウムアルコキシドを加水分解しても良い。
Further, if bauxite is treated with a strong alkali other than sodium hydroxide, such as calcium hydroxide, calcium aluminate can be obtained, and an activated alumina catalyst having a very low Na 2 O content can also be obtained.
Furthermore, aluminum alkoxide may be hydrolyzed as a method for producing an activated alumina catalyst containing almost completely no Na 2 O.
不純物としてのＳＯ３の含有量は１質量％以下であり、より好ましくは、０．０１質量％以下である。
ＳＯ３の含有量が１質量％を超える場合には、Ｎ２Ｏの除去性能が低下する。ＳＯ３の含有量を０．０１質量％以下としたのは、通常、ＳＯ３の検出に用いられる蛍光Ｘ線分析（ＸＲＦ）の検出限界であり、これ以下であれば確実にＮ２Ｏの除去性能が向上するからである。
なお、Ｎａ２Ｏの場合と同様に、アルミナ触媒の洗浄効率を考慮すれば、ＳＯ３の下限値は０．００１質量％であり、０．００１質量％未満としてもＮ２Ｏの除去性能がこれ以上飛躍的に向上するとは考えられないからである。
なお、Ｎａ２Ｏ及びＳＯ３以外の不純物は、含有量が多い場合でもＮ２Ｏの除去性能は著しく低下することはない。
The content of SO 3 as an impurity is 1% by mass or less, and more preferably 0.01% by mass or less.
When the content of SO 3 exceeds 1% by mass, N 2 O removal performance decreases. The content of SO 3 was 0.01% by mass or less is usually the detection limit of the fluorescent X-ray analysis to be used for the detection of SO 3 (XRF), ensures the N 2 O If this less This is because the removal performance is improved.
As in the case of Na 2 O, considering the cleaning efficiency of the alumina catalyst, the lower limit of SO 3 is 0.001% by mass, and even if it is less than 0.001% by mass, the N 2 O removal performance is low. It is because it is not thought that it improves dramatically more than this.
It should be noted that impurities other than Na 2 O and SO 3 do not significantly reduce N 2 O removal performance even when the content is large.
活性アルミナ触媒は、結晶形態で分類すると、α−アルミナと、γ−アルミナと、ベーマイトに分けられる。γ−アルミナを詳細に分類すると、κ、θ、δ、γ、η、χ、ρの７種類に分けられる。
ここで、活性アルミナ触媒がα−アルミナ、θ−アルミナ、又は、α−アルミナ及びθ−アルミナの混合物の場合、Ｎ２Ｏの除去性能が低いため、好ましくない。そのため、活性アルミナ触媒は、κ、δ、γ、η、χ、ρ、ベーマイト型のいずれか一種、又はそれらの混合物により構成されていることが好ましい。
また、活性アルミナ触媒がχ、ベーマイト型のいずれか一種、又はそれらの混合物で構成されている場合、Ｎａ２Ｏの含有量が多いと、上記塩酸による洗浄によりＮａ２Ｏの含有量を０．０１質量％未満まで容易に減少させることができる。
The active alumina catalyst is classified into α-alumina, γ-alumina, and boehmite when classified by crystal form. When γ-alumina is classified in detail, it can be divided into seven types: κ, θ, δ, γ, η, χ, and ρ.
Here, when the activated alumina catalyst is α-alumina, θ-alumina, or a mixture of α-alumina and θ-alumina, N 2 O removal performance is low, which is not preferable. Therefore, the activated alumina catalyst is preferably composed of any one of κ, δ, γ, η, χ, ρ, boehmite type, or a mixture thereof.
Further, when the activated alumina catalyst is composed of any one of χ, boehmite type, or a mixture thereof, if the content of Na 2 O is large, the content of Na 2 O is reduced to 0. 0 by washing with hydrochloric acid. It can be easily reduced to less than 01% by mass.
そして、活性アルミナ触媒は、細孔容積が０．２ｃｍ３／ｇ以上１．０ｃｍ３／ｇ以下、好ましくは０．３ｃｍ３／ｇ以上０．８ｃｍ３／ｇ以下であることが好ましい。細孔容積が０．２ｃｍ３／ｇ以上１．０ｃｍ３／ｇ以下の場合、流動層燃焼炉が７００℃程度でも、活性アルミナ触媒は良好なＮ２Ｏの除去性能を有する。 The activated alumina catalyst has a pore volume of 0.2 cm 3 / g or more and 1.0 cm 3 / g or less, preferably 0.3 cm 3 / g or more and 0.8 cm 3 / g or less. When the pore volume is 0.2 cm 3 / g or more and 1.0 cm 3 / g or less, the activated alumina catalyst has good N 2 O removal performance even when the fluidized bed combustion furnace is about 700 ° C.
また、活性アルミナ触媒は、比表面積が１００ｍ２／ｇ以上３００ｍ２／ｇ以下であることが好ましい。この範囲を外れると、酸点と考えられるアルミナの強い活性点が消失してＮ２Ｏの除去性能が低下したり、触媒強度が低下しすぎる、製造することが非常に難しくなる恐れがある。 The active alumina catalyst preferably has a specific surface area of 100 m 2 / g or more and 300 m 2 / g or less. If it is out of this range, the strong active sites of alumina considered to be acid sites disappear, the N 2 O removal performance is lowered, the catalyst strength is too low, and it may be very difficult to produce.
上述の構成を備えた活性アルミナ触媒は、流動層燃焼炉内において好適に使用される。
流動層燃焼炉は、流動媒体としての活性アルミナ触媒及び燃料が装入される流動層部と、その下側に配置された空気流入部とを備える。空気流入部から流動層部に空気が流入することにより、活性アルミナ触媒は燃料とともに流動状態となる。
流動層の燃焼温度は、温度制御部により７００℃〜９５０℃に制御されていることが好ましく、特に好ましくは７５０℃〜９００℃である。燃焼温度が７００℃未満であると、燃料の不完全燃焼や、燃料が本来持つ燃焼エネルギーを効率よく利用できなくなる恐れがあり、９５０℃を超えるとＮＯｘが多量に発生する等の恐れがある。前記温度範囲で制御すると、強力な温暖化ガスであるＮ２Ｏの発生量が増えるリスクが高くなるが、本発明の活性アルミナ触媒を用いる事で前記リスクを著しく軽減できるので、本発明の利用価値が非常に高くなる。
流動層燃焼炉としては、例えば、常圧型、加圧型、バブリング型、循環型などが挙げられる。
The activated alumina catalyst having the above-described configuration is preferably used in a fluidized bed combustion furnace.
The fluidized bed combustion furnace includes a fluidized bed portion in which an activated alumina catalyst and a fuel as a fluidized medium are charged, and an air inflow portion disposed below the fluidized bed portion. When air flows from the air inflow portion into the fluidized bed portion, the activated alumina catalyst becomes fluidized together with the fuel.
The combustion temperature of the fluidized bed is preferably controlled to 700 ° C. to 950 ° C. by the temperature control unit, and particularly preferably 750 ° C. to 900 ° C. If the combustion temperature is less than 700 ° C, incomplete combustion of the fuel or the combustion energy inherent in the fuel may not be used efficiently, and if it exceeds 950 ° C, a large amount of NOx may be generated. When the temperature is controlled within the above temperature range, the risk of increasing the amount of N 2 O, which is a powerful warming gas, increases. However, the use of the present invention can be significantly reduced by using the activated alumina catalyst of the present invention. The value is very high.
Examples of the fluidized bed combustion furnace include a normal pressure type, a pressure type, a bubbling type, and a circulation type.
［亜酸化窒素の除去方法］
次に、本実施形態の亜酸化窒素の除去方法について説明する。
まず、流動層燃焼炉内に、活性アルミナ触媒と燃料を装入する。装入後、流動層燃焼炉の下部から空気を流入させて、活性アルミナ触媒と燃料を流動させ、燃焼状態とする。そして、流動層燃焼炉の温度制御部により、流動層燃焼炉内の温度を７００〜９５０℃に制御する。この温度範囲では、燃焼ガス中にＮ２Ｏが含まれており、活性アルミナ触媒は、Ｎ２Ｏと接触することにより、Ｎ２Ｏを除去する。したがって、燃焼ガス中のＮ２Ｏを良好に除去することができる。なお、流動層燃焼炉内に活性アルミナ触媒を装入する構成を示したが、活性アルミナ触媒を投入する構成でもよい。
[Nitrous oxide removal method]
Next, the nitrous oxide removal method of this embodiment will be described.
First, an activated alumina catalyst and a fuel are charged into a fluidized bed combustion furnace. After the charging, air is introduced from the lower part of the fluidized bed combustion furnace to cause the activated alumina catalyst and the fuel to flow to be in a combustion state. And the temperature control part of a fluidized-bed combustion furnace controls the temperature in a fluidized-bed combustion furnace to 700-950 degreeC. In this temperature range, it includes the N 2 O in the combustion gases, activated alumina catalyst, by contacting the N 2 O, to remove the N 2 O. Therefore, N 2 O in the combustion gas can be removed well. In addition, although the structure which charged the activated alumina catalyst in the fluidized bed combustion furnace was shown, the structure which throws in an activated alumina catalyst may be sufficient.
［実施形態の効果］
本実施形態の活性アルミナ触媒は、不純物としてのＮａ２Ｏの含有量が特定の範囲であり、かつ、不純物としてのＳＯ３の含有量が特定値以下であるため、活性アルミナ触媒の製造効率を低下させることなく、良好にＮ２Ｏを除去できる。
そして、活性アルミナ触媒は、流動層燃焼時の温度が７００〜９５０℃という低温においてもＮ２Ｏを良好に除去することができ、ＮＯやＮＯ２といった他の温室効果ガスの生成も抑制することができる。
[Effect of the embodiment]
In the activated alumina catalyst of the present embodiment, the content of Na 2 O as an impurity is in a specific range, and the content of SO 3 as an impurity is not more than a specific value. N 2 O can be removed satisfactorily without lowering.
The activated alumina catalyst can satisfactorily remove N 2 O even at a low temperature of 700 to 950 ° C. during fluidized bed combustion, and suppresses the generation of other greenhouse gases such as NO and NO 2. Can do.
また、ＳＯ３の含有量が０．０１質量％以下であるため、さらに、Ｎ２Ｏを良好に除去することができる。 Moreover, since the content of SO 3 is 0.01% by mass or less, N 2 O can be further satisfactorily removed.
さらに、活性アルミナ触媒は、γ、χ、η、ρ、δ、ベーマイト型のいずれか一種、又はそれらの混合物であるため、優れたＮ２Ｏ除去性能を有する。また、活性アルミナ触媒を塩酸にて洗浄することにより容易にＮａ２Ｏの含有量を減少させることができるため、簡単な洗浄方法によりＮ２Ｏの除去性能に優れた活性アルミナ触媒を製造することができる。 Furthermore, since the activated alumina catalyst is any one of γ, χ, η, ρ, δ, boehmite type, or a mixture thereof, it has excellent N 2 O removal performance. Moreover, since the content of Na 2 O can be easily reduced by washing the activated alumina catalyst with hydrochloric acid, an activated alumina catalyst having excellent N 2 O removal performance can be produced by a simple washing method. Can do.
そして、本実施形態のＮ２Ｏの除去方法では、流動層燃焼炉内にて活性アルミナ触媒がＮ２Ｏを除去するため、流動層燃焼炉外の排ガス経路に活性アルミナ触媒を装入したり加熱したりするための装置を別途設ける必要が無いため、コストの低減が図れる。 In the N 2 O removal method of the present embodiment, the activated alumina catalyst removes N 2 O in the fluidized bed combustion furnace, so that the activated alumina catalyst is inserted into the exhaust gas path outside the fluidized bed combustion furnace. Since it is not necessary to provide a separate device for heating, the cost can be reduced.
（実施形態の変形例）
尚、本発明は、前述した実施形態に限定されるものではなく、以下に示すような変形をも含むものである。
前記実施形態では、流動層燃焼炉内に活性アルミナ触媒を装入する構成を示したがこれに限られず、流動層燃焼炉の外部の排ガス経路上に活性アルミナ触媒を配置してもよい。この場合、排ガス経路中では、活性アルミナ触媒の温度が低下して除去性能が低下する可能性があるため、活性アルミナ触媒を加熱する加熱装置を設置してもよい。
また、前記実施形態では、流動媒体として活性アルミナ触媒を使用する構成を示したが、これに限られない。活性アルミナ触媒と異なる他の流動媒体、例えば、石英砂、石灰石、石炭灰などを混合しても良い。
(Modification of the embodiment)
In addition, this invention is not limited to embodiment mentioned above, The deformation | transformation as shown below is also included.
In the above-described embodiment, the configuration in which the activated alumina catalyst is charged into the fluidized bed combustion furnace is shown. However, the present invention is not limited thereto, and the activated alumina catalyst may be disposed on the exhaust gas path outside the fluidized bed combustion furnace. In this case, in the exhaust gas path, there is a possibility that the temperature of the activated alumina catalyst is lowered and the removal performance is lowered. Therefore, a heating device for heating the activated alumina catalyst may be installed.
Moreover, in the said embodiment, although the structure which uses an activated alumina catalyst as a fluid medium was shown, it is not restricted to this. Other fluid media different from the activated alumina catalyst, such as quartz sand, limestone, and coal ash, may be mixed.
また、流動層燃焼炉内に活性アルミナ触媒を装入する構成を示したが、これに限られない。例えば、流動層燃焼炉内において、活性アルミナ触媒と異なる流動媒体を使用して流動層を形成し、この流動層上にフリーボード部を配置し、フリーボード部に活性アルミナ触媒を装入する構成でも良い。この場合、フリーボード部において、活性アルミナ触媒が燃焼ガス中のＮ２Ｏと接触し、Ｎ２Ｏを除去することができる。
さらに、流動層燃焼炉内に燃料が装入される構成も示したが、燃料としては、例えば、石炭、重油、石油コークス、産業廃棄物などでもよい。
Moreover, although the structure which inserts an activated alumina catalyst in a fluidized bed combustion furnace was shown, it is not restricted to this. For example, in a fluidized bed combustion furnace, a fluidized bed is formed using a fluidized medium different from the activated alumina catalyst, a freeboard portion is disposed on the fluidized bed, and the activated alumina catalyst is inserted into the freeboard portion. But it ’s okay. In this case, the freeboard section can be activated alumina catalyst is in contact with the N 2 O in the combustion gas, to remove the N 2 O.
Furthermore, although the configuration in which fuel is charged into the fluidized bed combustion furnace is shown, the fuel may be, for example, coal, heavy oil, petroleum coke, industrial waste, or the like.
以下、実施例及び比較例を挙げて、本発明をより具体的に説明するが、本発明は実施例等の内容に何ら限定されるものではない。
［実施例１〜３、比較例１〜７］
実施例１、２、比較例１〜７では、表１，２に示すような活性アルミナ単品を活性アルミナ触媒として使用した。
実施例３では、比較例２〜４と同様の出発原料により製造された活性アルミナ触媒であり、塩酸で洗浄したものを使用した。
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the content, such as an Example, at all.
[Examples 1 to 3, Comparative Examples 1 to 7]
In Examples 1 and 2 and Comparative Examples 1 to 7, activated alumina alone as shown in Tables 1 and 2 was used as an activated alumina catalyst.
In Example 3, an activated alumina catalyst produced from the same starting material as in Comparative Examples 2 to 4 and washed with hydrochloric acid was used.
（実験装置の構成）
図１に示すように、実験装置１は、Ｎ２Ｏガスを貯留するガス貯留部１１と、ガス貯留部１１に連結されたガス導入管１２と、ガス導入管１２が底部に連結された内径６ｍｍの石英管１３と、石英管１３の頂部に連結されたガス排出管１４とを備える。また、石英管１３の軸方向の略中央部には、石英管１３の周囲を包囲して活性アルミナ触媒を加熱する電気炉１５を備える。ガス導入管１２の略中央部には、ガス流量計１２１が配置され、ガス排出管１４の略中央部には、記録計１４２が接続されたＮ２Ｏ分析計１４１が配置されている。
(Configuration of experimental equipment)
As shown in FIG. 1, the experimental apparatus 1 has a
石英管１３に、充填長が１００ｍｍとなるように実施例及び比較例に係る活性アルミナ触媒を充填してアルミナ層２１を形成した。活性アルミナ触媒の充填量は１ｇであり、粒径が０．２５〜０．５ｍｍであった。
アルミナ層２１の上端には、薄い石英ウール層２２ａ、充填長３０ｍｍの石英砂層２３ａ及び薄い石英ウール層２２ｂからなる上部３層充填体を形成した。また、アルミナ層２１の下端には、同様に、薄い石英ウール層２２ｃ、充填長３０ｍｍの石英砂層２３ｂ及び薄い石英ウール層２２ｄからなる下部３層充填体を形成した。これら上部３層充填体及び下部３層充填体によりアルミナ層２１を保持固定している。
The
At the upper end of the
（実験方法）
窒素で希釈されてＮ２Ｏ濃度が５００ｐｐｍとなったＮ２Ｏガスを、ガス導入管１２からガス流量計１２１経由で流量１リットル／分（常温、常圧）の割合で石英管１３の底部に供給した。そして、電気炉１５でアルミナ層２１の温度を変化させながら、アルミナ層２１にＮ２Ｏガスを通過させた。そして石英管１３の頂部からガス排出管１４に排出された排ガスをＮ２Ｏ分析計１４１に導き、ここで排ガス中のＮ２Ｏ濃度を分析して各活性アルミナ触媒についてのＮ２Ｏ除去率を測定した。
流動層燃焼温度が８００〜８５０℃の場合ではどの活性アルミナ触媒も１００％近くのＮ２Ｏの除去率を示したため、より低温の６５０℃及び７００℃における活性アルミナ触媒のＮ２Ｏ除去率を測定して比較した。測定結果は表１、２に示す。なお、表１，２において、結晶形態は粉末Ｘ線回折装置を用いて決定し、組成比は下記要領でＸＲＦ(蛍光Ｘ線)装置を用いた元素分析により決定した。
組成の分析方法としては、試料に融剤となる四ほう酸リチウムを混合して、加熱し、ガラスビードを作成した上で、PANalytical社製Axios蛍光X線分析装置により、組成を定量した。
(experimental method)
N 2 O gas diluted with nitrogen to a N 2 O concentration of 500 ppm is passed through the
Since the fluidized bed combustion temperature showed the removal rate of any active alumina catalyst also near 100% N 2 O in the case of 800 to 850 ° C., the N 2 O removal ratio of active alumina catalyst in the cooler 650 ° C. and 700 ° C. Measured and compared. The measurement results are shown in Tables 1 and 2. In Tables 1 and 2, the crystal form was determined using a powder X-ray diffractometer, and the composition ratio was determined by elemental analysis using an XRF (fluorescent X-ray) apparatus in the following manner.
As a composition analysis method, lithium tetraborate serving as a flux was mixed with a sample and heated to prepare a glass bead, and then the composition was quantified using an Axios X-ray fluorescence analyzer manufactured by PANalytical.
表１、２から、実施例１〜３と比較例１〜５とを比較すると、実施例１〜３では、Ｎａ２Ｏの含有率が０．０５質量％以下、かつ、ＳＯ３の含有率が１質量％以下であるため、比較的低温の６５０℃であっても除去率が７０％以上であった。
また、比較例２，３では、７００℃の高温であればＮ２Ｏを良好に除去し、実施例に近いレベルであった。しかし、排出規制が厳しいＮＯｘの発生を抑えつつ、Ｎ２Ｏを除去させる場合には、反応温度が低いほうが好ましい。低温の６５０℃の場合、比較例２，３では、除去率は実施例１〜３よりも低下した。
さらに、実施例１〜３と比較例６，７とを比較すると、実施例１〜３の活性アルミナ触媒は、結晶形態がγ型の一種又はγ、χ、ベーマイト型の混合物であったため、高い除去率であった。一方、比較例６，７では、活性アルミナの結晶形態がα、θ型であったため、除去率は低く、不活性であることがわかった。
尚、実施例３は塩酸で洗浄したことにより、塩素量が４０００ｐｐｍと多く、流動層炉内で用いると、装置の腐食等の問題を起こす恐れが有るため、実施例１、実施例２のように、アルミナ中の塩素量は５００ｐｐｍ以下、特に１００ｐｐｍとする事が、より好ましい。
From Tables 1 and 2, when Examples 1 to 3 and Comparative Examples 1 to 5 are compared, in Examples 1 to 3, the content of Na 2 O is 0.05% by mass or less, and the content of SO 3 Is 1% by mass or less, so the removal rate was 70% or more even at a relatively low temperature of 650 ° C.
In Comparative Examples 2 and 3, N 2 O was removed well at a high temperature of 700 ° C., which was a level close to that of the example. However, when N 2 O is removed while suppressing the generation of NO x , which has strict emission regulations, a lower reaction temperature is preferable. In the case of 650 degreeC of low temperature, in the comparative examples 2 and 3, the removal rate fell rather than Examples 1-3.
Further, comparing Examples 1 to 3 with Comparative Examples 6 and 7, the activated alumina catalysts of Examples 1 to 3 were high because the crystal form was a kind of γ type or a mixture of γ, χ, boehmite type. The removal rate. On the other hand, in Comparative Examples 6 and 7, since the activated alumina crystal forms were α and θ types, it was found that the removal rate was low and inactive.
Since Example 3 is washed with hydrochloric acid, the amount of chlorine is as high as 4000 ppm, and if used in a fluidized bed furnace, it may cause problems such as corrosion of the apparatus. In addition, the amount of chlorine in the alumina is more preferably 500 ppm or less, particularly 100 ppm.
本発明は、活性アルミナ触媒を使用してＮ２Ｏを除去する方法に利用できる。特に、流動層燃焼炉内で良好に排ガス中のＮ２Ｏを除去する方法として利用できる。 The present invention can be used in a method for removing N 2 O using an activated alumina catalyst. In particular, it can be used as a method for removing N 2 O in exhaust gas satisfactorily in a fluidized bed combustion furnace.
１ 実験装置
１１ ガス貯留部
１２ ガス導入管
１３ 石英管
１４ ガス排出管
１５ 電気炉
２１ アルミナ層
１４１ 分析計
DESCRIPTION OF SYMBOLS 1
Claims (4)
下記（ａ）及び（ｂ）を満たすことを特徴とする活性アルミナ触媒。
（ａ）酸化ナトリウム（Ｎａ２Ｏ）の含有量が０．０１質量％以上０．０５質量％以下
（ｂ）三酸化硫黄（ＳＯ３）の含有量が１質量％以下 An activated alumina catalyst for removing nitrous oxide contained in combustion gas,
An activated alumina catalyst characterized by satisfying the following (a) and (b).
(A) Content of sodium oxide (Na 2 O) is 0.01% by mass or more and 0.05% by mass or less (b) Content of sulfur trioxide (SO 3 ) is 1% by mass or less
前記三酸化硫黄（ＳＯ３）の含有量が０．０１質量％以下である
ことを特徴とする活性アルミナ触媒。 The activated alumina catalyst according to claim 1,
Activated alumina catalyst content of the sulfur trioxide (SO 3) is equal to or less than 0.01 mass%.
γ、χ、η、ρ、δ、ベーマイト型のいずれか一種、又はそれらの混合物である
ことを特徴とする活性アルミナ触媒。 In the activated alumina catalyst according to claim 1 or 2,
An activated alumina catalyst characterized by being any one of γ, χ, η, ρ, δ, boehmite type, or a mixture thereof.
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