JP2013244469A - Method for producing denitration catalyst - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000000378 calcium silicate Substances 0.000 claims abstract description 29
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 29
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000004898 kneading Methods 0.000 claims abstract description 9
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 150000004715 keto acids Chemical class 0.000 claims abstract description 4
- 239000000306 component Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010304 firing Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 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
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 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 2
- 239000011575 calcium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 alkaline earth metal salt Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、脱硝触媒の製造法に関する。より詳細に、本発明は、アンモニア接触還元脱硝法に好適に使用できる高活性な脱硝触媒の製造法に関する。 The present invention relates to a method for producing a denitration catalyst. More specifically, the present invention relates to a method for producing a highly active denitration catalyst that can be suitably used for ammonia catalytic reduction denitration.
発電所、各種工場、自動車等から排出される排煙中の窒素酸化物（ＮＯX）は、光化学スモッグや酸性雨の原因物質である。窒素酸化物の除去方法として、アンモニア選択的接触還元（ＳＣＲ）脱硝法が、石炭火力発電所を中心に広く用いられている。このＳＣＲ脱硝法に用いられる触媒として、バナジウムおよびモリブデンまたはタングステンを触媒活性成分とした酸化チタン系触媒が知られている。この触媒は、上記触媒活性成分の塩類と、酸化チタンまたはその前駆体とを、水の存在下で混練し、得られたペーストを板状、ハニカム状または粒状に成型し、次いで乾燥および焼成することによって製造される。 Nitrogen oxides (NO x ) in the smoke emitted from power plants, various factories, automobiles, etc. are causative substances for photochemical smog and acid rain. As a method for removing nitrogen oxides, ammonia selective catalytic reduction (SCR) denitration is widely used mainly in coal-fired power plants. As a catalyst used in this SCR denitration method, a titanium oxide catalyst having vanadium and molybdenum or tungsten as catalytic active components is known. This catalyst is prepared by kneading the salt of the above-mentioned catalytically active component and titanium oxide or a precursor thereof in the presence of water, forming the resulting paste into a plate shape, honeycomb shape or granular shape, and then drying and firing. Manufactured by.
触媒原料であるＴｉＯ2は硫酸法で製造することができる。硫酸法によって作られたＴｉＯ2は硫酸根（ＳＯ4）を多く含有している。ところが、硫酸根を含有しているＴｉＯ2を用いると触媒調製の最終工程の焼成段階でＳＯ3が飛散することがある。これを防ぐために、焼成時の温度を硫酸根が飛散しない程度の低温にすることが考えられる。しかしながら、低温焼成で得られた触媒を用いると、脱硝操業時にＳＯ3が飛散し、脱硝反応器の後段に続く空気予熱器や電気集塵機などを腐食させることがある。このような腐食を防止するために、硫酸アルミニウムとアルカリ土類金属塩を添加し、触媒中の硫酸根を安定固定化することが提案されている（特許文献１）。 TiO 2 which is a catalyst raw material can be produced by a sulfuric acid method. TiO 2 produced by the sulfuric acid method contains a large amount of sulfate radicals (SO 4 ). However, when TiO 2 containing sulfate radicals is used, SO 3 may be scattered at the firing stage of the final step of catalyst preparation. In order to prevent this, it is conceivable that the temperature during firing is low enough to prevent the sulfate radicals from scattering. However, when a catalyst obtained by low-temperature firing is used, SO 3 is scattered during the denitration operation, which may corrode an air preheater or an electric dust collector following the denitration reactor. In order to prevent such corrosion, it has been proposed to add aluminum sulfate and an alkaline earth metal salt to stably fix the sulfate radical in the catalyst (Patent Document 1).
一般に、ガス用触媒は、多孔質なものの方がガスとの接触面積が広く性能が高いと言われている。触媒を多孔質化して触媒中の細孔を増加させる手段としては、触媒原料を混合して得られるペースト状物をできるだけ高水分化することや、無機繊維などを添加して焼成時の焼結による細孔の減少を防止するなどの方法が知られている（特許文献２）。また、ペーストに増粘剤を添加して保水性を高める方法が知られている。増粘剤としては、ポリビニルアルコールやポリアクリル酸アミド系の増粘剤や、カルボキシセルロースなどのセルロース系の増粘剤などが挙げられる（特許文献３）。しかしながら、一旦焼成したものを触媒原料として用いた場合には効果を発揮するが、予め焼成を行わないで、触媒成分を混練後直ちに成型する場合においては、触媒焼成時に発生する増粘剤の分解ガスと触媒成分とが反応した発熱により触媒が焼損する恐れがある。 In general, it is said that a porous catalyst for gas has a wider contact area with gas and higher performance. As a means to increase the pores in the catalyst by making the catalyst porous, the paste-like material obtained by mixing the catalyst raw materials is made to have as high a moisture as possible, or inorganic fibers are added and sintered at the time of firing. A method is known such as preventing the reduction of pores due to the above (Patent Document 2). Moreover, the method of adding a thickener to a paste and improving water retention is known. Examples of the thickener include polyvinyl alcohol and polyacrylic acid amide thickener, and cellulose thickener such as carboxycellulose (Patent Document 3). However, it is effective when it is fired once as a catalyst raw material. However, when the catalyst components are molded immediately after kneading without being fired in advance, the thickener decomposed during catalyst firing is decomposed. There is a possibility that the catalyst may burn out due to heat generated by the reaction of the gas and the catalyst component.
本発明の課題は、硫酸根を固定化することによりＳＯ3の飛散を防ぎ、かつ触媒を多孔質化することにより高活性な触媒を得ることができる製造法を提供することである。
ところで、リンによる触媒の劣化を防止することを目的とした排ガス脱硝触媒の製法として、特許文献４は、チタン、タングステン、モリブデンおよびバナジウムから選ばれた一つ以上の酸化物を含む組成物からなる成形体に、珪酸カルシウムを含有するスラリ状物を浸漬または塗布することを特徴とする排ガス脱硝触媒の製法を提案している。しかし、この文献には硫酸根の固定安定化および触媒の多孔質化に関する示唆がない。
An object of the present invention is to provide a production method capable of preventing the scattering of SO 3 by immobilizing sulfate radicals and obtaining a highly active catalyst by making the catalyst porous.
By the way, as a method for producing an exhaust gas denitration catalyst for the purpose of preventing deterioration of the catalyst due to phosphorus, Patent Document 4 is composed of a composition containing one or more oxides selected from titanium, tungsten, molybdenum and vanadium. A process for producing an exhaust gas denitration catalyst characterized by immersing or applying a slurry containing calcium silicate to a molded body is proposed. However, this document has no suggestion regarding the stabilization and fixation of sulfate radicals and the formation of a porous catalyst.
本発明者らは、上記課題を解決すべく鋭意検討した結果、ケイ酸カルシウムを酸化チタンと触媒活性成分とからなるペーストに添加することによって、硫酸根の固定安定化と触媒の多孔質化とを成し得ることを見出した。本発明は、この知見に基づき更に検討を重ねることによって完成するに至ったものである。 As a result of intensive studies to solve the above problems, the present inventors have added calcium silicate to a paste made of titanium oxide and a catalytically active component, thereby stabilizing and fixing sulfate radicals and making the catalyst porous. It was found that can be achieved. The present invention has been completed by further studies based on this finding.
すなわち、本発明は以下の態様を包含するものである。
〔１〕酸化チタンあるいはその前駆体、触媒活性成分、ケイ酸カルシウムおよび水を混練して触媒ペーストを得、
次いで該ペーストを成形することを含む脱硝触媒の製造法。
〔２〕触媒活性成分が、可溶性塩類である、〔１〕に記載の脱硝触媒の製造法。
〔３〕触媒活性成分が、Ｍｏ、ＷおよびＶからなる群から選ばれる少なくとも一つの元素を有するオキソ酸の塩である、〔１〕に記載の脱硝触媒の製造法。
〔４〕酸化チタンあるいはその前駆体が硫酸根（ＳＯ4）を含有するものであり、
ケイ酸カルシウムの量が、ＣａＯ／ＳＯ4のモル比で０．５超１．０以下となる量である、〔１〕〜〔３〕のいずれかひとつに記載の脱硝触媒の製造法。
〔５〕触媒ペーストの混練において無機繊維および／または無機ゾル状物をさらに用いる、〔１〕〜〔４〕のいずれかひとつに記載の脱硝触媒の製造法。
That is, the present invention includes the following aspects.
[1] Titanium oxide or a precursor thereof, a catalytically active component, calcium silicate and water are kneaded to obtain a catalyst paste,
Next, a method for producing a denitration catalyst comprising forming the paste.
[2] The method for producing a denitration catalyst according to [1], wherein the catalytically active component is a soluble salt.
[3] The method for producing a denitration catalyst according to [1], wherein the catalytically active component is a salt of oxo acid having at least one element selected from the group consisting of Mo, W and V.
[4] Titanium oxide or its precursor contains sulfate radical (SO 4 ),
The method for producing a denitration catalyst according to any one of [1] to [3], wherein the amount of calcium silicate is an amount that results in a molar ratio of CaO / SO 4 of more than 0.5 and 1.0 or less.
[5] The method for producing a denitration catalyst according to any one of [1] to [4], wherein inorganic fibers and / or inorganic sols are further used in kneading the catalyst paste.
本発明によれば、ＴｉＯ2中に含まれる硫酸根はケイ酸カルシウム（xCaO・ySiO2・zH2O）のＣａＯ成分と反応させてＣａＳＯ4を生成させることにより固定化させることができる（式１参照）。その際に、Ｃａイオンが抜けて、網目様の構造を有するＳｉＯ2が生成する。この構造の隙間が細孔となるため、多孔質な触媒にすることができる。また、多孔質な触媒はガスの拡散速度が向上するので脱硝活性を高くすることができる。
TiO2・aSO4・bH2O + xCaO・ySiO2・zH2O ->
TiO2 + xCaSO4 + ySiO2 + (a‐x)SO4 + (b+z)H2O + x/2O2 （式１）
According to the present invention, the sulfate radical contained in TiO 2 can be immobilized by reacting with the CaO component of calcium silicate (xCaO · ySiO 2 · zH 2 O) to form CaSO 4 (formula 1). At that time, Ca ions are released and SiO 2 having a network-like structure is generated. Since the gaps in this structure become pores, a porous catalyst can be obtained. Moreover, since the porous catalyst improves the gas diffusion rate, the denitration activity can be increased.
TiO 2・ aSO 4・ bH 2 O + xCaO ・ ySiO 2・ zH 2 O->
TiO 2 + xCaSO 4 + ySiO 2 + (a-x) SO 4 + (b + z) H 2 O + x / 2O 2 (Formula 1)
本発明に係る脱硝触媒の製造法は、酸化チタンあるいはその前駆体、触媒活性成分、ケイ酸カルシウムおよび水を混練して触媒ペーストを得、
次いで該ペーストを成形することを含む。
The method for producing a denitration catalyst according to the present invention is obtained by kneading titanium oxide or a precursor thereof, a catalytically active component, calcium silicate and water to obtain a catalyst paste,
Then forming the paste.
本発明で用いられるケイ酸カルシウムは、ＣａＯとＳｉＯ2を含有するものであれば特に限定されない。例えば、結晶質ケイ酸カルシウム水和物、非晶質ケイ酸カルシウム水和物、ウォラストナイト（ＣａＳｉＯ3）、けいカル肥料などが挙げられる。但し、アルカリ金属元素やＣａ以外のアルカリ土類金属元素の含有量が少ないケイ酸カルシウムが好ましい。アルカリ金属元素やＣａ以外のアルカリ土類金属元素の含有量が多いケイ酸カルシウムは、脱硝触媒の活性成分を被毒することがある。また、本発明のケイ酸カルシウムの添加量は、ＣａＯ／ＳＯ4のモル比で、好ましくは０．４５以上１．１以下、より好ましくは０．５以上１．０以下、さらに好ましくは０．５超１．０以下、よりさらに好ましくは０．５超０．８以下である。ケイ酸カルシウムの量が少なすぎると硫酸根の固定化の効果が得にくい傾向がある。ケイ酸カルシウムの量が多すぎると脱硝活性が低下する傾向がある。ケイ酸カルシウムを添加する場合、水以外にコロイダルシリカなどのバインダや、メタタングステン酸アンモニウム水溶液などの触媒活性成分が含まれていても特に問題はない。 The calcium silicate used in the present invention is not particularly limited as long as it contains CaO and SiO 2 . For example, crystalline calcium silicate hydrate, amorphous calcium silicate hydrate, wollastonite (CaSiO 3 ), silicic fertilizer and the like can be mentioned. However, calcium silicate with a low content of alkali metal elements and alkaline earth metal elements other than Ca is preferable. Calcium silicate with a high content of alkaline earth metal elements other than alkali metal elements and Ca may poison the active components of the denitration catalyst. The addition amount of the calcium silicate of the present invention is CaO / SO 4 molar ratio, preferably 0.45 or more and 1.1 or less, more preferably 0.5 or more and 1.0 or less, and still more preferably 0.00. It is more than 5 and 1.0 or less, more preferably more than 0.5 and 0.8 or less. If the amount of calcium silicate is too small, the effect of fixing sulfate sulfate tends to be difficult to obtain. If the amount of calcium silicate is too large, the denitration activity tends to decrease. When calcium silicate is added, there is no particular problem even if a binder such as colloidal silica or a catalytically active component such as an aqueous solution of ammonium metatungstate is contained in addition to water.
本発明で用いられる酸化チタンおよびその前駆体は、特に制限はないが、硫酸根を含んでいる酸化チタンおよびその前駆体が好ましい。硫酸法で製造されたＴｉＯ2やアルカリで洗浄する前のＴｉＯ2を用いることが好ましい。この他に、ＴｉＯ2原料としては、含水酸化チタンや酸化チタンのゾル状物の乾燥体、酸化チタンの前駆体、ＴｉＯ2−ＳｉＯ2の複合酸化物を用いることができる。また、酸化チタンと硫酸アルミニウムを水の存在下で混合し、硫酸根をＴｉＯ2表面に予め吸着させたものであってもよい。 The titanium oxide and its precursor used in the present invention are not particularly limited, but a titanium oxide containing a sulfate group and its precursor are preferable. It is preferable to use TiO 2 produced by a sulfuric acid method or TiO 2 before washing with an alkali. In addition, as the TiO 2 raw material, a dry product of hydrous titanium oxide or titanium oxide sol, a precursor of titanium oxide, or a composite oxide of TiO 2 —SiO 2 can be used. Alternatively, titanium oxide and aluminum sulfate may be mixed in the presence of water, and sulfate radicals may be adsorbed on the surface of TiO 2 in advance.
本発明で用いられる触媒活性成分としては、通常の脱硝触媒の原料に用いられるものを使用することができる。触媒活性成分である可溶性塩類は、Ｍｏ、ＷおよびＶからなる群から選ばれる少なくとも一つの元素を有するオキソ酸の塩であることが望ましい。Ｗ原料としては、該当する金属のＷＯ4型イオンを含む酸素酸あるいはヘテロポリ酸、メタあるいはパラタングステン酸アンモニウムなどのアンモニウム塩などが挙げられる。Ｍｏ原料としては、該当する金属のＭｏＯ4型イオンを含むアンモニウム塩であるモリブデン酸アンモニウム、もしくは、該当する金属の酸化物である三酸化モリブデンが挙げられる。Ｖ原料としては、メタバナジン酸アンモニウムなどのアンモニウム塩が挙げられる。触媒活性成分の添加量には特に制限は無いが、ＴｉＯ2に対し各々０atom％を超えて３atom％以下に選定される。ＴｉＯ2原料の比表面積が大きい場合には添加量を多めに、小さい場合に添加量を少なめに選定すると脱硝性能を高く維持でき、またＳＯ2の酸化性能を低く抑えることができ好都合である。これら触媒活性成分の添加方法はどのような方法であっても良いが、水の存在下でニーダを用いて混練するか、または加熱混練することが経済的であり優れている。
また、これら触媒活性成分となる原料の他に、無機繊維および／またはシリカゾルなどの無機ゾル状物のような、通常の脱硝触媒に添加される原料を加えることが好ましい。
As the catalytically active component used in the present invention, those used as a raw material for ordinary denitration catalysts can be used. The soluble salt which is a catalytically active component is desirably a salt of oxo acid having at least one element selected from the group consisting of Mo, W and V. Examples of the W raw material include oxygen acids or heteropolyacids containing WO 4 type ions of the corresponding metal, and ammonium salts such as meta or ammonium paratungstate. Examples of the Mo raw material include ammonium molybdate, which is an ammonium salt containing MoO 4 type ions of the corresponding metal, and molybdenum trioxide, which is an oxide of the corresponding metal. Examples of the V raw material include ammonium salts such as ammonium metavanadate. The amount of the catalytically active component added is not particularly limited, but is selected to be more than 0 atom% and not more than 3 atom% with respect to TiO 2 . When the specific surface area of the TiO 2 raw material is large, it is advantageous that the denitration performance can be kept high and the oxidation performance of SO 2 can be kept low by selecting a large addition amount and a small addition amount when it is small. Any method for adding these catalytically active components may be used, but it is economical and excellent to knead using a kneader in the presence of water or to knead by heating.
In addition to the raw materials to be the catalytically active components, it is preferable to add raw materials that are added to a normal denitration catalyst such as inorganic sols and / or inorganic sols such as silica sol.
本発明における脱硝触媒の製造法において、酸化チタンおよびその前駆体と、触媒活性成分である可溶性塩類と、ケイ酸カルシウムとの混合は、水と共に全量を一度に混練する方法； 酸化チタンおよびその前駆体と触媒活性成分とを混練し、次いでケイ酸カルシウムを添加して混合する方法などを採用することができる。効率良くＴｉＯ2中の硫酸根とケイ酸カルシウムとを反応させるために酸化チタンおよびその前駆体、触媒活性成分、ケイ酸カルシウムを一度に全量混練する方法が好ましい。また、混練で得られたペースト状触媒は、直ちに、板状、ハニカム状などの形状に成形することが好ましい。板状に成形する方法としては、例えば、金属製ラス基板にラス目を埋めるようにペーストを塗布し、次いで型曲げ加工、搾り加工、エンボス加工などによって凹凸を形成し、乾燥および焼成する工程を含む方法が挙げられる。得られた板状触媒は形成された凹凸がスペーサとなるように複数枚を重ね合せて積層構造体にして、脱硝反応器に取り付けることができる。 In the method for producing a denitration catalyst in the present invention, titanium oxide and a precursor thereof, a soluble salt which is a catalytically active component, and calcium silicate are mixed at once with water; titanium oxide and a precursor thereof A method of kneading the body and the catalytically active component and then adding and mixing calcium silicate can be employed. In order to efficiently react the sulfate radical in TiO 2 with calcium silicate, a method of kneading all of titanium oxide and its precursor, a catalytically active component, and calcium silicate at once is preferable. Further, the pasty catalyst obtained by kneading is preferably immediately formed into a plate shape, a honeycomb shape or the like. As a method of forming into a plate shape, for example, a process of applying a paste so as to fill a lath in a metal lath substrate, then forming irregularities by mold bending, squeezing, embossing, etc., and drying and firing The method of including is mentioned. The obtained plate-shaped catalyst can be attached to a denitration reactor by stacking a plurality of sheets so that the formed irregularities become spacers to form a laminated structure.
次に、実施例を示して、本発明をより詳細に説明する。但し、本発明はこれらの実施例によって何ら限定されるものではない。 Next, an Example is shown and this invention is demonstrated in detail. However, the present invention is not limited to these examples.
実施例１
メタバナジン酸アンモニウム１．２４ｇ、モリブデン酸アンモニウム０．４０ｇ、および蓚酸１．５４ｇを水５０ｇに溶解させ、これに酸化チタン（堺化学製ＣＳＰ−Ｍ、ＳＯ4含有率；６．５ｗｔ％、比表面積約１２０ｍ2／ｇ）６０ｇとケイ酸カルシウム（富田製薬製、トミタＡＤ ８５０Ｈ ２００Ｍ、化学式５ＣａＯ・６ＳｉＯ2・ｚＨ2Ｏ、ＣａＯ含有率；３１．７ｗｔ％）３．５６ｇを入れ、それらを混練した。その後、１２０℃で一時間乾燥した。加圧成型器を用いて、約１．３ｔｏｎ／ｃｍ2で加圧し、成型した。得られたディスクを砕き、ふるいで０．８５〜１．７ｍｍに整粒し、５００℃で２時間焼成して触媒を得た。本触媒におけるＣａＯ／ＳＯ4のモル比は０．５であり、本触媒の組成はＴｉ／Ｍｏ／Ｖ＝９８．２／０．３／１．５（原子比）である。
Example 1
1.24 g of ammonium metavanadate, 0.40 g of ammonium molybdate, and 1.54 g of oxalic acid were dissolved in 50 g of water, and titanium oxide (CSP-M manufactured by Sakai Chemical, SO 4 content; 6.5 wt%, specific surface area) 60 g of about 120 m 2 / g) and 3.56 g of calcium silicate (Tomita Pharmaceutical, Tomita AD 850H 200M, chemical formula 5CaO · 6SiO 2 · zH 2 O, CaO content: 31.7 wt%) were added and kneaded. . Then, it dried at 120 degreeC for 1 hour. Using a pressure molding machine, it was pressed at about 1.3 ton / cm 2 and molded. The obtained disc was crushed, sieved to 0.85 to 1.7 mm, and calcined at 500 ° C. for 2 hours to obtain a catalyst. The molar ratio of CaO / SO 4 in this catalyst is 0.5, and the composition of this catalyst is Ti / Mo / V = 98.2 / 0.3 / 1.5 (atomic ratio).
実施例２
ケイ酸カルシウムの量を５．７０ｇに変えた以外は実施例１と同じ手法で触媒を調製した。本触媒におけるＣａＯ／ＳＯ4のモル比は０．８である。
Example 2
A catalyst was prepared in the same manner as in Example 1 except that the amount of calcium silicate was changed to 5.70 g. The molar ratio of CaO / SO 4 in this catalyst is 0.8.
実施例３
ケイ酸カルシウムの量を７．１２ｇに変えた以外は実施例１と同じ手法で触媒を調製した。本触媒におけるＣａＯ／ＳＯ4のモル比は１．０である。
Example 3
A catalyst was prepared in the same manner as in Example 1 except that the amount of calcium silicate was changed to 7.12 g. The molar ratio of CaO / SO 4 in this catalyst is 1.0.
比較例１
ケイ酸カルシウムの量を０ｇに変えた以外は実施例１と同じ手法で触媒を調製した。本触媒におけるＣａＯ／ＳＯ4のモル比は０である。
Comparative Example 1
A catalyst was prepared in the same manner as in Example 1 except that the amount of calcium silicate was changed to 0 g. The molar ratio of CaO / SO 4 in this catalyst is zero.
比較例２
酸化チタン（堺化学製ＣＳＰ−Ｍ、ＳＯ4含有率；６．５ｗｔ％）を酸化チタン（石原産業製 ＭＣ９０ ＳＯ4含有率；１．４ｗｔ％、比表面積約９０ｍ2／ｇ）に変えた以外は比較例１と同じ手法で触媒を調製した。本触媒におけるＣａＯ／ＳＯ4のモル比は０である。
Comparative Example 2
Titanium oxide (CSP-M manufactured by Sakai Chemicals, SO 4 content: 6.5 wt%) was changed to titanium oxide (MC90 SO 4 content: 1.4 wt%, specific surface area about 90 m 2 / g manufactured by Ishihara Sangyo) Prepared a catalyst in the same manner as in Comparative Example 1. The molar ratio of CaO / SO 4 in this catalyst is zero.
実施例１〜３及び比較例１〜２で得られた脱硝触媒について、表１に示す条件にて脱硝率を測定した。その結果を表２に示す。本発明に係る実施例１〜３の触媒は、細孔容積がおよそ０．５４ｃｃ／ｇであり、比較例１および２の触媒の細孔容積よりも大きいことが分かる。また実施例１〜３の触媒は比較例１および２の触媒に比べて脱硝性能が高いことが分かる。 About the denitration catalyst obtained in Examples 1-3 and Comparative Examples 1-2, the denitration rate was measured on the conditions shown in Table 1. The results are shown in Table 2. It can be seen that the catalysts of Examples 1 to 3 according to the present invention have a pore volume of approximately 0.54 cc / g, which is larger than the pore volumes of the catalysts of Comparative Examples 1 and 2. It can also be seen that the catalysts of Examples 1 to 3 have higher denitration performance than the catalysts of Comparative Examples 1 and 2.
実施例４
メタバナジン酸アンモニウム１．２４ｇ、モリブデン酸アンモニウム０．４０ｇ、および蓚酸１．５４ｇを水４０ｇに溶解させ、これに酸化チタン（堺化学製ＣＳＰ−Ｍ、ＳＯ4含有率；６．５ｗｔ％、比表面積約１２０ｍ2／ｇ）６０ｇとケイ酸カルシウム（富田製薬製、トミタＡＤ ８５０Ｈ ２００Ｍ、化学式５ＣａＯ・６ＳｉＯ2・ｚＨ2Ｏ、ＣａＯ含有率；３１．７ｗｔ％）５．７０ｇとシリカゾル（日産化学工業製ＯＳゾル）１２．３ｇを入れ、ニーダで混練してペースト状にした。これに無機繊維（イビデン製イビウール）９．０ｇを添加し、さらにニーダで混練して触媒ペーストを調製した。
これとは別にＳＵＳ４３０製帯鋼をメタルラス加工して目開きが約２ｍｍの網状基材を作成した。
この網状基材に触媒ペーストを置き、加圧ローラに通過させることにより、基材の網目間および表面にペーストを圧着して厚さ０．７ｍｍの板状成形体を得た。次いで、該板状成形体を１５０℃で２時間乾燥させ、大気中５００℃で２時間焼成して板状触媒を得た。
Example 4
1.24 g of ammonium metavanadate, 0.40 g of ammonium molybdate and 1.54 g of oxalic acid were dissolved in 40 g of water, and titanium oxide (CSP-M, SO 4 content by Sakai Chemical; 6.5 wt%, specific surface area) about 120m 2 / g) 60g and calcium silicate (Tomita pharmaceutical Co., Ltd., Tomita AD 850H 200M, formula 5CaO · 6SiO 2 · zH 2 O , CaO content; 31.7wt%) 5.70g silica sol (Nissan chemical Industries, Ltd. (OS sol) 12.3 g was added and kneaded with a kneader to make a paste. To this, 9.0 g of inorganic fiber (Ibiden Ibi wool) was added and kneaded with a kneader to prepare a catalyst paste.
Separately, a SUS430 steel strip was metallized to create a reticulated base material having an opening of about 2 mm.
The catalyst paste was placed on the mesh substrate and passed through a pressure roller, whereby the paste was pressure-bonded between the mesh and the surface of the substrate to obtain a plate-shaped molded body having a thickness of 0.7 mm. Next, the plate-like molded body was dried at 150 ° C. for 2 hours and calcined in the atmosphere at 500 ° C. for 2 hours to obtain a plate-like catalyst.
比較例３
ケイ酸カルシウムの量を０ｇに変え、水の量を３０ｇに変えた以外は実施例４と同じ手法で板状触媒を調製した。本触媒におけるＣａＯ／ＳＯ4のモル比は０である。
Comparative Example 3
A plate catalyst was prepared in the same manner as in Example 4 except that the amount of calcium silicate was changed to 0 g and the amount of water was changed to 30 g. The molar ratio of CaO / SO 4 in this catalyst is zero.
比較例４
ケイ酸カルシウムの量を０ｇに変えた以外は実施例４と同じ手法で板状触媒の調製を試みた。ところが、調製したペーストは水分離しやすく、網状基材に塗布するのが困難であった。
Comparative Example 4
An attempt was made to prepare a plate catalyst in the same manner as in Example 4 except that the amount of calcium silicate was changed to 0 g. However, the prepared paste is easy to separate with water, and it is difficult to apply the paste to a reticulated substrate.
実施例４および比較例３で得られた脱硝触媒について、表３で示す条件で脱硝率を測定した。その結果を表４に示す。本発明に係る実施例４の脱硝触媒は、シリカゾル、無機繊維が混合された条件でも細孔容積が大きく、脱硝性能が高いことが分かる。
比較例３の触媒は、細孔容積が０．４００ｃｃ／ｇであり、脱硝率が実施例４よりも低くかった。
With respect to the denitration catalyst obtained in Example 4 and Comparative Example 3, the denitration rate was measured under the conditions shown in Table 3. The results are shown in Table 4. It can be seen that the denitration catalyst of Example 4 according to the present invention has a large pore volume and high denitration performance even under conditions where silica sol and inorganic fibers are mixed.
The catalyst of Comparative Example 3 had a pore volume of 0.400 cc / g, and the denitration rate was lower than that of Example 4.
Claims (5)
次いで該ペーストを成形することを含む脱硝触媒の製造法。 Titanium oxide or its precursor, catalytic active component, calcium silicate and water are kneaded to obtain a catalyst paste,
Next, a method for producing a denitration catalyst comprising forming the paste.
ケイ酸カルシウムの量が、ＣａＯ／ＳＯ4のモル比で０．５超１．０以下となる量である、請求項１〜３のいずれかひとつに記載の脱硝触媒の製造法。 Titanium oxide or its precursor contains sulfate radical (SO 4 ),
The amount of calcium silicate is an amount of 0.5 Ultra 1.0 in terms of a molar ratio of CaO / SO 4, preparation of the denitration catalyst according to any one of claims 1 to 3.
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