JP2013193938A - Denitration catalyst, method of preparing the same, and method of denitration - Google Patents
Denitration catalyst, method of preparing the same, and method of denitration Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 92
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000002131 composite material Substances 0.000 claims abstract description 78
- 238000003795 desorption Methods 0.000 claims abstract description 51
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 42
- 229910006774 Si—W Inorganic materials 0.000 claims abstract description 25
- 238000005259 measurement Methods 0.000 claims abstract description 21
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 239000010937 tungsten Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 229910004339 Ti-Si Inorganic materials 0.000 claims description 20
- 229910010978 Ti—Si Inorganic materials 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 34
- 239000000203 mixture Substances 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- 229910010413 TiO 2 Inorganic materials 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 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 9
- 239000001307 helium Substances 0.000 description 9
- 229910052734 helium Inorganic materials 0.000 description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 9
- 229940126062 Compound A Drugs 0.000 description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000003379 elimination reaction Methods 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003657 tungsten Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
本発明は、脱硝触媒、その調製方法、および脱硝方法に関する。特に、重油焚きボイラや石炭焚きボイラ、ガス焚きボイラ、ガスタービン、ガスエンジン、ディーゼルエンジン、火力発電所、ごみ焼却炉および各種工業プロセスから排出される排ガス中に含まれる窒素酸化物（ＮＯｘ）の除去に優れた脱硝触媒、その調製方法、および脱硝方法に関する。 The present invention relates to a denitration catalyst, a preparation method thereof, and a denitration method. In particular, heavy oil fired boilers, coal fired boilers, gas fired boilers, gas turbines, gas engines, diesel engines, thermal power plants, waste incinerators, and nitrogen oxides (NOx) contained in exhaust gas discharged from various industrial processes. The present invention relates to a denitration catalyst excellent in removal, a preparation method thereof, and a denitration method.
現在実用化されている排ガス中の窒素酸化物除去方法としては、アンモニアまたは尿素などの還元剤を用いて排ガス中の窒素酸化物を触媒上で接触還元して窒素と水に分解する選択的触媒還元法（ＳＣＲ法）が一般的である。近年、酸性雨に代表されるように窒素酸化物による環境汚染が世界的に深刻化するに伴い、高性能な触媒が求められている。 As a method for removing nitrogen oxides in exhaust gas that is currently in practical use, a selective catalyst that catalytically reduces nitrogen oxides in exhaust gas using a reducing agent such as ammonia or urea and decomposes it into nitrogen and water. The reduction method (SCR method) is common. In recent years, as environmental pollution caused by nitrogen oxides has become serious worldwide, as represented by acid rain, a high-performance catalyst has been demanded.
脱硝触媒に関する従来技術としては、例えば、窒素酸化物の除去に有効な触媒として二酸化チタンおよび／またはチタン複合酸化物からなる排ガス処理触媒について開示されているが（特許文献１）、充分な処理性能を有するとはいえなかった。 As a prior art relating to a denitration catalyst, for example, an exhaust gas treatment catalyst comprising titanium dioxide and / or a titanium composite oxide is disclosed as an effective catalyst for removing nitrogen oxides (Patent Document 1), but sufficient treatment performance is disclosed. Could not be said to have.
また、酸化チタンと酸化ケイ素の複合酸化物を触媒成分とする排ガス処理触媒が数多く提案されているが（特許文献２）、更なる活性の向上が望まれている。 Many exhaust gas treatment catalysts using a composite oxide of titanium oxide and silicon oxide as a catalyst component have been proposed (Patent Document 2), but further improvement in activity is desired.
これらの触媒が有効に作用しない原因として、排出されるガスの対象である重油焚きボイラや石炭焚きボイラ、ガス焚きボイラ、ガスタービン、ガスエンジン、ディーゼルエンジン、火力発電所、ごみ焼却炉および各種工業プロセスから排出される排ガスの差異より、触媒毒となるもの存在、水蒸気の存在および処理するガスと触媒との関係である空間速度、窒素酸化物（ＮＯｘ）の濃度などの関係から処理対象となる窒素酸化物（ＮＯｘ）が効率よく処理できないことにある。 The reasons why these catalysts do not work effectively include heavy oil-fired boilers, coal-fired boilers, gas-fired boilers, gas turbines, gas engines, diesel engines, thermal power plants, waste incinerators, and various industries. Due to the difference in exhaust gas discharged from the process, it becomes the object of treatment due to the existence of catalyst poisons, the presence of water vapor, the space velocity between the gas to be treated and the catalyst, the concentration of nitrogen oxides (NOx), etc. Nitrogen oxide (NOx) cannot be treated efficiently.
本発明は上記触媒の活性向上を目的としている。特にガス焚きボイラやガスタービンから生じる排ガスの処理に有効な触媒開発を目的としている。 The present invention aims to improve the activity of the catalyst. In particular, it aims to develop an effective catalyst for the treatment of exhaust gas generated from gas-fired boilers and gas turbines.
上記課題を解決するために本発明者らは鋭意検討の結果、下記技術を見出し発明を完成するに至ったものである。即ち、下記条件を満たすことを特徴とするチタンおよびタングステンの複合酸化物（以下「Ｔｉ−Ｗ複合酸化物」という）またはチタン、ケイ素およびタングステンの複合酸化物（以下「Ｔｉ−Ｓｉ−Ｗ複合酸化物」という）を含む脱硝触媒である。（１）アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ）により２５０〜３５０℃のアンモニア脱離量を測定すること（Ｌ−脱離量）。（２）アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ）により４５０〜５５０℃のアンモニア脱離量を測定すること（Ｈ−脱離量）。（３）Ｈ−脱離量／Ｌ−脱離量が０．７〜１．５であること。 As a result of diligent studies, the present inventors have found the following technique and have completed the invention. That is, a composite oxide of titanium and tungsten (hereinafter referred to as “Ti—W composite oxide”) or a composite oxide of titanium, silicon and tungsten (hereinafter referred to as “Ti—Si—W composite oxidation” characterized by satisfying the following conditions: A denitration catalyst containing a product. (1) Measure ammonia desorption amount at 250 to 350 ° C. by ammonia-temperature programmed desorption measurement (NH 3 -TPD) (L-desorption amount). (2) Measuring ammonia desorption amount at 450 to 550 ° C. by ammonia-temperature programmed desorption measurement (NH 3 -TPD) (H-desorption amount). (3) H-desorption amount / L-desorption amount is 0.7 to 1.5.
更に当該Ｔｉ−Ｗ複合酸化物またはＴｉ−Ｓｉ−Ｗ複合酸化物を含む触媒を用いた窒素酸化物（ＮＯｘ）の処理方法である。 Furthermore, this is a method for treating nitrogen oxide (NOx) using a catalyst containing the Ti—W composite oxide or Ti—Si—W composite oxide.
本発明にかかるＴｉ−Ｗ複合酸化物またはＴｉ−Ｓｉ−Ｗ複合酸化物を用いることで高活性な触媒を得ることができかつ効率よく排ガス中の窒素酸化物（ＮＯｘ）を処理することができ、特にガス焚きボイラやガスタービンから生じる排ガスの処理に有効に作用するものである。 By using the Ti—W composite oxide or Ti—Si—W composite oxide according to the present invention, a highly active catalyst can be obtained and nitrogen oxide (NOx) in exhaust gas can be efficiently treated. In particular, it effectively acts on the treatment of exhaust gas generated from a gas-fired boiler or gas turbine.
本発明は、下記条件を満たすことを特徴とするＴｉ−Ｗ複合酸化物またはＴｉ−Ｓｉ−Ｗ複合酸化物を含む脱硝触媒である。（１）アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ）により２５０〜３５０℃のアンモニア脱離量を測定すること（Ｌ−脱離量）。（２）アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ）により４５０〜５５０℃のアンモニア脱離量を測定すること（Ｈ−脱離量）。（３）Ｈ−脱離量／Ｌ−脱離量が０．７〜１．５であること。 The present invention is a denitration catalyst containing a Ti—W composite oxide or a Ti—Si—W composite oxide that satisfies the following conditions. (1) Measure ammonia desorption amount at 250 to 350 ° C. by ammonia-temperature programmed desorption measurement (NH 3 -TPD) (L-desorption amount). (2) Measuring ammonia desorption amount at 450 to 550 ° C. by ammonia-temperature programmed desorption measurement (NH 3 -TPD) (H-desorption amount). (3) H-desorption amount / L-desorption amount is 0.7 to 1.5.
好ましくは当該触媒がＴｉ−Ｗ複合酸化物、またはＴｉ−Ｓｉ−Ｗ複合酸化物を含むものであること。また当該触媒がチタンおよびケイ素との複合酸化物（以下「Ｔｉ−Ｓｉ複合酸化物」という）を添加することができること。 Preferably, the catalyst contains a Ti—W composite oxide or a Ti—Si—W composite oxide. The catalyst can add a composite oxide of titanium and silicon (hereinafter referred to as “Ti-Si composite oxide”).
当該Ｔｉ−Ｗ複合酸化物またはＴｉ−Ｓｉ−Ｗ複合酸化物は沈殿法により得られたものであることが好ましい。 The Ti-W composite oxide or Ti-Si-W composite oxide is preferably obtained by a precipitation method.
更に当該触媒を用いて窒素酸化物（ＮＯｘ）を処理することができる。 Further, nitrogen oxide (NOx) can be treated using the catalyst.
以下に、本発明を詳細に説明するが本発明の効果を奏するものであれば以下の説明に限定されるものではない。 Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description as long as the effects of the present invention are achieved.
（アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ））
当該測定方法は、予めサンプルにアンモニアを吸着させた後、不活性ガス（ヘリウム）を流入し、当該ガスの温度を一定の速度で上げ、脱離するアンモニアを測定するものである。アンモニアは触媒の酸点に付着しており、弱い酸点に吸着するアンモニアは低温で脱離し、強い酸点に吸着するアンモニアは高温において脱離することから、アンモニアの脱離温度と脱離量を測定することで、一定量のサンプル当たり、各酸点の有無、その量を測定することができるものである。以下に手順を示すと、
（１）１５０℃で２０時間乾燥させたサンプル０．１ｇを使用すること、
（２）測定に先立ち１００℃にてヘリウムガスを５０Ｎｍｌ／ｍｉｎ（ノルマル・ミリリットル／分）で１０分間、サンプルに通過させ表面を浄化すること、
（３）１００℃にてアンモニア標準ガス（アンモニア：１０％／ヘリウム：Ｂａｌａｎｃｅ）を５０Ｎｍｌ／ｍｉｎで６０分間、サンプルに通過させアンモニアを吸着させること、
（４）ヘリウムガスを１００℃にて５０Ｎｍｌ／ｍｉｎで５０分間、サンプルに通過させ余剰のアンモニアを除去すること、
（５）ヘリウムガスを５０Ｎｍｌ／ｍｉｎでサンプルに通過させ、１０℃／分の速度で１００℃から６００℃まで昇温すること、
（６）サンプルを通過した下流のガスを１２０℃に設定したＴＣＤ（検出器）にて連続的に測定すること。である。
測定装置として日本ベル株式会社のＢＥＬＣＡＴを用いた。
(Ammonia - TPD measurement (NH 3 -TPD))
In this measurement method, after ammonia is adsorbed on a sample in advance, an inert gas (helium) is introduced, the temperature of the gas is increased at a constant rate, and the desorbed ammonia is measured. Ammonia adheres to the acid sites of the catalyst, and ammonia adsorbed on weak acid sites desorbs at low temperatures, and ammonia adsorbed on strong acid sites desorbs at high temperatures. By measuring the presence / absence of each acid point and its amount per sample of a certain amount. The procedure is as follows:
(1) Use 0.1 g of sample dried at 150 ° C. for 20 hours,
(2) Purify the surface by passing helium gas through the sample at 50 Nml / min (normal milliliter / min) for 10 minutes at 100 ° C. prior to measurement;
(3) Ammonia standard gas (ammonia: 10% / helium: Balance) is passed through the sample at 50 Nml / min for 60 minutes at 100 ° C. to adsorb ammonia.
(4) Passing helium gas through the sample at 100 ° C. and 50 Nml / min for 50 minutes to remove excess ammonia;
(5) passing helium gas through the sample at 50 Nml / min and raising the temperature from 100 ° C. to 600 ° C. at a rate of 10 ° C./min;
(6) Continuously measure the downstream gas that has passed through the sample with a TCD (detector) set at 120 ° C. It is.
BELCAT manufactured by Nippon Bell Co., Ltd. was used as a measuring device.
Ｈ−脱離量とＬ−脱離量との関係は、Ｈ−脱離量／Ｌ−脱離量が０．７〜１．５であることが好ましい。０．７未満であれば脱硝性能が低くなり好ましくはないからである。 Regarding the relationship between the H-desorption amount and the L-desorption amount, the H-desorption amount / L-desorption amount is preferably 0.7 to 1.5. If it is less than 0.7, the denitration performance is lowered, which is not preferable.
（化合物成分）
上記アンモニア脱離量の値を満たす化合物組成であれば、特に成分に限定されるものではなく、当該成分更に通常触媒分野において用いられる成分を使用することもできる。
(Compound component)
The compound composition is not particularly limited as long as it is a compound composition satisfying the value of the ammonia desorption amount, and it is also possible to use the component and a component usually used in the catalyst field.
当該触媒としては、Ｔｉ−Ｗ複合酸化物、またはＴｉ−Ｓｉ−Ｗ複合酸化物を含むものが好ましい。また当該触媒はＴｉ−Ｓｉ複合酸化物を添加することができる。 As the said catalyst, the thing containing Ti-W complex oxide or Ti-Si-W complex oxide is preferable. In addition, Ti-Si composite oxide can be added to the catalyst.
Ｔｉ−Ｗ複合酸化物の組成は、チタンとタングステンとを質量比（酸化物換算）で９９／１〜７０／３０質量％（ＴｉＯ２／ＷＯ３）、好ましくは９９／１〜８０／２０質量％（ＴｉＯ２／ＷＯ３）、更に好ましくは９９／１〜９０／１０質量％（ＴｉＯ２／ＷＯ３）である。 The composition of the Ti—W composite oxide is 99/1 to 70/30 mass% (TiO 2 / WO 3 ), preferably 99/1 to 80/20 mass, in terms of mass ratio (as oxide) of titanium and tungsten. % (TiO 2 / WO 3 ), more preferably 99/1 to 90/10 mass% (TiO 2 / WO 3 ).
Ｔｉ−Ｓｉ−Ｗ複合酸化物の組成は、チタンとケイ素とタングステンとを質量比（酸化物換算）で９８／１／１〜４０／３０／３０質量％（ＴｉＯ２／ＳｉＯ２／ＷＯ３）、好ましくは９８／１／１〜６０／２０／２０質量％（ＴｉＯ２／ＳｉＯ２／ＷＯ３）、更に好ましくは９８／１／１〜７０／２０／１０質量％（ＴｉＯ２／ＳｉＯ２／ＷＯ３）である。 The composition of the Ti—Si—W composite oxide is 98/1/1 to 40/30/30 mass% (TiO 2 / SiO 2 / WO 3 ) in terms of mass ratio (as oxide) of titanium, silicon and tungsten. , Preferably 98/1/1 to 60/20/20% by mass (TiO 2 / SiO 2 / WO 3 ), more preferably 98/1/1 to 70/20/10% by mass (TiO 2 / SiO 2 / WO 3 ).
Ｔｉ−Ｓｉ複合酸化物の組成は、チタンとケイ素とを質量比（酸化物換算）で９９／１〜６０／４０質量％（ＴｉＯ２／ＳｉＯ２）、好ましくは９９／１〜７０／３０質量％（ＴｉＯ２／ＳｉＯ２）、更に好ましくは９９／１〜８０／２０質量％（ＴｉＯ２／ＳｉＯ２）である。 The composition of the Ti—Si composite oxide is 99/1 to 60/40 mass% (TiO 2 / SiO 2 ), preferably 99/1 to 70/30 mass by mass ratio (as oxide) of titanium and silicon. % (TiO 2 / SiO 2 ), more preferably 99/1 to 80/20 mass% (TiO 2 / SiO 2 ).
本発明にかかる当該Ｔｉ−Ｗ複合酸化物、Ｔｉ−Ｓｉ−Ｗ複合酸化物、Ｔｉ−Ｓｉ複合酸化物とは、ともにＸ線回折測定により酸化チタン、酸化ケイ素、酸化タングステンの鋭いピークが見られず、アモロファスといわれる程度の状態のものが測定されるものである。 In the Ti-W composite oxide, Ti-Si-W composite oxide, and Ti-Si composite oxide according to the present invention, sharp peaks of titanium oxide, silicon oxide, and tungsten oxide are observed by X-ray diffraction measurement. What is called an amorofus is measured.
（調製方法）
Ｔｉ−Ｗ複合酸化物の調製方法としては、（１）アンモニア水とタングステン源の混合水溶液に硫酸チタニルの硫酸水溶液を中和混合し、ｐＨ３〜１０好ましくはｐＨ４〜８でｐＨ調整して沈殿を生成させ、沈殿スラリーを濾過、水洗後、乾燥し、焼成する沈殿法、（２）一方の酸化物に他方の水溶液を含浸し乾燥し、焼成する含浸法、（３）各々の前駆体である水不溶物質を水と混合しスラリーとし混練し、乾燥し、焼成する混練法、（４）各々の酸化物前駆体を十分混合し焼成する固相反応法があるが、好ましくは沈殿法である。
(Preparation method)
The preparation method of the Ti-W composite oxide is as follows: (1) A mixed aqueous solution of ammonia water and a tungsten source is neutralized and mixed with a sulfuric acid aqueous solution of titanyl sulfate, pH is adjusted to 3 to 10, preferably 4 to 8, and precipitation is carried out. (2) impregnation method in which one oxide is impregnated with the other aqueous solution and dried and calcined, and (3) each precursor. There is a kneading method in which a water-insoluble substance is mixed with water, kneaded into a slurry, dried and fired, and (4) a solid-phase reaction method in which each oxide precursor is sufficiently mixed and fired, preferably a precipitation method. .
Ｔｉ−Ｓｉ−Ｗ複合酸化物の調製方法としては、（１）アンモニア水とケイ素源とタングステン源の混合水溶液に硫酸チタニルの硫酸水溶液を中和混合しｐＨ３〜１０好ましくはｐＨ４〜８でｐＨ調整して沈殿を生成させ、沈殿スラリーを濾過、水洗後、乾燥し、焼成する沈殿法、（２）一方の酸化物に他方の水溶液を含浸し乾燥し、焼成する含浸法、（３）各々の前駆体である水不溶物質を水と混合しスラリーとし混練し、乾燥し、焼成する混練法、（４）各々の酸化物前駆体を十分混合し焼成する固相反応法があるが、好ましくは沈殿法である。 The preparation method of Ti-Si-W composite oxide is as follows: (1) pH adjustment of pH 3-10, preferably pH 4-8, by neutralizing and mixing sulfuric acid aqueous solution of titanyl sulfate with mixed aqueous solution of ammonia water, silicon source and tungsten source. (2) impregnation method in which one oxide is impregnated with the other aqueous solution, dried and calcined, (3) There is a kneading method in which a water-insoluble substance as a precursor is mixed with water, kneaded into a slurry, dried and fired, and (4) a solid-phase reaction method in which each oxide precursor is sufficiently mixed and fired, preferably It is a precipitation method.
Ｔｉ−Ｓｉ複合酸化物の調製方法としては、（１）アンモニア水とケイ素源の混合水溶液に硫酸チタニルの硫酸水溶液を中和混合し、ｐＨ３〜１０好ましくはｐＨ４〜８でｐＨ調整して沈殿を生成させ、沈殿スラリーを濾過、水洗後、乾燥し、焼成する沈殿法、（２）一方の酸化物に他方の水溶液を含浸し乾燥し、焼成する含浸法、（３）各々の前駆体である水不溶物質を水と混合しスラリーとし混練し、乾燥し、焼成する混練法、（４）各々の酸化物前駆体を十分混合し焼成する固相反応法があるが、好ましくは沈殿法である。
The preparation method of the Ti-Si composite oxide is as follows: (1) A mixed aqueous solution of ammonia water and a silicon source is neutralized and mixed with a sulfuric acid aqueous solution of titanyl sulfate, pH is adjusted to 3 to 10, preferably
（触媒成分）
Ｔｉ−Ｗ複合酸化物、Ｔｉ−Ｓｉ−Ｗ複合酸化物、Ｔｉ−Ｓｉ複合酸化物を適宜含む触媒であるときは、Ｔｉ−Ｗ複合酸化物、Ｔｉ−Ｓｉ−Ｗ複合酸化物、Ｔｉ−Ｓｉ複合酸化物は別々に作り、触媒化時に調製した粉体を混合すること、Ｔｉ、Ｓｉ、Ｗの各々原料を混合水溶液とし加えることもできる。
(Catalyst component)
When the catalyst contains Ti-W composite oxide, Ti-Si-W composite oxide, Ti-Si composite oxide as appropriate, Ti-W composite oxide, Ti-Si-W composite oxide, Ti-Si The composite oxide can be prepared separately, and the powder prepared at the time of catalysis can be mixed, and each raw material of Ti, Si, and W can be added as a mixed aqueous solution.
Ｔｉ−Ｗ複合酸化物およびＴｉ−Ｓｉ複合酸化物の混合比は、Ｔｉ−Ｗ複合酸化物とＴｉ−Ｓｉ複合酸化物とを質量比（酸化物換算）で１００／０〜３０／７０質量％、好ましくは９９／１〜４０／６０質量％、更に好ましくは９５／５〜５０／５０質量％である。 The mixing ratio of the Ti—W composite oxide and the Ti—Si composite oxide is 100/0 to 30/70 mass% of the Ti—W composite oxide and the Ti—Si composite oxide in terms of mass ratio (oxide conversion). The ratio is preferably 99/1 to 40/60% by mass, and more preferably 95/5 to 50/50% by mass.
Ｔｉ−Ｓｉ−Ｗ複合酸化物およびＴｉ−Ｓｉ複合酸化物の混合比は、Ｔｉ−Ｓｉ−Ｗ複合酸化物とＴｉ−Ｓｉ複合酸化物とを質量比（酸化物換算）で１００／０〜３０／７０質量％、好ましくは１００／０〜４０／６０質量％、更に好ましくは１００／０〜５０／５０質量％である。 The mixing ratio of the Ti—Si—W composite oxide and the Ti—Si composite oxide is 100/0 to 30 in terms of mass ratio (as oxide) of the Ti—Si—W composite oxide and the Ti—Si composite oxide. / 70 mass%, preferably 100/0 to 40/60 mass%, more preferably 100/0 to 50/50 mass%.
上記成分の他に当該触媒の活性成分として、バナジウム、タングステン、モリブデン、鉄、マンガンおよびニッケルからなる群より選ばれる１種以上の元素またはその化合物を加えることができる。特にバナジウム、タングステンおよびモリブデンからなる群より選ばれる１種以上の元素またはその化合物を活性成分として含むものが好ましい。当該活性成分の含有量は、０．１〜２０質量％、好ましくは０．２〜１５質量％、更に好ましくは０．４〜１０質量％である。 In addition to the above components, one or more elements selected from the group consisting of vanadium, tungsten, molybdenum, iron, manganese, and nickel, or compounds thereof can be added as the active component of the catalyst. In particular, those containing one or more elements selected from the group consisting of vanadium, tungsten and molybdenum or compounds thereof as active ingredients are preferred. Content of the said active ingredient is 0.1-20 mass%, Preferably it is 0.2-15 mass%, More preferably, it is 0.4-10 mass%.
上記触媒成分は、水、成形助剤等を加え粘土状とし、使用する用途に適応した形状、例えばハニカム状、ペレット状、粉体状に成形されることがある。ハニカム状であれば、一辺５０〜２００ｍｍの角、目開きが一辺１〜１０ｍｍの角、リブ厚が０．１〜１．５ｍｍ、長さが２００〜２０００ｍｍのものが好ましい。 The catalyst component may be formed into a clay shape by adding water, a molding aid, and the like, and may be formed into a shape suitable for the intended use, for example, a honeycomb shape, a pellet shape, or a powder shape. In the case of a honeycomb, it is preferable that the corner has a side of 50 to 200 mm, the opening has a side of 1 to 10 mm, the rib thickness is 0.1 to 1.5 mm, and the length is 200 to 2000 mm.
（脱硝方法）
窒素酸化物（ＮＯｘ）を含むガスであれば何れのガスであってもよいが、好ましくはガス焚きボイラやガスタービンから生じる排ガスである。窒素酸化物（ＮＯｘ）の濃度は１０〜２０００ｐｐｍ（ＮＯｘ換算）、好ましくは２０〜５００ｐｐｍ（ＮＯｘ換算）、更に好ましくは４０〜１００ｐｐｍ（ＮＯｘ換算）である。これらのガスには水、ＳＯｘ、ダストなどが含まれていても処理することができる。
(Denitration method)
Any gas may be used as long as it contains nitrogen oxides (NOx), but it is preferably exhaust gas generated from a gas-fired boiler or a gas turbine. The concentration of nitrogen oxide (NOx) is 10 to 2000 ppm (NOx conversion), preferably 20 to 500 ppm (NOx conversion), more preferably 40 to 100 ppm (NOx conversion). These gases can be treated even if they contain water, SOx, dust or the like.
脱硝に際して、排ガス中にアンモニアまたは尿素を添加することができる。添加量は、窒素酸化物（ＮＯｘ換算）１モルに対して、アンモニア換算（尿素の場合は１／２モル）で０．２〜２．０モル、好ましくは０．５〜１．０モルである。 At the time of denitration, ammonia or urea can be added to the exhaust gas. The amount of addition is 0.2 to 2.0 mol, preferably 0.5 to 1.0 mol in terms of ammonia (1/2 mol in the case of urea) with respect to 1 mol of nitrogen oxide (NOx conversion). is there.
処理温度は、１５０〜５００℃、好ましくは２００〜４５０℃、更に好ましくは２５０〜４００℃である。 Processing temperature is 150-500 degreeC, Preferably it is 200-450 degreeC, More preferably, it is 250-400 degreeC.
空間速度は１０００〜１０００００ｈｒ−１（ＳＴＰ）、好ましくは２０００〜５００００ｈｒ−１（ＳＴＰ）、更に好ましくは３０００〜３００００ｈｒ−１（ＳＴＰ）である。 The space velocity is 1000 to 100000 hr −1 (STP), preferably 2000 to 50000 hr −1 (STP), more preferably 3000 to 30000 hr −1 (STP).
以下に実施例、比較例により、発明を詳細に説明するが、本発明の効果を奏するものであれば以下の実施例に限定されるものではない。 The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the effects of the present invention are exhibited.
（実施例１）
＜化合物Ａ（Ｔｉ−Ｗ複合酸化物）の調製＞
パラタングステン酸アンモニウム（ＷＯ３として９０重量％含有）２．３ｋｇ、モノエタノールアミン１ｋｇを水１０Ｌに混合・溶解させ、均一溶液を調製した。このタングステン含有溶液と１０質量％アンモニア水１００Ｌを混合した溶液に、硫酸チタニルの硫酸溶液（ＴｉＯ２として７０ｇ／Ｌ含有、硫酸濃度２９０ｇ／Ｌ）２６０Ｌをよく撹拌しながら徐々に滴下し、沈殿を生成させた後、適量の２５質量％アンモニア水を加えてｐＨを４に調整した。このスラリーをそのまま４０時間放置して熟成した後、濾過、洗浄し、１５０℃で２０時間乾燥した。これを空気雰囲気下５００℃で５時間焼成し、さらにハンマーミルを用いて粉砕し、化合物Ａ（Ｔｉ−Ｗ複合酸化物）を得た。
Example 1
<Preparation of Compound A (Ti-W Composite Oxide)>
A uniform solution was prepared by mixing and dissolving 2.3 kg of ammonium paratungstate (containing 90 wt% as WO 3 ) and 1 kg of monoethanolamine in 10 L of water. To a mixed solution of this tungsten-containing solution and 100 L of 10% by mass ammonia water, 260 L of a sulfuric acid solution of titanyl sulfate (containing 70 g / L as TiO 2 and a sulfuric acid concentration of 290 g / L) was gradually added dropwise with good stirring to precipitate. After the formation, an appropriate amount of 25% by mass aqueous ammonia was added to adjust the pH to 4. The slurry was left to mature for 40 hours, then filtered, washed and dried at 150 ° C. for 20 hours. This was calcined at 500 ° C. for 5 hours in an air atmosphere, and further pulverized using a hammer mill to obtain Compound A (Ti—W composite oxide).
化合物Ａの組成はＴｉＯ２／ＷＯ３の質量比（酸化物換算）で９０／１０質量％であった。さらに化合物ＡはＸ線回折測定により酸化チタン、酸化タングステンの鋭いピークが見られず、アモロファスといわれる状態のものが測定された。 The composition of Compound A was 90/10% by mass in terms of the mass ratio of TiO 2 / WO 3 (as oxide). Further, Compound A showed no sharp peaks of titanium oxide and tungsten oxide by X-ray diffraction measurement, and was in a state called amorofas.
（実施例２）
＜化合物Ｂ（Ｔｉ−Ｗ複合酸化物）の調製＞
パラタングステン酸アンモニウム（ＷＯ３として９０重量％含有）２．３ｋｇ、モノエタノールアミン１ｋｇを水１０Ｌに混合・溶解させ、均一溶液を調製した。このタングステン含有溶液と１０質量％アンモニア水２４０Ｌを混合した溶液に、硫酸チタニルの硫酸溶液（ＴｉＯ２として７０ｇ／Ｌ含有、硫酸濃度２９０ｇ／Ｌ）２６０Ｌをよく撹拌しながら徐々に滴下し、沈殿を生成させた後、適量の２５質量％アンモニア水を加えてｐＨを５に調整した。このスラリーをそのまま４０時間放置して熟成した後、濾過、洗浄し、１５０℃で２０時間乾燥した。これを空気雰囲気下５００℃で５時間焼成し、さらにハンマーミルを用いて粉砕し、化合物Ｂ（Ｔｉ−Ｗ複合酸化物）を得た。
(Example 2)
<Preparation of compound B (Ti-W composite oxide)>
A uniform solution was prepared by mixing and dissolving 2.3 kg of ammonium paratungstate (containing 90 wt% as WO 3 ) and 1 kg of monoethanolamine in 10 L of water. To a mixed solution of this tungsten-containing solution and 240 L of 10% by mass ammonia water, 260 L of a sulfuric acid solution of titanyl sulfate (containing 70 g / L as TiO 2 and a sulfuric acid concentration of 290 g / L) was gradually added dropwise with good stirring to precipitate. After the formation, an appropriate amount of 25% by mass aqueous ammonia was added to adjust the pH to 5. The slurry was left to mature for 40 hours, then filtered, washed and dried at 150 ° C. for 20 hours. This was calcined at 500 ° C. for 5 hours in an air atmosphere, and further pulverized using a hammer mill to obtain Compound B (Ti—W composite oxide).
化合物Ｂの組成はＴｉＯ２／ＷＯ３の質量比（酸化物換算）で９０／１０質量％であった。さらに化合物ＢはＸ線回折測定により酸化チタン、酸化タングステンの鋭いピークが見られず、アモロファスといわれる状態のものが測定された。 The composition of Compound B was 90/10% by mass in terms of the mass ratio of TiO 2 / WO 3 (as oxide). Further, Compound B showed no sharp peaks of titanium oxide and tungsten oxide by X-ray diffraction measurement, and was in a state called amorofas.
（実施例３）
＜化合物Ｃ（Ｔｉ−Ｓｉ−Ｗ複合酸化物）の調製＞
パラタングステン酸アンモニウム（ＷＯ３として９０重量％含有）１．４ｋｇ、モノエタノールアミン０．６ｋｇを水１０Ｌに混合・溶解させ、均一溶液を調製した。このタングステン含有溶液とシリカゾル（ＳｉＯ２として３０重量％含有）３．４ｋｇ、１０質量％アンモニア水２４０Ｌを混合した溶液に、硫酸チタニルの硫酸溶液（ＴｉＯ２として７０ｇ／Ｌ含有、硫酸濃度２９０ｇ／Ｌ）２６０Ｌをよく撹拌しながら徐々に滴下し、沈殿を生成させた後、適量の２５質量％アンモニア水を加えてｐＨを７に調整した。このスラリーをそのまま４０時間放置して熟成した後、濾過、洗浄し、１５０℃で２０時間乾燥した。これを空気雰囲気下５００℃で５時間焼成し、さらにハンマーミルを用いて粉砕し、化合物Ｃ（Ｔｉ−Ｓｉ−Ｗ複合酸化物）を得た。
(Example 3)
<Preparation of Compound C (Ti-Si-W Composite Oxide)>
1.4 kg of ammonium paratungstate (containing 90 wt% as WO 3 ) and 0.6 kg of monoethanolamine were mixed and dissolved in 10 L of water to prepare a uniform solution. A solution obtained by mixing this tungsten-containing solution with silica sol (containing 30 wt% as SiO 2 ) 3.4 kg, 10 mass% ammonia water 240 L, sulfuric acid solution of titanyl sulfate (containing 70 g / L as TiO 2 , sulfuric acid concentration 290 g / L) 260 L was gradually added dropwise with good stirring to form a precipitate, and then an appropriate amount of 25% by mass aqueous ammonia was added to adjust the pH to 7. The slurry was left to mature for 40 hours, then filtered, washed and dried at 150 ° C. for 20 hours. This was calcined at 500 ° C. for 5 hours in an air atmosphere, and further pulverized using a hammer mill to obtain Compound C (Ti—Si—W composite oxide).
化合物Ｃの組成はＴｉＯ２／ＳｉＯ２／ＷＯ３の質量比（酸化物換算）で８９／５／６質量％であった。さらに化合物ＣはＸ線回折測定により酸化チタン、酸化ケイ素、酸化タングステンの鋭いピークが見られず、アモロファスといわれる状態のものが測定された。 The composition of Compound C was 89/5/6 mass% in terms of mass ratio of TiO 2 / SiO 2 / WO 3 (as oxide). Further, Compound C showed no sharp peaks of titanium oxide, silicon oxide, and tungsten oxide by X-ray diffraction measurement, and a compound called amorofus was measured.
（比較例１）
市販のチタンおよびタングステンの混合酸化物（以下「Ｔｉ−Ｗ混合酸化物」という）であるＣｒｉｓｔａｌ Ｇｌｏｂａｌ社製のＤＴ−５２（商品名）を混合物ａとした。
(Comparative Example 1)
DT-52 (trade name) manufactured by Cristal Global, which is a commercially available mixed oxide of titanium and tungsten (hereinafter referred to as “Ti—W mixed oxide”) was used as the mixture a.
混合物ａの組成はＴｉＯ２／ＷＯ３の質量比（酸化物換算）で９０／１０質量％であった。 The composition of the mixture a was 90/10% by mass in terms of TiO 2 / WO 3 (as oxide).
（アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ））
実施例１〜３で得られた化合物Ａ〜Ｃおよび比較例１で得られた混合物ａを用いて、下記測定条件でアンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ）を行った。
(Ammonia - TPD measurement (NH 3 -TPD))
Using the compounds A to C obtained in Examples 1 to 3 and the mixture a obtained in Comparative Example 1, ammonia-temperature programmed desorption measurement (NH 3 -TPD) was performed under the following measurement conditions.
なお、アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ）には日本ベル株式会社のＢＥＬＣＡＴを用いた。 BELCAT manufactured by Nippon Bell Co., Ltd. was used for ammonia-temperature programmed desorption measurement (NH 3 -TPD).
＜測定条件＞
（１）１５０℃で２０時間乾燥させたサンプル０．１ｇを使用する。
（２）測定に先立ち１００℃にてヘリウムガスを５０Ｎｍｌ／ｍｉｎで１０分間、サンプルに通過させ表面を浄化する。
（３）１００℃にてアンモニア標準ガス（アンモニア：１０％／ヘリウム：Ｂａｌａｎｃｅ）を５０Ｎｍｌ／ｍｉｎで６０分間、サンプルに通過させアンモニアを吸着させる。
（４）ヘリウムガスを１００℃にて５０Ｎｍｌ／ｍｉｎで５０分間、サンプルに通過させ余剰のアンモニアを除去する。
（５）ヘリウムガスを５０Ｎｍｌ／ｍｉｎでサンプルに通過させ、１０℃／分の速度で１００℃から６００℃まで昇温する。
（６）サンプルを通過した下流のガスを１２０℃に設定したＴＣＤ（検出器）にて連続的に測定する。
<Measurement conditions>
(1) Use 0.1 g of sample dried at 150 ° C. for 20 hours.
(2) Prior to measurement, the surface is purified by passing helium gas through the sample at 50 Nml / min for 10 minutes at 100 ° C.
(3) At 100 ° C., ammonia standard gas (ammonia: 10% / helium: Balance) is passed through the sample at 50 Nml / min for 60 minutes to adsorb ammonia.
(4) Helium gas is passed through the sample at 100 N ° C. and 50 Nml / min for 50 minutes to remove excess ammonia.
(5) Helium gas is passed through the sample at 50 Nml / min, and the temperature is raised from 100 ° C. to 600 ° C. at a rate of 10 ° C./min.
(6) The downstream gas that has passed through the sample is continuously measured with a TCD (detector) set at 120 ° C.
上記条件において、化合物Ａ〜Ｃ（実施例１〜３）および混合物ａ（比較例１）のアンモニア脱離量を測定し、このときのピーク面積から２５０〜３５０℃のアンモニア脱離量（Ｌ−脱離量）、４５０〜５５０℃のアンモニア脱離量（Ｈ−脱離量）を求めた。 Under the above conditions, the amount of ammonia desorbed from the compounds A to C (Examples 1 to 3) and the mixture a (Comparative Example 1) was measured, and the ammonia desorbed amount (L− Desorption amount), and ammonia desorption amount (H-desorption amount) at 450 to 550 ° C. were determined.
Ｌ−脱離量、Ｈ−脱離量およびＨ−脱離量／Ｌ−脱離量の値を表１に示した。表１から分かるように化合物Ａ〜Ｃ（実施例１〜３）は混合物ａ（比較例１）に較べて、Ｈ−脱離量／Ｌ−脱離量の値が高いことが分かる。 The values of L-elimination amount, H-elimination amount, and H-elimination amount / L-elimination amount are shown in Table 1. As can be seen from Table 1, the compounds A to C (Examples 1 to 3) have higher H-elimination / L-desorption amounts than the mixture a (Comparative Example 1).
アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ）の結果を化合物Ａ（実施例１）は図１、化合物Ｂ（実施例２）は図２、化合物Ｃ（実施例３）は図３、混合物ａ（比較例１）は図４に示した。図１〜４から分かるように化合物Ａ〜Ｃ（実施例１〜３）は混合物ａ（比較例１）に較べて、４５０〜５５０℃におけるアンモニア脱離量（ピーク面積）が多いことが分かる。 The results of ammonia-temperature programmed desorption measurement (NH 3 -TPD) are shown in FIG. 1 for Compound A (Example 1), FIG. 2 for Compound B (Example 2), and FIG. 3 for Compound C (Example 3). a (Comparative Example 1) is shown in FIG. As can be seen from FIGS. 1 to 4, the compounds A to C (Examples 1 to 3) have a larger amount of ammonia desorption (peak area) at 450 to 550 ° C. than the mixture a (Comparative Example 1).
＜化合物Ｄ（Ｔｉ−Ｓｉ複合酸化物）の調製＞
シリカゾル（ＳｉＯ２として３０重量％含有）８ｋｇと１０質量％アンモニア水２４０Ｌを混合した溶液に、硫酸チタニルの硫酸溶液（ＴｉＯ２として７０ｇ／Ｌ含有、硫酸濃度２９０ｇ／Ｌ）２６０Ｌをよく撹拌しながら徐々に滴下し、沈殿を生成させた後、適量の２５質量％アンモニア水を加えてｐＨを８に調整した。このスラリーをそのまま４０時間放置して熟成した後、濾過、洗浄し、１５０℃で２０時間乾燥した。これを空気雰囲気下５５０℃で５時間焼成し、さらにハンマーミルを用いて粉砕し、化合物Ｄ（Ｔｉ−Ｓｉ複合酸化物）を得た。
<Preparation of compound D (Ti-Si composite oxide)>
To a solution obtained by mixing 8 kg of silica sol (containing 30 wt% as SiO 2 ) and 240 L of 10 mass% ammonia water, 260 L of sulfuric acid solution of titanyl sulfate (containing 70 g / L as TiO 2 , sulfuric acid concentration 290 g / L) is thoroughly stirred. After gradually dropping to form a precipitate, an appropriate amount of 25% by mass aqueous ammonia was added to adjust the pH to 8. The slurry was left to mature for 40 hours, then filtered, washed and dried at 150 ° C. for 20 hours. This was calcined at 550 ° C. for 5 hours in an air atmosphere, and further pulverized using a hammer mill to obtain Compound D (Ti—Si composite oxide).
化合物Ｄの組成はＴｉＯ２／ＳｉＯ２の質量比（酸化物換算）で８８／１２質量％であった。
＜触媒Ａの調製＞
上記の方法で調製したＴｉ−Ｓｉ複合酸化物粉体（化合物Ｄ）８．３ｋｇと、実施例２で得られたＴｉ−Ｗ複合酸化物粉体（化合物Ｂ）１１．７ｋｇとを混合した。次にメタバナジン酸アンモニウム（Ｖ２Ｏ５として７８重量％含有）１．５ｋｇ、シュウ酸２．１ｋｇ、モノエタノールアミン０．５ｋｇを水３Ｌに混合・溶解させた均一溶液とパラタングステン酸アンモニウム（ＷＯ３として９０重量％含有）０．９ｋｇ、モノエタノールアミン０．４ｋｇを水２Ｌに混合・溶解させた均一溶液を成型助剤と適量の水とともに、先に混合したＴｉ−Ｓｉ複合酸化物粉体（化合物Ｄ）とＴｉ−Ｗ複合酸化物粉体（化合物Ｂ）の混合粉体に加え、ニーダーで混練した後、押出成型機で外形８０ｍｍ角、長さ５００ｍｍ、目開き２．９ｍｍ、肉厚０．４ｍｍのハニカム状に成型した。これを８０℃で乾燥した後、空気雰囲気下４５０℃で５時間焼成し、触媒Ａを得た。
The composition of Compound D was 88/12% by mass in terms of a TiO 2 / SiO 2 mass ratio (as oxide).
<Preparation of catalyst A>
8.3 kg of the Ti—Si composite oxide powder (Compound D) prepared by the above method and 11.7 kg of the Ti—W composite oxide powder (Compound B) obtained in Example 2 were mixed. Next, 1.5 kg of ammonium metavanadate (containing 78 wt% as V 2 O 5 ), 2.1 kg of oxalic acid, and 0.5 kg of monoethanolamine were mixed and dissolved in 3 L of water and ammonium paratungstate (WO 3 as 90 wt% content) 0.9 kg, monoethanolamine 0.4kg homogeneous solution obtained by mixing and dissolving an appropriate amount of water and molding additive in water 2L, Ti-Si composite oxide powder was mixed into the earlier In addition to the mixed powder of (Compound D) and Ti—W complex oxide powder (Compound B), after kneading with a kneader, the outer shape is 80 mm square, the length is 500 mm, the opening is 2.9 mm, and the wall thickness is Molded into a 0.4 mm honeycomb. This was dried at 80 ° C. and then calcined at 450 ° C. for 5 hours in an air atmosphere to obtain Catalyst A.
触媒Ａの組成は化合物Ｄ／化合物Ｂ／Ｖ２Ｏ５／ＷＯ３の質量比（酸化物換算）で３８／５３／５／４質量％であった。 The composition of the catalyst A was 38/53/5/4 mass% in terms of mass ratio of compound D / compound B / V 2 O 5 / WO 3 (as oxide).
（実施例５）
＜触媒Ｂの調製＞
実施例４で得られたＴｉ−Ｓｉ複合酸化物粉体（化合物Ｄ）８．３ｋｇと、実施例３で得られたＴｉ−Ｓｉ−Ｗ複合酸化物粉体（化合物Ｃ）１１．７ｋｇとを混合した。次にメタバナジン酸アンモニウム（Ｖ２Ｏ５として７８重量％含有）１．５ｋｇ、シュウ酸２．１ｋｇ、モノエタノールアミン０．５ｋｇを水３Ｌに混合・溶解させた均一溶液とパラタングステン酸アンモニウム（ＷＯ３として９０重量％含有）０．９ｋｇ、モノエタノールアミン０．４ｋｇを水２Ｌに混合・溶解させた均一溶液を成型助剤と適量の水とともに、先に混合したＴｉ−Ｓｉ複合酸化物粉体（化合物Ｄ）とＴｉ−Ｓｉ−Ｗ複合酸化物粉体（化合物Ｃ）の混合粉体に加え、ニーダーで混練した後、押出成型機で外形８０ｍｍ角、長さ５００ｍｍ、目開き２．９ｍｍ、肉厚０．４ｍｍのハニカム状に成型した。これを８０℃で乾燥した後、空気雰囲気下４５０℃で５時間焼成し、触媒Ｂを得た。
(Example 5)
<Preparation of catalyst B>
8.3 kg of the Ti—Si composite oxide powder (Compound D) obtained in Example 4 and 11.7 kg of the Ti—Si—W composite oxide powder (Compound C) obtained in Example 3 Mixed. Next, 1.5 kg of ammonium metavanadate (containing 78 wt% as V 2 O 5 ), 2.1 kg of oxalic acid, and 0.5 kg of monoethanolamine were mixed and dissolved in 3 L of water and ammonium paratungstate (WO 3 as 90 wt% content) 0.9 kg, monoethanolamine 0.4kg homogeneous solution obtained by mixing and dissolving an appropriate amount of water and molding additive in water 2L, Ti-Si composite oxide powder was mixed into the earlier In addition to the mixed powder of (Compound D) and Ti—Si—W complex oxide powder (Compound C), after kneading with a kneader, the outer shape is 80 mm square, the length is 500 mm, the opening is 2.9 mm, Molded into a honeycomb with a thickness of 0.4 mm. This was dried at 80 ° C. and then calcined at 450 ° C. for 5 hours in an air atmosphere to obtain Catalyst B.
触媒Ｂの組成は化合物Ｄ／化合物Ｃ／Ｖ２Ｏ５／ＷＯ３の質量比（酸化物換算）で３８／５３／５／４質量％であった。 The composition of the catalyst B was 38/53/5/4 mass% in terms of a mass ratio of compound D / compound C / V 2 O 5 / WO 3 (as oxide).
（実施例６）
＜触媒Ｃの調製＞
実施例２で得られたＴｉ−Ｗ複合酸化物粉体（化合物Ｂ）２０ｋｇにメタバナジン酸アンモニウム（Ｖ２Ｏ５として７８重量％含有）１．５ｋｇ、シュウ酸２．１ｋｇ、モノエタノールアミン０．５ｋｇを水３Ｌに混合・溶解させた均一溶液とパラタングステン酸アンモニウム（ＷＯ３として９０重量％含有）０．９ｋｇ、モノエタノールアミン０．４ｋｇを水２Ｌに混合・溶解させた均一溶液を成型助剤と適量の水とともに加え、ニーダーで混練した後、押出成型機で外形８０ｍｍ角、長さ５００ｍｍ、目開き２．９ｍｍ、肉厚０．４ｍｍのハニカム状に成型した。これを８０℃で乾燥した後、空気雰囲気下４５０℃で５時間焼成し、触媒Ｃを得た。
(Example 6)
<Preparation of catalyst C>
20 kg of the Ti—W composite oxide powder (compound B) obtained in Example 2 was added to 1.5 kg of ammonium metavanadate (containing 78 wt% as V 2 O 5 ), 2.1 kg of oxalic acid, 0.1% of monoethanolamine. A uniform solution in which 5 kg is mixed and dissolved in 3 L of water, 0.9 kg of ammonium paratungstate (containing 90 wt% as WO 3 ), and a uniform solution in which 0.4 kg of monoethanolamine is mixed and dissolved in 2 L of water It was added together with an agent and an appropriate amount of water, kneaded with a kneader, and then formed into a honeycomb shape having an external shape of 80 mm square, a length of 500 mm, an opening of 2.9 mm, and a wall thickness of 0.4 mm by an extruder. This was dried at 80 ° C. and then calcined at 450 ° C. for 5 hours in an air atmosphere to obtain Catalyst C.
触媒Ｃの組成は化合物Ｂ／Ｖ２Ｏ５／ＷＯ３の質量比（酸化物換算）で９１／５／４質量％であった。 The composition of the catalyst C was 91/ 5 /4% by mass in terms of the mass ratio of compound B / V 2 O 5 / WO 3 (as oxide).
（実施例７）
＜触媒Ｄの調製＞
実施例３で得られたＴｉ−Ｓｉ−Ｗ複合酸化物粉体（化合物Ｃ）２０ｋｇにメタバナジン酸アンモニウム（Ｖ２Ｏ５として７８重量％含有）１．５ｋｇ、シュウ酸２．１ｋｇ、モノエタノールアミン０．５ｋｇを水３Ｌに混合・溶解させた均一溶液とパラタングステン酸アンモニウム（ＷＯ３として９０重量％含有）０．９ｋｇ、モノエタノールアミン０．４ｋｇを水２Ｌに混合・溶解させた均一溶液を成型助剤と適量の水とともに加え、ニーダーで混練した後、押出成型機で外形８０ｍｍ角、長さ５００ｍｍ、目開き２．９ｍｍ、肉厚０．４ｍｍのハニカム状に成型した。これを８０℃で乾燥した後、空気雰囲気下４５０℃で５時間焼成し、触媒Ｄを得た。
(Example 7)
<Preparation of catalyst D>
20 kg of the Ti—Si—W complex oxide powder (Compound C) obtained in Example 3 1.5 kg of ammonium metavanadate (containing 78 wt% as V 2 O 5 ), 2.1 kg of oxalic acid, monoethanolamine A homogeneous solution in which 0.5 kg is mixed and dissolved in 3 L of water, 0.9 kg of ammonium paratungstate (containing 90 wt% as WO 3 ), and a homogeneous solution in which 0.4 kg of monoethanolamine is mixed and dissolved in 2 L of water The mixture was added together with a molding aid and an appropriate amount of water, kneaded with a kneader, and then molded into a honeycomb shape having an outer shape of 80 mm square, a length of 500 mm, an aperture of 2.9 mm, and a wall thickness of 0.4 mm by an extruder. This was dried at 80 ° C. and then calcined at 450 ° C. for 5 hours in an air atmosphere to obtain Catalyst D.
触媒Ｄの組成は化合物Ｃ／Ｖ２Ｏ５／ＷＯ３の質量比（酸化物換算）で９１／５／４質量％であった。 The composition of the catalyst D was 91/5/4 mass% in terms of the mass ratio of compound C / V 2 O 5 / WO 3 (as oxide).
（比較例２）
＜触媒ａの調製＞
実施例４で得られたＴｉ−Ｓｉ複合酸化物粉体（化合物Ｄ）８．３ｋｇと、比較例１で得られたＴｉ−Ｗ混合酸化物粉体（混合物ａ）１１．７ｋｇとを混合した。次にメタバナジン酸アンモニウム（Ｖ２Ｏ５として７８重量％含有）１．５ｋｇ、シュウ酸２．１ｋｇ、モノエタノールアミン０．５ｋｇを水３Ｌに混合・溶解させた均一溶液とパラタングステン酸アンモニウム（ＷＯ３として９０重量％含有）０．９ｋｇ、モノエタノールアミン０．４ｋｇを水２Ｌに混合・溶解させた均一溶液を成型助剤と適量の水とともに、先に混合したＴｉ−Ｓｉ複合酸化物粉体（化合物Ｄ）とＴｉ−Ｗ混合酸化物粉体（混合物ａ）の混合粉体に加え、ニーダーで混練した後、押出成型機で外形８０ｍｍ角、長さ５００ｍｍ、目開き２．９ｍｍ、肉厚０．４ｍｍのハニカム状に成型した。これを８０℃で乾燥した後、空気雰囲気下４５０℃で５時間焼成し、触媒ａを得た。
(Comparative Example 2)
<Preparation of catalyst a>
8.3 kg of the Ti—Si composite oxide powder (compound D) obtained in Example 4 and 11.7 kg of the Ti—W mixed oxide powder (mixture a) obtained in Comparative Example 1 were mixed. . Next, 1.5 kg of ammonium metavanadate (containing 78 wt% as V 2 O 5 ), 2.1 kg of oxalic acid, and 0.5 kg of monoethanolamine were mixed and dissolved in 3 L of water and ammonium paratungstate (WO 3 as 90 wt% content) 0.9 kg, monoethanolamine 0.4kg homogeneous solution obtained by mixing and dissolving an appropriate amount of water and molding additive in water 2L, Ti-Si composite oxide powder was mixed into the earlier In addition to the mixed powder of (Compound D) and Ti—W mixed oxide powder (mixture a), after kneading with a kneader, external shape 80 mm square,
触媒ａの組成は化合物Ｄ／混合物ａ／Ｖ２Ｏ５／ＷＯ３の質量比（酸化物換算）で３８／５３／５／４質量％であった。 The composition of the catalyst a was 38/53/ 5 /4% by mass in terms of mass ratio of compound D / mixture a / V 2 O 5 / WO 3 (as oxide).
（比較例３）
＜触媒ｂの調製＞
比較例１で得られたＴｉ−Ｗ混合酸化物粉体（混合物ａ）２０ｋｇにメタバナジン酸アンモニウム（Ｖ２Ｏ５として７８重量％含有）１．５ｋｇ、シュウ酸２．１ｋｇ、モノエタノールアミン０．５ｋｇを水３Ｌに混合・溶解させた均一溶液とパラタングステン酸アンモニウム（ＷＯ３として９０重量％含有）０．９ｋｇ、モノエタノールアミン０．４ｋｇを水２Ｌに混合・溶解させた均一溶液を成型助剤と適量の水とともに加え、ニーダーで混練した後、押出成型機で外形８０ｍｍ角、長さ５００ｍｍ、目開き２．９ｍｍ、肉厚０．４ｍｍのハニカム状に成型した。これを８０℃で乾燥した後、空気雰囲気下４５０℃で５時間焼成し、触媒ｂを得た。
(Comparative Example 3)
<Preparation of catalyst b>
20 kg of the Ti—W mixed oxide powder (mixture a) obtained in Comparative Example 1, 1.5 kg of ammonium metavanadate (containing 78 wt% as V 2 O 5 ), 2.1 kg of oxalic acid, 0.1% of monoethanolamine A uniform solution in which 5 kg is mixed and dissolved in 3 L of water, 0.9 kg of ammonium paratungstate (containing 90 wt% as WO 3 ), and a uniform solution in which 0.4 kg of monoethanolamine is mixed and dissolved in 2 L of water It was added together with an agent and an appropriate amount of water, kneaded with a kneader, and then formed into a honeycomb shape having an external shape of 80 mm square, a length of 500 mm, an opening of 2.9 mm, and a wall thickness of 0.4 mm by an extruder. This was dried at 80 ° C. and then calcined at 450 ° C. for 5 hours in an air atmosphere to obtain catalyst b.
触媒ｂの組成は混合物ａ／Ｖ２Ｏ５／ＷＯ３の質量比（酸化物換算）で９１／５／４質量％であった。 The composition of the catalyst b was 91/ 5 /4% by mass in terms of mass ratio (as oxide) of the mixture a / V 2 O 5 / WO 3 .
（触媒評価）
実施例４〜７で得られた触媒Ａ〜Ｄおよび比較例２、３で得られた触媒ａ、ｂを溶融塩浴に浸漬されたステンレス製反応管に充填し、下記組成の合成ガスを下記条件下で触媒層に導入し、脱硝率の測定をおこなった。
(Catalyst evaluation)
Catalysts A to D obtained in Examples 4 to 7 and catalysts a and b obtained in Comparative Examples 2 and 3 were filled in a stainless steel reaction tube immersed in a molten salt bath, and synthesis gas having the following composition was added to the following composition gas: The denitration rate was measured by introducing the catalyst layer under the conditions.
脱硝率は反応管入口および反応管出口のＮＯｘ濃度をＮＯｘ計（化学発光式、日本サーモ株式会社製ＭＯＤＥＬ５１００）により測定し、下記式１に従い求めた。得られた脱硝率を表２に示した。表２から分かるように触媒Ａ〜Ｄ（実施例４〜７）は触媒ａ、ｂ（比較例２、３）に較べて、脱硝率が高いことが分かる。 The NOx removal rate was determined according to the following formula 1 by measuring the NOx concentration at the reaction tube inlet and the reaction tube outlet with a NOx meter (chemiluminescence type, MODEL 5100 manufactured by Nippon Thermo Co., Ltd.). The obtained denitration rate is shown in Table 2. As can be seen from Table 2, the catalysts A to D (Examples 4 to 7) have a higher denitration rate than the catalysts a and b (Comparative Examples 2 and 3).
＜反応条件＞
ガス温度：３５０℃
空間速度（ＳＴＰ）：２６０００ｈｒ−１
＜合成ガス組成＞
ＮＯｘ：１００ｐｐｍ，ｄｒｙ
ＮＨ３：１００ｐｐｍ，ｄｒｙ
Ｏ２：１５％，ｄｒｙ
Ｈ２Ｏ：１０％，ｗｅｔ
Ｎ２：ｂａｌａｎｃｅ
<Reaction conditions>
Gas temperature: 350 ° C
Space velocity (STP): 26000 hr −1
<Syngas composition>
NOx: 100ppm, dry
NH 3 : 100 ppm, dry
O 2 : 15%, dry
H 2 O: 10%, wet
N 2 : balance
本発明は排ガス処理分野、特に窒素酸化物（ＮＯｘ）を含む排ガスの処理に有効な技術である。 The present invention is a technique effective in the field of exhaust gas treatment, particularly in the treatment of exhaust gas containing nitrogen oxides (NOx).
Claims (5)
（１）アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ）により２５０〜３５０℃のアンモニア脱離量を測定すること（以下「Ｌ−脱離量」という）。
（２）アンモニア−昇温脱離測定（ＮＨ３−ＴＰＤ）により４５０〜５５０℃のアンモニア脱離量を測定すること（以下「Ｈ−脱離量」という）。
（３）Ｈ−脱離量／Ｌ−脱離量が０．７〜１．５であること。 A composite oxide of titanium and tungsten (hereinafter referred to as "Ti-W composite oxide") or a composite oxide of titanium, silicon and tungsten (hereinafter referred to as "Ti-Si-W composite oxide") characterized by satisfying the following conditions: Called).
(1) Measure ammonia desorption amount at 250 to 350 ° C. by ammonia-temperature programmed desorption measurement (NH 3 -TPD) (hereinafter referred to as “L-desorption amount”).
(2) Measuring ammonia desorption amount at 450 to 550 ° C. by ammonia-temperature programmed desorption measurement (NH 3 -TPD) (hereinafter referred to as “H-desorption amount”).
(3) H-desorption amount / L-desorption amount is 0.7 to 1.5.
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| CN103586017A (en) * | 2013-11-22 | 2014-02-19 | 西南化工研究设计院有限公司 | Preparation method of titanium and tungsten powder for flue gas denitration catalyst and product prepared through preparation method |
| CN106693953A (en) * | 2016-12-27 | 2017-05-24 | 内蒙古华元科技有限公司 | Ti-based catalyst for coking flue gas denitrification and preparation method thereof |
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| CN103586017B (en) * | 2013-11-22 | 2015-03-25 | 西南化工研究设计院有限公司 | Preparation method of titanium and tungsten powder for flue gas denitration catalyst and product prepared through preparation method |
| CN106693953A (en) * | 2016-12-27 | 2017-05-24 | 内蒙古华元科技有限公司 | Ti-based catalyst for coking flue gas denitrification and preparation method thereof |
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