JPS6336830A - Flue gas denitration catalyst - Google Patents
Flue gas denitration catalystInfo
- Publication number
- JPS6336830A JPS6336830A JP61178723A JP17872386A JPS6336830A JP S6336830 A JPS6336830 A JP S6336830A JP 61178723 A JP61178723 A JP 61178723A JP 17872386 A JP17872386 A JP 17872386A JP S6336830 A JPS6336830 A JP S6336830A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- active
- oxide
- flue gas
- denitrification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 239000003546 flue gas Substances 0.000 title claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000000975 co-precipitation Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002912 waste gas Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 229910000413 arsenic oxide Inorganic materials 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 11
- 229960002594 arsenic trioxide Drugs 0.000 abstract description 9
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 239000003500 flue dust Substances 0.000 abstract 1
- 230000000802 nitrating effect Effects 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 150000001495 arsenic compounds Chemical class 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229940093920 gynecological arsenic compound Drugs 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、窒素酸化物含有排ガスの脱硝用触媒に関し、
詳細には、窒素酸化物の他に触媒被毒となりやすいヒ素
等の煤じんを多量に含んだ排ガスにアンモニアを添加し
、窒素酸化物を接触還元し、窒素と水に転化して無害化
除去するに当り、触媒被毒成分の影響？はとんど受けな
い排煙脱硝触媒に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a catalyst for denitrification of exhaust gas containing nitrogen oxides,
In detail, in addition to nitrogen oxides, ammonia is added to the exhaust gas, which contains a large amount of soot and dust such as arsenic that tends to poison the catalyst, and the nitrogen oxides are catalytically reduced and converted into nitrogen and water, making them harmless. In doing so, is there an effect of catalyst poisoning components? Regarding exhaust gas denitrification catalysts, which are rarely used.
重力用大型ボイラ、自家発用ボイラ等の燃焼炉、焼却炉
、化学プラント等からの廃ガス中に含まれるＮＯｘによ
る大気汚染が社会問題となり、その防止策として、各種
の廃ガス脱硝装置の開発が進められた結果、現在では、
触媒の存在下でアンモニアを還元剤とした選択的接触還
元法が主流となっている。仁の脱硝装置に用いられる触
媒は、高活性であることはもちろん、その性能を長時間
安定に維持できることが要求される。Air pollution caused by NOx contained in waste gas from combustion furnaces such as large gravity boilers and private boilers, incinerators, chemical plants, etc. has become a social problem, and as a preventive measure, various types of waste gas denitrification equipment have been developed. As a result of progress, currently,
Selective catalytic reduction using ammonia as a reducing agent in the presence of a catalyst has become mainstream. The catalyst used in Jin's denitrification equipment is required not only to be highly active but also to be able to maintain its performance stably for a long period of time.
従来排煙脱硝用に開発された触媒はアルミナ、チタニア
上の担体に鉄、バナジウム、タングステン、モリブデン
などの酸化物を含浸法で単独にあるいは組合せて担持し
た触媒でちる。Catalysts that have been developed for exhaust gas denitrification are made by impregnating oxides such as iron, vanadium, tungsten, and molybdenum on alumina or titania carriers, either singly or in combination.
近年、本発明者らは、実機触媒の解析や種々の実験室試
験によって、脱硝触媒は廃ガス中に含まれるアルカリ金
属成分であるＮａやＫの畜槓以外に、Ａｓ 、 ！３ｅ
、 Ｔｅ等の被毒物質を蓄積することによって、性能
低下を大幅にきたし、触媒寿命が短くなることを見出し
た。In recent years, the present inventors have discovered through analysis of actual catalysts and various laboratory tests that denitrification catalysts not only remove Na and K, which are alkali metal components contained in waste gas, but also contain As,! 3e
It has been found that the accumulation of poisonous substances such as Te, etc. significantly reduces the performance and shortens the catalyst life.
Ｎａやに等のアルカリ金属は粒径は数μ〜数十μと比較
的大きいだめ、触媒の表面のみに蓄積するため、触媒活
性体への蓄積防止法として、活性金属を含まない固体酸
性物質を触媒表面に薄くコートシ、そのコート部分で廃
ガスダスト中のアルカリ金属を、固体酸性物質のイオン
交換能力を利用して捕集し、触媒活性体への被毒を抑制
する方法等が試みられており、種々の触媒活性低下防止
処理が検討されている。Since the particle size of alkali metals such as Na is relatively large, ranging from several microns to several tens of microns, they accumulate only on the surface of the catalyst, so as a method to prevent accumulation on the catalyst active body, solid acidic substances that do not contain active metals are used. Attempts have been made to coat the catalyst surface thinly, and use the coated part to collect alkali metals in the exhaust gas dust using the ion exchange ability of the solid acidic substance, thereby suppressing the poisoning of the catalyst active body. Therefore, various treatments for preventing a decrease in catalyst activity are being considered.
一方、廃ガスダスト中に含まれるヒ素酸化物・Ａｓ２Ｏ
，）は、分子状で触媒細孔内部にまで拡散侵入し、さら
に活性金属の酸化作用により蒸気圧の低いＡｓ２Ｏ，に
変化するため、活性金属の表面にＡ ｅ、Ｏ，が沈着し
触媒性能が急激に低下する。さらに、ヒ素酸化物は触媒
の活性金属と複合酸化物会形成しやすく、複合酸化物を
形成した触媒は活性点がｆ’Ｌとんど消失することが近
年明らかにされた。On the other hand, arsenic oxide/As2O contained in exhaust gas dust
, ) diffuses into the catalyst pores in molecular form and further changes to As2O, which has a low vapor pressure due to the oxidation action of the active metal, resulting in the deposition of Ae, O, on the surface of the active metal, which impairs catalyst performance. decreases rapidly. Furthermore, it has recently been revealed that arsenic oxide tends to form a composite oxide association with the active metal of the catalyst, and that active sites in catalysts that have formed a composite oxide almost disappear f'L.
石炭等の原料中に多量のヒ素化合物を含んでいる場合、
ヒ素酸化物の沈着による脱硝触媒の劣化を防止する方法
として、
■ 石炭等の原料を水洗前処理して、原料中からヒ素化
合物を除去する。If raw materials such as coal contain large amounts of arsenic compounds,
As a method to prevent the denitrification catalyst from deteriorating due to the deposition of arsenic oxides, (1) Pre-processing raw materials such as coal with water to remove arsenic compounds from the raw materials.
■ 脱硝触媒の前段に、ヒ素化合物分選択的に吸着する
吸着剤を設置する。■ Install an adsorbent that selectively adsorbs arsenic compounds before the denitrification catalyst.
■ 耐ヒ素性に優れた脱硝触媒を開発する。■ Develop a denitrification catalyst with excellent arsenic resistance.
等のヒ素化合物の被毒に対する対策が提案されている。Countermeasures against poisoning by arsenic compounds have been proposed.
ただし、■の原料の前処理は、原料の水洗、乾燥等の工
程追加により、多大な労力と費用を要し、■の吸着剤の
設置は、触媒層上に吸着剤を置くと、圧力損失が高くな
り、さらに、ヒ素化合物を完全に、長時間捕捉するには
高性能な吸着剤を多量に要することになる。上記理由に
より■、■の方法よりも■の耐ヒ素性に優れた触媒を開
発する法が好ましい脱硝触媒劣化防止方法と考えられる
。However, the pretreatment of the raw material in (■) requires a great deal of labor and expense due to additional processes such as washing and drying the raw material, and the installation of the adsorbent (in) (2) requires pressure loss when the adsorbent is placed on the catalyst layer. Moreover, a large amount of high-performance adsorbent is required to completely capture arsenic compounds for a long time. For the above reasons, the method (2) of developing a catalyst with superior arsenic resistance is considered to be a preferable method for preventing deterioration of the denitrification catalyst than methods (2) and (2).
ところで、耐ヒ素性に優れた脱硝触媒とは、Ａｓ、Ｏｌ
の酸化力が弱く、活性金属表面上に沈着することを防ぐ
触媒であり、また、ヒ素酸化物が触媒に吸着した場合は
、活性金属と複合酸化物を形成しない触媒である。さら
に、ＮＯｘの接触還元力は長時間高活性を維持したまま
である必要がある。By the way, denitrification catalysts with excellent arsenic resistance include As, Ol
It is a catalyst that has a weak oxidizing power and prevents it from being deposited on the surface of the active metal, and also does not form a composite oxide with the active metal when arsenic oxide is adsorbed on the catalyst. Furthermore, the catalytic reducing power of NOx needs to remain highly active for a long period of time.
従来広のＴ ｉ Ｏ，担体に含浸法により活性金属を担
持する脱硝触媒では、ＮＯＸの接触還元力を維持したま
までヒ素酸化物の沈着を防ぐことは困難でちる。それゆ
え、ヒ素酸化物を吸着せず、かつ脱硝活性が犬である脱
硝触媒及びその調製法の開発が望まれている。With conventional denitrification catalysts in which active metals are supported on a TiO carrier by an impregnation method, it is difficult to prevent arsenic oxide deposition while maintaining the catalytic reducing power of NOX. Therefore, it is desired to develop a denitrification catalyst that does not adsorb arsenic oxides and has a high denitrification activity, and a method for preparing the same.
そこで、本発明者らは、上記問題を克服すべく脱硝触媒
及びその調製法の開発を鋭意検討した結果、本発明を完
成したものであり、したがって本発明は、ヒ素酸化物の
沈着を防ぎ、高性能の脱硝作用を長時間維持することが
できる排煙脱硝触媒を提供することを目的とする。Therefore, the present inventors have completed the present invention as a result of intensive study on the development of a denitrification catalyst and its preparation method in order to overcome the above-mentioned problems.Therefore, the present invention has been developed to prevent the deposition of arsenic oxides, The purpose of the present invention is to provide a flue gas denitrification catalyst that can maintain high-performance denitrification effect for a long time.
そして、本発明は、上記目的分達成するため、触媒活性
金属と基材であるチタニアを共沈法により調整する点に
ある。すなわち、本発明は、窒素酸化物を含有する廃ガ
スにアンモニアを添加して、該ガス中の窒素酸化物を還
元し無害化する触媒において、触媒活性成分とチタニア
を共沈法により調製してなることを特徴とする排煙脱硝
触媒である。In order to achieve the above objectives, the present invention consists in adjusting the catalytically active metal and the base material titania by a coprecipitation method. That is, the present invention provides a catalyst that adds ammonia to waste gas containing nitrogen oxides to reduce and render the nitrogen oxides in the gas harmless, in which a catalyst active component and titania are prepared by a coprecipitation method. This is an exhaust gas denitrification catalyst characterized by:
本発明の共沈法により調製した脱硝触媒は、活性金属が
触媒全体に均一に分散しているだめ非晶質状態で安定で
あり、かつ活性金属酸化物がチタニアと安定な状態で複
合酸化物を形成しているため、廃ガスダスト中のヒ素酸
化物と活性金属とが結合して生成する複合酸化物の形成
を防ぐことができる。さらに、共沈法に調製した脱硝触
媒はＳＯ，の酸化及びＡｓ、０３ の酸化を低減する
ため、硫酸塩の生成及びＡ ｓ２０．の生成を抑制する
ことがわかった。The denitrification catalyst prepared by the coprecipitation method of the present invention is stable in an amorphous state because the active metal is uniformly dispersed throughout the catalyst, and the active metal oxide and titania are in a stable state and form a composite oxide. , it is possible to prevent the formation of complex oxides produced by the combination of arsenic oxides and active metals in exhaust gas dust. Furthermore, since the denitrification catalyst prepared by the coprecipitation method reduces the oxidation of SO, and the oxidation of As, 03, it reduces the generation of sulfate and As20. was found to inhibit the formation of
ＴｉＯ２と共沈法で調製でき、さらに高活性な脱硝性能
を有す活性金属としては、従来からの触媒組成スクリー
ニングテストより、Ｅｌｎ 、 Ｏｕ 。From conventional catalyst composition screening tests, active metals that can be prepared with TiO2 by coprecipitation and have even higher denitrification performance are Eln and Ou.
Ｃｏ 、 Ｆ′ｅ 、 Ｏｒ 、 Ｎｉ等が挙げられ、
これらの活性金属ヲ本発明における触媒活性成分として
使用するものであり、そして本発明では、各金属酸化物
ＳｎＯ、ＣｕＯ、Ｃｏｏ 、 ＦｅＯ、（！ｒ１０３
、 ＮｉＯの含有量はＴｌＯ２担体に対して１１２ ｗ
ｔ％〜４０ ｗｔチであることが望ましい。Examples include Co, F'e, Or, Ni, etc.
These active metals are used as catalyst active components in the present invention, and in the present invention, each metal oxide SnO, CuO, Coo, FeO, (!r103
, the content of NiO is 112 w relative to the TlO2 support
It is desirable that the amount is between t% and 40 wt.
〔実施例１〕
四塩化チタン５００１と塩化第１スズ２０？を純水８０
０２に溶解させ、適当量の１Ｍ溶液炭酸ナトリウムを加
え、ｐＨを９として共沈法により沈殿を生ぜしめた。こ
の沈殿を６０℃にて一昼夜熟成し、陰イオンを完全に除
去するまでろ過、洗浄を繰返し、さらに乾燥を１１０℃
、−昼夜性ないＴｉ（ＯＴ（）４−５ｎ（ＯＨ）ｔの粉
末を４０ｏｆ得た。この粉末を５５０℃、５ｈｒ焼成し
て複合酸化物触媒Ｔｉｅ、 −ＳｎＯを得た。この複合
酸化物にバインダー分添加してハニカム状に成型した触
媒（穴の形状；正方形、目開き６０ｆｉ、壁厚１、５５
ｍ ’）を触媒１とする。この触媒１の組成比（重量
比）はＴｉＯ２： ＳｎＯ−９６： Ａである。[Example 1] Titanium tetrachloride 5001 and stannous chloride 20? Pure water 80
02, an appropriate amount of 1M sodium carbonate solution was added, the pH was adjusted to 9, and a precipitate was produced by a coprecipitation method. This precipitate was aged at 60°C overnight, filtered and washed repeatedly until anions were completely removed, and then dried at 110°C.
, -40 of Ti(OT()4-5n(OH)t powder) which has no day/night property was obtained.This powder was fired at 550°C for 5 hours to obtain a composite oxide catalyst Tie, -SnO.This composite oxide A catalyst formed into a honeycomb shape by adding a binder to it (hole shape: square, opening 60fi, wall thickness 1.55
m') is catalyst 1. The composition ratio (weight ratio) of this catalyst 1 is TiO2:SnO-96:A.
〔実施例２〕
四塩化チタン５００２と硝酸銅２０り、四塩化チタン５
００？と硝酸クロム３０２．四塩化チタン５００？と硝
酸コバルトＡＯｆ、四塩化チタン５００２と硝酸鉄３０
ｆ、四塩化チタン５００ｔと硝０ニッケル２０２．を用
いて実施例１の同様の共沈法により複合水酸化物の粉末
を得た。この粉末を５５０℃、５ ｈｒ焼成して複合酸
化物触媒ＴｉＯ２−ＣｕＯ、Ｔ１０２−Ｃｒ２０ｇ 、
ＴｉＯ，−ｆ：！ｏｏ 。[Example 2] Titanium tetrachloride 5002, copper nitrate 20, titanium tetrachloride 5
00? and chromium nitrate 302. Titanium tetrachloride 500? and cobalt nitrate AOf, titanium tetrachloride 5002 and iron nitrate 30
f, 500 tons of titanium tetrachloride and 202 tons of nickel. A powder of a composite hydroxide was obtained by the same coprecipitation method as in Example 1. This powder was calcined at 550°C for 5 hours to form a composite oxide catalyst TiO2-CuO, T102-Cr20g,
TiO,-f:! oo.
Ｔｉ０２−Ｆｅ、０３ 、 ＴｉＯ２−ＮｉＯを得、各
々ハニカム成型体にした触媒を触媒２．触媒５．触媒４
．触媒５、触媒６とする。これらの組成比（゛重量部）
で各々、ＴｉＯ２：０ｕＯ＝ ９６ ： Ａ 、 Ｔｉ
Ｏ，：０ｒ２０３ ＝９４ ： ６ 、 ＴｉＯ２：
Ｃｏｏ−９２： ８ 、 Ｔｉｄｙ ：Ｆｅ２Ｏ，＋＝
ｇ９４ ： ６ 、 ＴｉＯ，：Ｎｉ０−９６ ： ４
である。Catalysts 2. Ti02-Fe, 03, and TiO2-NiO were obtained and formed into honeycomb bodies. Catalyst 5. catalyst 4
．． Let them be catalyst 5 and catalyst 6. These composition ratios (parts by weight)
respectively, TiO2:0uO=96: A, Ti
O,:0r203 =94:6, TiO2:
Coo-92: 8, Tidy:Fe2O, +=
g94: 6, TiO,:Ni0-96: 4
It is.
〔実施例３〕
四塩化チタン５００２と硝酸鉄２０２．硝酸銅１０９を
純水９００２に溶解させ、実施例１と同様の共沈法によ
り複合水酸化物Ｔｉ（ＯＨ）、 −Ｆｅ（ＯＨ）、−Ｃ
ｕ（ＯＨ）２の粉末を得た。この粉末を５５０℃、５ｈ
ｒ焼成して、複合酸化物触媒ＴｉＱ。[Example 3] Titanium tetrachloride 5002 and iron nitrate 202. Copper nitrate 109 was dissolved in pure water 9002, and composite hydroxides Ti(OH), -Fe(OH), -C were prepared by the same coprecipitation method as in Example 1.
A powder of u(OH)2 was obtained. This powder was heated to 550℃ for 5 hours.
After firing, the composite oxide catalyst TiQ is prepared.
−Ｆ〜０３−Ｃ！ｕｏ を得、ざらにハニカム成型体
にしたこの触媒を触媒７とする。この触媒の組成比（重
量比）はＴｉｅｌ： Ｆｅ、０３二〇ｕＯ１９Ａ：４：
２である。-F~03-C! This catalyst, which was obtained and made into a rough honeycomb molded body, is designated as catalyst 7. The composition ratio (weight ratio) of this catalyst is Tiel: Fe, 0320uO19A:4:
It is 2.
通常の含浸法による触媒の調製は下記のように行う。 The catalyst is prepared by a conventional impregnation method as follows.
四塩化チタンを５００ｔを純水８００ｆに溶解させ、適
当量の１Ｍ溶液炭酸ナトリウムの滴下（てよシチタン水
酸化物の沈殿を得た。この沈殿を６０℃で熟成し、ｒ過
、洗浄を行い陰イオンを除去した後、１１０℃−昼夜の
乾燥を行った。500t of titanium tetrachloride was dissolved in 800f of pure water, and an appropriate amount of 1M sodium carbonate solution was added dropwise to obtain a precipitate of titanium hydroxide.This precipitate was aged at 60°C, filtered and washed. After removing anions, drying was performed at 110° C. day and night.
さらに、５５０ ’Ｃ、１２ｈの焼成を行いＴ１へ担体
を調製した。このＴｉｅ、担体に）（インダーを添加し
てハニカム状に成型した後（穴の形状；６．Ｄ甥、壁厚
、正方形、目開き瓜Ｏｍ ｒ壁厚１．５５醪）、このハ
ニカムＴ１）担体を各々所定濃度の塩化第−スズ、硝酸
銅、硝酸クロム、硝酸コバルト、硝酸鉄、硝酸ニッケル
の水溶液中に１時間没潰し、１１０℃で一昼夜乾燥し、
５５０℃で３時間焼成した。本触媒ＴｉＯ２−ＳｎＯ、
Ｔｉｅ、 −０ｕＯ。Furthermore, calcination was carried out at 550'C for 12 hours to prepare a T1 carrier. This Tie, to the carrier) (After adding inder and forming into a honeycomb shape (hole shape: 6.D, wall thickness, square, opening size, wall thickness: 1.55 mm), this honeycomb T1) The carrier was immersed in an aqueous solution of stannous chloride, copper nitrate, chromium nitrate, cobalt nitrate, iron nitrate, and nickel nitrate at predetermined concentrations for one hour, and dried at 110°C overnight.
It was baked at 550°C for 3 hours. This catalyst TiO2-SnO,
Tie, -0uO.
ＴｉＯ２−Ｃｒ２Ｏ，、ＴｉＯ２−Ｃｏｏ 、 ＴｉＯ
２−Ｆｅ２Ｏ，、Ｔｉ０１− ＮｉＯを各々触媒８．触
媒９．触媒１０．触媒１１．触媒１２．触媒１５とする
。尚、触媒８〜１５の組成は触媒１〜６と同一組成のも
のをルーを製した。TiO2-Cr2O, TiO2-Coo, TiO
2-Fe2O, Ti01-NiO as catalysts 8. Catalyst 9. Catalyst 10. Catalyst 11. Catalyst 12. Let it be catalyst 15. Note that catalysts 8 to 15 had the same composition as catalysts 1 to 6, and a roux was prepared.
触媒１〜触媒１５の脱硝活性を調べるだめに、ヒ素酸化
物を含有したボイラー排ガスを使用して表１の試験条件
で脱硝性能を測定した結果（初期活性、５０００ｈガス
供給後）を表２に示す。さらに、５０００ｈｒ使用後の
触媒を脱硝装置よシ抜き取り、沈着したヒ素酸化物の含
有量を表２に記す。In order to investigate the denitrification activity of Catalysts 1 to 15, the denitrification performance was measured under the test conditions in Table 1 using boiler exhaust gas containing arsenic oxide. The results (initial activity, after 5000 hours of gas supply) are shown in Table 2. show. Further, the catalyst after 5000 hours of use was removed from the denitrification device, and the content of deposited arsenic oxides is shown in Table 2.
（表１）〔脱硝反応試験条件〕
表２に示すように、共沈法にて調製した触媒１〜触喋７
は脱硝活性は５０００ｈ使用後でも初期活性と同様の高
脱硝率を有し、また、触媒上に沈着したヒ素酸化物の含
有量も少ないことがわかる。さらに、本発明による共沈
法により調製した触媒は低ＳＯ，酸化性能を有する脱硝
触媒であり、従来型触媒にない耐ヒ素性を具備した触媒
であることが判明した。(Table 1) [Denitrification reaction test conditions] As shown in Table 2, catalysts 1 to 7 prepared by coprecipitation method
It can be seen that even after 5000 hours of use, the catalyst had a high denitrification rate similar to the initial activity, and the content of arsenic oxide deposited on the catalyst was small. Furthermore, it was found that the catalyst prepared by the coprecipitation method of the present invention is a denitrification catalyst with low SO and oxidation performance, and has arsenic resistance not found in conventional catalysts.
本発明は、以上詳記したように、触媒活性成分と基材で
あるチタニアを共沈法により鉤整したものであり、この
本発明の触媒は、ヒ素酸化物の沈着を防ぎ、高性能、の
脱硝作用を長期間にわたって維持する効果を奏するもの
である。As described in detail above, the present invention is a method in which a catalytic active component and titania as a base material are prepared by a coprecipitation method, and the catalyst of the present invention prevents the deposition of arsenic oxide, has high performance, It has the effect of maintaining the denitrification effect over a long period of time.
復代理人 内 １） 明 復代理人 萩 原 亮 − 復代理人 安 西 篤 夫Sub-agent: 1) Akira Sub-agent Ryo Hagi Hara - Sub-agent Atsuo Yasunishi
Claims (1)
該ガス中の窒素酸化物を還元し無害化する触媒において
、触媒活性成分とチタニアを共沈法により調製してなる
ことを特徴とする排煙脱硝触媒。By adding ammonia to the waste gas containing nitrogen oxides,
A flue gas denitrification catalyst for reducing nitrogen oxides in the gas to render them harmless, characterized in that the catalyst active component and titania are prepared by a coprecipitation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61178723A JPS6336830A (en) | 1986-07-31 | 1986-07-31 | Flue gas denitration catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61178723A JPS6336830A (en) | 1986-07-31 | 1986-07-31 | Flue gas denitration catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6336830A true JPS6336830A (en) | 1988-02-17 |
Family
ID=16053442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61178723A Pending JPS6336830A (en) | 1986-07-31 | 1986-07-31 | Flue gas denitration catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6336830A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306684A (en) * | 1991-06-18 | 1994-04-26 | N. E. Chemcat Corporation | Catalyst for purification of exhaust gases |
| US5336651A (en) * | 1990-05-03 | 1994-08-09 | Sakai Chemical Industry Co., Ltd. | Catalysts and methods for denitrization |
| JP2006298797A (en) * | 2005-04-18 | 2006-11-02 | Nippon Shokubai Co Ltd | Fixed bed reactor for vapor-phase catalytic oxidation and method for producing acrolein or acrylic acid |
-
1986
- 1986-07-31 JP JP61178723A patent/JPS6336830A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336651A (en) * | 1990-05-03 | 1994-08-09 | Sakai Chemical Industry Co., Ltd. | Catalysts and methods for denitrization |
| US5306684A (en) * | 1991-06-18 | 1994-04-26 | N. E. Chemcat Corporation | Catalyst for purification of exhaust gases |
| JP2006298797A (en) * | 2005-04-18 | 2006-11-02 | Nippon Shokubai Co Ltd | Fixed bed reactor for vapor-phase catalytic oxidation and method for producing acrolein or acrylic acid |
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