JPH04367740A - Catalyst and method for reducing and removing nitrogen oxide - Google Patents
Catalyst and method for reducing and removing nitrogen oxideInfo
- Publication number
- JPH04367740A JPH04367740A JP3167501A JP16750191A JPH04367740A JP H04367740 A JPH04367740 A JP H04367740A JP 3167501 A JP3167501 A JP 3167501A JP 16750191 A JP16750191 A JP 16750191A JP H04367740 A JPH04367740 A JP H04367740A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- nitrogen oxides
- reducing
- exhaust gas
- present
- 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
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 iron ion Chemical class 0.000 claims abstract description 18
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 17
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 15
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- 229910021536 Zeolite Inorganic materials 0.000 description 16
- 239000010457 zeolite Substances 0.000 description 16
- 238000005342 ion exchange Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 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 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、窒素酸化物、炭化水素
及び酸素を含有する排ガスから窒素酸化物を還元除去す
る触媒及びその使用方法に関するものであり、さらに詳
細には、低温での性能の優れた窒素酸化物還元除去用触
媒を提供するものである。[Field of Industrial Application] The present invention relates to a catalyst for reducing and removing nitrogen oxides from exhaust gas containing nitrogen oxides, hydrocarbons, and oxygen, and a method for using the same. The present invention provides an excellent catalyst for reducing and removing nitrogen oxides.
【０００２】0002
【従来の技術】窒素酸化物の発生源であるボイラ−、自
動車等の排ガス中から窒素酸化物を除去する方法として
、Ｖ２Ｏ５／ＴｉＯ２系を触媒としたアンモニアによる
選択的接触還元法、あるいは、貴金属を担持したアルミ
ナを触媒として未燃の炭化水素及び一酸化炭素により還
元する非選択的接触還元法等が工業的に実用化されてい
る。[Prior Art] As a method for removing nitrogen oxides from the exhaust gas of boilers, automobiles, etc., which are the sources of nitrogen oxides, there is a selective catalytic reduction method using ammonia using a V2O5/TiO2 system as a catalyst, or a method using precious metals. A non-selective catalytic reduction method in which unburned hydrocarbons and carbon monoxide are reduced using alumina supported on carbon monoxide as a catalyst has been put into practical use industrially.
【０００３】また、更には、特開昭６０−１２５２５０
号公報には、還元剤非共存下で窒素酸化物を直接接触分
解できる触媒として銅イオン交換したゼオライトを用い
る方法が提案されている。[0003] Furthermore, Japanese Patent Application Laid-Open No. 60-125250
The publication proposes a method using copper ion-exchanged zeolite as a catalyst that can directly catalytically decompose nitrogen oxides in the absence of a reducing agent.
【０００４】また、酸素過剰下でも、排ガス中の未燃の
一酸化炭素、炭化水素等の還元成分により窒素酸化物を
選択的に還元できる触媒として、Ｃｕ等の卑金属をゼオ
ライト等に含有させた触媒が提案されている。[0004] Furthermore, base metals such as Cu have been incorporated into zeolite as catalysts that can selectively reduce nitrogen oxides using reducing components such as unburned carbon monoxide and hydrocarbons in exhaust gas even under excessive oxygen conditions. Catalysts have been proposed.
【０００５】一方、鉄を含有する疎水性のゼオライト触
媒を用いて、一酸化炭素及び炭化水素を含む廃ガス中に
存在する窒素酸化物を減少させる方法が提案されている
（特開昭６３−２８３７２７）。この方法では、水等の
極性分子に比べ炭化水素等の非極性分子を選択的に吸着
する、いわゆる疎水性を有するゼオライトを用いること
が必須である。On the other hand, a method has been proposed for reducing nitrogen oxides present in waste gas containing carbon monoxide and hydrocarbons by using a hydrophobic zeolite catalyst containing iron (Japanese Unexamined Patent Application Publication No. 1986-1999). 283727). In this method, it is essential to use a zeolite having so-called hydrophobic properties, which selectively adsorbs non-polar molecules such as hydrocarbons compared to polar molecules such as water.
【０００６】しかしながら、これらの提案されている触
媒は、特に低温での十分な活性を有しておらず、未だ実
用化されるに至っていない。However, these proposed catalysts do not have sufficient activity, especially at low temperatures, and have not yet been put into practical use.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、酸素
存在下でも、還元剤であるアンモニアを使用することな
く、工業プラント、自動車等から排出される燃焼排ガス
中の窒素酸化物を効率良く除去し、特に低温においても
効率の良い窒素酸化物還元除去触媒、また、その使用方
法を提供するものである。[Problems to be Solved by the Invention] An object of the present invention is to efficiently remove nitrogen oxides from combustion exhaust gases emitted from industrial plants, automobiles, etc., even in the presence of oxygen, without using ammonia as a reducing agent. The purpose of the present invention is to provide a catalyst for reducing and removing nitrogen oxides that is efficient even at low temperatures, and a method for using the same.
【０００８】[0008]
【課題を解決するための手段】］本発明者等は、上記課
題について鋭意検討を重ねた結果、本発明を完成するに
至った。[Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive studies regarding the above problems.
【０００９】即ち本発明は、ＳｉＯ２／Ａｌ２Ｏ３モル
比が２０〜６０のＺＳＭ−５に鉄イオンを少なくとも１
ｗｔ％含有させたことを特徴とする、窒素酸化物、炭化
水素及び酸素を含む排ガスから窒素酸化物を還元除去す
る触媒、及び、鉄イオンを含有したＺＳＭ−５に窒素酸
化物、炭化水素及び酸素を含む排ガスを接触させること
を特徴とする窒素酸化物還元除去方法を提供するもので
ある。That is, the present invention provides ZSM-5 with a SiO2/Al2O3 molar ratio of 20 to 60 and at least one iron ion.
A catalyst for reducing and removing nitrogen oxides from exhaust gas containing nitrogen oxides, hydrocarbons, and oxygen, and containing iron ions in ZSM-5 containing nitrogen oxides, hydrocarbons, and The present invention provides a method for reducing and removing nitrogen oxides, which is characterized by contacting exhaust gas containing oxygen.
【００１０】以下、本発明をより詳細に説明する。The present invention will be explained in more detail below.
【００１１】本発明において用いられるＺＳＭ−５のＳ
ｉＯ２／Ａｌ２Ｏ３モル比は２０〜６０であることが必
須である。ＳｉＯ２／Ａｌ２Ｏ３モル比が２０〜６０の
ＺＳＭ−５は耐熱性に優れ、かつ、約１ｗｔ％以上の水
分吸着量を示すゼオライトである。[0011] S of ZSM-5 used in the present invention
It is essential that the iO2/Al2O3 molar ratio is 20-60. ZSM-5 having a SiO2/Al2O3 molar ratio of 20 to 60 is a zeolite that has excellent heat resistance and exhibits a water adsorption amount of about 1 wt% or more.
【００１２】ゼオライトの水分吸着量は、そのＳｉＯ２
／Ａｌ２Ｏ３モル比の増加と共に減少し、ＳｉＯ２／Ａ
ｌ２Ｏ３モル比２０で約１０ｗｔ％、４０で約２ｗｔ％
、６０で約１ｗｔ％、６０を越えると殆ど水分を吸着し
なくなる。一方、非極性分子であるシクロヘキサンにつ
いては、ＳｉＯ２／Ａｌ２Ｏ３モル比４０以上では約５
ｗｔ％と一定の吸着量を示す。[0012] The water adsorption amount of zeolite is determined by its SiO2
/Al2O3 molar ratio decreases, and SiO2/A
About 10 wt% at l2O3 molar ratio of 20, about 2 wt% at 40
, 60 is about 1 wt%, and when it exceeds 60, it hardly absorbs moisture. On the other hand, for cyclohexane, which is a nonpolar molecule, when the SiO2/Al2O3 molar ratio is 40 or more, the
It shows a constant adsorption amount as wt%.
【００１３】ＳｉＯ２／Ａｌ２Ｏ３モル比が２０よりも
低いと触媒の耐熱性が低下する。また、上述したように
、ＳｉＯ２／Ａｌ２Ｏ３モル比が６０を越えると水分を
殆ど吸着しなくなり、このようなＺＳＭ−５に鉄イオン
を含有させても、低温での性能の優れた触媒とはなり得
ない。好ましくは、ＳｉＯ２／Ａｌ２Ｏ３モル比が２０
〜３５である。[0013] When the SiO2/Al2O3 molar ratio is lower than 20, the heat resistance of the catalyst decreases. Furthermore, as mentioned above, when the SiO2/Al2O3 molar ratio exceeds 60, almost no moisture is adsorbed, and even if such ZSM-5 contains iron ions, it will not be a catalyst with excellent performance at low temperatures. I don't get it. Preferably, the SiO2/Al2O3 molar ratio is 20
~35.
【００１４】本発明の触媒を構成するＺＳＭ−５の製造
方法は特に限定されない。また、ＺＳＭ−５はそのまま
あるいはアンモニウム塩、鉱酸等で処理しＮＨ４イオン
交換或いはＨイオン交換してから使用することもできる
。The method for producing ZSM-5 constituting the catalyst of the present invention is not particularly limited. Further, ZSM-5 can be used as it is or after being treated with ammonium salt, mineral acid, etc. to exchange NH4 ions or H ions.
【００１５】本発明の触媒は、ＳｉＯ２／Ａｌ２Ｏ３モ
ル比が２０〜６０のＺＳＭ−５に鉄イオンを少なくとも
１ｗｔ％含有させることが必須である。鉄イオンが１ｗ
ｔ％未満では、低温での十分な活性が得られない。好ま
しくは、鉄イオン含有量が１．５ｗｔ％以上である。ま
た、その上限は特に限定されないが、３ｗｔ％以下であ
ることが好ましい。[0015] In the catalyst of the present invention, it is essential that ZSM-5 having a SiO2/Al2O3 molar ratio of 20 to 60 contains at least 1 wt% of iron ions. Iron ion is 1w
If it is less than t%, sufficient activity at low temperatures cannot be obtained. Preferably, the iron ion content is 1.5 wt% or more. Further, the upper limit is not particularly limited, but it is preferably 3 wt% or less.
【００１６】上記のＺＳＭ−５に鉄イオンを含有させる
方法は特に限定されないが、イオン交換法が好ましい。
イオン交換法としては、一般的に行われている方法、た
とえば鉄イオンを含有する水溶液を用いてイオン交換す
る方法を採用することができる。[0016] The method for incorporating iron ions into the above ZSM-5 is not particularly limited, but an ion exchange method is preferred. As the ion exchange method, a commonly used method such as a method of ion exchange using an aqueous solution containing iron ions can be adopted.
【００１７】鉄イオンは可溶性の塩の形で使用でき、可
溶性の塩としては、硝酸塩、酢酸塩、シュウ酸塩、塩酸
塩等が好適に使用できる。[0017] Iron ions can be used in the form of soluble salts, and nitrates, acetates, oxalates, hydrochlorides, etc. can be preferably used as the soluble salts.
【００１８】イオン交換時の鉄イオンの添加量は、ＺＳ
Ｍ−５中のＡｌに対しＦｅ／Ａｌ原子比で表わして０．
１〜５であることが望ましい。０．１未満では鉄イオン
が十分に交換されず、鉄イオン含有量が１．０ｗｔ％未
満になる恐れがあり、また、５を越えてもそれに見合う
だけの効果は期待できない。イオン交換のスラリー濃度
は、通常行われる０．１％〜３０％で良い。The amount of iron ions added during ion exchange is ZS
The Fe/Al atomic ratio is 0.0 compared to Al in M-5.
It is desirable that it is 1-5. If it is less than 0.1, iron ions may not be exchanged sufficiently and the iron ion content may become less than 1.0 wt%, and even if it exceeds 5, no commensurate effect can be expected. The slurry concentration for ion exchange may be 0.1% to 30%, which is usually carried out.
【００１９】また、処理条件は通常行われる室温〜１０
０℃の温度、１時間〜１０日の時間であることが望まし
い。室温未満の温度、１時間未満の時間では、鉄イオン
が十分に交換されず、鉄イオン含有量が１．０ｗｔ％未
満になる恐れがあり、１００℃を越える温度、５日を越
える時間では、それに見合うだけの効果は期待できない
。また、必要に応じて、イオン交換操作を繰返し行うこ
ともできる。[0019] The processing conditions are usually room temperature to 10
Preferably, the temperature is 0°C and the time is 1 hour to 10 days. If the temperature is below room temperature and the time is less than 1 hour, the iron ions may not be exchanged sufficiently and the iron ion content may become less than 1.0 wt%. We cannot expect the effect to be commensurate with that. Moreover, the ion exchange operation can be repeated as necessary.
【００２０】イオン交換処理した試料は、固液分離、洗
浄、乾燥して使用される。また、必要に応じて焼成して
から用いることもできる。The ion-exchanged sample is used after solid-liquid separation, washing and drying. Moreover, it can also be used after baking if necessary.
【００２１】本発明の触媒のＳｉＯ２／Ａｌ２Ｏ３モル
比は、使用したゼオライト基材のＳｉＯ２／Ａｌ２Ｏ３
モル比と実質的に変わらない。また、触媒の結晶構造も
イオン交換前後で本質的に異なるものではない。The SiO2/Al2O3 molar ratio of the catalyst of the present invention is the SiO2/Al2O3 molar ratio of the zeolite base material used.
The molar ratio is virtually unchanged. Further, the crystal structure of the catalyst is not essentially different before and after ion exchange.
【００２２】本発明の触媒は、粘土鉱物等のバインダー
と混合し成形して使用することもできる。また、予めゼ
オライトを成形し、その成形体に鉄イオンをイオン交換
等で含有させることもできる。ゼオライトを成形する際
に用いられるバインダーとしては、カオリン、アタパル
ガイト、モンモリロナイト、ベントナイト、アロフェン
、セピオライト等の粘土鉱物である。あるいは、バイン
ダーを用いずに成形体を直接合成したバインダレスゼオ
ライト成形体であっても良い。また更に、コージェライ
ト製あるいは金属製等のハニカム状基材にゼオライトを
コートして用いることもできる。The catalyst of the present invention can also be used by being mixed with a binder such as a clay mineral and molded. Alternatively, zeolite may be formed in advance and iron ions may be contained in the formed body through ion exchange or the like. Binders used in forming zeolite include clay minerals such as kaolin, attapulgite, montmorillonite, bentonite, allophane, and sepiolite. Alternatively, it may be a binderless zeolite molded product that is directly synthesized without using a binder. Furthermore, a honeycomb-shaped substrate made of cordierite or metal may be coated with zeolite.
【００２３】排ガス中の窒素酸化物の還元除去は、本発
明の触媒と窒素酸化物、炭化水素及び酸素を含む排ガス
を接触させることにより行なう。本発明で用いられる排
ガスは、窒素酸化物、炭化水素及び酸素を含むことが必
須である。また、排ガス中の炭化水素等の還元成分に対
して過剰量の酸素が含まれている場合においても窒素酸
化物を効率よく還元除去できる。更に、一酸化炭素，水
素，アンモニア，水分，硫黄酸化物等が含まれている場
合にも有効である。また、酸素の含まれていない排ガス
においても十分な効果を発揮する。The reduction and removal of nitrogen oxides in the exhaust gas is carried out by bringing the catalyst of the present invention into contact with the exhaust gas containing nitrogen oxides, hydrocarbons and oxygen. It is essential that the exhaust gas used in the present invention contains nitrogen oxides, hydrocarbons, and oxygen. Further, even when the exhaust gas contains an excessive amount of oxygen with respect to reducing components such as hydrocarbons, nitrogen oxides can be efficiently reduced and removed. Furthermore, it is also effective when carbon monoxide, hydrogen, ammonia, moisture, sulfur oxides, etc. are contained. In addition, sufficient effects are exhibited even in exhaust gas that does not contain oxygen.
【００２４】本発明で処理される排ガス中の各成分ガス
の濃度は特に限定されないが、通常、窒素酸化物が５０
〜２００００ｐｐｍ、炭化水素が１０〜２００００ｐｐ
ｍ、酸素が０．１〜２０％である。[0024] The concentration of each component gas in the exhaust gas treated in the present invention is not particularly limited, but usually nitrogen oxides are
~20000ppm, hydrocarbons 10~20000ppm
m, oxygen is 0.1-20%.
【００２５】処理される排ガスの空間速度及び温度は特
に限定されないが、好ましくは空間速度（体積基準）５
００〜３０００００ｈｒ−１、温度１００℃〜８００℃
、更に好ましくは空間速度１０００〜２０００００ｈｒ
−１、温度２００℃〜７００℃である。The space velocity and temperature of the exhaust gas to be treated are not particularly limited, but are preferably space velocity (volume basis) 5.
00~300000hr-1, temperature 100℃~800℃
, more preferably a space velocity of 1000 to 200000 hr
-1, the temperature is 200°C to 700°C.
【００２６】[0026]
【発明の効果】本発明の触媒は、燃焼排ガス中の窒素酸
化物を低温においても効率良く除去できるという効果が
ある。したがって、本発明の触媒を燃焼排ガスと接触さ
せることにより、低温においても窒素酸化物を容易に除
去することができる。Effects of the Invention The catalyst of the present invention has the effect of efficiently removing nitrogen oxides from combustion exhaust gas even at low temperatures. Therefore, by bringing the catalyst of the present invention into contact with combustion exhaust gas, nitrogen oxides can be easily removed even at low temperatures.
【００２７】[0027]
【実施例】以下、実施例において本発明をさらに詳細に
説明する。しかし、本発明はこれら実施例のみに限定さ
れるものではない。EXAMPLES The present invention will be explained in more detail in the following examples. However, the present invention is not limited to these examples.
【００２８】実施例１
攪拌状態にある実容積２リットルのオーバーフロータイ
プの反応槽に、珪酸ソーダ水溶液（ＳｉＯ２；１５３ｇ
／リットル，Ｎａ２Ｏ；５０ｇ／リットル，Ａｌ２Ｏ３
；０．８ｇ／リットル）と、硫酸アルミニウム水溶液（
Ａｌ２Ｏ３；３８．４ｇ／リットル，Ｈ２ＳＯ４；２７
５ｇ／リットル）とをそれぞれ３．２リットル／ｈｒ，
０．８リットル／ｈｒの速度で連続的に供給した。反応
温度は３０〜３２℃、排出されるスラリーのｐＨは６．
４〜６．６であった。Example 1 A sodium silicate aqueous solution (SiO2; 153 g
/liter, Na2O; 50g/liter, Al2O3
;0.8g/liter) and aluminum sulfate aqueous solution (
Al2O3; 38.4g/liter, H2SO4; 27
5g/liter) and 3.2liter/hr, respectively.
It was fed continuously at a rate of 0.8 liters/hr. The reaction temperature was 30-32°C, and the pH of the slurry discharged was 6.
It was 4-6.6.
【００２９】排出スラリーを固液分離し十分水洗した後
、Ｎａ２Ｏ；１．７２ｗｔ％，Ａｌ２Ｏ３；２．５８ｗ
ｔ％，ＳｉＯ２；３９．３ｗｔ％，Ｈ２Ｏ；５６．４ｗ
ｔ％の粒状無定形アルミノ珪酸塩均一化合物を得た。
該均一化合物２，８４０ｇと１．３９ｗｔ％のＮａＯＨ
水溶液５，１６０ｇとをオートクレーブに仕込み、１６
０℃で７２時間攪拌下で結晶化した。次いで、固液分離
、十分水洗し、乾燥してＺＳＭ−５型ゼオライトを得た
。得られたＺＳＭ−５型ゼオライト５０ｇを０．１Ｎ硝
酸ナトリウム水溶液２リットルに添加し、６０℃にて一
昼夜撹拌し、固液分離、洗浄した。この操作を２回繰返
した後乾燥しＮａ型ゼオライトを得た。化学分析の結果
、その組成は無水ベースにおける酸化物のモル比で表わ
して次の組成を有していた。After solid-liquid separation of the discharged slurry and thorough washing with water, Na2O: 1.72wt%, Al2O3: 2.58w
t%, SiO2; 39.3wt%, H2O; 56.4w
A granular amorphous aluminosilicate homogeneous compound of t% was obtained. 2,840 g of the homogeneous compound and 1.39 wt% NaOH
Charge 5,160 g of aqueous solution into an autoclave,
Crystallization was carried out under stirring at 0° C. for 72 hours. Next, solid-liquid separation, thorough washing with water, and drying were performed to obtain ZSM-5 type zeolite. 50 g of the obtained ZSM-5 type zeolite was added to 2 liters of 0.1N aqueous sodium nitrate solution, stirred at 60°C all day and night, solid-liquid separated, and washed. This operation was repeated twice and then dried to obtain Na-type zeolite. As a result of chemical analysis, its composition, expressed as molar ratio of oxides on an anhydrous basis, was as follows:
【００３０】１．０Ｎａ２Ｏ，Ａｌ２Ｏ３，２２．８Ｓ
ｉＯ２
このＮａ型ゼオライト１０ｇを、０．０１２Ｎ硝酸鉄水
溶液１リットルに添加した。６０℃にて一昼夜攪拌し、
洗浄、乾燥して触媒１を得た。化学分析の結果、その組
成は無水ベースにおける酸化物のモル比で表わして次の
組成を有していた。1.0Na2O, Al2O3, 22.8S
iO2 10 g of this Na-type zeolite was added to 1 liter of 0.012N iron nitrate aqueous solution. Stir overnight at 60°C,
Catalyst 1 was obtained by washing and drying. As a result of chemical analysis, its composition, expressed as molar ratio of oxides on an anhydrous basis, was as follows:
【００３１】０．２１Ｆｅ２Ｏ３，０．２７Ｎａ２Ｏ，
Ａｌ２Ｏ３，２３．１ＳｉＯ２
Ｆｅイオンの含有量は１．６９ｗｔ％であった。0.21Fe2O3, 0.27Na2O,
The content of Al2O3,23.1SiO2 Fe ions was 1.69 wt%.
【００３２】実施例２
実施例１で得られた触媒１の窒素酸化物接触還元能を調
べた。Example 2 The nitrogen oxide catalytic reduction ability of Catalyst 1 obtained in Example 1 was investigated.
【００３３】触媒をプレス成形した後、粉砕して４２〜
８０メッシュに整粒した。その０．１ｇを常圧固定床流
通式反応管に充填した。前処理として、Ｈｅガス流通下
５℃／ｍｉｎで昇温後、触媒温度５００℃で１時間保持
した。Ｈｅガス流通下で冷却後、ＮＯ：３０００ｐｐｍ
，Ｃ２Ｈ４：３０００ｐｐｍ，Ｏ２：２．０％含有する
Ｈｅガスを２０ｍｌ／ｍｉｎで流通させ、各温度におけ
る定常活性を調べた。このときの空間速度は６０００ｈ
ｒ−１であった。定常活性は、各温度で一定間隔で分析
を行い、出口ガス成分が一定組成になった場合のＮＯか
らＮ２への転化率で示した。After press-molding the catalyst, it is pulverized and
The particles were sized to 80 mesh. 0.1 g of the solution was filled into an atmospheric fixed bed flow reaction tube. As a pretreatment, the temperature was raised at 5° C./min under He gas flow, and then the catalyst temperature was maintained at 500° C. for 1 hour. After cooling under He gas flow, NO: 3000ppm
, C2H4: 3000 ppm, O2: 2.0% He gas was flowed at 20 ml/min, and the steady-state activity at each temperature was examined. The space velocity at this time is 6000h
It was r-1. The steady-state activity was analyzed at regular intervals at each temperature, and was expressed as the conversion rate from NO to N2 when the outlet gas component had a constant composition.
【００３４】Ｎ２への転化率は次式で表される。The conversion rate to N2 is expressed by the following formula.
【００３５】
ＸＮ２＝｛２×［Ｎ２］ｏｕｔ／［ＮＯ］ｉｎ｝×１０
０ＸＮ２：ＮＯからＮ２への転化率
［Ｎ２］ｏｕｔ：出口ガスのＮ２濃度
［ＮＯ］ｉｎ： 入口ガスのＮＯ濃度各温度における
Ｎ２への転化率を表１に示す。XN2={2×[N2]out/[NO]in}×10
0XN2: Conversion rate of NO to N2 [N2] out: N2 concentration of outlet gas [NO] in: NO concentration of inlet gas Table 1 shows the conversion rate of NO to N2 at each temperature.
【００３６】[0036]
【表１】
比較例１
実施例１で得られたＮａ型ゼオライト１０ｇを、０．０
２４Ｎ酢酸銅水溶液１リットルに添加した後、６０℃で
一昼夜攪拌し、洗浄、乾燥して比較触媒１を調製した。
化学分析の結果、その組成は無水ベースにおける酸化物
のモル比で表わして次の組成を有していた。[Table 1] Comparative Example 1 10 g of Na-type zeolite obtained in Example 1 was
After adding it to 1 liter of 24N copper acetate aqueous solution, it was stirred at 60° C. all day and night, washed, and dried to prepare Comparative Catalyst 1. As a result of chemical analysis, its composition, expressed as molar ratio of oxides on an anhydrous basis, was as follows:
【００３７】１．１２ＣｕＯ，０．０３Ｎａ２Ｏ，Ａｌ
２Ｏ３，２３．３ＳｉＯ２
比較例２
比較例１で得られた比較触媒１を用いて、実施例２と同
様にして比較触媒の接触還元能を調べた。1.12CuO, 0.03Na2O, Al
2O3,23.3SiO2 Comparative Example 2 Using Comparative Catalyst 1 obtained in Comparative Example 1, the catalytic reduction ability of the comparative catalyst was investigated in the same manner as in Example 2.
【００３８】その結果を表２に示す。The results are shown in Table 2.
【００３９】[0039]
【表２】
表１，表２から明らかなように、本発明の触媒は、窒素
酸化物、炭化水素及び酸素を含有するガスと接触させる
ことによりガス中の窒素酸化物を低温においても効率よ
く除去できる性能を有する。[Table 2] As is clear from Tables 1 and 2, the catalyst of the present invention efficiently removes nitrogen oxides from the gas even at low temperatures by contacting it with a gas containing nitrogen oxides, hydrocarbons, and oxygen. It has the ability to remove.
Claims (2)
のＺＳＭ−５に鉄イオンを少なくとも１ｗｔ％含有させ
たことを特徴とする、窒素酸化物、炭化水素及び酸素を
含む排ガスから、窒素酸化物を還元除去する触媒。Claim 1: SiO2/Al2O3 molar ratio is 20 to 60
A catalyst for reducing and removing nitrogen oxides from exhaust gas containing nitrogen oxides, hydrocarbons, and oxygen, characterized in that ZSM-5 containing at least 1 wt% of iron ions.
化水素及び酸素を含む排ガスを接触させることを特徴と
する窒素酸化物還元除去方法。2. A method for reducing and removing nitrogen oxides, which comprises bringing the catalyst according to claim 1 into contact with exhaust gas containing nitrogen oxides, hydrocarbons, and oxygen.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3167501A JPH04367740A (en) | 1991-06-13 | 1991-06-13 | Catalyst and method for reducing and removing nitrogen oxide |
| JP4174988A JPH05269386A (en) | 1991-06-13 | 1992-06-10 | Catalyst for reduction removing nitrogen oxide and method for reduction removing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3167501A JPH04367740A (en) | 1991-06-13 | 1991-06-13 | Catalyst and method for reducing and removing nitrogen oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04367740A true JPH04367740A (en) | 1992-12-21 |
Family
ID=15850857
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3167501A Pending JPH04367740A (en) | 1991-06-13 | 1991-06-13 | Catalyst and method for reducing and removing nitrogen oxide |
| JP4174988A Pending JPH05269386A (en) | 1991-06-13 | 1992-06-10 | Catalyst for reduction removing nitrogen oxide and method for reduction removing |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4174988A Pending JPH05269386A (en) | 1991-06-13 | 1992-06-10 | Catalyst for reduction removing nitrogen oxide and method for reduction removing |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JPH04367740A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007330866A (en) * | 2006-06-13 | 2007-12-27 | Toyota Motor Corp | Adsorbent for treating exhaust |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100527963B1 (en) * | 1999-12-31 | 2005-11-09 | 현대자동차주식회사 | Manufacturing method of hydrothermally stable Fe/ZSM-5 zeolite catalyst |
-
1991
- 1991-06-13 JP JP3167501A patent/JPH04367740A/en active Pending
-
1992
- 1992-06-10 JP JP4174988A patent/JPH05269386A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007330866A (en) * | 2006-06-13 | 2007-12-27 | Toyota Motor Corp | Adsorbent for treating exhaust |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05269386A (en) | 1993-10-19 |
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