JPH10137597A - Catalyst for purifying nitrogen oxide - Google Patents
Catalyst for purifying nitrogen oxideInfo
- Publication number
- JPH10137597A JPH10137597A JP8300301A JP30030196A JPH10137597A JP H10137597 A JPH10137597 A JP H10137597A JP 8300301 A JP8300301 A JP 8300301A JP 30030196 A JP30030196 A JP 30030196A JP H10137597 A JPH10137597 A JP H10137597A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- nitrogen oxides
- denitration
- copper
- oxide
- 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.)
- Withdrawn
Links
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002912 waste gas Substances 0.000 abstract 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- -1 silica compound Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 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 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910006219 ZrO(NO3)2·2H2O Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229940044658 gallium nitrate Drugs 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
- 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
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はボイラ等の排ガスか
ら排出される窒素酸化物を除去する触媒に関する。The present invention relates to a catalyst for removing nitrogen oxides discharged from exhaust gas from a boiler or the like.
【０００２】[0002]
【従来の技術】大気汚染防止の観点からボイラや各種燃
焼炉から発生する窒素酸化物（ＮＯx）を防止するため
の方法として、脱硝触媒を用いてアンモニア（ＮＨ3 ）
を排ガス中に添加することによって接触的に窒素と水に
分解する選択的接触還元法が幅広く用いられている。2. Description of the Related Art As a method for preventing nitrogen oxides (NO x ) generated from a boiler or various combustion furnaces from the viewpoint of air pollution prevention, ammonia (NH 3 ) is produced using a denitration catalyst.
The catalytic catalytic reduction method of decomposing into nitrogen and water catalytically by adding methane to exhaust gas has been widely used.
【０００３】[0003]
【発明が解決しようとする課題】これまでの脱硝触媒は
ＴｉＯ2 を担体として、Ｖ2 Ｏ5 を活性金属とする触媒
が一般的であった。この触媒は耐久性に優れている実績
を有しているが、反応温度は２５０〜４００℃の範囲が
活性温度域であった。最近、種々の排ガスに対する脱硝
の必要性が高まっており、とりわけ２００℃以下の低温
域の脱硝が必要となってきている。例えば、下記の低温
脱硝の用途が挙げられる。Conventional denitration catalysts have generally used TiO 2 as a carrier and V 2 O 5 as an active metal. Although this catalyst has a track record of being excellent in durability, the reaction temperature ranged from 250 to 400 ° C. in the active temperature range. In recent years, the need for denitration of various exhaust gases has been increasing, and in particular, denitration in a low temperature range of 200 ° C. or lower has become necessary. For example, the following uses for low-temperature denitration are listed.
【０００４】(1) ごみ焼却炉用脱硝：除塵後の脱硝（温
度域：１５０〜２００℃）。 (2) 脱硫前脱硝：乾式脱硝＋湿式脱硫一体型プロセス。
なお、脱硝後のリークアンモニアは脱硫効率向上に作用
する（温度域：７０〜１３０℃）。 (3) ガスタービン起動時脱硝：運転起動時に対応（温度
域：室温〜２５０℃）。 (4) トンネル脱硝：希薄ＮＯx 大容量ガスに対応（温度
域：室温）。 これまでの触媒では上記用途に適用することはできず、
より低温で高活性な触媒の出現が望まれていた。(1) Denitration for refuse incinerator: Denitration after dust removal (temperature range: 150 to 200 ° C.). (2) Denitration before desulfurization: Dry denitration + wet desulfurization integrated process.
The leaked ammonia after denitration acts to improve the desulfurization efficiency (temperature range: 70 to 130 ° C.). (3) Denitration at start of gas turbine: Corresponds to start of operation (temperature range: room temperature to 250 ° C). (4) Tunnel denitration: Corresponds to lean NO x large volume gas (temperature range: room temperature). Conventional catalysts cannot be applied to the above applications,
There has been a demand for a catalyst that is more active at lower temperatures.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記技術水
準に鑑み、より低温で高活性な窒素酸化物浄化用触媒の
開発につき鋭意研究の結果、下記構成(1) 〜(3) を有す
る触媒を発明するに至った。Means for Solving the Problems In view of the above technical level, the present inventors have conducted intensive studies on the development of a catalyst for purifying nitrogen oxides at a lower temperature and a higher activity. As a result, the following constitutions (1) to (3) were obtained. The inventors have invented a catalyst having the same.
【０００６】(1) 排ガス中にアンモニアを添加し、排ガ
ス中の窒素酸化物を接触的に還元除去する脱硝触媒であ
って、直径が１．３〜２０ｎｍの細孔を有し、比表面積
が５００ｍ2 ／ｇ以上であり、さらに、金属酸化物に対
するケイ素酸化物のモル比が５〜１０００であるメソポ
ーラスメタロシリケートに銅を担持してなることを特徴
とする窒素酸化物浄化用触媒。(1) A denitration catalyst for catalytically reducing and removing nitrogen oxides in exhaust gas by adding ammonia to the exhaust gas, which has pores having a diameter of 1.3 to 20 nm and a specific surface area of A catalyst for purifying nitrogen oxides, wherein copper is supported on a mesoporous metallosilicate having a molar ratio of silicon oxide to metal oxide of 5 to 1000 or more, which is 500 m 2 / g or more.
【０００７】(2) メソポーラスメタロシリケートを構成
する金属がアルミニウム、鉄、ガリウム、マンガン、ク
ロム、チタン、ジルコニウム、白金、パラジウム、銅、
亜鉛、バナジウム及びホウ素よりなる群のうちの少なく
とも１種の金属であることを特徴とする上記(1) 記載の
窒素酸化物浄化用触媒。(2) The metal constituting the mesoporous metallosilicate is aluminum, iron, gallium, manganese, chromium, titanium, zirconium, platinum, palladium, copper,
The nitrogen oxide purifying catalyst according to the above (1), which is at least one metal selected from the group consisting of zinc, vanadium and boron.
【０００８】(3) メソポーラスメタロシリケートの粉末
Ｘ線回折パターンの１つピークが１．８ｎｍより大きい
面間隔を有するか、または非晶質状態であることを特徴
とする上記(1) または(2) 記載の窒素酸化物浄化用触
媒。(3) The above (1) or (2), wherein one peak of the powder X-ray diffraction pattern of the mesoporous metallosilicate has a plane spacing larger than 1.8 nm or is in an amorphous state. 21. The catalyst for purifying nitrogen oxides according to the above.
【０００９】[0009]
【発明の実施の形態】本発明で用いるメソポーラスメタ
ロシリケートはシリカ化合物、他の金属化合物及びカチ
オン系界面活性剤を反応させて合成することができる。
使用する原料のうちのシリカ化合物としてはコロイダル
シリカ、フュームドシリカ、ケイ酸ナトリウム及びアル
コキシドシリカ等が用いられ、カチオン系界面活性剤と
してはＲ1 Ｒ2 Ｒ3 Ｒ4 Ｑ+ （但し、式中のＲ1 はアル
キル基、アリール基またはアリールアルキル基であり、
Ｒ2 Ｒ3 Ｒ4 は炭素数１〜１０のアルキル基または水素
であり、Ｑ+ は窒素またはリンである）で表される有機
テンプレートをケイ素１モルあたり０．０１〜１０モル
用いて水熱法により合成することができる。BEST MODE FOR CARRYING OUT THE INVENTION The mesoporous metallosilicate used in the present invention can be synthesized by reacting a silica compound, another metal compound and a cationic surfactant.
Among the raw materials used, colloidal silica, fumed silica, sodium silicate, alkoxide silica, and the like are used as the silica compound, and R 1 R 2 R 3 R 4 Q + (wherein, R 1 is an alkyl group, an aryl group or an arylalkyl group;
R 2 R 3 R 4 is an alkyl group having 1 to 10 carbon atoms or hydrogen, and Q + is nitrogen or phosphorus). It can be synthesized by a method.
【００１０】さらに、上記に示す他の金属化合物として
は、アルミニウム、鉄、ガリウム、マンガン、クロム、
チタン、ジルコニウム、白金、パラジウム、銅、亜鉛、
バナジウム及びホウ素よりなる群のうちの少なくとも１
種の金属の化合物であり、金属酸化物に対するケイ素酸
化物のモル比が５〜１０００になるように、これら金属
化合物を添加してシリカ化合物と水熱法により複合酸化
物を形成することによりメソポーラスメタロシリケート
を合成することができる。Further, the other metal compounds shown above include aluminum, iron, gallium, manganese, chromium,
Titanium, zirconium, platinum, palladium, copper, zinc,
At least one of the group consisting of vanadium and boron
The compound is a compound of a kind metal, and the metal oxide is added so that the molar ratio of the silicon oxide to the metal oxide is 5 to 1000 to form a composite oxide with the silica compound by a hydrothermal method. Metallosilicates can be synthesized.
【００１１】次に、上記メソポーラスメタロシリケート
に活性金属の銅を担持させる方法の一つとしてはイオン
交換法があげられ、メソポーラスメタロシリケート中の
金属上に銅を配位させることによって行いうる。Next, one of the methods of supporting the active metal copper on the mesoporous metallosilicate is an ion exchange method, which can be carried out by coordinating copper on the metal in the mesoporous metallosilicate.
【００１２】（作用）上記の銅を担持したメソポーラス
メタロシリケートが低温度域の脱硝反応で高性能を示す
理由の一つとして、高比表面積を有する担体に活性金属
である銅が高分散して担持されるためであると考えられ
る。すなわち、従来のＴｉＯ2 を主成分とする担体は比
表面積が７０ｍ2 ／ｇ程度であるのに対して、本発明に
おけるメソポーラスメタロシリケートの比表面積は、５
００ｍ2 ／ｇ以上、特に１０００ｍ2 ／ｇ以上を有し、
それにより低温度域でも高活性能を有するものと考えら
れる。(Function) One of the reasons why the mesoporous metallosilicate supporting copper exhibits high performance in a denitration reaction in a low temperature range is that copper as an active metal is highly dispersed in a carrier having a high specific surface area. This is considered to be due to being carried. That is, the specific surface area of the conventional carrier mainly composed of TiO 2 is about 70 m 2 / g, whereas the specific surface area of the mesoporous metallosilicate in the present invention is 5 m 2 / g.
00m 2 / g or more, particularly having a more 1000 m 2 / g,
Thereby, it is considered that the compound has high activity even in a low temperature range.
【００１３】[0013]
【実施例】以下、本発明の窒素酸化物浄化触媒の製法の
具体例をあげ、得られた触媒の効果を明らかにする。EXAMPLES Hereinafter, specific examples of the method for producing the nitrogen oxide purifying catalyst of the present invention will be described to clarify the effects of the obtained catalyst.
【００１４】（実施例１）１３０．９ｇのシリカゾル
（日産化学製：スノーテックス２０，ＳｉＯ2 ：２０％
含有）と水：５１．１ｇに硝酸アルミニウム｛Ａｌ（Ｎ
Ｏ3 ）3 ・９Ｈ2 Ｏ｝：４．１ｇを溶解させた溶液を混
合させてＡ液とする。水２１２．７ｇに水酸化ナトリウ
ム（ＮａＯＨ）：１１．５ｇ溶解させ、ドデシルトリメ
チルアンモニウムクロライド（ＤＴＭＣ）：８２．９ｇ
を添加してＢ液とする。水１００ｇにＨ2 ＳＯ4 ：１
３．０ｇを添加してＣ液とする。Example 1 130.9 g of silica sol (manufactured by Nissan Chemical: Snowtex 20, SiO 2 : 20%)
Aluminum nitrate @ Al (N
O 3) 3 · 9H 2 O }: 4.1g were mixed solution prepared by dissolving the A solution. Sodium hydroxide (NaOH): 11.5 g is dissolved in 212.7 g of water, and dodecyltrimethylammonium chloride (DTMC): 82.9 g
To make solution B. H 2 SO 4 : 1 in 100 g of water
Add 3.0 g to make solution C.
【００１５】１リットルのオートクレーブを用いて、ま
ず、Ａ液を添加する。次にＢ液（アルカリ液）とＣ液
（酸液）を同一割合の滴下速度で供給しスラリゲルを形
成する。滴下後、室温で２時間攪拌を行う。なお、この
時の溶液のｐＨは９．５であった。次に、スラリ溶液を
１４０℃に加熱し、４８時間攪拌しながら水熱合成を行
った。合成後、スラリを洗浄、濾過し、固形分を乾燥し
た後、空気雰囲気下で５５０℃、５時間焼成を行った。
このサンプルを試料１とする。First, the solution A is added using a 1 liter autoclave. Next, the liquid B (alkali liquid) and liquid C (acid liquid) are supplied at the same dropping rate to form a slurry gel. After the addition, the mixture is stirred at room temperature for 2 hours. The pH of the solution at this time was 9.5. Next, the slurry solution was heated to 140 ° C., and hydrothermal synthesis was performed while stirring for 48 hours. After the synthesis, the slurry was washed, filtered, and the solid content was dried, and then calcined at 550 ° C. for 5 hours in an air atmosphere.
This sample is referred to as Sample 1.
【００１６】試料１の粉末Ｘ線回折パターン（ＣｕＫα
線使用）を図１に、Ｎ2 吸着法による細孔径分布を図２
に示す。図１より、この試料１は回折ピークを有さない
ことから、非晶質物質であることがわかる。また、図２
より平均細孔径は２．６ｎｍ（２６Å）である。さら
に、ＢＥＴ法により窒素吸着化表面積は１５３０ｍ2 ／
ｇでありＩＣＰ法によるＳｉＯ2 ／Ａｌ2 Ｏ3 （モル
比）は７９であった。The powder X-ray diffraction pattern of Sample 1 (CuKα
Fig. 1 shows the pore size distribution by the N 2 adsorption method.
Shown in FIG. 1 shows that this sample 1 is an amorphous substance because it has no diffraction peak. FIG.
More average pore diameter is 2.6 nm (26 °). Further, the nitrogen adsorption surface area was 1530 m 2 /
g and SiO 2 / Al 2 O 3 (molar ratio) by ICP method was 79.
【００１７】（実施例２）実施例１の合成方法におい
て、Ｃ液に添加するＨ2 ＳＯ4 量を６．０ｇとして、ス
ラリのｐＨを１３．４の状態で水熱合成を実施例１と同
様の方法で行って試料２を得た。この試料２の粉末Ｘ線
回折パターン（ＣｕＫα線使用）を図３に示す。図３よ
り、試料２は回折パターン２θ＝２．８°、４．６°、
５．５°、７．２°にピークを有することがわかり、各
々の面間隔が３．２ｎｍ、１．９ｎｍ、１．６ｎｍ、
１．２ｎｍである。なお、細孔径分布は試料１とほぼ同
様であった。またＢＥＴ法による比表面積は１４６０ｍ
2 ／ｇであり、ＩＣＰ法によるＳｉＯ2 ／Ａｌ2 Ｏ3 は
７８であった。(Example 2) In the synthesis method of Example 1, the amount of H 2 SO 4 to be added to the solution C was 6.0 g, and the hydrothermal synthesis was carried out with the slurry pH being 13.4. Sample 2 was obtained in the same manner. FIG. 3 shows a powder X-ray diffraction pattern (using CuKα rays) of Sample 2. 3, the diffraction pattern 2θ = 2.8 °, 4.6 °,
It can be seen that there are peaks at 5.5 ° and 7.2 °, and the respective plane spacings are 3.2 nm, 1.9 nm, 1.6 nm,
1.2 nm. The pore size distribution was almost the same as that of Sample 1. The specific surface area by the BET method is 1460m
2 / g, and the ratio of SiO 2 / Al 2 O 3 by the ICP method was 78.
【００１８】（実施例３）実施例２の合成方法におい
て、Ａ液を調製する際、硝酸アルミニウムの代わりに、
硝酸鉄｛Ｆｅ（ＮＯ3 ）3 ・９Ｈ2 Ｏ｝：４．４ｇ、三
塩化バナジウム（ＶＣｌ3 ）：１．７ｇ、硝酸マンガン
｛Ｍｎ（ＮＯ3 ）2 ・５Ｈ2 Ｏ｝：１．９ｇ、硝酸ガリ
ウム｛Ｇａ（ＮＯ3 ）3 ・６Ｈ2 Ｏ｝：４．３ｇ、硝酸
クロム｛Ｃｒ（ＮＯ3 ）3 ・９Ｈ2 Ｏ｝：４．４ｇ、硫
酸チタニル（ＴｉＯＳＯ4 ）：１．０ｇ、ホウ酸（Ｈ3
ＢＯ3 ）：０．７ｇ、塩化白金酸（Ｈ2 ＰｔＣｌ6 ・６
Ｈ2 Ｏ）：１．５ｇ、硝酸パラジウム｛Ｐｄ（ＮＯ3 ）
2 ｝：０．７ｇ、硝酸銅｛Ｃｕ（ＮＯ3 ）2 ・６Ｈ
2 Ｏ｝：２．０ｇ、硝酸亜鉛｛Ｚｎ（ＮＯ3 ）2 ・６Ｈ
2 Ｏ｝：２．０ｇ、オキシ硝酸ジルコニウム｛ＺｒＯ
（ＮＯ3 ）2 ・２Ｈ2 Ｏ｝：１．６ｇを添加し、実施例
２と同様の水熱合成法によってメソポーラスメタロシリ
ケートを合成した。これらの試料を試料３〜１４とす
る。なお、これら試料３〜１４の物性値を前記試料１，
２と共に後記表１に示す。Example 3 In the synthesis method of Example 2, when preparing solution A, instead of aluminum nitrate,
Iron nitrate {Fe (NO 3 ) 3 .9H 2 O}: 4.4 g, vanadium trichloride (VCl 3 ): 1.7 g, manganese nitrate {Mn (NO 3 ) 2 .5H 2 O}: 1.9 g, gallium nitrate {Ga (NO 3) 3 · 6H 2 O}: 4.3g, chromium nitrate {Cr (NO 3) 3 · 9H 2 O}: 4.4g, titanyl sulfate (TiOSO 4): 1.0g, boric Acid (H 3
BO 3): 0.7g, chloroplatinic acid (H 2 PtCl 6 · 6
H 2 O): 1.5 g, palladium nitrate @ Pd (NO 3 )
2}: 0.7 g, copper nitrate {Cu (NO 3) 2 · 6H
2 O}: 2.0g, zinc nitrate {Zn (NO 3) 2 · 6H
2 O: 2.0 g, zirconium oxynitrate {ZrO
(NO 3) 2 · 2H 2 O}: was added 1.6g, was synthesized mesoporous metallosilicate by the same hydrothermal synthesis method as in Example 2. These samples are referred to as samples 3 to 14. In addition, the physical property values of these samples 3 to 14
2 are shown in Table 1 below.
【００１９】（実施例４）実施例１の合成法において、
Ａ液を調製する際、硝酸アルミニウムの添加量を８．２
ｇ、１６．４ｇとして、実施例１と同様の方法により合
成した。これらの試料を試料１５、１６とする。Example 4 In the synthesis method of Example 1,
When preparing solution A, the amount of aluminum nitrate added was adjusted to 8.2.
g and 16.4 g were synthesized in the same manner as in Example 1. These samples are referred to as samples 15 and 16.
【００２０】さらに実施例１の合成法において、Ａ液を
調製する際、コロイダルシリカの代わりにオルトケイ酸
エチル：９１ｇ、微粒子シリカ（トクソウ製ファインシ
ールＫ−４１）：２６ｇを添加して実施例１と同様に合
成し、試料１７、１８を得た。また実施例１において、
コロイダルシリカ及び水酸化ナトリウムの代わりに３号
ケイ酸ソーダを（ＳｉＯ2 ：２９．１％、Ｎａ2 Ｏ：
９．５％）９０ｇをＢ液に添加し、実施例１と同様に合
成し、試料１９を得た。Further, in the synthesis method of Example 1, when preparing the solution A, 91 g of ethyl orthosilicate and 26 g of fine-particle silica (fine seal K-41 made by Tokusoh) were added instead of colloidal silica. Samples 17 and 18 were obtained in the same manner as described above. In Example 1,
No. 3 sodium silicate was used instead of colloidal silica and sodium hydroxide (SiO 2 : 29.1%, Na 2 O:
90 g (9.5%) was added to the solution B, and the mixture was synthesized in the same manner as in Example 1 to obtain a sample 19.
【００２１】（実施例５）実施例１の合成法においてＢ
液を調製する際、ドデシルトリメチルアンモニウムクロ
ライド（ＤＴＭＡＣ）の添加量を４１ｇ、２１ｇとして
実施例１と同様に合成し、試料２０．２１を得た。(Example 5) In the synthesis method of Example 1, B
When preparing the solution, the amount of dodecyltrimethylammonium chloride (DTMAC) added was 41 g and 21 g, and the synthesis was performed in the same manner as in Example 1 to obtain a sample 20.21.
【００２２】また、実施例１の合成法においてＢ液を調
製する際、ドデシルトリメチルクロライドの代わりにヘ
キサデシルトリメチルアンモニウムクロライド（ＨＤＴ
ＭＡＣ）及びオクタデシルトリメチルアンモニウムクロ
ライド（ＯＤＴＭＡＣ）を各々８２ｇ添加し、実施例１
と同様に水熱合成し、試料２２、２３を得た。以上の実
施例より、合成した試料１〜試料２３の比表面積を後記
表１に示す。In preparing the solution B in the synthesis method of Example 1, hexadecyltrimethylammonium chloride (HDT) was used instead of dodecyltrimethylchloride.
MAC) and octadecyltrimethylammonium chloride (ODTMAC) in an amount of 82 g each.
Samples 22 and 23 were obtained by hydrothermal synthesis in the same manner as described above. Table 1 below shows the specific surface areas of Samples 1 to 23 synthesized from the above Examples.
【００２３】（実施例６）試料１〜２３各々１０ｇを、
酢酸銅０．１ｍｏｌ／リットルの３０℃の水溶液２リッ
トルに添加して６時間攪拌してイオン交換を行った。イ
オン交換後、十分試料を洗浄して１１０℃で１２時間乾
燥を行った。乾燥後の銅の担持量をＣｕＯ換算にて下記
表１に併せて示し、粉末触媒１〜２３とする。Example 6 10 g of each of Samples 1 to 23 was
It was added to 2 liters of a 30 mol aqueous solution of copper acetate 0.1 mol / l and stirred for 6 hours to perform ion exchange. After the ion exchange, the sample was sufficiently washed and dried at 110 ° C. for 12 hours. The supported amount of copper after drying is shown in Table 1 below in terms of CuO, and is referred to as powder catalysts 1 to 23.
【００２４】[0024]
【表１】 [Table 1]
【００２５】（実施例７）粉末触媒１〜２３を脱硝反応
試験を行った。反応試験条件を下記表２に示す。Example 7 A denitration reaction test was performed on the powdered catalysts 1 to 23. The reaction test conditions are shown in Table 2 below.
【００２６】[0026]
【表２】 [Table 2]
【００２７】脱硝率はＮＯx （ＮＯ＋ＮＯ2 ）の減少率
より求めた。ＮＯ及びＮＯ2 の濃度は質量分析計により
求めた。触媒１〜２３の脱硝率を前記表１に併せて示
す。表１に示すように、本発明触媒は少量のサンプルに
て低温において高活性を示し、窒素酸化物浄化用触媒と
して有望である。The denitration rate was determined from the reduction rate of NO x (NO + NO 2 ). NO and NO 2 concentrations were determined by mass spectrometry. The denitration rates of the catalysts 1 to 23 are also shown in Table 1 above. As shown in Table 1, the catalyst of the present invention shows high activity at a low temperature in a small amount of sample, and is promising as a catalyst for purifying nitrogen oxides.
【００２８】[0028]
【発明の効果】以上の結果のとおり、本発明触媒は低温
域で高活性な窒素酸化物浄化用触媒であり、有望な触媒
として実用化が期待できる。As described above, the catalyst of the present invention is a catalyst for purifying nitrogen oxides which is highly active in a low temperature range and is expected to be put to practical use as a promising catalyst.
【図１】本発明の一実施例に係る試料（触媒）１のＸ線
回折パターンを示すグラフ。FIG. 1 is a graph showing an X-ray diffraction pattern of a sample (catalyst) 1 according to one example of the present invention.
【図２】本発明の一実施例に係る試料１の細孔径分布を
示すグラフ。FIG. 2 is a graph showing a pore size distribution of Sample 1 according to one example of the present invention.
【図３】本発明の一実施例に係る試料２のＸ線回折パタ
ーンを示すグラフ。FIG. 3 is a graph showing an X-ray diffraction pattern of Sample 2 according to one example of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 23/80 ＺＡＢ Ｂ０１Ｄ 53/36 ＺＡＢ 23/835 ＺＡＢ １０２Ｄ 23/84 ＺＡＢ １０２Ｈ 23/89 ＺＡＢ Ｂ０１Ｊ 23/74 ３０１Ａ 23/82 ＺＡＢＡ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI B01J 23/80 ZAB B01D 53/36 ZAB 23/835 ZAB 102D 23/84 ZAB 102H 23/89 ZAB B01J 23/74 301A 23/82 ZABA
Claims (3)
中の窒素酸化物を接触的に還元除去する脱硝触媒であっ
て、直径が１．３〜２０ｎｍの細孔を有し、比表面積が
５００ｍ2 ／ｇ以上であり、さらに、金属酸化物に対す
るケイ素酸化物のモル比が５〜１０００であるメソポー
ラスメタロシリケートに銅を担持してなることを特徴と
する窒素酸化物浄化用触媒。1. A denitration catalyst for adding ammonia to an exhaust gas to catalytically reduce and remove nitrogen oxides in the exhaust gas, having pores having a diameter of 1.3 to 20 nm and a specific surface area of 500 m 2 / g or more, further, nitrogen oxide purification catalyst molar ratio of silicon oxide to metal oxide is characterized by being obtained by carrying copper mesoporous metallosilicate is 5 to 1,000.
る金属がアルミニウム、鉄、ガリウム、マンガン、クロ
ム、チタン、ジルコニウム、白金、パラジウム、銅、亜
鉛、バナジウム及びホウ素よりなる群のうちの少なくと
も１種の金属であることを特徴とする請求項１記載の窒
素酸化物浄化用触媒。2. The metal constituting the mesoporous metallosilicate is at least one metal selected from the group consisting of aluminum, iron, gallium, manganese, chromium, titanium, zirconium, platinum, palladium, copper, zinc, vanadium and boron. 2. The catalyst for purifying nitrogen oxides according to claim 1, wherein:
線回折パターンの１つピークが１．８ｎｍより大きい面
間隔を有するか、または非晶質状態であることを特徴と
する請求項１または２記載の窒素酸化物浄化用触媒。3. Powder X of mesoporous metallosilicate
3. The catalyst for purifying nitrogen oxides according to claim 1, wherein one peak of the line diffraction pattern has a plane spacing larger than 1.8 nm or is in an amorphous state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8300301A JPH10137597A (en) | 1996-11-12 | 1996-11-12 | Catalyst for purifying nitrogen oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8300301A JPH10137597A (en) | 1996-11-12 | 1996-11-12 | Catalyst for purifying nitrogen oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10137597A true JPH10137597A (en) | 1998-05-26 |
Family
ID=17883141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8300301A Withdrawn JPH10137597A (en) | 1996-11-12 | 1996-11-12 | Catalyst for purifying nitrogen oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10137597A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001019731A1 (en) * | 1999-09-09 | 2001-03-22 | Kubota Corporation | Novel compound and microporous material and method for production thereof |
| WO2004096888A1 (en) * | 2003-05-02 | 2004-11-11 | The Circle For The Promotion Of Science And Engineering | Catalysts and processes for production of polymers |
| US7632769B2 (en) | 2004-07-26 | 2009-12-15 | Hiroshi Okamoto | Zirconia porous body and manufacturing method thereof |
| JP2010051836A (en) * | 2008-08-26 | 2010-03-11 | Babcock Hitachi Kk | Nitrogen oxide purifying catalyst and nitrogen oxide purifying method |
| JP2013136034A (en) * | 2011-12-28 | 2013-07-11 | Isuzu Motors Ltd | Urea scr catalyst and exhaust gas post-treatment system |
| CN114790406A (en) * | 2022-05-20 | 2022-07-26 | 浙江桃花源环保科技有限公司 | Fuel additive for inhibiting generation of nitrogen-containing pollutants in biomass fuel combustion |
-
1996
- 1996-11-12 JP JP8300301A patent/JPH10137597A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001019731A1 (en) * | 1999-09-09 | 2001-03-22 | Kubota Corporation | Novel compound and microporous material and method for production thereof |
| WO2004096888A1 (en) * | 2003-05-02 | 2004-11-11 | The Circle For The Promotion Of Science And Engineering | Catalysts and processes for production of polymers |
| US7632769B2 (en) | 2004-07-26 | 2009-12-15 | Hiroshi Okamoto | Zirconia porous body and manufacturing method thereof |
| US7642210B2 (en) | 2004-07-26 | 2010-01-05 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Zirconia porous body and manufacturing method thereof |
| JP2010051836A (en) * | 2008-08-26 | 2010-03-11 | Babcock Hitachi Kk | Nitrogen oxide purifying catalyst and nitrogen oxide purifying method |
| JP2013136034A (en) * | 2011-12-28 | 2013-07-11 | Isuzu Motors Ltd | Urea scr catalyst and exhaust gas post-treatment system |
| CN114790406A (en) * | 2022-05-20 | 2022-07-26 | 浙江桃花源环保科技有限公司 | Fuel additive for inhibiting generation of nitrogen-containing pollutants in biomass fuel combustion |
| CN114790406B (en) * | 2022-05-20 | 2023-05-30 | 浙江桃花源环保科技有限公司 | Fuel additive for inhibiting generation of nitrogenous pollutants in biomass fuel combustion |
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|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20040203 |