JPH0299143A - Catalyst for removing nitrogen oxide - Google Patents
Catalyst for removing nitrogen oxideInfo
- Publication number
- JPH0299143A JPH0299143A JP63253387A JP25338788A JPH0299143A JP H0299143 A JPH0299143 A JP H0299143A JP 63253387 A JP63253387 A JP 63253387A JP 25338788 A JP25338788 A JP 25338788A JP H0299143 A JPH0299143 A JP H0299143A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- catalyst
- mordenite
- nitrogen oxides
- removing nitrogen
- 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 122
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000013065 commercial product Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229940086367 carbon dioxide 12 % Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、ボイラー等から排出される燃焼後の排ガス中
に含まれる窒素酸化物を、アンモニアを還元剤として接
触還元法により除去する際に使用する触媒に関する。よ
り詳しく述べれば、４００〜７００℃もの高い排ガス温
度において、排ガスに含まれる窒素酸化物を高い除去率
で除去するための固体酸触媒に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a method for removing nitrogen oxides contained in post-combustion exhaust gas discharged from a boiler etc. by a catalytic reduction method using ammonia as a reducing agent. Concerning the catalyst used. More specifically, the present invention relates to a solid acid catalyst for removing nitrogen oxides contained in exhaust gas at a high removal rate at exhaust gas temperatures as high as 400 to 700°C.
〈従来の技術〉
大気汚染防止を目的として行われる、ボイラー等から排
出される燃焼後の排ガス中に含まれる窒素酸化物の除去
については、触媒の存在下、アンモニアを還元剤として
用いる接触還元法が、現在、工業的方法として最も普及
している。<Prior art> For the purpose of air pollution prevention, the removal of nitrogen oxides contained in post-combustion exhaust gas discharged from boilers, etc. is carried out using a catalytic reduction method that uses ammonia as a reducing agent in the presence of a catalyst. However, it is currently the most popular industrial method.
上記接触還元法は、排ガス中の窒素酸化物とアンモニア
とを触媒の存在のもとに反応させて、水と窒素ガス（Ｎ
２）に還元処理する方法である。The above catalytic reduction method involves reacting nitrogen oxides and ammonia in exhaust gas in the presence of a catalyst, and then reacting with water and nitrogen gas (N
2) is a method of reduction processing.
上記方法において用いる還元触媒としては、比表面積の
大きな活性酸化チタンを担体とし、該担体に活性成分と
しての酸化タングステン、酸化バナジウム、酸化鉄、酸
化モリブデン、酸化スズなどを担持させたものが知られ
ている。Known reduction catalysts used in the above method include activated titanium oxide with a large specific surface area as a carrier, on which active ingredients such as tungsten oxide, vanadium oxide, iron oxide, molybdenum oxide, and tin oxide are supported. ing.
また、大きな比表面積を有する酸化アルミニウムを担体
とし、この担体に酸化タングステン、酸化バナジウムな
どの金属酸化物を担持させた触媒も知られている。Also known are catalysts in which aluminum oxide having a large specific surface area is used as a carrier, and metal oxides such as tungsten oxide and vanadium oxide are supported on this carrier.
ところで、重油又は石炭の燃焼ガスのように硫黄酸化物
を含有する排ガス中に含まれる窒素酸化物を除去するた
めの触媒の担体として用いられる金属酸化物としては、
硫黄酸化物に対する耐被毒性の点で、酸化チタンが最も
好適であると言われている。By the way, metal oxides used as catalyst carriers for removing nitrogen oxides contained in exhaust gas containing sulfur oxides, such as combustion gas of heavy oil or coal, include:
Titanium oxide is said to be the most suitable in terms of its resistance to poisoning by sulfur oxides.
〈発明が解決しようとする課題〉
しかしながら、上記従来の触媒は、酸化チタンを担体と
するものも含め、いずれも排ガス温度が２５０〜４００
℃と低い場合にしか好適に使用し得ない。これは、排ガ
ス温度が２５０℃未満の場合は、酸性硫安等の発生が避
けられず、より下流に配される他の機器の腐蝕の原因に
なるとともに、触媒の細孔の閉塞などにより触媒劣化の
原因になるからである。また、排ガス温度が４００℃を
越える場合は、ＮＨ３の酸化によりＮｏが生成するとい
う逆反応が次第に優勢となるため、脱硝性能が著しく低
下するとともに、触媒の熱劣化が不可避的に生じるから
である。<Problems to be Solved by the Invention> However, all of the above conventional catalysts, including those using titanium oxide as a carrier, have exhaust gas temperatures of 250 to 400.
It can only be suitably used at temperatures as low as ℃. This is because when the exhaust gas temperature is below 250°C, the generation of acidic ammonium sulfate, etc. is unavoidable, which causes corrosion of other equipment located further downstream, and also causes catalyst deterioration due to blockage of catalyst pores, etc. This is because it causes Furthermore, if the exhaust gas temperature exceeds 400°C, the reverse reaction of oxidizing NH3 to generate No will gradually become dominant, resulting in a marked decline in denitrification performance and unavoidable thermal deterioration of the catalyst. .
このため、上記従来の触媒は、４００℃を越える高温下
にある排ガス中の窒素酸化物除去用触媒としては、満足
のいくものではなかった。For this reason, the above-mentioned conventional catalyst was not satisfactory as a catalyst for removing nitrogen oxides from exhaust gas at a high temperature exceeding 400°C.
本発明は以上の事情に鑑みなされたものであって、その
目的とするところは、４００〜７００℃の高温において
も高い窒素酸化物除去率を可能ならしめる触媒を提供す
ることにある。The present invention was made in view of the above circumstances, and its object is to provide a catalyst that enables a high nitrogen oxide removal rate even at high temperatures of 400 to 700°C.
く課題を解決するための手段〉
上記目的を達成するための本発明に係る窒素酸化物除去
用触媒は、組成式：ＭＡ−Ｈ（ｘ−ｚ −Ｂ）・Ｎａ（
ｚ−Ｃ） ［（八Ω０２）ｘ・（ＳｉＯ２）ｙ］ ・
ｍＨ２Ｏで表され、且つ、前記組成式中の金属Ｍの酸化
物生成エンタルピー−△Ｈ０が８０ （Ｋｃａｌ ／酸
素グラム原子）以上である金属置換モルデナイトを含有
する。Means for Solving the Problems> The catalyst for removing nitrogen oxides according to the present invention for achieving the above objects has a composition formula: MA-H(x-z-B)・Na(
z-C) [(8Ω02)x・(SiO2)y] ・
It contains metal-substituted mordenite, which is expressed as mH2O and has an oxide formation enthalpy -ΔH0 of metal M in the above compositional formula of 80 (Kcal/oxygen gram atom) or more.
ただし、上記組成式において、金属Ｍは原子価が（Ｂ＋
Ｃ）／Ａである多価金属、
（ｚ−ｃ）／ｘ（モル比）は０．３５以下、ｙ／ｘ （
モル比）は５以上、Ａ／ｘ（モル比）は０．３以上であ
る。However, in the above compositional formula, the valence of metal M is (B+
C)/A polyvalent metal, (z-c)/x (molar ratio) is 0.35 or less, y/x (
molar ratio) is 5 or more, and A/x (molar ratio) is 0.3 or more.
本発明において、（ｚ−ｃ）／ｘが０．３５以下のもの
に特定したのは、置換されたＨ＋によって形成される酸
型モルデナイトの強酸点にアンモニアが強く結合し、こ
れによって高温下においてアンモニアが酸化されてＮｏ
が生成してしまうという逆反応を効果的に抑制すること
ができるからである。In the present invention, (z-c)/x is specified to be 0.35 or less because ammonia strongly binds to the strong acid site of acid type mordenite formed by substituted H+, and this causes Ammonia is oxidized and No
This is because it is possible to effectively suppress the reverse reaction in which .
また、ｙ／ｘが５以上のものに特定したのは、ｙ ／
ｘが大きくなるにつれて酸型モルデナイトの耐熱性が向
上し、５以上の場合に４００℃〜７００℃もの高温領域
においても安定な担体になるからである。In addition, those with y/x of 5 or more were specified as y/x.
This is because the heat resistance of acid type mordenite improves as x increases, and when x is 5 or more, it becomes a stable support even in a high temperature range of 400°C to 700°C.
なお、５≦ｙ／ｘ＜１５のものが好ましい。Note that 5≦y/x<15 is preferable.
ｙ／ｘが１５以上の場合、酸型モルデナイトの酸強度が
低下してしまい、上記高温領域で好適に機能する触媒を
得ることが困難になるからである。This is because when y/x is 15 or more, the acid strength of the acid type mordenite decreases, making it difficult to obtain a catalyst that functions suitably in the above-mentioned high temperature range.
金属Ｍを酸化物生成エンタルピー−ΔＨ’が８０以上の
ものに特定し、且つ、Ａ／ｘを０．３以上に特定したの
は、この場合に、金属Ｍにより形成された活性点のＮＨ
３に対する酸化力が適切に制御され、Ｎ２が生成し易く
なり、触媒反応が良好に進行するからである。The reason why we specified the metal M as having an oxide formation enthalpy -ΔH' of 80 or more and specifying A/x as 0.3 or more is that the NH of the active site formed by the metal M
This is because the oxidizing power for 3 is appropriately controlled, N2 is easily generated, and the catalytic reaction progresses favorably.
上記本発明に係る窒素酸化物除去用触媒は、種々の方法
を用いて調製することができる。The catalyst for removing nitrogen oxides according to the present invention can be prepared using various methods.
先ず、組成式：Ｎａｘ［（ＡΩ０２）ｘ。First, the composition formula: Nax[(AΩ02)x.
（Ｓ ｉｏｚ ） ）’］ ・ｍＨｚ Ｏ（上記酸型
モ／ｌ／ テｆイトの組成式において、Ａ−０，１３＋
ｃ−Ｑ。(S ioz ))'] ・mHz O (In the composition formula of the acid type mo/l/tefite, A-0,13+
c-Q.
ｘ ｍ ｚ ＋Ｂの場合に相当する）で表されるＮ型モ
ルデナイトを出発物質として用いる方法について説明す
る。A method using N-type mordenite (corresponding to the case of x m z +B) as a starting material will be described.
この方法において用いられるＮ型モルデナイトの市販品
としては、ＮＭ−１００Ｐ （商品名、日本化学社製）
、ＴＳＺ−６０ＯＮＡＡ （商品名、東ソー社製）
、ＴＳＺ−６２ＯＮＡＡ （商品名、東ソー社製）及び
ＴＳＺ−６４ＯＮＡＡ （商品名、東ソー社製）が例示
される。Commercially available N-type mordenite used in this method includes NM-100P (trade name, manufactured by Nihon Kagaku Co., Ltd.).
, TSZ-60ONAA (product name, manufactured by Tosoh Corporation)
, TSZ-62ONAA (trade name, manufactured by Tosoh Corporation) and TSZ-64ONAA (trade name, manufactured by Tosoh Corporation).
市販の上記Ｎ型モルデナイトを０．ＩＮ（規定濃度）の
ＨＣＮ、１〜３ＮのＮＨａＣＮ溶液などに、常温又は加
熱下で必要回数繰り返し浸漬することにより、Ｎａ＋の
一部をＨ＋又はＮＨ４＋で置換して、（ｚ−ｃ）／ｘが
０．３５以下の酸型モルデナイトを調製する（ステップ
１）。The commercially available N-type mordenite was 0. By repeatedly immersing IN (specified concentration) HCN, 1-3N NHaCN solution, etc. at room temperature or under heating as many times as necessary, a part of Na+ is replaced with H+ or NH4+, and (z-c)/x Acid type mordenite with a value of 0.35 or less is prepared (Step 1).
次いで、１〜３ＮのＨＣΩ溶液に、常温又は加熱下で必
要回数繰り返し浸漬して、所望のｙ／ｘの酸型モルデナ
イトを調製する（ステップ２）。Next, acid type mordenite of desired y/x is prepared by repeatedly immersing it in a 1 to 3N HCΩ solution at room temperature or under heating a necessary number of times (Step 2).
さらに、その酸化物の生成エンタルピー〜△Ｈ０が８０
以上の金属Ｍの塩化物溶液などを用いて常温又は加熱下
で浸漬処理を必要回数繰り返し、金属ＭでＨ＋の一部を
置換することにより、＾／Ｘが０．３以上の金属置換モ
ルデナイトを調製する（ステップ３）。なお、ステップ
１〜３の処理は、上記の順序で行う必要はない。例えば
、ステップ２の操作の後にステップ３の操作を、又は、
その逆の順序で操作を行うことにより、（Ｚ−Ｃ）／Ｘ
がある値の金属置換モルデナイトを作製する。得られた
金属置換モルデナイトの（ｚ−ｃ）／ｘが０．３５を越
える場合にのみ、さらにステップ１の操作を行って、最
終的に（ｚ−ｃ）／ｘが０６３５以下の所定の金属置換
モルデナイトを調製する。Furthermore, the enthalpy of formation of the oxide ~△H0 is 80
Metal-substituted mordenite with ^/X of 0.3 or more can be obtained by repeating the immersion treatment a necessary number of times at room temperature or under heating using the above chloride solution of metal M, and replacing a part of H+ with metal M. Prepare (Step 3). Note that the processes of steps 1 to 3 do not need to be performed in the above order. For example, after the operation in step 2, the operation in step 3 is performed, or
By performing the operations in the reverse order, (Z-C)/X
A metal-substituted mordenite with a certain value is prepared. Only when (z-c)/x of the obtained metal-substituted mordenite exceeds 0.35, the operation in step 1 is further performed to finally obtain a predetermined metal whose (z-c)/x is 0635 or less. Prepare substituted mordenite.
次に、組成式Ｈ（ｘ −（ｚ−ｃ） ）Ｎａ （ｚ−ｃ
） ［（ＡｆＩ０２ ） ｘ ・（ＳｉＯ２）ｙコ
・ｍＨｚ０（上記金属置換モルデナイトの組成式におい
て、Ａ−０、且つ、Ｂ＋ｃ−０の場合に相当する）で表
される酸型モルデナイトを出発物質として用いる方法に
ついて述べる。Next, the composition formula H(x-(z-c))Na(z-c
) [(AfI02) x ・(SiO2)y co
- A method using acid type mordenite represented by mHz0 (corresponding to A-0 and B+c-0 in the composition formula of the metal-substituted mordenite) as a starting material will be described.
上記酸型モルデナイトの市販品としては、ＴＳＺ−６０
０ＨＯＡ （商品名、東ソー社製）、ＴＳＺ−６２０Ｈ
ＯＡ （商品名、東ソー社製）及びＴＳＺ−６４０ＨＯ
Ａ （商品名、東ソー社製）が例示される。As a commercially available product of the above acid type mordenite, TSZ-60
0HOA (product name, manufactured by Tosoh Corporation), TSZ-620H
OA (product name, manufactured by Tosoh Corporation) and TSZ-640HO
A (trade name, manufactured by Tosoh Corporation) is exemplified.
上記酸型モルデナイトを用いる場合には、Ｎ型モルデナ
イトを用いる場合におけるステップ１の操作は基本的に
は省略することができ、ステップ２の操作及びステップ
３の操作を順序を問わず行えばよい。When using the above-mentioned acid type mordenite, the operation of step 1 when using N type mordenite can basically be omitted, and the operation of step 2 and step 3 may be performed in any order.
ステップ２の操作及びステップ３の操作により得られた
金属置換モルデナイトを、濾別、乾燥後、３００〜８０
０℃の温度で焼成する。After filtering and drying the metal-substituted mordenite obtained by the operations in step 2 and step 3,
Calcinate at a temperature of 0°C.
なお、上記ステップ３の操作において用いる金属酸化物
としては、Ｎｂ２０５、Ｃｒ２０３ＺｎＯ，ＣｅＯ２、
Ｔａ２０５、Ｌａ２０ｓ及びＨｆＯ２が例示される。Note that the metal oxides used in the operation of step 3 above include Nb205, Cr203ZnO, CeO2,
Examples include Ta205, La20s and HfO2.
また、賦形性等を高めるために、触媒調製段階において
、成形助剤、無機繊維等の成形体補強剤、有機結着剤な
どを適宜配合してもよい。Further, in order to improve shapeability etc., a molding aid, a molded body reinforcing agent such as an inorganic fiber, an organic binder, etc. may be appropriately blended in the catalyst preparation stage.
〈実施例〉
以下、実施例と共に比較例を挙げて本発明を説明するが
、本発明はこれら実施例により何ら限定されるものでは
ない。<Examples> Hereinafter, the present invention will be explained by giving Examples and Comparative Examples, but the present invention is not limited to these Examples in any way.
（実施例１）
組成式：ＮａＸ［（ＡｐＯ２）ｘ・
（Ｓ ｉ ０２ ） ｙ ］ ・ｍＩ（ｔＯであられ
され、且つ、ｙ／ｘが６．３のＮ型モルデナイトの市販
品、ＮＭ−１００Ｐ （商品名、日本化学社製）５００
ｇを２ＮのＮＨ４Ｃｇ溶液３１に浸漬し、７０〜８０℃
の温度で２時間攪拌した後、濾別した。この操作を数回
繰返し行い、Ｈ（ｘ −（ｚ−ｃ） １φＮａ（ｚ−ｃ
） ［（ＡｊｌｌＯｇ）ｘΦ（Ｓ ｉ Ｏｔ ）ｙ
ｌ ・ｍＨｚ ０で表される、（ｚ−ｃ）／ｘが０，
０１のケーキ状の酸型モルデナイトを得た。次いで、こ
の酸型モルデナイトを、０，１モル／ｇのＣｅＣｌ３溶
液５１中に浸漬して、還流器付き三日フラスコ中で９０
〜１００℃の温度で５時間攪拌後、濾別した。これら浸
漬、攪拌および濾別の各操作を繰返し行うことにより、
組成式：ＭＡ −Ｈ（ｘ−ｚ−Ｂ）Ｎａ （ｚ−ｃ）
［（Ａ、ｌＪ ０２ ） ｘ ・（Ｓ ｉｏｚ ）
ｙｌ ・ｍＨｚ Ｏで示される、Ａ／ｘが０．５７の
ケーキ状の金属置換モルデナイトを調製した。この金属
置換モルデナイトを、１００℃の温度で８時間乾燥した
後、さらに５００℃の温度で３時間焼成した。次いで焼
成物を冷却後、サンプルミルにて粉砕した。次いでセラ
ミックファイバー製基材を上記金属置換モルデナイトを
含有するスラリー中（濃度５００ｇ／Ｎ）に浸漬し、過
剰のスラリーを除去して乾燥した後、８００℃の温度で
３時間焼成し、窒素酸化物除去用の金属置換モルデナイ
ト担持触媒を得た。このとき、セラミックファイバー基
材に対する金属置換型モルデナイトの重量は２倍であっ
た。(Example 1) Compositional formula: NaX[(ApO2)x・(S i 02 ) y ] ・mI (commercial product of N-type mordenite, NM-100P, which is abraded with tO and has a y/x of 6.3) (Product name, manufactured by Nihon Kagaku Co., Ltd.) 500
g was immersed in 2N NH4Cg solution 31 and heated to 70-80℃.
After stirring at a temperature of 2 hours, the mixture was filtered. Repeat this operation several times to obtain H(x - (z-c) 1φNa(z-c
) [(AjllOg)xΦ(S i Ot )y
l ・mHz 0, (z-c)/x is 0,
A cake-like acid type mordenite of No. 01 was obtained. Next, this acid type mordenite was immersed in a 0.1 mol/g CeCl solution 51 and heated for 90 min in a reflux-equipped three-day flask.
After stirring for 5 hours at a temperature of ~100°C, it was filtered off. By repeating these soaking, stirring and filtration operations,
Compositional formula: MA-H(x-z-B)Na (z-c)
[(A, lJ 02 ) x ・(S ioz )
A cake-like metal-substituted mordenite with A/x of 0.57, expressed as yl .mHz O, was prepared. After drying this metal-substituted mordenite at a temperature of 100°C for 8 hours, it was further calcined at a temperature of 500°C for 3 hours. Next, the fired product was cooled and then ground in a sample mill. Next, the ceramic fiber base material was immersed in the slurry containing the metal-substituted mordenite (concentration 500 g/N), excess slurry was removed and dried, and then fired at a temperature of 800°C for 3 hours to remove nitrogen oxides. A metal-substituted mordenite supported catalyst for removal was obtained. At this time, the weight of the metal-substituted mordenite was twice that of the ceramic fiber base material.
（実施例２）
浸漬、攪拌および濾別の各操作の繰返し回数を変えたこ
と以外は実施例１と全く同様にして、＾／Ｘが０．４６
の窒素酸化物除去用触媒を得た。(Example 2) The same procedure as in Example 1 was carried out except that the number of repetitions of each operation of dipping, stirring, and filtration was changed, and ^/X was 0.46.
A catalyst for removing nitrogen oxides was obtained.
（実施例３）
浸漬、攪拌および濾別の各操作の繰返し回数を変えたこ
と以外は実施例１と全く同様にして、Ａｌｘが０．２９
の窒素酸化物除去用触媒を得た。(Example 3) Al
A catalyst for removing nitrogen oxides was obtained.
（比較例１）
Ｃｅ０２溶液の濃度を０．０５モル／Ωに、処理温度を
４０〜５０℃に変えたこと以外は実施例１と全く同様に
して、Ａｌｘが０．２１の窒素酸化物除去用触媒を得た
。(Comparative Example 1) Nitrogen oxides with Alx of 0.21 were removed in the same manner as in Example 1 except that the concentration of the Ce02 solution was changed to 0.05 mol/Ω and the treatment temperature was changed to 40 to 50°C. A catalyst for use was obtained.
（実施例４）
２ＮのＮＨ４ＣＮ溶液に代えてＩＮの
ＮＨ４ＣΩ溶液を用い、また７０〜８０℃の攪拌温度を
常温に代えたこと以外は実施例１と全く同様にして、（
ｚ−ｃ）／ｘが０．１７の窒素酸化物除去用触媒を得た
。(Example 4) In the same manner as in Example 1, except that IN NH4CΩ solution was used instead of 2N NH4CN solution, and the stirring temperature of 70 to 80°C was changed to room temperature, (
A catalyst for removing nitrogen oxides with z−c)/x of 0.17 was obtained.
（実施例５）
浸漬、攪拌および濾別の各操作の繰返し回数を変えたこ
と以外は実施例４と全く同様にして、（ｚ−ｃ）／ｘが
０．３１の窒素酸化物除去用触媒を得た。(Example 5) A catalyst for removing nitrogen oxides with (z-c)/x of 0.31 was prepared in the same manner as in Example 4 except that the number of repetitions of each operation of dipping, stirring, and filtration was changed. I got it.
（比較例２）
浸漬、攪拌および濾別の各操作の繰返し回数を変えたこ
と以外は実施例４と全く同様にして、（ｚ−ｃ）／ｘが
０．３８の窒素酸化物除去用触媒を得た。(Comparative Example 2) A catalyst for removing nitrogen oxides with (z-c)/x of 0.38 was prepared in exactly the same manner as in Example 4 except that the number of repetitions of each operation of dipping, stirring, and filtration was changed. I got it.
（実施例６）
ＣｅＣΩ３溶液に代えてＬａ２Ｏ３溶液を用いたこと以
外は、実施例１と全く同様にしてＡｌｘが０．５２の窒
素酸化物除去用触媒を得た。(Example 6) A catalyst for removing nitrogen oxides having Alx of 0.52 was obtained in exactly the same manner as in Example 1 except that a La2O3 solution was used in place of the CeCΩ3 solution.
（実施例７）
ＣｅＣｊ）３溶液に代えてＴａＣｆ１ｓの塩酸酸性溶液
を用いたこと以外は、実施例１と全く同様にしてＡｌｘ
が０．５５の窒素酸化物除去用触媒を得た。(Example 7) Alx
A catalyst for removing nitrogen oxides with 0.55 was obtained.
（実施例８）
ＣｅＣ［３溶液に代えてＮｂＣＮ３の塩酸酸性溶液を用
いたこと以外は、実施例１と全く同様にしてＡｌｘが０
，６１の窒素酸化物除去用触媒を得た。(Example 8) Al
, 61 was obtained.
（実施例９）
ＣｅＣ，Ｑ３溶液に代えてＣｒ２ＣＪ７３６Ｈ２０溶液
を用いたこと以外は、実施例１と全く同様にしてＡｌｘ
が０゜５６の窒素酸化物除去用触媒を得た。(Example 9) Alx
A catalyst for removing nitrogen oxides with a diameter of 0°56 was obtained.
（比較例３）
ＣｅＣΩ３溶液に代えてＩｎＣＲ３溶液を用いたこと以
外は、実施例１と全く同様にしてＡｌｘが０．５５の窒
素酸化物除去用触媒を得た。(Comparative Example 3) A catalyst for removing nitrogen oxides having Alx of 0.55 was obtained in exactly the same manner as in Example 1, except that an InCR3 solution was used in place of the CeCΩ3 solution.
（比較例４）
ＣｅＣ，Ｑ３溶液に代えてＦｅＣΩ３−６Ｈ２０溶液を
用いたこと以外は、実施例１と全く同様にしてＡｌｘが
０．５７の窒素酸化物除去用触媒を得た。(Comparative Example 4) A catalyst for removing nitrogen oxides having Alx of 0.57 was obtained in exactly the same manner as in Example 1, except that a FeCΩ3-6H20 solution was used in place of the CeC,Q3 solution.
（実施例１０）
実施例１で得た酸型モルデナイト５００ｇを、３Ｎ濃度
のＨＣＩＪ５Ω中に浸漬し、還流器付三日フラスコ中で
、９０〜１００℃で５時間酸処理をした後、濾別した。(Example 10) 500 g of acid type mordenite obtained in Example 1 was immersed in HCIJ5Ω with a 3N concentration, acid-treated at 90 to 100°C for 5 hours in a 3-day flask equipped with a reflux device, and then filtered. did.
この操作を数回繰返し行い最終的にｙ ／ ｘが７．６
のケーキ状の酸型モルデナイトを得、以後、実施例１と
全く同様にしてＡｌｘが０．５７の窒素酸化物除去用触
媒を得た。Repeat this operation several times until finally y/x is 7.6
A cake-like acid type mordenite was obtained, and thereafter, in exactly the same manner as in Example 1, a catalyst for removing nitrogen oxides having Alx of 0.57 was obtained.
（実施例１１）
実施例］０において、最終的にｙ ／ ｘが１２．１の
ものを得たこと以外は実施例１０と全く同様にしてＡｌ
ｘが０．５７の窒素酸化物除去用触媒を得た。(Example 11) In Example 0, Al
A catalyst for removing nitrogen oxides with x of 0.57 was obtained.
（実施例１２）
実施例１０において、ｙ／ｘが１５．２のものを得たこ
と以外は、実施例１０と全く同様にしてＡｌｘが０．５
７の窒素酸化物除去用触媒を得た。(Example 12) Alx was 0.5 in the same manner as in Example 10 except that y/x was 15.2.
A catalyst for removing nitrogen oxides No. 7 was obtained.
（実施例１３）
実施例１において、ＮＭ−１００Ｐの代わりに、ｙ ／
ｘが５，１のＮ型モルデナイトの別の市販品、ＴＳＺ
−６０ＯＮＡＡ （東ソー社製）を用いたこと以外は、
実施例１と全く同様にして窒素酸化物除去用触媒を得た
。(Example 13) In Example 1, instead of NM-100P, y/
Another commercial product of N-type mordenite, TSZ, where x is 5,1
-60ONAA (manufactured by Tosoh Corporation) was used.
A catalyst for removing nitrogen oxides was obtained in exactly the same manner as in Example 1.
（実施例１４）
実施例１において、ＮＭ−１００Ｐの代わりに、ｙ／ｘ
が７，５のＮ型モルデナイトの市販品、ＴＳＺ−６２Ｏ
ＮＡＡ （東ソー社製）を用いたこと以外は、実施例１
と全く同様にして窒素酸化物除去用触媒を得た。(Example 14) In Example 1, instead of NM-100P, y/x
TSZ-62O, a commercial product of N-type mordenite with 7.5
Example 1 except that NAA (manufactured by Tosoh Corporation) was used.
A catalyst for removing nitrogen oxides was obtained in exactly the same manner as above.
（実施例１５）
実施例１において、ＮＭ−１００Ｐの代わりに、ｙ／ｘ
が９．５のＮ型モルデナイトの市販品、ＴＳＺ−６４Ｏ
ＮＡＡ （東ソー社製）を用いたこと以外は、実施例１
と全く同様にして酸化物除去用触媒を得た。(Example 15) In Example 1, instead of NM-100P, y/x
TSZ-64O, a commercial product of N-type mordenite with a value of 9.5
Example 1 except that NAA (manufactured by Tosoh Corporation) was used.
A catalyst for removing oxides was obtained in exactly the same manner as above.
（実施例１６）
実施例１において、ＮＭ−１００Ｐの代わりに、ｙ ／
ｘが７．５、（ｚ−ｃ）／ｘが０．０９の酸型モルデ
ナイトの市販品、ＴＳＺ−３２０ＨＯＡ（東ソー社製）
を用い、２ＮのＮＨ４（ｌによる処理を省略したこと以
外は、実施例１と全く同様にして窒素酸化物除去用触媒
を得た。(Example 16) In Example 1, instead of NM-100P, y/
Commercially available acid mordenite with x of 7.5 and (z-c)/x of 0.09, TSZ-320HOA (manufactured by Tosoh Corporation)
A catalyst for removing nitrogen oxides was obtained in exactly the same manner as in Example 1, except that the treatment with 2N NH4 (l) was omitted.
（比較例５）
実施例１において、ＮＭ−１００Ｐの代わりに、ｙ ／
ｘが２．８の酸型ゼオライトの市販品、ＴＳＺ−３２
０ＨＯＡ （東ソー社製）を用いたこと以外は、実施例
１と全く同様にして窒素酸化物除去用触媒を得た。(Comparative Example 5) In Example 1, instead of NM-100P, y/
Commercially available acid type zeolite with x of 2.8, TSZ-32
A catalyst for removing nitrogen oxides was obtained in exactly the same manner as in Example 1, except that 0HOA (manufactured by Tosoh Corporation) was used.
（比較例６）
実施例１において、ＮＭ−１００Ｐの代わりに、ｙ ／
ｘが３．１、（ｚ−ｃ）／ｘが０，０１の酸型モルデ
ナイトの市販品、ＴＳＺ−３３０ＨＵＡ（東ソー社製）
を用い、２ＮのＮＨ４１１）による処理を省略したこと
以外は、実施例１と全く同様にして窒素酸化物除去用触
媒を得た。(Comparative Example 6) In Example 1, instead of NM-100P, y/
Commercially available acid type mordenite with x of 3.1 and (z-c)/x of 0.01, TSZ-330HUA (manufactured by Tosoh Corporation)
A catalyst for removing nitrogen oxides was obtained in exactly the same manner as in Example 1, except that the treatment with 2N NH411) was omitted.
実施例１〜１６及び比較例１〜６で得たそれぞれの触媒
を反応器に充填し、窒素酸化物２００Ｄ ｐｍ ｓアン
モニア２００ｐｐｍ、水蒸気１０容量％、酸素２容量％
、二酸化炭素１２容量％、二酸化イオウ８００ｐｐｍ、
残部窒素からなる混合ガスを温度４００〜７００℃、空
間速度１０６７５Ｈｒ−’の条件で接触させて上記混合
ガスから窒素酸化物（ＮＯｘ）を接触還元除去した。Each of the catalysts obtained in Examples 1 to 16 and Comparative Examples 1 to 6 was charged into a reactor, and nitrogen oxides 200 D pm s ammonia 200 ppm, water vapor 10% by volume, and oxygen 2% by volume.
, carbon dioxide 12% by volume, sulfur dioxide 800ppm,
Nitrogen oxides (NOx) were catalytically reduced and removed from the mixed gas by contacting the mixed gas with the balance consisting of nitrogen at a temperature of 400 to 700° C. and a space velocity of 10,675 Hr-'.
上記窒素酸化物除去率は次式にて定義される百分率であ
る。The nitrogen oxide removal rate is a percentage defined by the following formula.
窒素酸化物除去率（％）
−（Ｃ１−Ｃｏ）Ｘ１００／Ｃ１
Ｃ：触媒層入口におけるＮｏｘａ度
Ｃ＝触媒層出口におけるＮ Ｏｘ ａ度第１表に実施例
１〜１６で得た触媒についての試験結果を、また第２表
に比較例１〜６で得た触媒についての試験結果を示す。Nitrogen oxide removal rate (%) - (C1-Co) Table 2 shows the test results for the catalysts obtained in Comparative Examples 1 to 6.
（以下、余白）
上記第１表及び第２表から明らかなように、本発明に係
る窒素酸化物除去用触媒である実施例１〜１６で得た触
媒は、いずれも比較例１〜６で得た触媒に比べて高い窒
素酸化物除去率を示す。(Hereinafter, blank space) As is clear from Tables 1 and 2 above, the catalysts obtained in Examples 1 to 16, which are the catalysts for removing nitrogen oxides according to the present invention, were all the catalysts obtained in Comparative Examples 1 to 6. It exhibits a higher nitrogen oxide removal rate than the obtained catalyst.
〈発明の効果〉
以上詳述したように、本発明に係る窒素酸化物除去用触
媒は、排ガスの温度が高い場合でも、窒素酸化物の除去
率が高い等、本発明は優れた特有の効果を奏する。<Effects of the Invention> As detailed above, the catalyst for removing nitrogen oxides according to the present invention has excellent unique effects such as a high removal rate of nitrogen oxides even when the exhaust gas temperature is high. play.
特許出願人 堺化学工業株式会社Patent applicant: Sakai Chemical Industry Co., Ltd.
Claims (1)
＿２）ｘ・（ＳｉＯ＿２）ｙ］・ｍＨ＿２Ｏで表され、
且つ、 前記組成式中の金属Ｍの酸化物生成エンタルピー−△Ｈ
＿ｆ°が８０（Ｋｃａｌ／酸素グラム原子）以上である
金属置換モルデナイトを含有することを特徴とする窒素
酸化物除去用触媒。 ただし、上記組成式において、金属Ｍは原子価が（Ｂ＋
ｃ）／Ａである多価金属、（ｚ−ｃ）／ｘ（モル比）は
０．３５以下、ｙ／ｘ（モル比）は５以上、Ａ／ｘ（モ
ル比）は０．３以上である。[Claims] 1. Compositional formula: MA・H(x-z-B)・Na(z-c)・[(AlO
_2) x・(SiO_2)y]・mH_2O,
And, the enthalpy of oxide formation of metal M in the composition formula -ΔH
A catalyst for removing nitrogen oxides, comprising metal-substituted mordenite whose _f° is 80 (Kcal/oxygen gram atom) or more. However, in the above compositional formula, the valence of metal M is (B+
c) polyvalent metal that is /A, (z-c)/x (molar ratio) is 0.35 or less, y/x (molar ratio) is 5 or more, A/x (molar ratio) is 0.3 or more It is.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63253387A JPH0299143A (en) | 1988-10-06 | 1988-10-06 | Catalyst for removing nitrogen oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63253387A JPH0299143A (en) | 1988-10-06 | 1988-10-06 | Catalyst for removing nitrogen oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0299143A true JPH0299143A (en) | 1990-04-11 |
Family
ID=17250659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63253387A Pending JPH0299143A (en) | 1988-10-06 | 1988-10-06 | Catalyst for removing nitrogen oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0299143A (en) |
-
1988
- 1988-10-06 JP JP63253387A patent/JPH0299143A/en active Pending
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