JPH02238206A - Method and device for catalytic combustion - Google Patents
Method and device for catalytic combustionInfo
- Publication number
- JPH02238206A JPH02238206A JP1058214A JP5821489A JPH02238206A JP H02238206 A JPH02238206 A JP H02238206A JP 1058214 A JP1058214 A JP 1058214A JP 5821489 A JP5821489 A JP 5821489A JP H02238206 A JPH02238206 A JP H02238206A
- Authority
- JP
- Japan
- Prior art keywords
- combustion
- catalyst
- gas
- catalytic combustion
- region
- 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
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 107
- 238000002485 combustion reaction Methods 0.000 claims abstract description 97
- 239000007789 gas Substances 0.000 claims abstract description 81
- 239000010410 layer Substances 0.000 claims description 26
- 239000002737 fuel gas Substances 0.000 claims description 16
- 239000002356 single layer Substances 0.000 claims description 3
- 239000000567 combustion gas Substances 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 5
- 239000012808 vapor phase Substances 0.000 abstract 3
- 239000012071 phase Substances 0.000 abstract 1
- 241000264877 Hippospongia communis Species 0.000 description 34
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 26
- 229910052863 mullite Inorganic materials 0.000 description 26
- 239000000463 material Substances 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 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 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 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 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 101100172879 Caenorhabditis elegans sec-5 gene Proteins 0.000 description 1
- 229910000669 Chrome steel Inorganic materials 0.000 description 1
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 1
- -1 Fe2O3 Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C2900/00—Special features of, or arrangements for combustion apparatus using fluid fuels or solid fuels suspended in air; Combustion processes therefor
- F23C2900/13002—Catalytic combustion followed by a homogeneous combustion phase or stabilizing a homogeneous combustion phase
Abstract
Description
【発明の詳細な説明】
く産業上の利用分野〉
本発明は、バーナー、ガスタービン、ボイラー等におい
て、燃料ガスを酸化反応させて熱エネルギーを発生させ
る接触燃焼方法とその燃焼装置に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a catalytic combustion method and combustion apparatus for oxidizing fuel gas to generate thermal energy in a burner, gas turbine, boiler, or the like.
く従来の技術と発明が解決しようとする問題点〉通常、
燃焼とは空気中で可燃物質が酸化されて炎を発生させる
化学変化をいう。しかしながら、通常の燃焼では燃焼反
応の制御が非常に困難であると共に、窒素酸化物Ｎｏ
等の有害物質が発生Ｘ
するという問題がある。Problems to be solved by conventional techniques and inventions>Usually,
Combustion is a chemical change in which combustible substances are oxidized in the air and produce flame. However, in normal combustion, it is very difficult to control the combustion reaction, and nitrogen oxides
There is a problem that harmful substances such as X are generated.
そこで、大気汚染防止のためＮｏ の生成を抑Ｘ
制し、かつ安定燃焼を容易にする観点から、固体触媒上
で燃料ガス（ＣＨ４）と空気とを完全酸化反応させる触
媒燃焼方式が提案されている。かかる触媒燃焼方式では
触媒表面で燃料ガスにいわゆる無炎燃焼反応を起こさせ
ることにより、燃料ガスをＣＯ２とＨ２ ０とに変化さ
せ、同時に熱エネルギーを得る。Therefore, from the viewpoint of suppressing the generation of NO and facilitating stable combustion in order to prevent air pollution, a catalytic combustion method has been proposed in which fuel gas (CH4) and air undergo a complete oxidation reaction on a solid catalyst. There is. In such a catalytic combustion method, the fuel gas is changed into CO2 and H20 by causing a so-called flameless combustion reaction on the surface of the catalyst, and at the same time, thermal energy is obtained.
しかしながら、触媒燃焼では、触媒の耐熱性に問題があ
るため、通常１１００〜１０００℃以下の温度で燃焼が
行われているが、ガスタービン、ボイラーなどのように
熱あるいは動力の形でエネルギーを回収する場合には、
エネルギー効率を向上させるために、ガス温度は高いほ
うが好ましく、従って触媒燃焼方式を使用することは困
難であった。このため、１２００〜１３００℃程度の温
度での燃焼に充分に耐えうる耐熱性触媒の開発が要望さ
れているのが現状である。However, in catalytic combustion, there is a problem with the heat resistance of the catalyst, so combustion is usually carried out at temperatures below 1100 to 1000 degrees Celsius, but energy is recovered in the form of heat or power, such as in gas turbines and boilers. If you do,
In order to improve energy efficiency, it is preferable for the gas temperature to be high, so it has been difficult to use a catalytic combustion method. Therefore, there is currently a demand for the development of a heat-resistant catalyst that can sufficiently withstand combustion at temperatures of about 1200 to 1300°C.
本発明は叙上の問題に鑑みてなされたものであって、公
知の触媒を使用して触媒の劣化を生じさせることなく、
長期間にわたって安定に高温燃焼（すなわち燃焼ガスの
完全酸化分解）を行わせることができ、Ｎｏ 等の有
害物質を発生させるこＸ
とのない接触燃焼方法とその燃焼装置を提供することを
目的とする。The present invention has been made in view of the above problems, and uses a known catalyst without causing deterioration of the catalyst.
The purpose of the present invention is to provide a catalytic combustion method and its combustion device that can stably perform high-temperature combustion (that is, complete oxidative decomposition of combustion gas) over a long period of time and do not generate harmful substances such as No. do.
く問題点を解決するための手段および作用〉本発明の接
触燃焼方法は、燃料ガスを触媒燃焼領域に導いて１１０
０℃以下の温度で触媒燃焼させ、ついで前記触媒燃焼領
域を通過したガスを気相燃焼領域に導いて１５００℃以
下の温度で気相燃焼させるものである。Means and operation for solving the above problems> The catalytic combustion method of the present invention leads fuel gas to a catalytic combustion region and
Catalytic combustion is performed at a temperature of 0° C. or lower, and then the gas that has passed through the catalytic combustion region is guided to a gas phase combustion region and gas phase combustion is performed at a temperature of 1500° C. or lower.
かかる本発明によれば、触媒燃焼が１１００℃以下の比
較的低温度域で行われるため、触媒を劣化させることが
なく、長期間にわたって安定に使用することができる。According to the present invention, catalytic combustion is performed at a relatively low temperature range of 1100° C. or lower, so the catalyst does not deteriorate and can be used stably over a long period of time.
また、触媒燃焼での未燃焼ガスや部分酸化生成物はより
高温度域で気相燃焼させるため、完全酸化分解が可能と
なり、ＮＯｘ等の有害物質を発生させることがない。従
って、本発明における触媒燃焼には従来公知の種々の触
媒が使用可能となる。Further, unburned gas and partial oxidation products from catalytic combustion are burned in a gas phase at a higher temperature range, so complete oxidative decomposition is possible, and no harmful substances such as NOx are generated. Therefore, various conventionally known catalysts can be used for catalytic combustion in the present invention.
ここで、気相燃焼とはＣＨ４等の有機物を空気存在下、
触媒なしで酸化分解することをいう。かかる気相燃焼で
は、完全酸化分解反応を行わせる上で、燃焼速度を促進
させることが必要である。Here, gas phase combustion refers to organic matter such as CH4 in the presence of air.
This refers to oxidative decomposition without a catalyst. In such gas phase combustion, it is necessary to accelerate the combustion rate in order to carry out a complete oxidative decomposition reaction.
そこで、本発明では、気相燃焼を促進させる構造を有す
る接触燃焼装置が使用される。より詳しくは、本発明の
接触燃焼装置は、燃料ガスの流路に、燃料ガスの流れ方
向に沿って、触媒燃焼を起こさせる触媒層と、気相燃焼
を起こさせる構造体層とをこの順に設けると共に、前記
構造体層がハニカム状物または多数の独立した小孔を有
する網状物もしくは板状物であることを特徴とする。Therefore, in the present invention, a catalytic combustion device having a structure that promotes gas phase combustion is used. More specifically, the catalytic combustion device of the present invention includes a catalyst layer that causes catalytic combustion and a structure layer that causes gas phase combustion in a fuel gas flow path along the flow direction of the fuel gas in this order. In addition, the structure layer is characterized in that it is a honeycomb-like object or a net-like object or a plate-like object having a large number of independent small holes.
以下、図面を用いてこの発明の接触燃焼方法とその燃焼
装置を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The catalytic combustion method and combustion apparatus of the present invention will be explained in detail below with reference to the drawings.
第１図は本発明にかかる接触燃焼装置の概略図である。FIG. 1 is a schematic diagram of a catalytic combustion apparatus according to the present invention.
同図において、（１）は所定の断面積を有するガス流路
（反応器）であり、燃料ガスは矢印で示す方向に流され
る。ガス流路（１）内にはガスの流れ方向に沿ってブレ
ヒータ（２Ｊ１触媒層口）および構造体層（４）が順次
配置される。触媒層Ｇ）は燃焼ガスの触媒燃焼領域Ａと
なり、構造体層（４）は気相燃焼領域Ｂとなる。In the figure, (1) is a gas flow path (reactor) having a predetermined cross-sectional area, and fuel gas is flowed in the direction shown by the arrow. A bre-heater (2J1 catalyst layer inlet) and a structure layer (4) are sequentially arranged in the gas flow path (1) along the gas flow direction. The catalyst layer G) becomes the catalytic combustion region A of combustion gas, and the structure layer (4) becomes the gas phase combustion region B.
燃料ガスは、プレヒータ（２）で約３００℃以上に予熱
された後、触媒燃焼領域Ａに導入され、触媒燃焼される
。このとき、触媒の劣化を防止するために、触媒燃焼領
域Ａを通過したガスは、温度が１１００℃以下、より好
ましくは１０００℃以下となるようにする。一方、気相
燃焼領域Ｂでは、ガスタービンやボイラーの燃焼温度を
高めエネルギー効率を向上させるためにガスの燃焼温度
を高めることが望まれるが、１５００℃を越えると、空
気中のＮ２と０２とが反応してＮｏ が生成すＸ
るので、燃焼温度は１５００℃以下とするのが好ましい
。After the fuel gas is preheated to about 300° C. or higher by the preheater (2), it is introduced into the catalytic combustion area A and catalytically combusted. At this time, in order to prevent deterioration of the catalyst, the temperature of the gas that has passed through the catalytic combustion area A is set to be 1100° C. or lower, more preferably 1000° C. or lower. On the other hand, in gas phase combustion region B, it is desirable to raise the combustion temperature of the gas in order to increase the combustion temperature of gas turbines and boilers and improve energy efficiency. The combustion temperature is preferably 1500° C. or lower because X reacts with No and generates No.
第２図のグラフは予熱、触媒燃焼および気相燃焼での上
限温度をそれぞれ３００℃、１１００℃および１５００
℃とした時のガスの温度変化を示している。The graph in Figure 2 shows the upper limit temperatures for preheating, catalytic combustion, and gas phase combustion at 300°C, 1100°C, and 1500°C, respectively.
It shows the temperature change of the gas when it is set to °C.
本発明における前記触媒層（３）としては、通常の触媒
燃焼において使用される触媒層がいずれも好適に使用可
能であり、例えばハニカム型担体や網状物、板状物など
の担体に直接触媒成分を担持させたもの、あるいはこれ
らの担体を基体としてこれに担体成分を付着させた後、
触媒成分を担持させたものなどがあげられる。前記ハニ
カム型担体としては、コージェライト、ムライト、γ−
アルミナなどから作られたものがあげられる。また、前
記網状物、板状物は反応性および圧力損失を考慮して径
が３０μｍ以下の小孔を多数有するものを使用するのが
好ましい。As the catalyst layer (3) in the present invention, any catalyst layer used in normal catalytic combustion can be suitably used. For example, the catalyst component may be directly applied to a carrier such as a honeycomb carrier, a net-like material, or a plate-like material. or after using these carriers as a base and attaching carrier components to them,
Examples include those on which a catalyst component is supported. As the honeycomb type carrier, cordierite, mullite, γ-
Examples include those made from alumina, etc. Furthermore, in consideration of reactivity and pressure loss, it is preferable to use a net-like material or a plate-like material having a large number of small pores having a diameter of 30 μm or less.
網状物、板状物の材質としては、例えばＳＵＳ４３０等
のステンレス鋼があげられるが、より耐熱性が要求され
る場合はクロム・ニッケル鋼、マンガン番クロム鋼、ニ
ッケル・クロム争コバルト鋼、クロム・アルミニウム鋼
などの金属系のほか、アルミナ、ムライト、コージェラ
イトなどのセラミック系が使用可能であり、これらは金
網の形態あるいは薄板をパンチング加工、ラス加工した
形態で使用される。さらに、有機繊維を網状に加工した
ものに担体成分としてセラミックスラリーを付着させ高
温で焼成したもの、有機紙をパンチング加工したものに
上記セラミックスラリーを付着させ高温で焼成したもの
、無機繊維紙にバンチング加工したものなども使用可能
である。Examples of materials for mesh and plate-like objects include stainless steel such as SUS430, but if higher heat resistance is required, chrome-nickel steel, manganese-grade chrome steel, nickel-chrome cobalt steel, chrome-nickel steel, etc. In addition to metals such as aluminum steel, ceramics such as alumina, mullite, and cordierite can be used, and these are used in the form of wire mesh or in the form of punched or lathed thin plates. In addition, we have produced organic fibers processed into a net shape with ceramic slurry attached as a carrier component and fired at high temperatures, organic paper punched with the above ceramic slurry attached and fired at high temperatures, and inorganic fiber paper with bunching. Processed products can also be used.
前記担体成分としては、例えば従来から使用されている
ＡＮｚ ０３ 、ＳｉＯｚ 、ＴｉＯｚ、Ｚ ｒ Ｏ
２ 、耐熱性が要求される場合にはＢａ０・６ＡＤｚ
Ｏｓ 、ＳｒＯ●６Ａｆｆｚ Ｏｓ 、ＣａＯ働６Ａｆ
Ｉ２ ０３ 、Ｍｇ０・９Ａｇｚ０３などのマグネトプ
ランバイト型複合酸化物、
Ｌａ・β−ＡＮｚ ０３ 、Ａｉ）ｚ ０３−Ｔｉ０２
、ＢａＯ−Ａｇ２ ０３ −Ｔ ｉ ０２などを使用す
るのが好ましい。Examples of the carrier component include conventionally used ANz 03 , SiOz , TiOz, Z r O
2. Ba0・6ADz when heat resistance is required
Os, SrO6Affz Os, CaO6Af
I2 03 , magnetoplumbite-type composite oxides such as Mg0・9Agz03, La・β-ANz 03 , Ai)z 03-Ti02
, BaO-Ag2 03 -T i 02 and the like are preferably used.
また、触媒成分としては、従来公知のものが使用可能で
あり、例えばＰｔ，Ｐｄなどの貴金属系触媒，Ｍｎ０２
，Ｃｏ３０４ ＳＣ ｒ２ ０３ ，Ｃ ｕ Ｏ Ｓ
Ｆ ｅ ２ ０ ３などの金属酸化物、Ｌａ ＡＯ
３ （ただし、ＡはＣＯ、Ｍｎ，Ｆｅ，１−ｘ
ＣｕＳＮｉ，ＣｒＳＣｅ，ｘはＯ〜０．５）などのべロ
ブス力イト型酸化物あるいはこれらの複合触媒（Ｐｔ−
Ｐｄ，ＣＯ３ ０４ −Ｍｎ０２ 、ＣｕＯ−Ｆ ｅｚ
０３ 、Ｐ ｔ−Ｌａ Ａ０３など）な１−ｘ
どかあげられ、これらは１種または２種以上を混合して
使用することができる。In addition, conventionally known catalyst components can be used, such as noble metal catalysts such as Pt and Pd, Mn02
, Co304 SC r2 03 , C u O S
Metal oxides such as Fe2O3, LaAO
3 (A is CO, Mn, Fe, 1-x CuSNi, CrSCe, x is O~0.5) or a composite catalyst of these (Pt-
Pd, CO3 04 -Mn02 , CuO-F ez
03, Pt-La A03, etc.) and 1-x, and these can be used alone or in combination of two or more.
また、前記触媒層（３）は単一層である必要はなく、種
々の触媒成分を複数層にわたって配置することができる
。例えば、燃料がメタンガスである場合には、燃焼開始
温度が低い田触媒と燃焼開始温度が高いが完全酸化能の
高い汽触媒とを組み合わせ、第３図に示すように、ガス
の流れ方向に沿って〜触媒一円一円混合触媒一Ｐｔ触媒
のように配置するのが燃焼性を高める上で好ましい。特
に、この例では一一円混合触媒における田／汽比を段階
的に変えて、より燃焼性を高めるようにしている。また
、第３図に示す各触媒層の長さは１／４、１／４、２／
４の割合にしているが、通常は、触媒層（３）の全長に
対して、田触媒領域が１／６〜１／４、出−Ｐｔ混合触
媒領域が１／６〜１／３、ＰＴ触媒領域が５／１２〜２
／３の範囲であるのが、触媒燃焼性を向上させると共に
、気相燃焼領域Ｂでの燃焼を充分に行わせる上で好まし
い。Further, the catalyst layer (3) does not need to be a single layer, and various catalyst components can be arranged in multiple layers. For example, when the fuel is methane gas, a rice catalyst with a low combustion start temperature and a steam catalyst with a high combustion start temperature but high complete oxidation ability are combined, and as shown in Fig. In order to improve combustibility, it is preferable to arrange the catalysts in a manner such that one catalyst is mixed with one Pt catalyst. In particular, in this example, the rice/steam ratio in the 11 yen mixed catalyst is changed in stages to further improve combustibility. In addition, the length of each catalyst layer shown in Fig. 3 is 1/4, 1/4, 2/4.
Normally, the total length of the catalyst layer (3) is 1/6 to 1/4 for the Pt catalyst area, 1/6 to 1/3 for the Pt mixed catalyst area, and 1/6 to 1/3 for the Pt mixed catalyst area. Catalyst area is 5/12~2
The range of /3 is preferable in order to improve the catalytic combustibility and to ensure sufficient combustion in the gas phase combustion region B.
気相燃焼領域Ｂを構成する構造体層（４）では、ガスを
１５００℃以下で燃焼させることから、構造体層（４）
は１５００℃程度の温度に耐えうろことが要求され、従
って、例えばアルミナ、ジルコニア、ムライト、コジエ
ライトなどの材質から作られる。In the structure layer (4) constituting the gas phase combustion region B, since the gas is burned at 1500°C or lower, the structure layer (4)
It is required to withstand temperatures of about 1500° C., and is therefore made of materials such as alumina, zirconia, mullite, and codierite.
また、構造体層（４）の構造としては、圧力損失を考慮
したとき、前述の触媒層（３）におけるのと同様なハニ
カム状物や径が３０μｍ以上の小孔を多数有する網状物
、板状物等があげられる。圧力損失は触媒燃焼領域Ａと
気相燃焼領域Ｂとの全体で５００ｍｍＨｚ Ｏ以下であ
るのが実用上好ましい。In addition, considering the pressure loss, the structure of the structure layer (4) may be a honeycomb-like material similar to that in the catalyst layer (3) described above, a net-like material having many small holes with a diameter of 30 μm or more, or a plate. Examples include things like this. It is practically preferable that the pressure loss in the entire catalytic combustion region A and gas phase combustion region B is 500 mmHz O or less.
気相燃焼領域Ｂにおいて、気相燃焼を促進させる上で、
燃焼ガスの線速度と構造体層（４）の開口率が重要なフ
ァクターとなる。すなわち、線速度が遅い場合（特にハ
ニカム状物において）には気相燃焼が起こりにくくなる
。また、開口率は低いほど、ガスの乱れが生じ、気相燃
焼を起こさせるのに好適な条件となるが、圧力損失゜が
大きくなるという問題がある。従って、これらを勘案す
ると、好ましい気相燃焼条件としては、線速度が通常０
．５Ｎｍ／秒以上、好ましくはハニカム状物でＩＮｍ／
秒以上、なかんづ＜３Ｎｍ／秒以上、網状物、板状物で
ＩＮｍ／秒以上であるのが適当であり、これらの線速度
に対して構造体層（４）は開口率が７０％以上、好まし
くは４０〜６０％であるのが適当である。In promoting gas phase combustion in gas phase combustion region B,
The linear velocity of the combustion gas and the aperture ratio of the structure layer (4) are important factors. That is, when the linear velocity is low (particularly in a honeycomb-like material), gas phase combustion is less likely to occur. Furthermore, the lower the aperture ratio, the more turbulent the gas will be, which will be a more suitable condition for causing gas-phase combustion, but there will be a problem in that the pressure loss will be larger. Therefore, taking these into consideration, the preferred gas phase combustion conditions are that the linear velocity is usually 0.
．． 5 Nm/sec or more, preferably INm/sec with a honeycomb-like object
It is appropriate that the linear velocity is at least 3 Nm/sec, in particular <3 Nm/sec or more, and at least INm/sec for net-like or plate-like materials, and the aperture ratio of the structure layer (4) is 70% for these linear velocities. As mentioned above, preferably 40 to 60% is appropriate.
く発明の効果〉
本発明の触媒燃焼方法によれば、触媒燃焼と気相燃焼と
を組み合わせたので、触媒燃焼を触媒の耐熱温度である
１１００℃以下で行うことができ、従って通常の触媒を
使用して長期間にわたって安定した触媒燃焼を行わせる
ことができる。また、気相燃焼を１５００℃以下の温度
で行わせるので、気相燃焼時に空気中のＮ２と０２とが
反応してＮｏ を生じさせることがなく、大気汚染の
防止Ｘ
にも大きく寄与することができる。Effects of the Invention According to the catalytic combustion method of the present invention, since catalytic combustion and gas-phase combustion are combined, catalytic combustion can be performed below 1100°C, which is the allowable temperature limit of the catalyst. It can be used to achieve stable catalytic combustion over a long period of time. In addition, since gas phase combustion is performed at a temperature of 1500°C or lower, N2 and 02 in the air do not react with each other during gas phase combustion to produce NO, which greatly contributes to the prevention of air pollution. I can do it.
本発明の触媒燃焼装置によれば、気相燃焼を起こさせる
構造体層が、ハニカム状物または多数の独立した小孔を
有する網状物もしくは板状物であるため、気相燃焼が促
進されるという効果がある。According to the catalytic combustion device of the present invention, the structure layer that causes gas-phase combustion is a honeycomb-like material or a net-like material or a plate-like material having a large number of independent small holes, so that gas-phase combustion is promoted. There is an effect.
従って、本発明の方法および装置はガスタービンやバー
ナー等のように、燃料ガスから熱あるいは動力の形でエ
ネルギーを回収する装置に好適に採用しうるものである
。Therefore, the method and device of the present invention can be suitably employed in devices that recover energy in the form of heat or power from fuel gas, such as gas turbines and burners.
く実施例〉
以下、参考例、実施例および比較例をあげて本発明を詳
細に説明する。Examples> Hereinafter, the present invention will be explained in detail with reference to Reference Examples, Examples, and Comparative Examples.
参考例１（触媒成分の調製）
硝酸バリウムと硝酸アルミニウムとを酸化物換算（Ｂａ
Ｏ、Ａｌｌ ２ ０３ ）でそれぞれ１５４ｇおよび６
１２ｇ秤量し、これに蒸留水１０ｇを加え、溶解した。Reference Example 1 (Preparation of catalyst components) Barium nitrate and aluminum nitrate were converted into oxides (Ba
154 g and 6
12g was weighed out, and 10g of distilled water was added thereto to dissolve it.
ついで、常温で、この水溶液を高速ディスパーサー（回
転数５０００ｒｐｍ）で攪拌しながら、炭酸アンモニウ
ム水溶液（５０ｇ／ｆｆ）を徐々に投入し、沈澱反応を
行わせた。このとき、最終ｐＨは７．０とした。さらに
、常温で８時間熟成させた後、沈澱物を濾別し、充分に
水洗し、１００℃で１８時間乾燥さ・せ、１２００℃で
３時間焼成してマグネトブランバイ斗型のＢａ０・６Ａ
ＮｚＯ３を得た。このものの比表面積は２５．８ｍ ２
／ ｇであった。Then, at room temperature, while stirring this aqueous solution with a high-speed disperser (rotation speed: 5000 rpm), an aqueous ammonium carbonate solution (50 g/ff) was gradually added to cause a precipitation reaction. At this time, the final pH was set to 7.0. Furthermore, after aging at room temperature for 8 hours, the precipitate was filtered out, thoroughly washed with water, dried at 100°C for 18 hours, and fired at 1200°C for 3 hours to form a magnetobranchite Ba0.6A.
NzO3 was obtained. The specific surface area of this product is 25.8 m 2
/g.
このＢａ０・６Ａｇ２０３に塩化白金酸および／または
塩化パラジウム水溶液を含浸させ、噴霧乾燥した後、１
０００℃で１時間焼成し、Ｂａ０・６ＡＮｚＯ３に田、
ｈ一田、ｈを担持した触媒粉をそれぞれ得た。これらの
触媒活性金属（Ｒｊ，円一円、Ｐｔ）の担持率はいずれ
も０．５重量％とした。また、汽一円触媒はＰｔ ／
Ｐａ比が０、２５／０．３７５、
０．２５／０．２５および
０．３７５／０、２５
の３種類を調−した。After impregnating this Ba0.6Ag203 with chloroplatinic acid and/or palladium chloride aqueous solution and spray drying, 1
After firing at 000℃ for 1 hour, the Ba0.6ANzO3
Catalyst powders supporting h Ichida and h were obtained, respectively. The supporting ratio of these catalytically active metals (Rj, 1 yen, Pt) was 0.5% by weight. In addition, the steam catalyst is Pt/
Three types were prepared with Pa ratios of 0, 25/0.375, 0.25/0.25 and 0.375/0,25.
参考例２（金網）
２０Ｃｒ−５Ａｊ７のクロム・アルミニウム鋼線（直径
１８０μ）を平織した４８メッシュの金網を９００℃で
１時間焼成し、表面にＡ１ｌｚｏ３ウィス力一を生成さ
せた。Reference Example 2 (Wire Mesh) A 48-mesh wire mesh made of a plain weave of 20Cr-5Aj7 chromium aluminum steel wire (diameter 180μ) was fired at 900° C. for 1 hour to generate A1lzo3 wire on the surface.
参考例３（ムライトパンチングシ一ト）アルミナとシリ
カとをモル比で３：２の割合で配合したアルミナ・シリ
カ粉１００ｇと、ニチアス製のムライト繊維２０ｇとに
水１ｇを加え、叩解したのち、手抄機により厚さ０．２
ｍｍのシートを得た。これに、貫通孔径０．５ｍｍ、ピ
ッチ１．５ｍｍのパンチング加工を施した。Reference Example 3 (Mullite punching sheet) After adding 1 g of water to 100 g of alumina/silica powder, which is a mixture of alumina and silica in a molar ratio of 3:2, and 20 g of mullite fiber manufactured by Nichias, and beating the mixture, Thickness 0.2 by hand paper machine
A sheet of mm was obtained. This was punched with a through hole diameter of 0.5 mm and a pitch of 1.5 mm.
参考例４（ムライトハニカム）
徳山曹達■製のシリカ（ファインシール）と住友化学工
業■製のアルミナ（Ａ−１１）とをモル比で３＝２の割
合で混合した混合物２０ｋｇにメチルセルロース４ｋｇ
，水６ｋｇを加え、加湿混合した後、充分に混練を行い
、金型を装着した押出成形機にて押出しを行い、通風乾
燥後、１５００℃で３時間焼成し、下記に示す種々のム
ライトハニカムを得た。Reference Example 4 (Mullite Honeycomb) 4 kg of methylcellulose was added to 20 kg of a mixture of silica (Fine Seal) manufactured by Tokuyama Soda ■ and alumina (A-11) manufactured by Sumitomo Chemical ■ in a molar ratio of 3=2.
, 6 kg of water was added, humidified and mixed, thoroughly kneaded, extruded using an extruder equipped with a mold, dried through ventilation, and fired at 1500°C for 3 hours to produce various mullite honeycombs shown below. I got it.
（開口率％） （ピッチ） （壁厚ｍｍ）８３
３． ３ ０． ３７４
１． ８ 屹２５
６９ １．８ ０。３６０
１． ８ ０． ４４４ １．
８ ０． ６参考例５（金網触媒）
参考例１で得た触媒粉（平均粒径３５μ）の５０ｇと、
アルミナゾル（１０重量％）の１０ｍ（ｌと、シリカゾ
ル（２０重量％）の１０ｍ［と、水３０ｒ＋ｌとを充分
に混合したスラリーに、参考例２で得た金網を浸漬し、
ついで熱風ドライヤにて乾燥した。これを５００℃で１
時間焼成して、平均担持率が１２．４％の金網触媒を得
た。(Opening ratio %) (Pitch) (Wall thickness mm) 83
3. 3 0. 374
1. 8 屹25 69 1.8 0.360
1. 8 0. 444 1.
8 0. 6 Reference Example 5 (wire mesh catalyst) 50 g of the catalyst powder (average particle size 35 μ) obtained in Reference Example 1,
The wire mesh obtained in Reference Example 2 was immersed in a slurry sufficiently mixed with 10 m (l) of alumina sol (10 wt%), 10 m (l) of silica sol (20 wt%), and 30 r+l of water,
It was then dried with a hot air dryer. 1 at 500℃
After firing for several hours, a wire mesh catalyst with an average support rate of 12.4% was obtained.
参考例６（パンチングシ一ト触媒）
金網に代えてパンチングシ一トを使用したほかは参考例
５と同様にして、平均担持率が２９．５％のパンチング
シ一ト触媒を得た。Reference Example 6 (Punched Sheet Catalyst) A punched sheet catalyst with an average loading rate of 29.5% was obtained in the same manner as in Reference Example 5, except that a punched sheet was used instead of the wire mesh.
参考例７（ハニカム触媒）
参考例１で得た触媒粉１００ｇと、アルミナゾル（１０
重量％）の２０ｍＲと、シリカゾル（２０重二％）の２
０ｒｒｌと、水８０ｍｇとを充分に混合したスラリーに
ハニカム担体を浸漬し、ついで過剰スラリーを除去した
後、通風乾燥した。Reference Example 7 (Honeycomb Catalyst) 100 g of catalyst powder obtained in Reference Example 1 and alumina sol (10
20mR of silica sol (20wt%) and 20mR of silica sol (20wt%)
The honeycomb carrier was immersed in a slurry in which 0rrl and 80 mg of water were thoroughly mixed, and then, after removing the excess slurry, it was dried by ventilation.
これを５００℃で１時間焼成して、平均担持率が３４．
３％のハニカム触媒を得た。This was baked at 500°C for 1 hour, and the average support rate was 34.
A 3% honeycomb catalyst was obtained.
実施例１
第４図に示す燃焼装置を作製した。すなわち、ガス流路
（反応器）内の触媒燃焼領域Ａに、出、Ｐｔ − Ｐｔ
ｔおよびＰｔを担持した参考例５の各金網触媒を以下の
枚数で配置した。Example 1 A combustion device shown in FIG. 4 was manufactured. That is, in the catalytic combustion area A in the gas flow path (reactor), Pt - Pt
Each of the wire mesh catalysts of Reference Example 5 supporting t and Pt was arranged in the following numbers.
田の金網触媒・・・３枚、
Ｐｔ−円の金網触媒・・・３枚
汽のの金網触媒・・・６枚
ただし、Ｐｔ − Ｐａ触媒域ではＰｔ／Ｆｂ比が０、
２５／０．３７５
旧２５／０． ２５
０．３７５／０、２５
の３種類の金網触媒を各１枚ずつガスの流れ方向に沿っ
てこの順に配置して構成した。Rice wire mesh catalyst: 3 sheets, Pt-circle wire mesh catalyst: 3 sheets Steam wire mesh catalyst: 6 sheets However, in the Pt-Pa catalyst area, the Pt/Fb ratio is 0,
25/0.375 Old 25/0. Three types of wire mesh catalysts, 25 0.375/0 and 25 , were arranged in this order along the gas flow direction.
また、気相燃焼領域Ｂは、参考例３で得た開口率３５％
のムライトパンチングシ一ト６枚を配置して構成した。In addition, the gas phase combustion region B has an aperture ratio of 35% obtained in Reference Example 3.
It was constructed by arranging six sheets of mullite punching sheets.
実施例２
円一田触媒域において、Ｐｔ／円が０．２５／０．２５
の汽一出金網触媒３枚のみを使用したほかは実施例１と
同様にして燃焼装置を作製した。Example 2 In the Yen-Ichita catalyst area, Pt/yen is 0.25/0.25
A combustion device was produced in the same manner as in Example 1 except that only three pieces of the steam wire mesh catalyst were used.
実施例３
第５図に示すように、触媒燃焼領域Ａに、以下の金網触
媒を使用したほかは実施例１と同様にして燃焼装置を作
製した。Example 3 As shown in FIG. 5, a combustion apparatus was produced in the same manner as in Example 1 except that the following wire mesh catalyst was used in the catalytic combustion area A.
田の金網触媒・・・６枚、
Ｐｔの金網触媒・・・６枚
実施例４
第６図に示すように、触媒燃焼領域Ａに、Ｐｔの金網触
媒（ Ｐｔ担持率０、５重量％）の１２枚のみを使用し
たほかは実施例１と同様にして燃焼装置を作製した。Field wire mesh catalyst: 6 sheets Pt wire mesh catalyst: 6 sheets Example 4 As shown in Figure 6, a Pt wire mesh catalyst (Pt loading rate 0.5% by weight) was placed in the catalytic combustion area A. A combustion device was produced in the same manner as in Example 1, except that only 12 sheets were used.
実施例５
Ｐｔの金網触媒に代えて、円の金網触媒（Ｐｔ担持率０
．５重量％）の１２枚のみを使用したほかは実施例４と
同様にして燃焼装置を作製した。Example 5 Instead of a Pt wire mesh catalyst, a circular wire mesh catalyst (Pt loading rate 0) was used.
．． A combustion device was produced in the same manner as in Example 4, except that only 12 sheets containing 5% by weight) were used.
実施例６
気相燃焼領域Ｂを構成するムライトパンチングシ一トに
代えて開口率６９％のムライトハニカム（ガス流れ方向
の長さが２４１）を使用したほかは実施例２と同様にし
て第４図に示す燃焼装置を作製した。Example 6 The fourth example was prepared in the same manner as in Example 2, except that a mullite honeycomb with an aperture ratio of 69% (length in the gas flow direction was 241 mm) was used instead of the mullite punched sheet constituting the gas phase combustion region B. The combustion device shown in the figure was constructed.
実施例７
気相燃焼領域Ｂを構成する開口率６９％のムライトハニ
カムに代えて、開口率６０％のムライトハニカムを使用
したほかは実施例６と同様にして第４図に示す燃焼装置
を作製した。Example 7 The combustion device shown in FIG. 4 was produced in the same manner as in Example 6 except that a mullite honeycomb with an aperture ratio of 60% was used in place of the mullite honeycomb with an aperture ratio of 69% constituting the gas phase combustion region B. did.
実施例８
気相燃焼領域Ｂを構成する開口率６９％のムライトハニ
カムに代えて、開口率４４％のムライトハニカムを使用
したほかは実施例６と同様にして第４図に示す燃焼装置
を作製した。Example 8 The combustion device shown in FIG. 4 was produced in the same manner as in Example 6 except that a mullite honeycomb with an aperture ratio of 44% was used in place of the mullite honeycomb with an aperture ratio of 69% constituting the gas phase combustion region B. did.
実施例９
実施例６の燃焼装置（第４図）において、ガス流路の断
面積を３倍にし、かつガスの線速度を１７３倍とした上
で、触媒容積が実施例４と同じになるように、触媒燃焼
領域Ａに、以下の金網触媒を使用した。Example 9 In the combustion device of Example 6 (Figure 4), the cross-sectional area of the gas flow path was tripled, the linear velocity of the gas was increased 173 times, and the catalyst volume was the same as in Example 4. The following wire mesh catalyst was used in the catalytic combustion area A.
円の金網触媒・・・１枚
円一円の金網触媒・・・１枚
（Ｐｔ／Ｐｄ−０．２５／０．２５）
Ｐｔの金網触媒・・・２枚
さらに、気相燃焼領域には開口率６９％のムライトハニ
カムを長さ１２ｍｍで使用して燃焼装置を作製した。Circular wire mesh catalyst... 1 piece Circle wire mesh catalyst... 1 piece (Pt/Pd-0.25/0.25) Pt wire mesh catalyst... 2 pieces In addition, in the gas phase combustion area A combustion device was fabricated using a mullite honeycomb with an aperture ratio of 69% and a length of 12 mm.
実施例１０
実施例６の燃焼装置（第４図）において、ガス流路の断
面積を１７２倍にし、かつガスの線速度を１７３倍とし
た上で、触媒容積が実施例６と同じになるように、触媒
燃焼領域Ａに、以下の金網触媒を使用した。Example 10 In the combustion device of Example 6 (Fig. 4), the cross-sectional area of the gas flow path was increased by 172 times, the linear velocity of the gas was increased by 173 times, and the catalyst volume was the same as in Example 6. The following wire mesh catalyst was used in the catalytic combustion area A.
田の金網触媒・・・６枚、
円一田の金網触媒・・・６枚
（Ｐｔ／円−０．２５／０．２５）
円の金網触媒・・・１２枚
さらに、気相燃焼領域には開口率６９％のムライトハニ
カムを長さ１２ｍｍで使用して燃焼装置を作製した。Rice wire mesh catalyst: 6 sheets, Yen-ichida wire mesh catalyst: 6 sheets (Pt/yen -0.25/0.25) Circle wire mesh catalyst: 12 sheets In addition, in the gas phase combustion region fabricated a combustion device using a mullite honeycomb with a length of 12 mm and an aperture ratio of 69%.
実施例１１
気相燃焼領域Ｂを構成する開口率６９％のムライトハニ
カムに代えて、開口率８３％のムライトハニカムを使用
したほかは実施例６と同様にして第４図に示す燃焼装置
を作製した。Example 11 The combustion device shown in FIG. 4 was produced in the same manner as in Example 6 except that a mullite honeycomb with an aperture ratio of 83% was used in place of the mullite honeycomb with an aperture ratio of 69% constituting the gas phase combustion region B. did.
実施例１２
第５図に示す燃焼装置において、触媒燃焼領域Ａに、以
下のハニカム触媒を使用した。なお、以下の説明におい
て、長さとあるのは、ガスの流れ方向の長さを示すもの
とする。Example 12 In the combustion apparatus shown in FIG. 5, the following honeycomb catalyst was used in the catalytic combustion area A. Note that in the following description, length refers to the length in the gas flow direction.
円のハニカム触媒
（Ｐｔ担持率０．５重量％）・・・長さ４５ｆｆｌＩＩ
Ｉｈのハニカム触媒
（Ｐｔ担持率０．５重量％）・・・長さ４５ｍ＋ｎさら
に、気相燃焼領域には開口率６０％のムライトハニカム
（ピッチ１．８ｍｍ，壁厚０．４ｍｍ）を長さ４５ｍｍ
で使用して燃焼装置を作製した。Circular honeycomb catalyst (Pt loading rate 0.5% by weight)...Length 45fflII
Ih honeycomb catalyst (Pt loading rate 0.5% by weight)...Length 45m+n Furthermore, in the gas phase combustion region, a mullite honeycomb (pitch 1.8mm, wall thickness 0.4mm) with an aperture ratio of 60% was installed. 45mm
A combustion device was created using it.
実施例１３
開口率６０％のムライトハニカムに代えて、開口率４４
％のムライトハニカム（ピッチ１．８ｍｍ，壁厚０．６
ｍｍ）を使用したほかは実施例１２と同様にして燃焼装
置を作製した。Example 13 Instead of mullite honeycomb with an aperture ratio of 60%, an aperture ratio of 44
% mullite honeycomb (pitch 1.8mm, wall thickness 0.6
A combustion device was produced in the same manner as in Example 12, except that 2 mm) was used.
実施例１４
開口率６０％、長さ４５ｍｍのムライトハニカムに代え
て、開口率４４％、長さ２２．５ｍｍのムライトハニカ
ム（ピッチ１．８ｍｍ，壁厚０．６ｍｍ）を使用したほ
かは実施例１２と同様にして燃焼装置を作製した。Example 14 Example except that a mullite honeycomb with an aperture ratio of 44% and a length of 22.5 mm (pitch 1.8 mm, wall thickness 0.6 mm) was used instead of a mullite honeycomb with an aperture ratio of 60% and a length of 45 mm. A combustion device was produced in the same manner as in No. 12.
実施例１５
実施例１２の燃焼装置（第５図）において、ガス流路の
断面積を５倍にし、かつガスの線速度を１７５倍（ＩＮ
ｍ／秒）とした上で、触媒燃焼領域Ａに、以下のハニカ
ム触媒を使用した。Example 15 In the combustion apparatus of Example 12 (Fig. 5), the cross-sectional area of the gas flow path was increased by 5 times, and the linear velocity of the gas was increased by 175 times (IN
m/sec), and the following honeycomb catalyst was used in the catalytic combustion region A.
田のハニカム触媒
（Ｐｔ担持率０．５重量％）・・・長さ９ＩＩＩＰｔの
ハニカム触媒
（Ｐｔ担持率０．５重量％）・・・長さ９■諷さらに、
気相燃焼領域には開口率６０％のムライトハニカムを長
さ９ ｍｍで使用して燃焼装置を作製した。Honeycomb catalyst (Pt loading rate 0.5% by weight)...Length 9IIIPt honeycomb catalyst (Pt loading rate 0.5% by weight)...Length 9■ In addition,
A combustion device was fabricated using a 9 mm long mullite honeycomb with an aperture ratio of 60% in the gas phase combustion region.
実施例１６
実施例１２の燃焼装置（第５図）において、ガス流路の
断面積を２倍にし、かつガスの線速度を１／２倍とした
上で、触媒燃焼領域Ａに、以下のハニカム触媒を使用し
た。Example 16 In the combustion apparatus of Example 12 (Fig. 5), the cross-sectional area of the gas flow path was doubled, the linear velocity of the gas was increased to 1/2, and the following was added to the catalytic combustion area A. A honeycomb catalyst was used.
田のハニカム触媒
（Ｐｔ担持率０．５重量％）・・・長さ２２．５ｍｍ円
のハニカム触媒
（Ｐｔ担持率０．５重量％）・・・長さ２２．５ｍｍさ
らに、気相燃焼領域には開口率６０％のムライトハニカ
ムを長さ２２．５ｍｍで使用して燃焼装置を作製した。Honeycomb catalyst (Pt loading rate: 0.5% by weight)...Length: 22.5mm Circular honeycomb catalyst (Pt loading rate: 0.5% by weight)...Length: 22.5mm Furthermore, gas phase combustion region A combustion device was manufactured using a mullite honeycomb with a length of 22.5 mm and an aperture ratio of 60%.
比較例１
第７図に示すように、ガス流路内の触媒燃焼領域Ａに、
以下の金網触媒を使用し、気相燃焼領域を使用しない燃
焼装置を作製した。Comparative Example 1 As shown in FIG. 7, in the catalytic combustion area A in the gas flow path,
A combustion device using the following wire mesh catalyst and not using a gas phase combustion region was fabricated.
田の金網触媒・・・３枚
氏の金網触媒・・・１５枚
比較例２
第８図に示すように、ガス流路内の触媒燃焼領域Ａに、
以下の金網触媒を使用し、気相燃焼領域を使用しない燃
焼装置を作製した。Field wire mesh catalyst: 3 sheets Field wire mesh catalyst: 15 sheets Comparative example 2 As shown in Fig. 8, in the catalytic combustion area A in the gas flow path,
A combustion device using the following wire mesh catalyst and not using a gas phase combustion region was fabricated.
円の金網触媒・・・６枚
ｈの金網触媒・・・６枚
燃焼試験
第４図に示すように、反応器となるガス流路内の各所定
位置の温度Ｔ −Ｔ ｉ，を測定できるようＯ
に温度測定器を設置し、ガス流路の人口よりメタンガス
と空気との所定量をそれぞれ流量計を介して導入した。Circular wire mesh catalyst: 6 wire mesh catalysts: 6 wire combustion test As shown in Figure 4, the temperature T -T i at each predetermined position in the gas flow path that becomes the reactor can be measured. A temperature measuring device was installed in the chamber, and predetermined amounts of methane gas and air were introduced into the gas flow path through flowmeters, respectively.
このとき、空気は予めブレヒータ（５）によって予熱し
、燃焼直前のガス温度Ｔ をＯ
３５０℃と設定した。At this time, the air was preheated in advance by a breech heater (5), and the gas temperature T immediately before combustion was set at O 350°C.
このとき、実施例１では、メタンガスと空気とを混合し
た燃料ガス中のメタンガス濃度が２％、３％および４％
のそれぞれについて試験し、他の実施例および比較例で
は３％に設定して試験した。At this time, in Example 1, the methane gas concentration in the fuel gas mixed with methane gas and air was 2%, 3%, and 4%.
In other Examples and Comparative Examples, the test was conducted with the concentration set to 3%.
ただし、メタンガス濃度が４％の場合にはＰｔの金網触
媒枚数を４枚とし、さらにムライトパンチングシ一トの
枚数を８枚とした。However, when the methane gas concentration was 4%, the number of Pt wire mesh catalysts was 4, and the number of mullite punching sheets was 8.
また、燃料ガスの線速度（ＬＶ）は触媒の空間容積（Ｓ
Ｖ）との関係から以下のように設定した。In addition, the linear velocity (LV) of the fuel gas is the spatial volume (S) of the catalyst
The following settings were made in relation to V).
（１）金網触媒（開口率１８％）
ＳＶ−１，０００，０００ｈｒ−
ＬＶ−０．２Ｎｍ／秒
０．６Ｎｍ／秒
１．２Ｎｍ／秒
（２）ハニカム触媒
Ｓ Ｖ − ２ ０ ０ ． ０ ０ ０ ｈｒ−Ｌ
Ｖ−０．５Ｎｍ／秒
ＩＮｍ／秒
３Ｎｍ／秒
５Ｎｍ／秒
燃焼後の排ガス組成は赤外線吸収式のＣＨ４メーターお
よびＣＯ２メーターによって測定し、これからメタンか
ら炭酸ガスへの変換率を求めた。(1) Wire mesh catalyst (opening ratio 18%) SV-1,000,000hr- LV-0.2Nm/sec 0.6Nm/sec 1.2Nm/sec (2) Honeycomb catalyst SV-200. 0 0 0 hr-L
V-0.5 Nm/sec INm/sec 3 Nm/sec 5 Nm/sec The exhaust gas composition after combustion was measured by an infrared absorption type CH4 meter and CO2 meter, and the conversion rate from methane to carbon dioxide gas was determined from this.
これらの試験結果を第１表に示す。The results of these tests are shown in Table 1.
（以下余白）
第１表から、実施例では、触媒燃焼領域と気相燃焼領域
とを組み合わせることにより、高い燃焼効率が得られて
いることがわかる。特に、田触媒とＰｔ触媒とを併用す
ることにより、より好ましくは田触媒とＲｊ − Ｐｔ
触媒と円触媒とを併用することにより、燃焼性が大幅に
向上している。(The following is a blank space) From Table 1, it can be seen that in the examples, high combustion efficiency is obtained by combining the catalytic combustion region and the gas phase combustion region. In particular, by using a combination of a catalyst and a Pt catalyst, it is more preferable to use a combination of a catalyst and a Pt catalyst.
By using a catalyst and a circular catalyst together, combustibility is greatly improved.
一方、比較例１でも高い燃焼効率が得られているが、こ
のものは次に述べるように耐久性に問題がある。On the other hand, although high combustion efficiency was obtained in Comparative Example 1, this product had a problem in durability as described below.
耐久試験
実施例１の燃焼装置と比較例１のそれについて、それぞ
れ連続燃焼試験を行い、開始時、１００時間後、１００
０時間後、５０００時間後における変換率を求めた。そ
の結果を第２表に示す。Continuous combustion tests were conducted on the combustion apparatus of Durability Test Example 1 and that of Comparative Example 1, and the
The conversion rates after 0 hours and 5000 hours were determined. The results are shown in Table 2.
（以下余白）
第２表から、実施例１は比較例１に比べて触媒の耐久性
が向上していることがわかる。これは、実施例１では触
媒燃焼が１１００℃以下であるので、触媒の劣化が起こ
らないのに対して、比較例１では１５００℃近くで燃焼
させているために、触媒が劣化したためと考えられる。(The following is a blank space) From Table 2, it can be seen that the durability of the catalyst in Example 1 is improved compared to Comparative Example 1. This is thought to be because in Example 1, the catalytic combustion was at 1,100°C or lower, so no catalyst deterioration occurred, whereas in Comparative Example 1, combustion was performed at nearly 1,500°C, which caused the catalyst to deteriorate. .
なお、参考例６で得たパンチングシ一ト触媒を使用した
場合も上記燃焼試験および耐久試験と略同様の結果が得
られた。さらに、気相燃焼の構造体層または触媒層の担
体として市販のコージェライトハニカム（例えばピッチ
１．３ａ＋ｍ，壁厚０．２■、日本電装製およびピッチ
１．８ｍｍ，壁厚０．３ ｓｖ，日本碍子製）を用いた
場合も同様であった。In addition, when the punched sheet catalyst obtained in Reference Example 6 was used, substantially the same results as the above combustion test and durability test were obtained. Furthermore, commercially available cordierite honeycomb (for example, pitch 1.3a+m, wall thickness 0.2cm, manufactured by Nippon Denso; pitch 1.8mm, wall thickness 0.3 sv, The same was true when using Nippon Insulator).
第１図は本発明にかかる接触燃焼装置を示す概略説明図
、第２図は燃焼装置内でのガスの流れと温度との関係を
示すグラフ、第３図は本発明における触媒層を構成する
田触媒と汽触媒との割合を示すグラフ、第４図〜第６図
は本発明の実施例で使用した燃焼装置を示す概略説明図
、第７図および第８図は比較例１および２の燃焼装置を
示す概略説明図である。Fig. 1 is a schematic explanatory diagram showing a catalytic combustion device according to the present invention, Fig. 2 is a graph showing the relationship between gas flow and temperature within the combustion device, and Fig. 3 constitutes a catalyst layer in the present invention. Graphs showing the proportions of rice and steam catalysts, Figures 4 to 6 are schematic explanatory diagrams showing combustion equipment used in Examples of the present invention, and Figures 7 and 8 are graphs showing the ratios of Comparative Examples 1 and 2. It is a schematic explanatory view showing a combustion device.
Claims (1)
を配置したものである請求項２の 接触燃焼装置。 ４、前記構造体層が、線速度約０．５Ｎｍ ／秒以上の燃料ガスに対して７０％以下 の開口率を有する構造体からなる請求項 ２の接触燃焼装置。[Claims] 1. Fuel gas is introduced into a catalytic combustion region and catalytically combusted at a temperature of 1,100°C or less, and then the gas that has passed through the catalytic combustion region is led to a gas phase combustion region at a temperature of 1,500°C or less. A catalytic combustion method characterized by gas phase combustion. 2. A catalyst layer that causes catalytic combustion and a structure layer that has a structure that causes gas phase combustion are provided in the flow path of the fuel gas in order along the flow direction of the fuel gas, and the structure layer is A catalytic combustion device characterized in that it is a honeycomb-like object or a net-like object or a plate-like object having a large number of independent small holes. 3. The catalytic combustion apparatus according to claim 2, wherein the catalyst layer includes a Pb single layer, a Pb-Pt mixed layer, and a Pt single layer arranged in this order along the flow direction of the fuel gas. 4. The catalytic combustion apparatus according to claim 2, wherein the structure layer is made of a structure having an aperture ratio of 70% or less for fuel gas having a linear velocity of about 0.5 Nm 2 /sec or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1058214A JPH02238206A (en) | 1989-03-10 | 1989-03-10 | Method and device for catalytic combustion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1058214A JPH02238206A (en) | 1989-03-10 | 1989-03-10 | Method and device for catalytic combustion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02238206A true JPH02238206A (en) | 1990-09-20 |
Family
ID=13077805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1058214A Pending JPH02238206A (en) | 1989-03-10 | 1989-03-10 | Method and device for catalytic combustion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02238206A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248251A (en) * | 1990-11-26 | 1993-09-28 | Catalytica, Inc. | Graded palladium-containing partial combustion catalyst and a process for using it |
| US5250489A (en) * | 1990-11-26 | 1993-10-05 | Catalytica, Inc. | Catalyst structure having integral heat exchange |
| US5258349A (en) * | 1990-11-26 | 1993-11-02 | Catalytica, Inc. | Graded palladium-containing partial combustion catalyst |
| US5259754A (en) * | 1990-11-26 | 1993-11-09 | Catalytica, Inc. | Partial combustion catalyst of palladium on a zirconia support and a process for using it |
| US5281128A (en) * | 1990-11-26 | 1994-01-25 | Catalytica, Inc. | Multistage process for combusting fuel mixtures |
| US5326253A (en) * | 1990-11-26 | 1994-07-05 | Catalytica, Inc. | Partial combustion process and a catalyst structure for use in the process |
| US5425632A (en) * | 1990-11-26 | 1995-06-20 | Catalytica, Inc. | Process for burning combustible mixtures |
| EP0668471A2 (en) * | 1994-02-17 | 1995-08-23 | PFEFFERLE, William C. | Catalytic method |
| US5453003A (en) * | 1991-01-09 | 1995-09-26 | Pfefferle; William C. | Catalytic method |
| NL1004051C2 (en) * | 1996-09-17 | 1998-03-18 | Gastec Nv | Catalytic radiation burner. |
| EP1334307A2 (en) * | 2000-10-27 | 2003-08-13 | Catalytica Energy Systems, Inc. | Method of thermal nox reduction in catalytic combustion systems |
-
1989
- 1989-03-10 JP JP1058214A patent/JPH02238206A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5511972A (en) * | 1990-11-26 | 1996-04-30 | Catalytica, Inc. | Catalyst structure for use in a partial combustion process |
| US5250489A (en) * | 1990-11-26 | 1993-10-05 | Catalytica, Inc. | Catalyst structure having integral heat exchange |
| US5258349A (en) * | 1990-11-26 | 1993-11-02 | Catalytica, Inc. | Graded palladium-containing partial combustion catalyst |
| US5259754A (en) * | 1990-11-26 | 1993-11-09 | Catalytica, Inc. | Partial combustion catalyst of palladium on a zirconia support and a process for using it |
| US5281128A (en) * | 1990-11-26 | 1994-01-25 | Catalytica, Inc. | Multistage process for combusting fuel mixtures |
| US5326253A (en) * | 1990-11-26 | 1994-07-05 | Catalytica, Inc. | Partial combustion process and a catalyst structure for use in the process |
| US5405260A (en) * | 1990-11-26 | 1995-04-11 | Catalytica, Inc. | Partial combustion catalyst of palladium on a zirconia support and a process for using it |
| US5425632A (en) * | 1990-11-26 | 1995-06-20 | Catalytica, Inc. | Process for burning combustible mixtures |
| US5248251A (en) * | 1990-11-26 | 1993-09-28 | Catalytica, Inc. | Graded palladium-containing partial combustion catalyst and a process for using it |
| US5453003A (en) * | 1991-01-09 | 1995-09-26 | Pfefferle; William C. | Catalytic method |
| EP0668471A2 (en) * | 1994-02-17 | 1995-08-23 | PFEFFERLE, William C. | Catalytic method |
| EP0668471A3 (en) * | 1994-02-17 | 1997-06-11 | William C Pfefferle | Catalytic method. |
| NL1004051C2 (en) * | 1996-09-17 | 1998-03-18 | Gastec Nv | Catalytic radiation burner. |
| WO1998012476A1 (en) * | 1996-09-17 | 1998-03-26 | Gastec N.V. | Catalytic radiant heater |
| EP1334307A2 (en) * | 2000-10-27 | 2003-08-13 | Catalytica Energy Systems, Inc. | Method of thermal nox reduction in catalytic combustion systems |
| EP1334307A4 (en) * | 2000-10-27 | 2007-07-04 | Kawasaki Heavy Ind Ltd | Method of thermal nox reduction in catalytic combustion systems |
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