JP2000300961A - Method and facility for denitration of exhaust gas - Google Patents
Method and facility for denitration of exhaust gasInfo
- Publication number
- JP2000300961A JP2000300961A JP11112075A JP11207599A JP2000300961A JP 2000300961 A JP2000300961 A JP 2000300961A JP 11112075 A JP11112075 A JP 11112075A JP 11207599 A JP11207599 A JP 11207599A JP 2000300961 A JP2000300961 A JP 2000300961A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- denitration
- gas
- combustion catalyst
- section
- 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
- 238000000034 method Methods 0.000 title claims description 21
- 239000007789 gas Substances 0.000 claims abstract description 137
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 238000002485 combustion reaction Methods 0.000 claims abstract description 56
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 2
- 239000003546 flue gas Substances 0.000 claims 2
- 238000007872 degassing Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 150000004760 silicates Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 description 15
- 239000000446 fuel Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 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
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、製鉄原料を焼結す
る焼結炉からの排ガスなど、ＣＯやＨ2 などの可燃性ガ
スを含み、温度が２００℃以下の低温である排ガス中の
窒素酸化物を除去するための排ガス脱硝方法及び脱硝装
置に関する。[0001] The present invention relates to a nitrogen gas in an exhaust gas containing a combustible gas such as CO or H 2 and having a low temperature of 200 ° C. or less, such as an exhaust gas from a sintering furnace for sintering a steelmaking raw material. The present invention relates to an exhaust gas denitration method and a denitration apparatus for removing oxides.
【０００２】[0002]
【従来の技術】排ガス中のＮＯX 排出抑制は近年ますま
す厳しくなっており、製鉄関連分野などにおいてもＮＯ
X 排出量の低減が必要となっている。とりわけ、焼結炉
からの排ガスは、事業用ボイラなどの燃焼排ガスにくら
べて排ガス温度が低く、従来から広く実用されている触
媒を用いたアンモニア添加触媒還元法による脱硝処理を
そのまま適用することはできない。The NO X emissions BACKGROUND ART In exhaust gas has recently become increasingly stringent, NO also in such iron-related fields
It is necessary to reduce X emissions. In particular, the exhaust gas from the sintering furnace has a lower exhaust gas temperature than the combustion exhaust gas from commercial boilers and the like. Can not.
【０００３】そのため、従来から広く実用されている触
媒を用いたアンモニア添加触媒還元法による脱硝処理を
この種の排ガスの脱硝に適用するためには、それらの触
媒が有効に機能する温度である３００℃程度まで排ガス
を加熱する必要があった。この加熱を、新に燃料を使用
してバーナで行うことは可能であるが、そのために多大
な燃料を必要とする上、そのバーナ燃焼により新なＮＯ
X が生成するなど問題が多い。[0003] Therefore, in order to apply the denitration treatment by the ammonia-added catalyst reduction method using a conventionally widely used catalyst to the denitration of this kind of exhaust gas, it is necessary to set the temperature at which the catalyst functions effectively. It was necessary to heat the exhaust gas to about ° C. This heating can be performed by a burner using a new fuel. However, a large amount of fuel is required for the heating, and a new NO.
There are many problems such as generation of X.
【０００４】[0004]
【発明が解決しょうとする課題】本発明は、前記した問
題点に鑑み、温度が200 °Ｃ以下で可燃性ガスを含む低
温の排ガス中の窒素酸化物を効率的に除去するための排
ガス脱硝方法と排ガス脱硝装置を提供することを課題と
している。SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention provides an exhaust gas denitration for efficiently removing nitrogen oxides in a low-temperature exhaust gas containing a combustible gas at a temperature of 200 ° C. or less. It is an object to provide a method and an exhaust gas denitration apparatus.
【０００５】[0005]
【課題を解決するための手段】本発明は、前記課題を解
決するために、排ガス中のＣＯ、Ｈ2 などの可燃性ガス
の燃焼熱を利用することにより排ガス温度を脱硝処理に
適した温度まで上昇させること、特にその可燃性ガスの
燃焼を主として触媒燃焼によって行うことを特徴として
いる。Means for Solving the Problems The present invention, in order to solve the above problems, suitable for exhaust gas temperature denitration by utilizing CO in the exhaust gas, the combustion heat of the combustible gas such as H 2 Temperature The combustion of the combustible gas is performed mainly by catalytic combustion.
【０００６】即ち、本発明は、ＣＯ、Ｈ2 などの可燃性
ガスを含む排ガスを、熱交換部、ガス加熱用バーナ部、
燃焼触媒部、脱硝装置部がこの順に配設されたガス流路
を通過させ、同ガス流路を通過した後の排ガスを前記熱
交換部を通して排出させるようにした排ガス脱硝方法を
提供する。That is, according to the present invention, an exhaust gas containing a combustible gas such as CO or H 2 is supplied to a heat exchange section, a gas heating burner section,
Provided is an exhaust gas denitration method in which a combustion catalyst section and a denitration apparatus section pass through a gas flow path provided in this order, and exhaust gas after passing through the gas flow path is discharged through the heat exchange section.
【０００７】本発明のこの排ガス脱硝方法によれば、熱
交換部で加温された排ガスが、ガス加熱用バーナ部で昇
温された後、燃焼触媒部に流れる。燃焼触媒部では燃焼
触媒が一旦作動すれば、その発生熱で燃焼触媒における
可燃性ガスの燃焼が継続するので、ガス加熱用バーナを
停止ないしは供給燃料量を最小限に絞れる。こうして、
本発明のこの排ガス脱硝方法によれば、ＣＯ、Ｈ2 など
の可燃性ガスを含む低温の排ガスの温度を、触媒が有効
に機能する、脱硝処理に適した温度まで経済的に上昇さ
せ、効果的に脱硝処理することができる。According to the exhaust gas denitration method of the present invention, the exhaust gas heated in the heat exchange section flows to the combustion catalyst section after being heated in the gas heating burner section. In the combustion catalyst section, once the combustion catalyst is activated, the combustion heat of the combustible gas is continued by the generated heat, so that the gas heating burner can be stopped or the supplied fuel amount can be reduced to a minimum. Thus,
According to the exhaust gas denitration method of the present invention, the temperature of a low-temperature exhaust gas containing a combustible gas such as CO or H 2 can be economically increased to a temperature suitable for denitration treatment in which the catalyst functions effectively. Denitration treatment can be performed.
【０００８】前記した本発明の排ガス脱硝方法におい
て、前記ガス加熱用バーナ部を出た排ガスの一部を、前
記燃焼触媒部をバイパスさせるようにすると、前記脱硝
装置部に流入する排ガス温度を調節することができて好
ましい。In the exhaust gas denitration method according to the present invention, the temperature of the exhaust gas flowing into the denitration device is controlled by allowing a part of the exhaust gas exiting the gas heating burner to bypass the combustion catalyst. It is preferable to be able to do so.
【０００９】本発明の排ガス脱硝方法において燃焼触媒
部に使用する燃焼触媒としては、Ｐｔ、Ｐｄ、Ｉｒ、Ｒ
ｈの少なくとも一種以上の活性金属を含み、担体にＴｉ
Ｏ2、ＺｒＯ2 、ＳｉＯ2 、ＴｉＯ2 −ＺｒＯ2 複合酸
化物、ＴｉＯ2 −ＳｉＯ2 複合酸化物、結晶性シリケー
トの少なくとも一種以上を組み合わせてなる燃焼触媒を
用いることができる。In the exhaust gas denitration method of the present invention, Pt, Pd, Ir, R
h at least one active metal, and the carrier has Ti
A combustion catalyst comprising a combination of at least one of O 2 , ZrO 2 , SiO 2 , TiO 2 -ZrO 2 composite oxide, TiO 2 -SiO 2 composite oxide, and crystalline silicate can be used.
【００１０】また、前記課題を解決するため、本発明
は、熱交換部、ガス加熱用バーナ部、燃焼触媒部、脱硝
装置部がこの順に配設された排ガス流路、及び前記燃焼
触媒部をバイパスするバイパス排ガス流路を有し、同バ
イパスガス流路を流れるガス流量を調節可能に構成した
排ガス脱硝装置を提供する。[0010] In order to solve the above-mentioned problems, the present invention provides an exhaust gas flow path in which a heat exchange section, a gas heating burner section, a combustion catalyst section, and a denitration apparatus section are arranged in this order, and the combustion catalyst section. Provided is an exhaust gas denitration apparatus having a bypass exhaust gas flow path for bypassing and configured to be capable of adjusting a gas flow rate flowing through the bypass gas flow path.
【００１１】本発明のこの排ガス脱硝装置における脱硝
装置部には、Ｐｔ、Ｐｄ、Ｉｒ、Ｒｈの少なくとも一種
以上の活性金属を含み、担体にＴｉＯ2 、ＺｒＯ2 、Ｓ
ｉＯ 2 、ＴｉＯ2 −ＺｒＯ2 複合酸化物、ＴｉＯ2 −Ｓ
ｉＯ2 複合酸化物、結晶性シリケートの少なくとも一種
以上を組み合わせてなる燃焼触媒を用いることができ
る。[0011] Denitration in the exhaust gas denitration apparatus of the present invention
At least one of Pt, Pd, Ir, Rh
It contains the above active metals and the carrier is TiOTwo, ZrOTwo, S
iO Two, TiOTwo-ZrOTwoComposite oxide, TiOTwo-S
iOTwoAt least one of a composite oxide and a crystalline silicate
Combustion catalysts that combine the above can be used
You.
【００１２】本発明の排ガス脱硝装置によれば、前記し
た本発明の排ガス脱硝方法を効果的に実施して可燃性ガ
スを含む低温の排ガスを脱硝処理することができる。According to the exhaust gas denitration apparatus of the present invention, the low-temperature exhaust gas containing flammable gas can be denitrated by effectively performing the above-described exhaust gas denitration method of the present invention.
【００１３】[0013]
【発明の実施の形態】以下、本発明を図１、図２を用い
実施の形態に基づいて具体的に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to FIGS.
【００１４】（第１実施形態）先ず、図１に示す第１実
施形態について説明する。図１において、１は熱交換器
を有する熱交換部、２はガス加熱用バーナ部、３は燃焼
触媒部、４は脱硝装置部を示している。図１に示すよう
に、可燃性ガスを含む排ガスは、熱交換部１に導かれ脱
硝装置４を出た排ガスと熱交換され加熱される。熱交換
器１を通過したガスは、次いでガス加熱用バーナ部２に
送られる。(First Embodiment) First, a first embodiment shown in FIG. 1 will be described. In FIG. 1, reference numeral 1 denotes a heat exchange section having a heat exchanger, 2 denotes a gas heating burner section, 3 denotes a combustion catalyst section, and 4 denotes a denitration apparatus section. As shown in FIG. 1, the exhaust gas containing the combustible gas is exchanged with the exhaust gas that has been guided to the heat exchange unit 1 and exited from the denitration device 4 and is heated. The gas that has passed through the heat exchanger 1 is then sent to a gas heating burner section 2.
【００１５】ガス加熱用バーナ部２は、主として装置の
起動時に後流の燃焼触媒部３の燃焼触媒が有効に働く温
度まで排ガスを昇温させるのに用いているのである。従
って、燃焼触媒部３が一旦働き出したら、ガス加熱用バ
ーナ部２は作動を停止あるいは供給する燃料量を最小限
に絞って経済的な運転を行い、燃費を節減する。燃焼触
媒部３で昇温した排ガスは、脱硝装置部４に供給され、
ガス中に含まれる窒素酸化物が除去される。脱硝装置部
４から排出される高温の排ガスは、熱交換部１に導かれ
て被処理排ガスと熱交換された後、煙突から排出され
る。The gas heating burner section 2 is mainly used to raise the temperature of the exhaust gas to a temperature at which the combustion catalyst of the downstream combustion catalyst section 3 works effectively when the apparatus is started. Therefore, once the combustion catalyst unit 3 starts working, the gas heating burner unit 2 stops operating or reduces the amount of supplied fuel to a minimum, performs economical operation, and saves fuel consumption. The exhaust gas heated in the combustion catalyst unit 3 is supplied to the denitration device unit 4,
Nitrogen oxides contained in the gas are removed. The high-temperature exhaust gas discharged from the denitration device unit 4 is guided to the heat exchange unit 1 and exchanges heat with the exhaust gas to be processed, and then discharged from the chimney.
【００１６】前記した燃焼触媒部３に用いる燃焼触媒と
しては、活性金属としてＰｔ、Ｐｄ、Ｉｒ、Ｒｈの少な
くとも一種以上を含み、担体にＴｉＯ2 、ＺｒＯ2 、Ｓ
ｉＯ 2 、ＴｉＯ2 −ＳｉＯ2 複合酸化物、ＴｉＯ2 −Ｚ
ｒＯ2 複合酸化物、結晶性シリケートの少なくとも一種
以上を組み合わせた触媒を使用することができる。前記
結晶性シリケートとしては、例えば表１に示されるＸ線
回析パターンを有し、脱水された状態におけるモル比で
表して、数式１のものを用いることができる。The combustion catalyst used in the combustion catalyst section 3 and
Therefore, Pt, Pd, Ir and Rh as active metals are low.
At least one or more TiO2Two, ZrOTwo, S
iO Two, TiOTwo-SiOTwoComposite oxide, TiOTwo-Z
rOTwoAt least one of a composite oxide and a crystalline silicate
A catalyst combining the above can be used. Said
Examples of the crystalline silicate include X-rays shown in Table 1.
It has a diffraction pattern and the molar ratio in the dehydrated state
The expression 1 can be used.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【数１】 (Equation 1)
【００１９】Ａｌ2 Ｏ3 を担体にした触媒は、ガス中に
含まれることがある硫黄酸化物に対する耐久性に乏しく
適当ではない。脱硝装置部４に用いる触媒としては、広
く実用化されているバナジウム、タングステン、モリブ
デンを活性成分とした酸化チタン系列のものが好まし
く、脱硝装置部４入口のガス温度は、２５０〜４５０
℃、好ましくは３００〜４００℃程度にするのがよい。A catalyst using Al 2 O 3 as a carrier is not suitable because it has poor durability against sulfur oxides which may be contained in a gas. The catalyst used in the denitration unit 4 is preferably a titanium oxide series containing vanadium, tungsten and molybdenum as active components, and the gas temperature at the inlet of the denitration unit 4 is 250 to 450.
° C, preferably about 300 to 400 ° C.
【００２０】（第２実施形態）次に、図２に示す第２実
施形態について説明する。図２において、５はバイパス
排ガス流路で、このバイパス排ガス流路は、ガス加熱用
バーナ部２を出た排ガスの少なくとも一部の調節された
量が燃焼触媒部３をバイパスできるように、ガス加熱用
バーナ部２の出口と脱硝装置部４の入口の間に設けられ
ている。その他の構成は図１に示した第１実施形態と実
質同じであり、同じ構成部分には図１と同じ符号を付し
てある。(Second Embodiment) Next, a second embodiment shown in FIG. 2 will be described. In FIG. 2, reference numeral 5 denotes a bypass exhaust gas passage. The bypass exhaust gas passage is provided with a gas so that at least a part of the regulated amount of the exhaust gas exiting the gas heating burner unit 2 can bypass the combustion catalyst unit 3. It is provided between the outlet of the heating burner unit 2 and the inlet of the denitration unit 4. Other configurations are substantially the same as those of the first embodiment shown in FIG. 1, and the same components are denoted by the same reference numerals as in FIG.
【００２１】この図２に示す第２実施形態のものでは、
燃焼触媒部３に流れされる排ガス量をバイパス排ガス流
路５で調節することによって、脱硝装置４部の入口にお
けるガス温度を制御することができる。従って、燃焼触
媒部３の性能に変化が生じても脱硝装置部４に流れる排
ガスの温度を調節して脱硝装置部４を安定して運転する
ことができるものとなっている。In the second embodiment shown in FIG.
The gas temperature at the inlet of the denitration device 4 can be controlled by adjusting the amount of exhaust gas flowing to the combustion catalyst unit 3 in the bypass exhaust gas channel 5. Therefore, even if the performance of the combustion catalyst unit 3 changes, the temperature of the exhaust gas flowing to the denitration device unit 4 is adjusted, and the denitration device unit 4 can be stably operated.
【００２２】[0022]
【実施例】（燃焼触媒の調製）アナターゼ型ＴｉＯ
2 （比表面積７０ｍ2 ／ｇ）粉末に塩化白金酸水溶液を
含浸し、１１０℃で蒸発乾固させ、５００℃で５時間焼
成した。ＴｉＯ2 粉末にＰｔを１ｗｔ％担持させた燃焼
触媒粉末を得た。燃焼触媒粉末の調製と同様の方法
でアナターゼ型ＴｉＯ2 粉末の代わりに正方晶ＺｒＯ2
粉末、非晶質ＳｉＯ2 粉末、ＴｉＯ2 ・ＳｉＯ2 複合酸
化物（ＴｉＯ 2 ：ＳｉＯ2 ＝９０：１０重量比）粉末、
ＴｉＯ2 ・ＺｒＯ2 複合酸化物（ＴｉＯ2 ：ＺｒＯ2 ＝
９０：１０）粉末、表１に示した結晶構造を有し次ぎの
組成式を示す結晶性シリケート（０. １Ｎａ2 Ｏ・０.
９Ｈ2 Ｏ（０. １Ｆｅ2 Ｏ3 ・０. ９Ａｌ2 Ｏ3 ・０.
１ＣａＯ）・３０ＳｉＯ2 ）を用いて粉末触媒を調製し
た。各触媒を燃焼触媒粉末、、、、とする。EXAMPLES (Preparation of Combustion Catalyst) Anatase TiO
Two(Specific surface area 70mTwo/ G) Add chloroplatinic acid aqueous solution to powder
Impregnate, evaporate to dryness at 110 ° C, bake at 500 ° C for 5 hours
Done. TiOTwoCombustion with 1wt% Pt supported on powder
A catalyst powder was obtained. Method similar to the preparation of combustion catalyst powder
With anatase TiOTwoTetragonal ZrO instead of powderTwo
Powder, amorphous SiOTwoPowder, TiOTwo・ SiOTwoComplex acid
(TiO2) Two: SiOTwo= 90:10 weight ratio) powder,
TiOTwo・ ZrOTwoComplex oxide (TiOTwo: ZrOTwo=
90:10) powder, having the crystal structure shown in Table 1 and
A crystalline silicate (0.1 Na) having a composition formulaTwoO ・ 0.
9HTwoO (0.1FeTwoOThree・ 0.9AlTwoOThree・ 0.
1CaO) .30SiOTwo) To prepare a powder catalyst
Was. Each catalyst is a combustion catalyst powder,.
【００２３】更に、燃焼触媒粉末と同様の方法によっ
て、塩化白金酸水溶液の代わりに硝酸パラジウム水溶液
を用いて、ＴｉＯ2 担体にＰｄを１％担持させた燃焼触
媒粉末を得た。Further, in the same manner as in the combustion catalyst powder, a combustion catalyst powder in which 1% of Pd was supported on a TiO 2 carrier was obtained using an aqueous solution of palladium nitrate instead of the aqueous solution of chloroplatinic acid.
【００２４】このように調製した燃焼触媒粉末〜を
用いて、４. ２ｍｍピッチ（壁厚０. ５ｍｍ）のコージ
ェライト製ハニカム素材に基材表面積当たり粉末触媒を
２００ｇ／ｍ2 コートして、ハニカム状燃焼触媒〜
を得た。Using the combustion catalyst powder thus prepared, a cordierite honeycomb material having a pitch of 4.2 mm (wall thickness: 0.5 mm) was coated with a powder catalyst at a rate of 200 g / m 2 per substrate surface area. Combustion catalyst ~
I got
【００２５】（脱硝試験）前記したように調製した燃焼
触媒〜を用いて本発明に基づき次の脱硝反応試験を
行った。まず脱硝装置として、図１の装置の構成におい
て、ガス加熱用バーナ部２の代わりに、投げ込み型の電
熱ヒータを使用し、熱交換部１にはshll &tube タイプ
のものを、また脱硝装置の触媒として３. ３ｍｍピッチ
のＴｉＯ2系格子状触媒を充填して、全系を充分に保温
をした状態で脱硝反応試験を実施した。燃焼触媒部２に
おける燃焼触媒としては前記したように調製した燃焼触
媒〜を用い、排ガスとしては表2に記載の組成のガ
スを用いた。(Denitration test) The following denitration reaction test was carried out based on the present invention using the combustion catalyst prepared as described above. First, as the denitration apparatus, in the configuration of the apparatus in FIG. 1, a throw-in type electric heater is used in place of the gas heating burner section 2, a shll & tube type heat exchange section 1 is used, and a catalyst of the denitration apparatus is used. A TiO 2 -based lattice catalyst having a pitch of 3.3 mm was filled, and a denitration reaction test was performed in a state where the entire system was sufficiently kept warm. As the combustion catalyst in the combustion catalyst section 2, the combustion catalyst prepared as described above was used, and as the exhaust gas, a gas having a composition shown in Table 2 was used.
【００２６】[0026]
【表2】 [Table 2]
【００２７】燃焼触媒〜を１. ２リットル、脱硝触
媒を１. ６リットル充填し、熱交換部の入口から、前記
した表２の組成をもつ５０℃のガスを３０Ｎｍ3 ／ｈｒ
で供給した。電熱ヒータをＯＮにして、燃焼触媒部入口
が２５０℃に到達したところで、脱硝装置部の前にＮＨ
3 をＮＨ3 ／ＮＯX （モル比）＝０. ８で注入を開始す
るとともに、電熱ヒータをＯＦＦにした。各燃焼触媒
〜のケースで状態で電熱ヒータをＯＦＦの状態で良好
な脱硝率を維持した。その結果を表３に示してある。1.2 liters of the combustion catalyst and 1.6 liters of the denitration catalyst were charged, and a gas having the composition shown in Table 2 at 50 ° C. and 30 Nm 3 / hr was supplied from the inlet of the heat exchange section.
Supplied with When the electric heater was turned on and the inlet of the combustion catalyst reached 250 ° C., NH 4 was placed in front of the denitration unit.
The injection of 3 was started at NH 3 / NO x (molar ratio) = 0.8, and the electric heater was turned off. In each of the combustion catalysts, a good denitration rate was maintained with the electric heater turned off. The results are shown in Table 3.
【００２８】[0028]
【表３】 [Table 3]
【００２９】[0029]
【発明の効果】以上説明したように、本発明による排ガ
ス脱硝方法では、ＣＯ、Ｈ2 などの可燃性ガスを含む排
ガスを、熱交換部、ガス加熱用バーナ部、燃焼触媒部、
脱硝装置部がこの順に配設されたガス流路を通過させ、
同ガス流路を通過した後の排ガスを前記熱交換部を通し
て排出させるようにしている。As described above, in the exhaust gas denitration method according to the present invention, the exhaust gas containing combustible gas such as CO and H 2 is supplied to the heat exchange section, the gas heating burner section, the combustion catalyst section, and the like.
The denitration unit passes through the gas passages arranged in this order,
Exhaust gas after passing through the gas flow path is discharged through the heat exchange section.
【００３０】本発明の排ガス処理方法においては、燃焼
触媒としてＰｔ、Ｐｄ、Ｉｒ、Ｒｈの少なくとも一種以
上の活性金属を含み、担体にＴｉＯ2 、ＺｒＯ2 、Ｓｉ
Ｏ2、ＴｉＯ2 −ＺｒＯ2 複合酸化物、ＴｉＯ2 −Ｓｉ
Ｏ2 複合酸化物、結晶性シリケートの少なくとも一種以
上を組み合わせてなるものなどを用いる。In the exhaust gas treatment method of the present invention, at least one active metal of Pt, Pd, Ir and Rh is contained as a combustion catalyst, and TiO 2 , ZrO 2 and Si are contained in a carrier.
O 2 , TiO 2 -ZrO 2 composite oxide, TiO 2 -Si
An oxide obtained by combining at least one or more of an O 2 composite oxide and a crystalline silicate is used.
【００３１】本発明のこの排ガス脱硝方法によれば、排
ガスは熱交換部で加温された後、ガス加熱用バーナ部で
昇温され、燃焼触媒部に流れる。燃焼触媒は一旦作動す
れば、その発生熱で燃焼触媒における可燃性ガスの燃焼
が継続するので、ガス加熱用バーナを停止ないしは供給
燃料量を最小限に絞って、低温の排ガスを、触媒が有効
に機能する温度脱硝処理に適した温度まで経済的に上昇
させることができ、これによって排ガスを効果的に脱硝
処理することができる。また、本発明は、毒性のあるＣ
Ｏの排出を無くすることができる有用な排ガス処理を提
供している。According to the exhaust gas denitration method of the present invention, after the exhaust gas is heated in the heat exchange section, the temperature is raised in the gas heating burner section and flows to the combustion catalyst section. Once the combustion catalyst operates, the combustible gas combustion in the combustion catalyst continues with the heat generated, so the gas heating burner is stopped or the amount of supplied fuel is reduced to a minimum, so that the catalyst can effectively use low-temperature exhaust gas. The temperature can be economically increased to a temperature suitable for the temperature denitration treatment, whereby the exhaust gas can be effectively denitrated. The present invention also relates to a toxic C
A useful exhaust gas treatment that can eliminate O emissions is provided.
【００３２】本発明の排ガス脱硝方法において、前記ガ
ス加熱用バーナ部を出た排ガスの一部を、前記燃焼触媒
部をバイパスさせるようにしたものでは、前記脱硝装置
部に流入する排ガス温度を調節することができて効果的
な脱硝を行うことができる。In the exhaust gas denitration method of the present invention, the temperature of the exhaust gas flowing into the denitration device is controlled by allowing a part of the exhaust gas leaving the gas heating burner to bypass the combustion catalyst. And effective denitration can be performed.
【００３３】また本発明による排ガス脱硝装置では、熱
交換部、ガス加熱用バーナ部、燃焼触媒部、脱硝装置部
がこの順に配設された排ガス流路、及び前記燃焼触媒部
をバイパスするバイパス排ガス流路を有し、同バイパス
排ガス流路を流れるガス流量を調節可能に構成されてい
る。Further, in the exhaust gas denitration apparatus according to the present invention, an exhaust gas flow path in which a heat exchange section, a gas heating burner section, a combustion catalyst section, and a denitration apparatus section are arranged in this order, and a bypass exhaust gas bypassing the combustion catalyst section. It has a flow path and is configured to be able to adjust a gas flow rate flowing through the bypass exhaust gas flow path.
【００３４】本発明のこの排ガス脱硝装置によれば、前
記した本発明の排ガス脱硝方法を効果的に実施して可燃
性ガスを含む低温の排ガスを適切に脱硝処理することが
できる。According to the exhaust gas denitration apparatus of the present invention, the low-temperature exhaust gas containing flammable gas can be appropriately denitrated by effectively performing the above-described exhaust gas denitration method of the present invention.
【図１】 本発明の第１実施形態における排ガスの流路
を示す説明図。FIG. 1 is an explanatory view showing a flow path of exhaust gas in a first embodiment of the present invention.
【図２】 本発明の第２実施形態における排ガスの流路
を示す説明図。FIG. 2 is an explanatory view showing a flow path of exhaust gas in a second embodiment of the present invention.
１ 熱交換部 ２ ガス加熱用バーナ部 ３ 燃焼触媒部 ４ 脱硝装置部 ５ バイパス排ガス流路 DESCRIPTION OF SYMBOLS 1 Heat exchange part 2 Gas heating burner part 3 Combustion catalyst part 4 Denitration equipment part 5 Bypass exhaust gas flow path
───────────────────────────────────────────────────── フロントページの続き (72)発明者 米村 将直 広島市西区観音新町四丁目６番22号 三菱 重工業株式会社広島研究所内 (72)発明者 服部 晃 長崎市飽の浦町１番１号 三菱重工業株式 会社長崎造船所内 (72)発明者 栗崎 隆 長崎市飽の浦町１番１号 三菱重工業株式 会社長崎造船所内 Ｆターム(参考） 4D048 AA06 AB01 AB02 BA02X BA03X BA06X BA07X BA08X BA09X BA14X BA30X BA31Y BA33Y BA39X BA41X BA42X BB02 CC26 CC32 CC38 CC47 CC52 CC54 DA01 DA05 DA06 4G069 AA03 BA02A BA02B BA04A BA04B BA05A BA05B BA07A BA07B BA13B BB02A BB02B BB06A BB06B BC50A BC50B BC51A BC51B BC66B BC71A BC72A BC72B BC74A BC75A BC75B BD05A BD05B CA02 CA07 CA08 CA11 CA13 CA14 EA19 EB15Y EB17Y EC02Y EC22Y EC26 ZA33A ZA33B ZA36A ZA37A ZA38A ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masanao Yonemura 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima Mitsubishi Heavy Industries, Ltd. Hiroshima Research Institute (72) Inventor Akira Hattori 1-1-1, Akunouramachi, Nagasaki-shi Mitsubishi Heavy Industries Inside Nagasaki Shipyard Co., Ltd. (72) Takashi Kurizaki 1-1, Akunouramachi, Nagasaki-shi F-term in Nagasaki Shipbuilding Co., Ltd.Mitsubishi Heavy Industries Co., Ltd. F-term (reference) CC26 CC32. ZA33B ZA36A ZA37A ZA38A
Claims (5)
ス中の窒素酸化物を除去する方法であって、同排ガス
を、熱交換部、ガス加熱用バーナ部、燃焼触媒部、脱硝
装置部がこの順に配設されたガス流路を通過させ、同ガ
ス流路を通過した後の排ガスを前記熱交換部を通して排
出させることを特徴とする排ガス脱硝方法。1. A method for removing nitrogen oxides in an exhaust gas containing a flammable gas such as CO and H 2 , wherein the exhaust gas is subjected to a heat exchange section, a gas heating burner section, a combustion catalyst section, and a denitration apparatus. An exhaust gas denitration method, wherein the exhaust gas passes through the gas flow path arranged in this order, and the exhaust gas after passing through the gas flow path is discharged through the heat exchange section.
ナ部を出た排ガスの一部を前記燃焼触媒部をバイパスさ
せることによって前記脱硝装置部に流入する排ガス温度
を調節することを特徴とする排ガス脱硝方法。2. A method according to claim 1, wherein the temperature of the exhaust gas flowing into the denitration device is adjusted by bypassing a part of the exhaust gas exiting the gas heating burner through the combustion catalyst. Exhaust gas denitration method.
Ｒｈの少なくとも一種以上の活性金属を含み、担体にＴ
ｉＯ2 、ＺｒＯ2 、ＳｉＯ2 、ＴｉＯ2 −ＺｒＯ2 複合
酸化物、ＴｉＯ2 −ＳｉＯ2 複合酸化物、結晶性シリケ
ートの少なくとも一種以上を組み合わせてなる燃焼触媒
を用いたことを特徴とする排ガス脱硝方法。3. The combustion catalyst section includes Pt, Pd, Ir,
Containing at least one active metal of Rh,
iO 2, ZrO 2, SiO 2 , TiO 2 -ZrO 2 composite oxide, TiO 2 -SiO 2 composite oxide, an exhaust gas denitration, characterized in that using a comprising a combination of at least one or more combustion catalysts crystalline silicate Method.
媒部、脱硝装置部がこの順に配設された排ガス流路、及
び前記燃焼触媒部をバイパスするバイパス排ガス流路を
有し、同バイパスガス流路を流れるガス流量を調節可能
に構成したことを特徴とする排ガス脱硝装置。4. A flue gas passage in which a heat exchange unit, a gas heating burner unit, a combustion catalyst unit, and a denitration unit are disposed in this order, and a bypass flue gas passage that bypasses the combustion catalyst unit. An exhaust gas denitration apparatus characterized in that a gas flow rate flowing through a bypass gas flow path is adjustable.
Ｐｔ、Ｐｄ、Ｉｒ、Ｒｈの少なくとも一種以上の活性金
属を含み、担体にＴｉＯ2 、ＺｒＯ2 、ＳｉＯ 2 、Ｔｉ
Ｏ2 −ＺｒＯ2 複合酸化物、ＴｉＯ2 −ＳｉＯ2 複合酸
化物、結晶性シリケートの少なくとも一種以上を組み合
わてなる燃焼触媒を設置したことを特徴とする排ガス脱
硝装置。5. The denitration device according to claim 4, wherein:
Activated gold of at least one of Pt, Pd, Ir, Rh
Genus, and the carrier is TiOTwo, ZrOTwo, SiO Two, Ti
OTwo-ZrOTwoComposite oxide, TiOTwo-SiOTwoComplex acid
Combination of at least one of oxides and crystalline silicates
Exhaust gas degassing characterized by installing a personal combustion catalyst
Glass equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11112075A JP2000300961A (en) | 1999-04-20 | 1999-04-20 | Method and facility for denitration of exhaust gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11112075A JP2000300961A (en) | 1999-04-20 | 1999-04-20 | Method and facility for denitration of exhaust gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000300961A true JP2000300961A (en) | 2000-10-31 |
Family
ID=14577454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11112075A Pending JP2000300961A (en) | 1999-04-20 | 1999-04-20 | Method and facility for denitration of exhaust gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000300961A (en) |
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