JPH10225641A - Low temperature denitration catalyst and its production and low temperature denitration method - Google Patents
Low temperature denitration catalyst and its production and low temperature denitration methodInfo
- Publication number
- JPH10225641A JPH10225641A JP9030790A JP3079097A JPH10225641A JP H10225641 A JPH10225641 A JP H10225641A JP 9030790 A JP9030790 A JP 9030790A JP 3079097 A JP3079097 A JP 3079097A JP H10225641 A JPH10225641 A JP H10225641A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- activated carbon
- low
- denitration
- catalyst
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIPBPJZISZCBJQ-UHFFFAOYSA-N 1-[(2-methylpropan-2-yl)oxycarbonyl]-3-(pyridin-4-ylmethyl)piperidine-3-carboxylic acid Chemical compound C1N(C(=O)OC(C)(C)C)CCCC1(C(O)=O)CC1=CC=NC=C1 JIPBPJZISZCBJQ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 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 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、低温脱硝触媒及び
その製造方法ならびに低温脱硝方法に関する。The present invention relates to a low-temperature denitration catalyst, a method for producing the same, and a low-temperature denitration method.
【０００２】[0002]
【従来技術】従来より、ボイラ等の固定式窒素酸化物発
生源における脱硝手段としては、酸化バナジウムを触媒
とし、アンモニアを還元剤として用い、窒素酸化物（Ｎ
Ｏｘ）を選択的に還元する方法が広く知られており、実
用化されるに至っている。2. Description of the Related Art Conventionally, as a denitration means in a fixed type nitrogen oxide generating source such as a boiler, vanadium oxide is used as a catalyst, ammonia is used as a reducing agent, and nitrogen oxide (N
A method for selectively reducing Ox) is widely known and has been put to practical use.
【０００３】しかしながら、この触媒を用いる場合は、
脱硝活性を上げるために３００℃以上に反応温度を高め
る必要がある。すなわち、反応温度を高温にすれば、担
体であるチタニアがシンタリングを起こし、触媒性能の
低下を引き起こす。その結果として、非常に高価なバナ
ジウム触媒を比較的頻繁に交換する必要も生じる。However, when using this catalyst,
It is necessary to raise the reaction temperature to 300 ° C. or higher in order to increase the denitration activity. That is, if the reaction temperature is set to a high temperature, titania as a carrier causes sintering, which causes a decrease in catalytic performance. As a result, it is also necessary to replace very expensive vanadium catalysts relatively frequently.
【０００４】また、高い反応温度が要求されると、脱硝
装置も、ボイラ出口直後、廃熱ボイラの伝熱部途中等の
限られた箇所にしか設置できないため、装置の複雑化、
耐熱材料の仕様による高額化、交換時の作業性の悪さ等
の問題も生じる。When a high reaction temperature is required, the denitration device can be installed only in a limited place, such as immediately after the boiler outlet, or in the middle of the heat transfer section of the waste heat boiler.
Problems such as an increase in cost due to the specification of the heat-resistant material and poor workability at the time of replacement also occur.
【０００５】さらに、かかる従来技術では、集塵機出口
の１５０℃以下の排気ガス或いは低温の製鉄所の焼結排
気ガスの脱硝に適用しようとすると再加熱が必要とな
り、経済的な見地よりその適用は事実上困難である。Further, in the prior art, reheating is required to apply to denitration of exhaust gas of 150 ° C. or less at the outlet of the dust collector or sintering exhaust gas of a low-temperature steelworks. Practically difficult.
【０００６】[0006]
【発明が解決しようとする課題】従って、本発明は、特
に比較的低温で排気ガスの脱硝を行うことを主な目的と
する。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to denitrate exhaust gas at a relatively low temperature.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記の従来
技術の問題に鑑み、鋭意研究を重ねた結果、特定の構成
からなる触媒を一定条件下で用いる場合には、低温下で
あっても有効に脱硝できることを見出し、本発明を完成
するに至った。Means for Solving the Problems In view of the above-mentioned problems in the prior art, the present inventor has conducted intensive studies, and as a result, when a catalyst having a specific constitution is used under a certain condition, the temperature is low. The present inventors have found that the denitration can be carried out effectively even after this, and have completed the present invention.
【０００８】すなわち、本発明は、下記の低温脱硝触媒
及びその製造方法ならびに低温脱硝方法に係るものであ
る。That is, the present invention relates to the following low-temperature denitration catalyst, a method for producing the same, and a low-temperature denitration method.
【０００９】１．Ｍｎ、Ｆｅ、Ｃｏ及びＮｉの少なくと
も１種の金属酸化物が活性炭素繊維に担持されている低
温脱硝触媒。1. A low-temperature denitration catalyst in which at least one metal oxide of Mn, Fe, Co and Ni is supported on activated carbon fibers.
【００１０】２．Ｍｎ、Ｆｅ、Ｃｏ及びＮｉの少なくと
も１種の金属塩の水溶液を活性炭素繊維に含浸し、減圧
脱気した後、乾燥し、次いで酸化性雰囲気下２００〜３
００℃で加熱処理して当該金属塩を金属酸化物とする低
温脱硝触媒の製造方法。[0010] 2. An activated carbon fiber is impregnated with an aqueous solution of at least one metal salt of Mn, Fe, Co, and Ni, degassed under reduced pressure, dried, and then dried under an oxidizing atmosphere at 200 to 3 times.
A method for producing a low-temperature denitration catalyst in which a heat treatment is performed at 00 ° C. to convert the metal salt into a metal oxide.
【００１１】３．上記１項に記載の触媒に、窒素酸化物
を含むガスを還元剤の存在下で接触させることを特徴と
する排気ガスの低温脱硝方法。3. 2. A low-temperature exhaust gas denitration method, comprising contacting a gas containing nitrogen oxide with the catalyst according to the above item 1 in the presence of a reducing agent.
【００１２】[0012]
【発明の実施の形態】以下、本発明をその実施の形態と
ともに詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail along with its embodiments.
【００１３】本発明の低温脱硝触媒は、Ｍｎ、Ｆｅ、Ｃ
ｏ及びＮｉの少なくとも１種の金属酸化物が活性炭素繊
維に担持されているものである。The low-temperature denitration catalyst of the present invention comprises Mn, Fe, C
At least one metal oxide of o and Ni is supported on activated carbon fibers.
【００１４】担持させる金属酸化物としては、マンガン
酸化物（ＭｎＯ2、ＭｎＯ、Ｍｎ2Ｏ3等）、鉄酸化物
（Ｆｅ2Ｏ3、Ｆｅ3Ｏ4等）、コバルト酸化物（Ｃｏ2Ｏ3
等）及びニッケル酸化物（ＮｉＯ等）の少なくとも１種
を用いることができ、これらの酸化物の中においては、
本発明の効果が得られる限り特にその酸化物の種類は制
限されない。これらの中でも、マンガン酸化物が好まし
く、特に二酸化マンガン（ＭｎＯ2）がより好ましい。
金属酸化物の担持量は、最終製品の用途等に応じて適宜
変更でき、通常は活性炭素繊維に対して５〜３０重量％
程度、好ましくは１０〜１５重量％とする。As metal oxides to be supported, manganese oxides (MnO 2 , MnO, Mn 2 O 3 etc.), iron oxides (Fe 2 O 3 , Fe 3 O 4 etc.), cobalt oxides (Co 2 O 3 ) Three
And nickel oxides (NiO and the like) can be used. Among these oxides,
The type of the oxide is not particularly limited as long as the effects of the present invention can be obtained. Of these, manganese oxides are preferred, and manganese dioxide (MnO 2 ) is particularly preferred.
The supported amount of the metal oxide can be appropriately changed according to the use of the final product, and is usually 5 to 30% by weight based on the activated carbon fiber.
Degree, preferably 10 to 15% by weight.
【００１５】活性炭素繊維としては、金属酸化物を担持
できる限り特に制限されず、公知のピッチ系、ＰＡＮ系
等のものが使用でき、また市販の活性炭素繊維も使用す
ることができる。この中でも、特にピッチ系活性炭素繊
維が好ましい。また、活性炭素繊維の比表面積は、最終
製品の用途等に応じて適宜設定することができるが、通
常は５００〜１５００ｍ2／ｇ程度、好ましくは７００
〜１０００ｍ2／ｇとする。The activated carbon fibers are not particularly limited as long as they can support the metal oxide, and known pitch-based and PAN-based fibers can be used, and commercially available activated carbon fibers can also be used. Among these, pitch-based activated carbon fibers are particularly preferred. Further, the specific surface area of the activated carbon fiber can be appropriately set according to the use of the final product or the like, but is usually about 500 to 1500 m 2 / g, preferably about 700 m 2 / g.
１０００1000 m 2 / g.
【００１６】本発明の低温脱硝触媒は、例えば次の方法
により製造することができる。まず、Ｍｎ、Ｆｅ、Ｃｏ
及びＮｉの少なくとも１種の金属塩の水溶液を活性炭素
繊維に含浸し、減圧脱気した後、乾燥し、次いで酸化性
雰囲気下２００〜３００℃で加熱処理して当該金属塩を
金属酸化物とする。The low-temperature denitration catalyst of the present invention can be produced, for example, by the following method. First, Mn, Fe, Co
And an aqueous solution of at least one metal salt of Ni is impregnated into activated carbon fibers, degassed under reduced pressure, dried, and then heat-treated at 200 to 300 ° C. in an oxidizing atmosphere to convert the metal salt into a metal oxide. I do.
【００１７】上記金属塩としては、水溶性のものであれ
ば特に制限されないが、特に硝酸塩（例えば、硝酸マン
ガン（II）、硝酸鉄（III）等）を用いることが好まし
い。これら金属塩は、水和物も含まれる。水溶液の濃度
は、最終製品の担持量が上記範囲になれば特に限定され
ないが、通常は０．５〜１５重量％程度、好ましくは５
〜１０重量％とすれば良い。The metal salt is not particularly limited as long as it is water-soluble, but it is particularly preferable to use a nitrate (eg, manganese (II) nitrate, iron (III) nitrate, etc.). These metal salts include hydrates. The concentration of the aqueous solution is not particularly limited as long as the amount of the final product carried falls within the above range, but is usually about 0.5 to 15% by weight, preferably 5 to 15% by weight.
The content may be set to 10 to 10% by weight.
【００１８】次いで、上記水溶液に活性炭素繊維を含浸
させる。含浸させた活性炭素繊維を減圧下で脱気処理し
た後、乾燥する。減圧する程度は、通常１０-1〜１０Ｔ
ｏｒｒ程度の圧力下とすれば良いが、この範囲外であっ
ても良い。また、乾燥温度も、特に制限されず、通常は
１００℃以下とすれば良い。Next, the aqueous solution is impregnated with activated carbon fibers. The impregnated activated carbon fibers are degassed under reduced pressure, and then dried. The degree of pressure reduction is usually 10 -1 to 10 T
The pressure may be set to about orr, but may be outside this range. Further, the drying temperature is not particularly limited, and may be usually 100 ° C. or lower.
【００１９】乾燥後、活性炭素繊維を加熱処理する。加
熱温度は、含浸されている金属塩が金属酸化物として担
持できる限りは特に制限されないが、通常は２００〜３
００℃程度、好ましくは２８０〜３００℃とすれば良
い。加熱雰囲気は、酸化性雰囲気下（例えば空気中）と
すれば良く、好ましくは空気気流下とする。空気気流を
用いる場合の流通量は、通常０．１〜１．０ｍ3／ｍｉ
ｎ程度とすれば良い。After drying, the activated carbon fibers are heat-treated. The heating temperature is not particularly limited as long as the impregnated metal salt can be supported as a metal oxide.
The temperature may be about 00 ° C, preferably 280 to 300 ° C. The heating atmosphere may be an oxidizing atmosphere (for example, in the air), preferably an air stream. The flow rate when using an air stream is usually 0.1 to 1.0 m 3 / mi.
It may be about n.
【００２０】本発明の低温脱硝方法は、上記の本発明触
媒に、窒素酸化物を含むガスを還元剤の存在下で接触さ
せることを特徴とする。The low-temperature denitration method of the present invention is characterized in that a gas containing nitrogen oxide is brought into contact with the above-mentioned catalyst of the present invention in the presence of a reducing agent.
【００２１】本発明方法では、還元剤の存在下で窒素酸
化物を含むガスとの接触を行うが、還元剤としては公知
のものをそのまま使用でき、例えばアンモニア、水素、
炭化水素等が使用できる。この中でも、特にアンモニア
が好ましい。還元剤の含有量は、上記ガス中の窒素酸化
物の濃度と等モル又はそれ以上の量とすれば良い。In the method of the present invention, contact with a gas containing nitrogen oxides is carried out in the presence of a reducing agent, and any known reducing agent can be used as it is, for example, ammonia, hydrogen,
Hydrocarbons and the like can be used. Of these, ammonia is particularly preferred. The content of the reducing agent may be equal to or more than the concentration of the nitrogen oxide in the gas.
【００２２】窒素酸化物を含むガスの組成は、排気ガス
等の組成のままでも良いが、特に窒素酸化物１０〜５０
００ｐｐｍ（好ましくは２０〜３００ｐｐｍ）、酸素３
ｖｏｌ％以上（好ましくは３〜１０ｖｏｌ％）及び水蒸
気８０ｖｏｌ％以下（好ましくは５〜２０ｖｏｌ％）を
含む組成とすることが好ましい。また、接触させる際の
温度も特に制限されないが、通常は２００℃以下、好ま
しくは１００〜１５０℃で行えば良い。The composition of the gas containing nitrogen oxides may be the same as the composition of the exhaust gas or the like.
00 ppm (preferably 20 to 300 ppm), oxygen 3
It is preferable that the composition contains not less than vol% (preferably 3 to 10 vol%) and not more than 80 vol% of steam (preferably 5 to 20 vol%). The temperature at the time of contact is not particularly limited, but it is usually 200 ° C. or lower, preferably 100 to 150 ° C.
【００２３】接触させる方法は、特に制限されず、公知
の方法に従えば良い。例えば、触媒を反応管等に充填
し、その中に窒素酸化物を含むガスを流通させれば良
い。このガスの流通量は、用いる触媒量等に応じて適宜
定めることができる。The method of contact is not particularly limited, and may be in accordance with a known method. For example, a catalyst may be filled in a reaction tube or the like, and a gas containing nitrogen oxide may be passed through the reaction tube. The flow rate of this gas can be appropriately determined according to the amount of the catalyst used and the like.
【００２４】[0024]
【作用】本発明においては、低温脱硝触媒を通過する間
に、ガス中に含まれる窒素酸化物が還元剤（例えばアン
モニア）と反応し、無害な窒素と水蒸気に分解される。
その反応例を示すと下記（１）（２）の通りである。In the present invention, while passing through the low-temperature denitration catalyst, nitrogen oxides contained in the gas react with a reducing agent (eg, ammonia) and are decomposed into harmless nitrogen and water vapor.
Examples of the reaction are as follows (1) and (2).
【００２５】 ４ＮＯ＋４ＮＨ3＋Ｏ2→４Ｎ2＋６Ｈ2Ｏ …（１） ６ＮＯ2＋８ＮＨ3→７Ｎ2＋１２Ｈ2Ｏ …（２） 活性炭素繊維の表面の金属酸化物にＮＯが吸着され、金
属酸化物の強い酸化性能によりＮＯ2となる。生成した
反応性の高いＮＯ2がアンモニアと反応し、Ｎ2とＨ2Ｏ
に還元される。Ｎ2とＨ2Ｏが脱離した後の金属酸化物は
酸素により酸化され、酸化性金属酸化物表面が再生され
る。これらの反応が２００℃以下の低温で進行するの
は、特に、活性炭素繊維のもつ２ｎｍ以下のミクロポア
中でこれらの反応物質が凝縮し、ミクロな領域で高圧反
応するためである。4NO + 4NH 3 + O 2 → 4N 2 + 6H 2 O (1) 6NO 2 + 8NH 3 → 7N 2 + 12H 2 O (2) NO is adsorbed on the metal oxide on the surface of the activated carbon fiber, and It becomes NO 2 due to strong oxidation performance. The generated highly reactive NO 2 reacts with ammonia, and N 2 and H 2 O
Is reduced to After N 2 and H 2 O have been eliminated, the metal oxide is oxidized by oxygen, and the oxidizable metal oxide surface is regenerated. The reason why these reactions proceed at a low temperature of 200 ° C. or less is that these reactants are condensed in the micropores of 2 nm or less of the activated carbon fiber and react at high pressure in a micro region.
【００２６】[0026]
【発明の効果】本発明の脱硝方法によれば、排気ガス中
等において低濃度から高濃度で含まれる窒素酸化物を特
に１５０℃以下という低温下でも効率的に除去し、これ
を主として窒素と水に還元することが可能である。特
に、常温〜１５０℃の温度で低濃度〜高濃度の窒素酸化
物を通常４０〜８０％という高い除去率で脱硝すること
ができる。According to the denitration method of the present invention, nitrogen oxides contained at low to high concentrations in exhaust gas and the like can be efficiently removed even at a low temperature of 150 ° C. or lower, and nitrogen and water are mainly removed. It is possible to reduce to In particular, nitrogen oxides having a low concentration to a high concentration can be denitrated at a temperature of normal temperature to 150 ° C. with a high removal rate of usually 40 to 80%.
【００２７】このような本発明方法では、ボイラ、エン
ジン、タービン等から排出される燃焼排気ガスの脱硝に
有効であり、特に排煙処理装置、廃熱処理装置等の出口
における比較的低温（通常２００℃以下）の排気ガスを
効率良く脱硝することができる。The method of the present invention is effective for denitration of combustion exhaust gas discharged from a boiler, an engine, a turbine, or the like. (Lower than or equal to ° C.) exhaust gas can be efficiently denitrated.
【００２８】[0028]
【実施例】以下、実施例を示し、本発明の特徴をより一
層明確にする。The following examples are provided to further clarify the features of the present invention.
【００２９】実施例１〜９ 表１に示す条件で金属酸化物を活性炭素繊維に担持させ
て触媒をそれぞれ製造した。Examples 1 to 9 Metal oxides were supported on activated carbon fibers under the conditions shown in Table 1 to produce catalysts.
【００３０】[0030]
【表１】 [Table 1]
【００３１】活性炭素繊維としては、ピッチ系活性炭素
繊維（アドール（株）製）を用いた。試料名は「Ａ７」
であり、その比表面積は７００ｍ2／ｇである。このピ
ッチ系活性炭素繊維に、硝酸マンガン（II）６水和物、
硝酸鉄（III）９水和物又は硝酸コバルト（II）６水和
物の水溶液をそれぞれ含浸させた。含浸させた水溶液の
濃度は、表１に示すように、最終的な金属酸化物の担持
量として５〜１５重量％の範囲となるように調整した。As the activated carbon fibers, pitch-based activated carbon fibers (manufactured by Adol Co., Ltd.) were used. Sample name is "A7"
And the specific surface area is 700 m 2 / g. Manganese (II) nitrate hexahydrate,
An aqueous solution of iron (III) nitrate 9 hydrate or cobalt (II) nitrate hexahydrate was impregnated, respectively. As shown in Table 1, the concentration of the impregnated aqueous solution was adjusted so that the final amount of supported metal oxide was in the range of 5 to 15% by weight.
【００３２】その後、デシケーター内で室温下、真空ポ
ンプにより１０-1Ｔｏｒｒまで減圧し、各試料について
脱気処理を施した。この処理によって、活性炭素繊維の
ミクロポア内への脱気と金属塩の浸透を促進することが
できる。次いで、これを１００℃の熱風下で１昼夜乾燥
し、さらに空気気流下２００〜３００℃の範囲で１時間
加熱処理し、上記金属硝酸塩を熱分解して金属酸化物と
し、触媒をそれぞれ得た。Thereafter, the pressure was reduced to 10 -1 Torr by a vacuum pump at room temperature in a desiccator, and each sample was degassed. By this treatment, degassing of the activated carbon fibers into the micropores and penetration of the metal salt can be promoted. Next, this was dried under hot air of 100 ° C. for one day and night, and further heat-treated in an air stream at a temperature in the range of 200 to 300 ° C. for 1 hour, thereby thermally decomposing the metal nitrate to form a metal oxide, thereby obtaining catalysts. .
【００３３】次に、得られた触媒を反応管（内径１５ｍ
ｍ）に２．５ｇを充填し、温度６０〜１５０℃でガスを
５００ｃｃ／ｍｉｎで流通した。ガス組成は、ＮＯ：２
００ｐｐｍ、ＮＨ3：２００ｐｐｍ、Ｏ2：１０．５ｖｏ
ｌ％、Ｎ2バランス、水分：８．１ｖｏｌ％とした。反
応管より出口ガスを、化学発光式ＮＯｘ計（「ＥＣＬ−
８８ＵＳ」、柳本製作所（株）製）により分析し、次式
により脱硝率を算出した。Next, the obtained catalyst was placed in a reaction tube (inside diameter 15 m).
m) was charged with 2.5 g, and gas was flowed at a temperature of 60 to 150 ° C. at 500 cc / min. The gas composition is NO: 2
00 ppm, NH 3 : 200 ppm, O 2 : 10.5 vo
l%, N 2 balance, moisture: it was 8.1vol%. The outlet gas from the reaction tube was used as a chemiluminescent NOx meter (“ECL-
88US ", manufactured by Yanagimoto Mfg. Co., Ltd.), and the denitration rate was calculated by the following equation.
【００３４】脱硝率（％）＝入口ＮＯ濃度(ppm)−出口
ＮＯ濃度(ppm)／入口ＮＯ濃度(ppm)×１００ なお、脱硝率は、反応開始後３０時間後の安定化した状
態の定常反応中における値を示す。Denitration rate (%) = Inlet NO concentration (ppm)-Outlet NO concentration (ppm) / Inlet NO concentration (ppm) x 100 The denitration rate is a steady state in a stabilized state 30 hours after the start of the reaction. The values during the reaction are shown.
【００３５】比較例１〜３ 比較例１及び２として、金属酸化物を担持しないピッチ
系活性炭素繊維（いずれもアドール（株）製、試料名
「Ａ１５」及び「Ａ７」、比表面積はそれぞれ１５００
ｍ2／ｇ及び７００ｍ2／ｇ）、並びに比較例３として従
来技術であるバナジウム系触媒（Ｖ2Ｏ5／ＴｉＯ2）を
用いて脱硝した。その結果も図１に示す。Comparative Examples 1 to 3 As Comparative Examples 1 and 2, pitch-based activated carbon fibers not supporting a metal oxide (both manufactured by Adol Co., Ltd., sample names "A15" and "A7", specific surface area of 1500, respectively)
m 2 / g and 700 m 2 / g) and, as Comparative Example 3, denitration using a vanadium-based catalyst (V 2 O 5 / TiO 2 ) which is a conventional technique. The results are also shown in FIG.
【００３６】図１の結果より、本発明の触媒を用いた脱
硝によれば、もとの活性炭素繊維（比較例１及び２）或
いは従来技術（バナジウム系触媒：比較例３）に比べ
て、全般的に１５０℃以下の低温における脱硝活性に優
れていることがわかる。殊に、活性炭素繊維「Ａ７」に
Ｍｎを１５％担持し、３００℃で熱分解して得た触媒を
用いた実施例１では、脱硝率が９４％にも達した。From the results shown in FIG. 1, the denitration using the catalyst of the present invention shows that compared to the original activated carbon fiber (Comparative Examples 1 and 2) or the prior art (vanadium-based catalyst: Comparative Example 3). It can be seen that the denitration activity at a low temperature of 150 ° C. or lower is generally excellent. In particular, in Example 1 in which the activated carbon fiber "A7" supported 15% of Mn and was thermally decomposed at 300 ° C. and used a catalyst, the denitration ratio reached as high as 94%.
【図１】実施例及び比較例における脱硝効果と温度との
関係を示す図である。FIG. 1 is a diagram showing a relationship between a denitration effect and a temperature in Examples and Comparative Examples.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 23/755 Ｂ０１Ｊ 23/74 ３０１Ａ 32/00 ＺＡＢ ３１１Ａ ３２１Ａ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI B01J 23/755 B01J 23/74 301A 32/00 ZAB 311A 321A
Claims (9)
種の金属酸化物が活性炭素繊維に担持されている低温脱
硝触媒。At least one of Mn, Fe, Co and Ni
A low-temperature denitration catalyst in which a kind of metal oxide is supported on activated carbon fibers.
１記載の低温脱硝触媒。2. The low-temperature denitration catalyst according to claim 1, wherein the metal oxide is manganese dioxide.
０ｍ2／ｇのピッチ系活性炭素繊維である請求項１記載
の低温脱硝触媒。3. The activated carbon fiber has a specific surface area of 500 to 150.
0 m 2 / g cold denitration catalyst of claim 1 wherein the pitch-based activated carbon fibers.
種の金属塩の水溶液を活性炭素繊維に含浸し、減圧脱気
した後、乾燥し、次いで酸化性雰囲気下２００〜３００
℃で加熱処理して当該金属塩を金属酸化物とする低温脱
硝触媒の製造方法。4. At least one of Mn, Fe, Co and Ni.
Activated carbon fibers are impregnated with an aqueous solution of the seed metal salt, degassed under reduced pressure, dried, and then dried under an oxidizing atmosphere at 200 to 300
A method for producing a low-temperature denitration catalyst in which the metal salt is subjected to a heat treatment at 0 ° C. to make the metal salt a metal oxide.
製造方法。5. The method according to claim 4, wherein the heat treatment is performed in an air stream.
方法。6. The method according to claim 4, wherein the metal salt is a nitrate.
載の製造方法。7. The method according to claim 4, wherein the drying temperature is 100 ° C. or lower.
に、窒素酸化物を含むガスを還元剤の存在下で接触させ
ることを特徴とする排気ガスの低温脱硝方法。8. A low-temperature exhaust gas denitration method comprising contacting a gas containing nitrogen oxide with the catalyst according to claim 1 in the presence of a reducing agent.
〜５０００ｐｐｍ、酸素３ｖｏｌ％以上及び水蒸気８０
ｖｏｌ％以下を含有し、かつ、当該ガスの温度が２００
℃以下である請求項８記載の排気ガスの低温脱硝方法。9. The gas containing nitrogen oxides may be nitrogen oxides 10.
~ 5000 ppm, oxygen 3 vol% or more and steam 80
vol% or less and the temperature of the gas is 200
9. The low-temperature denitration method for exhaust gas according to claim 8, wherein the temperature is not higher than 0.degree.
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| JP03079097A JP3843520B2 (en) | 1997-02-14 | 1997-02-14 | Low temperature denitration catalyst, production method thereof, and low temperature denitration method |
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|---|---|---|---|
| JP03079097A JP3843520B2 (en) | 1997-02-14 | 1997-02-14 | Low temperature denitration catalyst, production method thereof, and low temperature denitration method |
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| Publication Number | Publication Date |
|---|---|
| JPH10225641A true JPH10225641A (en) | 1998-08-25 |
| JP3843520B2 JP3843520B2 (en) | 2006-11-08 |
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| JP2005279508A (en) * | 2004-03-30 | 2005-10-13 | Matsushita Electric Ind Co Ltd | Prior-to-drying pretreatment method of three-dimensional structure body, exhausted gas purification filter and production method thereof |
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|---|---|---|---|---|
| JP2005279508A (en) * | 2004-03-30 | 2005-10-13 | Matsushita Electric Ind Co Ltd | Prior-to-drying pretreatment method of three-dimensional structure body, exhausted gas purification filter and production method thereof |
| JP2014043819A (en) * | 2012-08-28 | 2014-03-13 | Ihi Corp | Denitrification apparatus, and denitrification method |
| CN102989466A (en) * | 2012-12-27 | 2013-03-27 | 北京石油化工学院 | Flue gas desulfurization and denitrification catalyst for reduction method and applications of catalyst |
| CN102989466B (en) * | 2012-12-27 | 2015-04-15 | 北京石油化工学院 | Flue gas desulfurization and denitrification catalyst for reduction method and applications of catalyst |
| EP3017859A1 (en) | 2014-11-10 | 2016-05-11 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst for selective reduction of nox and exhaust gas purifying method |
| EP3207986A1 (en) | 2016-02-17 | 2017-08-23 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purification catalyst and production method thereof |
| CN108176403A (en) * | 2018-01-24 | 2018-06-19 | 四川农业大学 | A kind of activated carbon fiber-loaded Co3O4The preparation method of catalysis material |
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| CN116037115A (en) * | 2023-01-29 | 2023-05-02 | 石河子大学 | Foam nickel-based CO-SCR denitration catalyst and preparation method thereof |
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