JPH11347409A - Catalyst for treatment of waste gas, treatment of waste gas and treating device - Google Patents
Catalyst for treatment of waste gas, treatment of waste gas and treating deviceInfo
- Publication number
- JPH11347409A JPH11347409A JP10159024A JP15902498A JPH11347409A JP H11347409 A JPH11347409 A JP H11347409A JP 10159024 A JP10159024 A JP 10159024A JP 15902498 A JP15902498 A JP 15902498A JP H11347409 A JPH11347409 A JP H11347409A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- catalyst
- gas treatment
- waste gas
- activated carbon
- 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 68
- 239000002912 waste gas Substances 0.000 title abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 131
- 239000000126 substance Substances 0.000 claims abstract description 40
- 150000002013 dioxins Chemical class 0.000 claims abstract description 33
- 239000000460 chlorine Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 36
- 239000000428 dust Substances 0.000 claims description 30
- 150000001491 aromatic compounds Chemical class 0.000 claims description 10
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 7
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 7
- 150000003071 polychlorinated biphenyls Chemical class 0.000 claims description 7
- 229910001038 basic metal oxide Inorganic materials 0.000 claims description 6
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 5
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 150000008422 chlorobenzenes Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 abstract description 11
- 239000002440 industrial waste Substances 0.000 abstract description 7
- 239000010802 sludge Substances 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 235000017168 chlorine Nutrition 0.000 description 23
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 238000000354 decomposition reaction Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 7
- 229920002239 polyacrylonitrile Polymers 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- -1 dioxins Chemical class 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000001309 chloro group Chemical class Cl* 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000004045 organic chlorine compounds Chemical class 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001784 detoxification Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- GBUCDGDROYMOAN-UHFFFAOYSA-N 1,2,5-trichloro-3-phenylbenzene Chemical class ClC1=CC(Cl)=C(Cl)C(C=2C=CC=CC=2)=C1 GBUCDGDROYMOAN-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- JAYCNKDKIKZTAF-UHFFFAOYSA-N 1-chloro-2-(2-chlorophenyl)benzene Chemical class ClC1=CC=CC=C1C1=CC=CC=C1Cl JAYCNKDKIKZTAF-UHFFFAOYSA-N 0.000 description 1
- IYZWUWBAFUBNCH-UHFFFAOYSA-N 2,6-dichlorobiphenyl Chemical class ClC1=CC=CC(Cl)=C1C1=CC=CC=C1 IYZWUWBAFUBNCH-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 150000004827 dibenzo-1,4-dioxins Chemical class 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NFBOHOGPQUYFRF-UHFFFAOYSA-N oxanthrene Chemical compound C1=CC=C2OC3=CC=CC=C3OC2=C1 NFBOHOGPQUYFRF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、排ガス中の塩素含
有化合物の塩素を引き抜き、排出される排ガスを浄化す
る技術に関し、特に都市ゴミ焼却炉，産業廃棄物焼却
炉，汚泥焼却炉等の各種焼却炉、溶融炉等から排出され
る排ガス中に含有されるダイオキシン類等の塩素化芳香
族化合物等を無害化するための排ガス処理用触媒、排ガ
ス処理方法及び処理装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for extracting chlorine contained in a chlorine-containing compound in exhaust gas and purifying exhaust gas, and particularly for various kinds of municipal waste incinerators, industrial waste incinerators, sludge incinerators and the like. The present invention relates to an exhaust gas treatment catalyst, an exhaust gas treatment method, and an apparatus for detoxifying chlorinated aromatic compounds such as dioxins contained in exhaust gas discharged from an incinerator, a melting furnace, and the like.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】都市ゴ
ミ焼却炉，産業廃棄物焼却炉，汚泥焼却炉等の各種焼却
炉から排出される排ガス中には、焼却対象物の種類や焼
却条件によって、窒素酸化物の他、ダイオキシン類やＰ
ＣＢ類に代表される有害な塩素化芳香族化合物、高縮合
度芳香族炭化水素等の有害物質が含有されることがあ
り、このような有害物質はいわゆる環境ホルモンと称さ
れ、人体や動植物に被害をもたらし、自然環境を破壊す
るものとして、深刻な社会問題化している。2. Description of the Related Art Exhaust gas discharged from various incinerators, such as municipal waste incinerators, industrial waste incinerators, and sludge incinerators, depends on the type of incineration target and the incineration conditions. , Nitrogen oxides, dioxins and P
Harmful substances such as harmful chlorinated aromatic compounds represented by CBs and highly condensed aromatic hydrocarbons may be contained. Such harmful substances are called so-called environmental hormones, It is a serious social problem as it causes damage and destroys the natural environment.
【０００３】従来、排ガス中に含まれる上記有害物質の
除去のため、脱硝触媒又はダイオキシン類等の分解用触
媒として、チタニア（ＴｉＯ2 ）を担体とし、活性成分
として五酸化バナジウム（Ｖ2 Ｏ5 ），三酸化タングス
テン（ＷＯ3 ）等の金属酸化物等を少なくとも一つ担持
したものが使用されている。Conventionally, to remove the above harmful substances contained in exhaust gas, titania (TiO 2 ) has been used as a carrier as a denitration catalyst or a decomposition catalyst such as dioxins, and vanadium pentoxide (V 2 O 5 ) as an active ingredient. ), And at least one metal oxide such as tungsten trioxide (WO 3 ) is supported.
【０００４】このような触媒は、酸化分解触媒であり、
塩素化芳香族化合物をＣＯ2 ，Ｈ2Ｏ，他の塩化物等へ
分解するものであり、これによりダイオキシン類は分解
されるものの、完全に分解されない場合には、ダイオキ
シン類の前駆体で止まる場合もある。また、従来の酸化
触媒では、その比表面積が５０〜８０ｍ2 ／ｇ程度と小
さく、触媒性能を向上させるために、分解温度を高くす
る必要があるが、４００℃以下の温度領域ではダイオキ
シン類の再生成がなされる場合があり、問題となる。す
なわち、酸化触媒を用いてダイオキシン類を分解しても
完全に分解されない場合には、ダイオキシン類の前駆体
の再合成によりダイオキシン類を再度発生してしまうお
それがある。[0004] Such a catalyst is an oxidative decomposition catalyst,
It decomposes chlorinated aromatic compounds into CO 2 , H 2 O, and other chlorides. Dioxins are decomposed by this, but if they are not completely decomposed, they stop at dioxin precursors. In some cases. In addition, in the conventional oxidation catalyst, the specific surface area is as small as about 50 to 80 m 2 / g, and it is necessary to increase the decomposition temperature in order to improve the catalytic performance. Regeneration may occur, which is problematic. That is, when the dioxins are not completely decomposed even if they are decomposed by using the oxidation catalyst, the dioxins may be generated again by resynthesizing the dioxin precursor.
【０００５】このため、ダイオキシン類の再生成しない
２５０℃以下の低温におけるダイオキシン類の分解処理
が望まれている。[0005] For this reason, there is a demand for a treatment for decomposing dioxins at a low temperature of 250 ° C. or lower without regenerating dioxins.
【０００６】また、従来においては、排ガスの煤塵の除
去と同時にダイオキシン類を吸着して除去する試みが提
案されているが、例えば除塵装置（例えばバグフィル
タ）で煤塵と共にダイオキシン類を除去した場合には、
該除塵装置のフィルタには、ダイオキシン類が吸着され
ているので、該ダイオキシン類を吸着したフィルタを別
途処理，二次処理する必要があり、手間がかかるという
問題がある。同様に、ダイオキシン類含んだ有害物質を
高温で溶融処理する場合も該溶融物の二次処理が必要と
なり、別途処理工程が増大するという問題がある。Conventionally, attempts have been made to adsorb and remove dioxins simultaneously with the removal of dust from exhaust gas. For example, when dioxins are removed together with dust using a dust remover (eg, a bag filter). Is
Since dioxins are adsorbed on the filter of the dust removing device, it is necessary to separately treat and secondary-treat the filter adsorbing the dioxins, which is troublesome. Similarly, when a toxic substance containing dioxins is melted at a high temperature, secondary processing of the melt is required, and there is a problem that the number of additional processing steps is increased.
【０００７】本発明は、上記問題に鑑み、ダイオキシン
類等の有害な塩素化芳香族化合物等の有害物質の脱塩素
を行い、排ガス中の有害物質を確実に分解する排ガス処
理用触媒、排ガス処理方法及び処理装置を提供すること
を課題とする。SUMMARY OF THE INVENTION In view of the above problems, the present invention provides an exhaust gas treatment catalyst for dechlorinating harmful substances such as harmful chlorinated aromatic compounds such as dioxins, and for reliably decomposing harmful substances in exhaust gas. It is an object to provide a method and a processing device.
【０００８】[0008]
【課題を解決するための手段】前記課題を解決する［請
求項１］の発明は、排ガスを浄化する排ガス処理用触媒
であって、活性炭素繊維が塩基性を有することを特徴と
する。Means for Solving the Problems The invention according to claim 1 for solving the above problems is an exhaust gas treatment catalyst for purifying exhaust gas, wherein the activated carbon fiber has basicity.
【０００９】［請求項２］の発明は、請求項１におい
て、塩基性の活性炭素繊維が塩基性を強化してなること
を特徴とする。A second aspect of the present invention is characterized in that, in the first aspect, the basic activated carbon fiber is formed by reinforcing the basicity.
【００１０】［請求項３］の発明は、請求項１又は２に
おいて、塩基性の活性炭素繊維に窒素化合物を添着して
なることを特徴とする。[0010] The invention of claim 3 is characterized in that, in claim 1 or 2, a nitrogen compound is impregnated on basic activated carbon fiber.
【００１１】［請求項４］の発明は、請求項１又は２に
おいて、塩基性の活性炭素繊維に塩基性を有する金属酸
化物を担持してなることを特徴とする。[0011] The invention of claim 4 is characterized in that, in claim 1 or 2, the basic activated carbon fiber carries a basic metal oxide.
【００１２】［請求項５］の発明は、請求項１又は２に
おいて、塩基性の活性炭素繊維に窒素化合物及び塩基性
を有する金属酸化物を複合的に担持してなることを特徴
とする。The invention of claim 5 is characterized in that, in claim 1 or 2, the basic activated carbon fiber supports the nitrogen compound and the basic metal oxide in a complex manner.
【００１３】［請求項６］の発明は、請求項１乃至５に
おいて、塩基性の活性炭素繊維の比表面積が５００ｍ2
／ｇ以上であることを特徴とする。The invention of claim 6 is the invention according to claims 1 to 5, wherein the specific surface area of the basic activated carbon fiber is 500 m 2.
/ G or more.
【００１４】［請求項７］の発明は、排ガス中の有害物
質を請求項１乃至６の触媒に接触させ、排ガス中の有害
物質の塩素を引き抜き分解処理することを特徴とする。[0014] The invention of claim 7 is characterized in that the harmful substance in the exhaust gas is brought into contact with the catalyst of claim 1 to 6, and the chlorine of the harmful substance in the exhaust gas is extracted and decomposed.
【００１５】［請求項８］の発明は、請求項７におい
て、上記排ガス中の有害物質がダイオキシン類，ポリ塩
化ビフェニル類，クロルベンゼン類，クロロフェノール
及びクロロトルエンから選ばれる少なくとも一種の塩素
化芳香族化合物であることを特徴とする。The invention according to claim 8 is the invention according to claim 7, wherein the harmful substance in the exhaust gas is at least one chlorinated aromatic substance selected from dioxins, polychlorinated biphenyls, chlorobenzenes, chlorophenol and chlorotoluene. It is a group III compound.
【００１６】［請求項９］の発明は、排ガスを浄化する
排ガス処理装置であって、排ガス中の煤塵を除塵する除
塵装置と、該除塵装置の後流側に設けた請求項１乃至６
の排ガス処理用触媒を有する触媒装置とからなることを
特徴とする。According to a ninth aspect of the present invention, there is provided an exhaust gas treating apparatus for purifying exhaust gas, wherein the dust removing apparatus removes dust in the exhaust gas, and the exhaust gas treating apparatus is provided downstream of the dust removing apparatus.
And a catalyst device having the exhaust gas treatment catalyst.
【００１７】［請求項１０］の発明は、排ガスを浄化す
る排ガス処理装置であって、請求項１乃至６の排ガス処
理用触媒を有する触媒装置と、該触媒装置の後流側に設
けた排ガス中の煤塵を除塵する除塵装置とからなること
を特徴とする。According to a tenth aspect of the present invention, there is provided an exhaust gas treating apparatus for purifying an exhaust gas, wherein the catalytic device having the exhaust gas treating catalyst according to any one of the first to sixth aspects and an exhaust gas provided downstream of the catalytic device are provided. And a dust removing device for removing dust and dust therein.
【００１８】［請求項１１］の発明は、請求項９又は１
０において、上記触媒装置に塩基性物質を導入する手段
を設けたことを特徴とする。The invention of claim 11 is the invention of claim 9 or 1
0, wherein a means for introducing a basic substance is provided in the catalyst device.
【００１９】［請求項１２］の発明は、請求項９又は１
０において、脱硝装置を設けたことを特徴とする。The invention of claim 12 is the invention of claim 9 or 1
0, a denitration device is provided.
【００２０】［請求項１３］の発明は、請求項９乃至１
１において、上記触媒装置に導入する排ガスの温度を１
００〜４００℃としたことを特徴とする。The invention of claim 13 is the invention of claims 9 to 1
In 1, the temperature of the exhaust gas introduced into the catalyst device is set to 1
The temperature is set to 00 to 400 ° C.
【００２１】[0021]
【発明の実施の形態】以下、本発明の実施形態を説明す
るが、本発明はこれに限定されるものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.
【００２２】本発明に係る触媒は、例えば焼却炉等から
排出される塩素を含有する化合物等を含む排ガスを浄化
する排ガス処理用触媒であって、活性炭素繊維が塩基性
を有するものである。ここで、一般に炭素繊維とは、ア
クリル繊維，強力レーヨン，石油ピッチ，石炭ピッチ等
を溶融紡糸したピッチ繊維を用い、空気中で２００〜４
００℃で熱酸化架橋反応を行った後、窒素中で８００〜
１５００℃で熱処理し、２０００℃で熱処理して炭素含
有量の高い黒鉛化した繊維をいい、窒素含有量が0.１重
量％以下のものである。本発明の塩基性を有する活性炭
素繊維とは、上記炭素繊維に被処理化合物中の塩素を引
き抜く反応性を有する窒素を含有させたものをいう。上
記塩基性の活性炭素繊維の製造の一例としては、窒素基
を含有する含窒素炭化水素高分子を炭化，不溶化したも
のや、活性炭素繊維へ窒素化合物を添着したものを、焼
成して炭素繊維とすることで得られる。また、ＰＡＮ
（ポリアクリロニトリル）繊維を高温で焼成した炭素繊
維はＰＡＮ繊維原料に窒素基を含有しているので、その
ままでも塩基性活性炭素繊維として使用することができ
る。さらに、このＰＡＮ系の活性炭素繊維に窒素基を有
するピリジン等をＣＶＤ法により焼成することで活性炭
素繊維に窒素基の含有量を高くした塩基性活性炭素繊維
（窒素含有量：５重量％）とすることができる。The catalyst according to the present invention is an exhaust gas treatment catalyst for purifying an exhaust gas containing, for example, a chlorine-containing compound discharged from an incinerator or the like, wherein the activated carbon fibers have basicity. Here, in general, carbon fibers are pitch fibers obtained by melt-spinning acrylic fibers, high-strength rayon, petroleum pitch, coal pitch, etc., and are used in the air at 200 to 4 mm.
After performing the thermal oxidative crosslinking reaction at 00 ° C.,
It refers to a graphitized fiber which is heat-treated at 1500 ° C. and heat-treated at 2000 ° C. and has a high carbon content, and has a nitrogen content of 0.1% by weight or less. The basic activated carbon fiber of the present invention means a carbon fiber containing the reactive nitrogen for extracting chlorine in the compound to be treated. Examples of the production of the basic activated carbon fiber include carbonized and insolubilized nitrogen-containing hydrocarbon polymers containing a nitrogen group, and activated carbon fibers impregnated with a nitrogen compound. Is obtained. Also, PAN
Since carbon fibers obtained by firing (polyacrylonitrile) fibers at a high temperature contain a nitrogen group in the PAN fiber raw material, they can be used as basic activated carbon fibers as they are. Further, the PAN-based activated carbon fiber is baked with pyridine or the like having a nitrogen group by a CVD method to increase the content of the nitrogen group in the activated carbon fiber (nitrogen content: 5% by weight). It can be.
【００２３】上記塩基性の活性炭素繊維は、繊維状の炭
素繊維にミクロの細孔を有するものであり、該細孔に窒
素を担持させ、窒素の活性点を無数に有することで、塩
素引き抜き活性が非常に高いものとなる。なお、酸化分
解触媒である金属触媒（ＴｉＯ2 ，Ｖ2 Ｏ5 ，ＷＯ3 ，
Ａｕ，Ｐｔ等）を活性物質として担持させた炭素繊維と
本発明の塩基性の活性炭素繊維との相違は、前者が該ガ
ス中の有害物質の分解作用が酸化分解であり、ダイオキ
シン類を分解してもダイオキシン類の前駆体（例えばク
ロルベンゼン，クロロフェノール等）となる場合がある
が、後者の本発明の塩基性の活性炭素繊維触媒は、塩素
引き抜きによる還元分解反応であるのでダイオキシン類
を分解した場合には、例えばベンゼン，フェノール等に
分解され、ダイオキシン類の前駆体の発生がないので、
両者の作用・機構が大きく異なる点である。The above-mentioned basic activated carbon fiber is a fibrous carbon fiber having micropores. Nitrogen is supported on the pores, and by having an infinite number of active sites of nitrogen, chlorine is extracted. The activity is very high. In addition, metal catalysts (TiO 2 , V 2 O 5 , WO 3 ,
Au, Pt, etc.) as the active substance is different from the basic activated carbon fiber of the present invention in that the harmful substance in the gas is decomposed by oxidative decomposition and dioxins are decomposed. However, the basic activated carbon fiber catalyst of the present invention, which is a reductive decomposition reaction by extracting chlorine, may be used as a dioxin precursor (eg, chlorobenzene, chlorophenol, etc.). When decomposed, it is decomposed into, for example, benzene and phenol, and there is no generation of dioxin precursors.
The point is that the operation and mechanism of both are greatly different.
【００２４】本発明で塩基性の活性炭素繊維が塩基性を
強化してなるとは、窒素含有比率が高いものをいい、窒
素の担持量が１〜２５重量％のもの、特に５〜２５重量
％のものが好適である。これは、窒素の担持量が１重量
％未満の場合には、中性の活性炭素繊維や酸化触媒を担
持した活性炭素繊維と同様に有効な塩素引き抜き反応が
良好に進行しないからである。一方、窒素の担持量が２
５重量％を超えるような担持の場合は、担持による増量
効果に更なる効果が発現せず、また、細孔に窒素を担持
するにも限界があるからである。In the present invention, the term "basic activated carbon fiber having enhanced basicity" means that the content of nitrogen is high, and the content of nitrogen is 1 to 25% by weight, particularly 5 to 25% by weight. Are preferred. This is because when the amount of nitrogen supported is less than 1% by weight, the effective chlorine extraction reaction does not proceed as well as neutral activated carbon fibers or activated carbon fibers supporting an oxidation catalyst. On the other hand, if the amount of nitrogen
This is because, in the case of loading exceeding 5% by weight, no further effect is exerted on the effect of increasing the amount of loading, and there is a limit in loading nitrogen in the pores.
【００２５】上記塩基性活性成分として、窒素を含有さ
せるものとは異なり塩素引き抜き反応性を有する金属酸
化物を担持するようにしてもよい。本発明で上記塩素引
き抜き反応性を有する金属酸化物は、例えば酸化スズ
（ＳｎＯ）を挙げることができるが、本発明はこれに限
定されるものではなく、例えばＭｇＯ，ＣａＯ，Ｓｒ
Ｏ，ＢａＯ，ＺｒＯ2 ，ＺｎＯ及びこれらのＳｉＯ2 と
の複合酸化物，Ａｌ2 Ｏ3 ，ＴｉＯ2 との複合酸化物を
挙げることができる。As the above-mentioned basic active ingredient, a metal oxide having chlorine extraction reactivity different from that containing nitrogen may be supported. In the present invention, the metal oxide having the chlorine abstraction reactivity includes, for example, tin oxide (SnO). However, the present invention is not limited to this. For example, MgO, CaO, Sr
O, BaO, ZrO 2 , ZnO, and composite oxides of these with SiO 2 and composite oxides with Al 2 O 3 and TiO 2 can be mentioned.
【００２６】また、他の塩基性活性成分として、塩素引
き抜き反応性を有するロジウム（Ｒｈ）を担持するよう
にしてもよい。As another basic active ingredient, rhodium (Rh) having chlorine extraction reactivity may be supported.
【００２７】上記塩基性活性成分としては、各々を単独
で活性炭素繊維に担持してもよく、また複数種の活性成
分を複合的（例えば、ＰＡＮ系活性炭素繊維に酸化スズ
又は／及びロジウムを担持させる）ようにしてもよい。As the above-mentioned basic active ingredients, each of them may be independently carried on activated carbon fibers, or a plurality of kinds of active ingredients may be combined (for example, tin oxide and / or rhodium may be added to PAN-based activated carbon fibers). Carried).
【００２８】本発明の塩基性の活性炭素繊維の比表面積
は、従来の酸化触媒の比表面積（６０〜８０ｍ2 ／ｇ）
よりも数十倍から数百倍と高く、５００ｍ2 ／ｇ以上の
ものが好ましく、５００〜１００００ｍ2 ／ｇの範囲の
ものが好適である。このように、本発明の塩基性の活性
炭素繊維触媒は、比表面積が大きいので活性が高く、ダ
イオキシン類のような高沸点の分子量の大きいものを良
好に分解することができ、有利である。The specific surface area of the basic activated carbon fiber of the present invention is the specific surface area of a conventional oxidation catalyst (60 to 80 m 2 / g).
It is several tens times to several hundred times higher than that, preferably 500 m 2 / g or more, and more preferably 500 to 10000 m 2 / g. As described above, the basic activated carbon fiber catalyst of the present invention has a high specific surface area and thus has a high activity, and can advantageously decompose a high-boiling-point substance having a high molecular weight such as dioxins.
【００２９】排ガス処理に使用される触媒は、ガスとの
接触面積を大とすることが好ましいことは当然である
が、繊維状触媒の充填密度の程度によっては排ガスの流
動背圧が上がり好ましくない。この対策としては通常は
繊維状触媒をその比表面積を過度に低下させることなく
所定の密度に圧縮して得た、例えばハニカム状の成型体
が使用される。また、塩基性の活性炭素繊維を板状にし
たり、石膏ボード等のボードや布に貼着するようにして
もよい。It is natural that the catalyst used in the exhaust gas treatment preferably has a large contact area with the gas. However, depending on the packing density of the fibrous catalyst, the flow back pressure of the exhaust gas is undesirably increased. . As a countermeasure, for example, a honeycomb-shaped molded body obtained by compressing a fibrous catalyst to a predetermined density without excessively reducing its specific surface area is used. Further, the basic activated carbon fiber may be made into a plate shape, or may be attached to a board or cloth such as a gypsum board.
【００３０】ここで、本発明の触媒で分解処理する排ガ
スの対象としては都市ゴミ焼却炉，産業廃棄物焼却炉，
汚泥焼却炉等の各種焼却炉、溶融炉等から排出される排
ガスや、ゴミ固化燃料（ＲＤＦ）製造プラント等の各種
プラント、その他一般の化学合成施設からの排ガス等が
対象となり、特に限定されるものではない。また、排ガ
ス中のに含まれる有害物質とは、窒素酸化物の他、ダイ
オキシン類やＰＣＢ類に代表される有害な塩素化芳香族
化合物等の有害物質をいうが、本発明の塩素引き抜き作
用により分解できる排ガス中の有害物質（又は環境ホル
モン）であればこれらに限定されるものではない。Here, the waste gas to be decomposed by the catalyst of the present invention is an incinerator for municipal waste, an incinerator for industrial waste,
Exhaust gas discharged from various incinerators such as sludge incinerators, melting furnaces, etc., exhaust gas from various plants such as solidified fuel (RDF) production plants, and other general chemical synthesis facilities are targeted, and are particularly limited. Not something. The harmful substances contained in the exhaust gas mean harmful substances such as harmful chlorinated aromatic compounds represented by dioxins and PCBs in addition to nitrogen oxides. The harmful substances (or environmental hormones) in the exhaust gas that can be decomposed are not limited to these.
【００３１】ここで、上記ダイオキシン類とは、ポリ塩
化ジベンゾ−ｐ−ダイオキシン類（ＰＣＤＤｓ）及びポ
リ塩化ジベンゾフラン類（ＰＣＤＦｓ）の総称であり、
塩素系化合物とある種の有機塩素化合物の燃焼時に微量
発生するといわれ、化学的に無色の結晶である。塩素の
数によって二塩化物から八塩化物まであり、異性体には
ＰＣＤＤｓで７５種類、ＰＣＤＦｓで１３５種類におよ
び、これらのうち、特に四塩化ジベンゾ−ｐ−ダイオキ
シン（Ｔ4 ＣＤＤ）は、最も強い毒性を有するものとし
て知られている。なお、有害な塩素化芳香族化合物とし
ては、ダイオキシン類の他にその前駆体となる種々の有
機塩素化合物（例えば、フェノール，ベンゼン等の芳香
族化合物（例えばクロルベンゼン類，クロロフェノール
及びクロロトルエン等）、塩素化アルキル化合物等）が
含まれており、排ガス中から除去する必要がある。Here, the above dioxins are a general term for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs).
It is said to be generated in trace amounts during the combustion of chlorine compounds and certain organic chlorine compounds, and is a chemically colorless crystal. There are 75 types of PCDDs and 135 types of PCDFs depending on the number of chlorines, from dichloride to octachloride. Of these, dibenzo-p-dioxin tetrachloride (T 4 CDD) is the most common. It is known to be highly toxic. In addition, as harmful chlorinated aromatic compounds, in addition to dioxins, various organic chlorine compounds (for example, aromatic compounds such as phenol and benzene (for example, chlorobenzenes, chlorophenol and chlorotoluene) ), Chlorinated alkyl compounds, etc.) and must be removed from the exhaust gas.
【００３２】また、ＰＣＢ類（ポリ塩化ビフェニル類）
はビフェニールに塩素原子が数個付加した化合物の総称
であり、塩素の置換数、置換位置により異性体がある
が、２，６−ジクロロビフェニル、２，2'−ジクロロビ
フェニル、２，３，５−トリクロロビフェニル等が代表
的なものであり、毒性が強く、焼却した場合にはダイオ
キシン類が発生するおそれがあるものとして知られてお
り、排ガス中から除去する必要がある。PCBs (polychlorinated biphenyls)
Is a generic term for compounds in which several chlorine atoms are added to biphenyl, and there are isomers depending on the number and positions of substitution of chlorine, and 2,6-dichlorobiphenyl, 2,2′-dichlorobiphenyl, 2,3,5 -Trichlorobiphenyl and the like are typical, are known to be highly toxic, and may generate dioxins when incinerated, and must be removed from exhaust gas.
【００３３】また、上記有機塩素化合物以外に、排ガス
中には、例えば高縮合度芳香族炭化水素等や、ホルムア
ルデヒド，ベンゼン又はフェノールのような気体状有機
化合物を含む排ガスが発生することもある。これらの有
機化合物もまた、環境汚染物質であり、人間の健康を著
しく損ねるので、排ガスから除去する必要があるが、炭
素繊維本来の吸着作用によりこれらの有害物質も除去が
可能となる。In addition to the above-mentioned organic chlorine compounds, the exhaust gas may contain exhaust gas containing, for example, aromatic hydrocarbons having a high degree of condensation and gaseous organic compounds such as formaldehyde, benzene or phenol. Since these organic compounds are also environmental pollutants and significantly impair human health, it is necessary to remove them from the exhaust gas. However, these harmful substances can be removed by the inherent adsorption action of carbon fiber.
【００３４】また、本発明で処理される有害物質として
窒素酸化物を挙げることもできる。この窒素酸化物と
は、通常ＮＯ及びＮＯ2 の他、これらの混合物をいい、
ＮＯｘとも称されている。しかし、該ＮＯｘにはこれら
以外に各種酸化数の、しかも不安定な窒素酸化物も含ま
れている場合が多い。従ってｘは特に限定されるもので
はないが通常１〜２の値である。雨水等で硝酸、亜硝酸
等になり、またはＮＯは光化学スモッグの主因物質の一
つであるといわれており、人体には有害な化合物であ
る。本発明では、排ガス中にアンモニア等の塩基物質を
導入することにより、脱硝が可能となる。In addition, the harmful substances treated in the present invention can include nitrogen oxides. This nitrogen oxide generally means NO and NO 2 , and a mixture thereof.
It is also called NOx. However, the NOx often contains various oxidation numbers and unstable nitrogen oxides in addition to the above. Accordingly, x is not particularly limited, but is usually a value of 1 to 2. It becomes nitric acid, nitrous acid, etc. in rainwater or NO, or NO is said to be one of the main causes of photochemical smog, and is a harmful compound to the human body. In the present invention, denitration becomes possible by introducing a basic substance such as ammonia into exhaust gas.
【００３５】本発明による上記触媒を使用することによ
り、上述した有害物質である窒素酸化物，ダイオキシン
類，高縮合度芳香族炭化水素等の有害物質や気体状有機
化合物を接触的に還元又は分解して無害化処理すること
ができる。ここで、上記有害物質の内排ガス中のダイオ
キシン類，ダイオキシン類の前駆体，ＰＣＢ等の塩素化
芳香族化合物、高縮合度芳香族炭化水素は、本発明の塩
基性の活性炭素繊維触媒の塩素引き抜き作用により無害
化処理がなされる。また窒素酸化物については本発明の
触媒を充填した装置の前流側に塩基性物質（例えばアン
モニア等）導入手段を存在させ、還元反応により無害化
処理が行われる。By using the above-mentioned catalyst according to the present invention, the above-mentioned harmful substances such as nitrogen oxides, dioxins, and aromatic hydrocarbons having a high degree of condensation, and gaseous organic compounds are catalytically reduced or decomposed. And can be detoxified. Here, dioxins, dioxin precursors, chlorinated aromatic compounds such as PCB, and high-condensation degree aromatic hydrocarbons in the exhaust gas of the above harmful substances are used as chlorine in the basic activated carbon fiber catalyst of the present invention. Detoxification processing is performed by the drawing action. As for nitrogen oxides, a means for introducing a basic substance (for example, ammonia or the like) is provided upstream of the apparatus filled with the catalyst of the present invention, and detoxification treatment is performed by a reduction reaction.
【００３６】図１〜図５に上記触媒を用いた排ガス浄化
装置の概略の一例を示すが、本発明の触媒を用いた触媒
装置はこれに何ら限定されるものではない。FIGS. 1 to 5 schematically show an example of an exhaust gas purifying apparatus using the above-mentioned catalyst, but the catalytic apparatus using the catalyst of the present invention is not limited to this.
【００３７】図１に示すように、本実施の形態にかかる
排ガス処理装置は、都市ゴミ，産業廃棄物，汚泥等の各
種ゴミを焼却する各種焼却炉１１から排出される排ガス
１２を冷却するガス冷却装置１３と、冷却後の排ガス中
の有害物質を分解処理する触媒装置１４と、有害物質を
分解・除去した排ガスを外部へ排出する煙突１５とから
構成されている。As shown in FIG. 1, the exhaust gas treatment apparatus according to the present embodiment is a gas treatment system for cooling exhaust gas 12 discharged from various incinerators 11 for incinerating various kinds of garbage such as municipal waste, industrial waste and sludge. It comprises a cooling device 13, a catalyst device 14 for decomposing harmful substances in the exhaust gas after cooling, and a chimney 15 for discharging the exhaust gas obtained by decomposing and removing harmful substances to the outside.
【００３８】また、図２には、上記排ガス処理装置に排
ガス除塵装置を設けた場合を示す。すなわち、図１に示
すように、本実施の形態にかかる排ガス処理装置は、都
市ゴミ，産業廃棄物，汚泥等の各種ゴミを焼却する各種
焼却炉１１から排出される排ガス１２を冷却するガス冷
却装置１３と、冷却後の排ガス中の煤塵を除去する排ガ
ス除塵装置１６と、除塵後の排ガス中の有害物質を分解
処理する触媒装置１４と、有害物質を分解・除去した排
ガスを外部へ排出する煙突１５とから構成されている。
上記除塵装置１６により後流の触媒装置１４の負荷が低
減されることになる。除塵装置としては、電気除塵装
置，バグフィルタ等の煤塵処理装置を用いればよい。FIG. 2 shows a case where an exhaust gas removing device is provided in the exhaust gas treating device. That is, as shown in FIG. 1, the exhaust gas treatment apparatus according to the present embodiment is a gas cooling system that cools exhaust gas 12 discharged from various incinerators 11 that incinerate various types of garbage such as municipal waste, industrial waste, and sludge. A device 13, an exhaust gas removing device 16 for removing soot and dust in the exhaust gas after cooling, a catalyst device 14 for decomposing and processing harmful substances in the exhaust gas after dust removal, and discharging the exhaust gas obtained by decomposing and removing harmful substances to the outside. And a chimney 15.
The load on the downstream catalyst device 14 is reduced by the dust removing device 16. As the dust removing device, a dust removing device such as an electric dust removing device or a bag filter may be used.
【００３９】また、図３には、上記排ガス処理装置に脱
硝装置を設けた場合を示す。すなわち、図１に示すよう
に、本実施の形態にかかる排ガス処理装置は、都市ゴ
ミ，産業廃棄物，汚泥等の各種ゴミを焼却する各種焼却
炉１１から排出される排ガス１２を冷却するガス冷却装
置１３と、冷却後の排ガス中の煤塵を除去する排ガス除
塵装置１６と、除塵後の排ガス中の有害物質を分解処理
する触媒装置１４と、触媒装置１４の後流側に設けた脱
硝を行う脱硝装置１７と、有害物質を分解・除去した排
ガスを外部へ排出する煙突１５とから構成されている。
上記除塵装置１６により脱硝を独立して行うことができ
る。なお、本発明の触媒を用いた触媒装置１４は低温型
であるので、後流の脱硝装置１７も低温型のものとすれ
ばよい。しかしながら、脱硝装置１７で脱硝効率を向上
させるために、排ガスを再加熱した場合であっても、本
発明の触媒装置１４で塩素を引き抜き反応によりダイオ
キシン類前駆体の発生がないので、問題が生じることは
ない。FIG. 3 shows a case in which a denitration device is provided in the exhaust gas treatment device. That is, as shown in FIG. 1, the exhaust gas treatment apparatus according to the present embodiment is a gas cooling system that cools exhaust gas 12 discharged from various incinerators 11 that incinerate various types of garbage such as municipal waste, industrial waste, and sludge. A device 13, an exhaust gas removing device 16 for removing dust in the exhaust gas after cooling, a catalytic device 14 for decomposing and processing harmful substances in the exhaust gas after dust removal, and a denitration provided on the downstream side of the catalytic device 14 are performed. It is composed of a denitration device 17 and a chimney 15 that discharges exhaust gas obtained by decomposing and removing harmful substances to the outside.
The denitration device 16 can perform denitration independently. Since the catalyst device 14 using the catalyst of the present invention is of a low-temperature type, the downstream denitration device 17 may be of a low-temperature type. However, even when the exhaust gas is reheated in order to improve the denitration efficiency in the denitration device 17, a problem arises because no dioxin precursor is generated by the chlorine extraction reaction in the catalyst device 14 of the present invention. Never.
【００４０】一方、高温型の脱硝装置を用いる場合に
は、図４に示すように、ガス冷却装置１３の前流側に設
けたり、図５に示すように、排ガス除塵装置１４の後流
側に設けたり、或いは排ガス除塵装置１６に脱硝機能を
併用するようにしてもよい。On the other hand, when a high-temperature type denitration device is used, it is provided upstream of the gas cooling device 13 as shown in FIG. 4 or downstream of the exhaust gas dust removal device 14 as shown in FIG. Or the exhaust gas dust removal device 16 may be provided with a denitration function.
【００４１】上述した排ガス浄化装置によれば、触媒装
置１４で塩素の引き抜きによりダイオキシン類の前駆体
の発生がなく、効率的な排ガス中の浄化が可能となる。According to the exhaust gas purifying apparatus described above, the catalytic device 14 does not generate a precursor of dioxins due to the extraction of chlorine, so that the exhaust gas can be efficiently purified.
【００４２】なお、除塵装置１６での効率のよい捕集を
行うために低温に冷却した場合において、再加熱する場
合であってもダイオキシン類の再生成率が低い２５０℃
を限度とするのがよい。In the case of cooling to a low temperature in order to perform efficient collection in the dust removing device 16, even when reheating, the regeneration rate of dioxins is low at 250 ° C.
Should be the limit.
【００４３】本発明の排ガス浄化装置では、脱硝及びダ
イオキシン類の除去を一つの触媒装置１３で同時に行う
こともでき、その場合には、図１及び図２の装置におい
て、塩基性物質として例えばアンモニアを注入する注入
ノズルを介してアンモニアを触媒装置１４内に導入すれ
ばダイオキシン類の分解と脱窒素とを同時に行うことが
できる。In the exhaust gas purifying apparatus of the present invention, the denitration and the removal of dioxins can be simultaneously performed by one catalyst device 13. In this case, in the devices shown in FIGS. If ammonia is introduced into the catalyst device 14 through an injection nozzle for injecting nitrogen, decomposition of dioxins and denitrification can be performed simultaneously.
【００４４】[0044]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.
【００４５】［実施例１］窒素含有率が７重量％の塩基
性のＰＡＮ系活性炭素繊維（比表面積：１２００ｍ2 ／
ｇ）を用い、ダイオキシン類の代用試験物質であるｏ−
ジクロロベンゼンの分解率を測定した。ｏ−ジクロロベ
ンゼンを１ｐｐｍ、Ｏ2 を５％、Ｈ2 Ｏを１０％、残り
Ｎ2 からなる模擬ガスを作成し、上記触媒を詰めた円筒
管の外周にヒータを設け、流通式により常圧で測定し
た。測定条件は、温度を２５０℃と３５０℃とし、ＳＶ
（空間速度）をＳＶ＝５００ｈ-1，ＳＶ＝１０００
ｈ-1，ＳＶ＝５０００ｈ-1，ＳＶ＝１０００ｈ-1とし
た。分解率は、模擬ガス中のＨＣｌ，Ｃｌ2 の発生量を
測定して求めた。この結果を「表１」に示す。Example 1 Basic PAN-based activated carbon fibers having a nitrogen content of 7% by weight (specific surface area: 1200 m 2 /
g), using o- which is a substitute test substance for dioxins
The decomposition rate of dichlorobenzene was measured. o- dichlorobenzene 1 ppm, O 2 and 5%, 10% H 2 O, to create a simulated gas of the remaining N 2, a heater is provided on the outer circumference of the cylindrical tube filled with the catalyst, ordinary pressure by flow-type Was measured. The measurement conditions were as follows.
(Space velocity): SV = 500h −1 , SV = 1000
h -1, SV = 5000h -1, was SV = 1000h -1. The decomposition rate was determined by measuring the amount of HCl and Cl 2 generated in the simulation gas. The results are shown in Table 1.
【００４６】[0046]
【表１】 [Table 1]
【００４７】［実施例２］実施例１の塩基性の活性炭素
繊維に、ピリジンを添加しＣＶＤ法で焼成することによ
り、Ｎ2 の添加率が高いのもの（窒素含有率１２重量
％）としたＰＡＮ系活性炭素繊維（比表面積：１２００
ｍ2 ／ｇ）を用いた以外は、実施例１と同様にして分解
率を測定した。この結果を「表２」に示す。Example 2 By adding pyridine to the basic activated carbon fiber of Example 1 and calcining it by a CVD method, a fiber having a high N 2 addition rate (nitrogen content: 12% by weight) was obtained. PAN-based activated carbon fiber (specific surface area: 1200
m 2 / g), the decomposition rate was measured in the same manner as in Example 1. The results are shown in "Table 2".
【００４８】[0048]
【表２】 [Table 2]
【００４９】［実施例３］実施例２の高い窒素比率（窒
素含有率１２重量％）の塩基性の活性炭素繊維を用い、
模擬ガスとして、実施例１のｏ−ジクロロベンゼンの代
わりに、ｐ−クロロフェノールを１ｐｐｍ含んだガスと
以外は、実施例１と同様にして分解率を測定した。この
結果を「表３」に示す。Example 3 Using the basic activated carbon fiber of Example 2 having a high nitrogen ratio (nitrogen content: 12% by weight),
The decomposition rate was measured in the same manner as in Example 1 except that the simulation gas was a gas containing 1 ppm of p-chlorophenol instead of the o-dichlorobenzene of Example 1. The results are shown in Table 3.
【００５０】[0050]
【表３】 [Table 3]
【００５１】［実施例４］実施例１の塩基性の活性炭素
繊維の代わりに酸化スズ（ＳｎＯ）を担持したフェノー
ル系活性炭素繊維（窒素含有率１０重量％、比表面積：
１９００ｍ2 ／ｇ）を用いた以外は、実施例１と同様に
して分解率を測定した。この結果を「表４」に示す。Example 4 A phenolic activated carbon fiber carrying tin oxide (SnO) instead of the basic activated carbon fiber of Example 1 (nitrogen content: 10% by weight, specific surface area:
The decomposition rate was measured in the same manner as in Example 1 except that 1900 m 2 / g) was used. The results are shown in Table 4.
【００５２】[0052]
【表４】 [Table 4]
【００５３】［実施例５］実施例１の塩基性の活性炭素
繊維の代わりにＲｈを５重量％担持したフェノール系活
性炭素繊維（比表面積：１９００ｍ2 ／ｇ）を用いた以
外は、実施例１と同様にして分解率を測定した。この結
果を「表５」に示す。Example 5 The procedure of Example 1 was repeated except that the basic activated carbon fiber of Example 1 was replaced with a phenol-based activated carbon fiber carrying 5% by weight of Rh (specific surface area: 1900 m 2 / g). The decomposition rate was measured in the same manner as in Example 1. The results are shown in "Table 5".
【００５４】[0054]
【表５】 [Table 5]
【００５５】［比較例１］実施例１において、窒素含有
率０重量％のフェノール系活性炭素繊維（比表面積：１
２００ｍ2 ／ｇ）を用いた以外は、実施例１と同様にし
て分解率を測定した。 この結果を「表６」に示す。Comparative Example 1 In Example 1, the phenolic activated carbon fiber having a nitrogen content of 0% by weight (specific surface area: 1)
The decomposition rate was measured in the same manner as in Example 1 except that 200 m 2 / g) was used. The results are shown in "Table 6".
【００５６】[0056]
【表６】 [Table 6]
【００５７】「表１」〜「表５」から明らかなように、
本発明にかかる触媒を使用することによりダイオキシン
類分解率の向上は著しく、ＳＶ＝１０００ｈ-1で、すべ
て分解率９５％以上を確保することができることが判明
した。また、「表２」に示すように、窒素量が高いと分
解効率が高くなることが判明した。なお、「表６」に示
すように、窒素量が零の場合には、塩素引き抜き作用が
発現されず、ＳＶ値が低い場合に吸着によってのみ除去
がなされていた。As is clear from Tables 1 to 5,
It was found that the use of the catalyst according to the present invention significantly improved the decomposition rate of dioxins, and it was possible to secure a decomposition rate of 95% or more in all cases at SV = 1000 h -1 . Further, as shown in Table 2, it was found that the decomposition efficiency was higher when the amount of nitrogen was higher. As shown in Table 6, when the amount of nitrogen was zero, the effect of extracting chlorine was not exhibited, and when the SV value was low, removal was performed only by adsorption.
【００５８】[0058]
【発明の効果】以上説明したように、本発明の「請求項
１］の発明によれば、排ガスを浄化する排ガス処理用触
媒であって、活性炭素繊維が塩基性を有するので、排ガ
ス中の有害物質の塩素含有化合物の塩素を引き抜き、排
出される排ガスを浄化することができる。As described above, according to the invention of claim 1 of the present invention, an exhaust gas treatment catalyst for purifying exhaust gas, wherein activated carbon fibers have basicity, The chlorine contained in the chlorine-containing compound as a harmful substance is extracted, and the exhaust gas discharged can be purified.
【００５９】［請求項２］の発明によれば、請求項１に
おいて、塩基性の活性炭素繊維が塩基性を強化してなる
ので、塩素引き抜き活性が高く効率的な浄化が可能とな
る。According to the second aspect of the present invention, in the first aspect, since the basic activated carbon fiber is strengthened in the basicity, the chlorine-extracting activity is high and efficient purification can be performed.
【００６０】［請求項３］の発明によれば、請求項１又
は２において、塩基性の活性炭素繊維に窒素化合物を添
着してなるので、塩素引き抜き活性が高く効率的な浄化
が可能となる。According to the third aspect of the present invention, in the first or second aspect, a nitrogen compound is impregnated on the basic activated carbon fiber, so that the chlorine-extracting activity is high and efficient purification can be performed. .
【００６１】［請求項４］の発明によれば、請求項１又
は２において、塩基性の活性炭素繊維に塩基性を有する
金属酸化物を担持してなるので、塩素引き抜き活性が高
く効率的な浄化が可能となる。According to the fourth aspect of the present invention, in the first or second aspect, the basic activated carbon fibers carry a basic metal oxide, so that the chlorine-extracting activity is high and the efficiency is high. Purification becomes possible.
【００６２】［請求項５］の発明によれば、請求項１又
は２において、塩基性の活性炭素繊維に窒素化合物及び
塩基性を有する金属酸化物を複合的に担持してなるの
で、塩素引き抜き活性が高く効率的な浄化が可能とな
る。According to the invention of claim 5, in claim 1 or 2, the nitrogen compound and the basic metal oxide are supported on the basic activated carbon fiber in a complex manner, so that chlorine is extracted. It has high activity and enables efficient purification.
【００６３】［請求項６］の発明によれば、請求項１乃
至５において、塩基性の活性炭素繊維の比表面積が５０
０ｍ2 ／ｇ以上であるので、塩素引き抜き活性が高く効
率的な浄化が可能となる。According to the sixth aspect of the present invention, in the first to fifth aspects, the specific surface area of the basic activated carbon fiber is 50 or more.
Since it is 0 m 2 / g or more, high chlorine extraction activity enables efficient purification.
【００６４】［請求項７］の発明によれば、排ガス中の
有害物質を請求項１乃至６の触媒に接触させ、排ガス中
の有害物質の塩素を引き抜き分解処理するので、排ガス
中の有害物質を分解処理することができる。According to the invention of claim 7, the harmful substances in the exhaust gas are brought into contact with the catalysts of claims 1 to 6, and the chlorine of the harmful substance in the exhaust gas is extracted and decomposed. Can be decomposed.
【００６５】［請求項８］の発明によれば、特に、上記
排ガス中の有害物質がダイオキシン類，ポリ塩化ビフェ
ニル類，クロルベンゼン類，クロロフェノール及びクロ
ロトルエンから選ばれる少なくとも一種の塩素化芳香族
化合物を分解処理することができる。According to the invention of claim 8, in particular, the harmful substance in the exhaust gas is at least one chlorinated aromatic selected from dioxins, polychlorinated biphenyls, chlorobenzenes, chlorophenol and chlorotoluene. The compound can be degraded.
【００６６】［請求項９］の発明によれば、排ガスを浄
化する排ガス処理装置であって、排ガス中の煤塵を除塵
する除塵装置と、該除塵装置の後流側に設けた請求項１
乃至６の排ガス処理用触媒を有する触媒装置とからなる
ことを特徴とする。According to the ninth aspect of the present invention, there is provided an exhaust gas treating apparatus for purifying exhaust gas, wherein the dust removing apparatus is provided on a downstream side of the dust removing apparatus for removing dust in the exhaust gas.
And catalyst devices having exhaust gas treatment catalysts according to any one of (1) to (6).
【００６７】［請求項１０］の発明によれば、排ガスを
浄化する排ガス処理装置であって、請求項１乃至６の排
ガス処理用触媒を有する触媒装置と、該触媒装置の後流
側に設けた排ガス中の煤塵を除塵する除塵装置とからな
るので、高比表面積の排ガス処理触媒により排ガス中の
ダイオキシン類，ダイオキシン類の前駆体，ＰＣＢ等の
塩素化芳香族化合物、高縮合度芳香族炭化水素の酸化分
解が可能となる。According to a tenth aspect of the present invention, there is provided an exhaust gas purifying apparatus for purifying an exhaust gas, comprising: a catalytic device having the exhaust gas treating catalyst according to any one of the first to sixth aspects; It consists of a dust removal device that removes soot and dust in the exhaust gas. Therefore, a high specific surface area exhaust gas treatment catalyst is used to control dioxins, dioxin precursors, chlorinated aromatic compounds such as PCBs, and highly condensed aromatic hydrocarbons in the exhaust gas. Oxidative decomposition of hydrogen becomes possible.
【００６８】［請求項１１］の発明によれば、請求項９
又は１０において、上記触媒装置に塩基性物質を導入す
る手段を設けたので、また塩基性ガスの添加により脱硝
が可能となり、両者の併合した分解が可能となる。According to the invention set forth in claim 11, claim 9 is provided.
In or 10, since means for introducing a basic substance is provided in the catalyst device, denitration becomes possible by addition of a basic gas, and combined decomposition of the two becomes possible.
【００６９】［請求項１２］の発明によれば、請求項９
又は１０において、脱硝装置を設けたので、排ガス中の
塩素含有化合物の分解と、脱硝装置による脱硝とを独立
して行うことができる。According to the invention of claim 12, claim 9 is
In or 10, since the denitration device is provided, the decomposition of the chlorine-containing compound in the exhaust gas and the denitration by the denitration device can be performed independently.
【００７０】［請求項１３］の発明によれば、請求項９
乃至１１において、上記触媒装置に導入する排ガスの温
度を１００〜４００℃としたので、低温で排ガス中の有
害物質の分解除去が可能となる。According to the thirteenth aspect, the ninth aspect is provided.
In Nos. 1 to 11, the temperature of the exhaust gas introduced into the catalyst device is set to 100 to 400 ° C., so that it is possible to decompose and remove harmful substances in the exhaust gas at a low temperature.
【図１】排ガス処理装置の一例を示す概略図である。FIG. 1 is a schematic view showing an example of an exhaust gas treatment device.
【図２】排ガス処理装置の一例を示す概略図である。FIG. 2 is a schematic diagram illustrating an example of an exhaust gas treatment device.
【図３】排ガス処理装置の一例を示す概略図である。FIG. 3 is a schematic diagram illustrating an example of an exhaust gas treatment device.
【図４】排ガス処理装置の一例を示す概略図である。FIG. 4 is a schematic diagram illustrating an example of an exhaust gas treatment device.
【図５】排ガス処理装置の一例を示す概略図である。FIG. 5 is a schematic diagram illustrating an example of an exhaust gas treatment device.
１１ 焼却炉 １２ 排ガス １３ ガス冷却装置 １４ 触媒装置 １５ 煙突 １６ 排ガス処理装置 １７ 脱硝装置 DESCRIPTION OF SYMBOLS 11 Incinerator 12 Exhaust gas 13 Gas cooling device 14 Catalytic device 15 Chimney 16 Exhaust gas treatment device 17 Denitration device
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 35/06 Ｂ０１Ｄ 53/36 Ｇ (72)発明者 持田 勲 福岡県福岡市東区香椎２丁目28番10号──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI B01J 35/06 B01D 53/36 G (72) Inventor Isao Mochida 2-28-10 Kashii, Higashi-ku, Fukuoka City, Fukuoka Prefecture
Claims (13)
って、 活性炭素繊維が塩基性を有することを特徴とする排ガス
処理用触媒。An exhaust gas treatment catalyst for purifying exhaust gas, wherein the activated carbon fiber has basicity.
徴とする排ガス処理用触媒。2. The exhaust gas treatment catalyst according to claim 1, wherein the basic activated carbon fiber is made more basic.
を特徴とする排ガス処理用触媒。3. The exhaust gas treatment catalyst according to claim 1, wherein a nitrogen compound is attached to basic activated carbon fibers.
ることを特徴とする排ガス処理用触媒。4. The exhaust gas treatment catalyst according to claim 1, wherein the activated carbon fiber carries a basic metal oxide.
金属酸化物を複合的に担持してなることを特徴とする排
ガス処理用触媒。5. The exhaust gas treatment catalyst according to claim 1, wherein the nitrogen compound and the basic metal oxide are compositely supported on the basic activated carbon fiber.
であることを特徴とする排ガス処理用触媒。6. The exhaust gas treating catalyst according to claim 1, wherein the specific surface area of the basic activated carbon fiber is 500 m 2 / g or more.
触媒に接触させ、排ガス中の有害物質の塩素を引き抜き
分解処理することを特徴とする排ガス処理方法。7. An exhaust gas treatment method comprising contacting a harmful substance in an exhaust gas with the catalyst according to claim 1 to extract and decompose chlorine of the harmful substance in the exhaust gas.
フェニル類，クロルベンゼン類，クロロフェノール及び
クロロトルエンから選ばれる少なくとも一種の塩素化芳
香族化合物であることを特徴とする排ガス処理方法。8. The method according to claim 7, wherein the harmful substance in the exhaust gas is at least one chlorinated aromatic compound selected from dioxins, polychlorinated biphenyls, chlorobenzenes, chlorophenol and chlorotoluene. Exhaust gas treatment method.
排ガス処理装置であって、排ガス中の煤塵を除塵する除
塵装置と、該除塵装置の後流側に設けた請求項１乃至６
の排ガス処理用触媒を有する触媒装置とからなることを
特徴とする排ガス処理装置。9. An exhaust gas treatment apparatus for purifying exhaust gas discharged from an incinerator, wherein the apparatus is provided on a downstream side of the dust removal apparatus for removing dust in the exhaust gas.
An exhaust gas treatment device comprising: a catalyst device having the exhaust gas treatment catalyst according to the above.
って、 請求項１乃至６の排ガス処理用触媒を有する触媒装置
と、該触媒装置の後流側に設けた排ガス中の煤塵を除塵
する除塵装置とからなることを特徴とする排ガス処理装
置。10. An exhaust gas treatment device for purifying exhaust gas, comprising: a catalyst device having the exhaust gas treatment catalyst according to claim 1; and a dust removal device provided on a downstream side of the catalyst device for removing dust in exhaust gas. An exhaust gas treatment device comprising: a device.
装置に塩基性物質を導入する手段を設けたことを特徴と
する排ガス処理装置。11. An exhaust gas treatment apparatus according to claim 9, wherein a means for introducing a basic substance is provided in said catalyst device.
を設けたことを特徴とする排ガス処理装置。12. The exhaust gas treatment device according to claim 9, wherein a denitration device is provided.
装置に導入する排ガスの温度を１００〜４００℃とした
ことを特徴とする排ガス処理装置。13. The exhaust gas treatment device according to claim 9, wherein the temperature of the exhaust gas introduced into the catalyst device is set to 100 to 400 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15902498A JP3776593B2 (en) | 1998-06-08 | 1998-06-08 | Exhaust gas treatment catalyst, exhaust gas treatment method and treatment apparatus |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15902498A JP3776593B2 (en) | 1998-06-08 | 1998-06-08 | Exhaust gas treatment catalyst, exhaust gas treatment method and treatment apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11347409A true JPH11347409A (en) | 1999-12-21 |
| JP3776593B2 JP3776593B2 (en) | 2006-05-17 |
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|---|---|---|---|
| JP15902498A Expired - Lifetime JP3776593B2 (en) | 1998-06-08 | 1998-06-08 | Exhaust gas treatment catalyst, exhaust gas treatment method and treatment apparatus |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011065125A1 (en) * | 2009-11-26 | 2011-06-03 | 日清紡ホールディングス株式会社 | Carbon catalyst for decomposition of hazardous substance, hazardous-substance-decomposing material, and method for decomposition of hazardous substance |
| CN114405267A (en) * | 2021-12-31 | 2022-04-29 | 北京市生态环境保护科学研究院 | Method for improving adsorption efficiency of industrial organic waste gas |
-
1998
- 1998-06-08 JP JP15902498A patent/JP3776593B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011065125A1 (en) * | 2009-11-26 | 2011-06-03 | 日清紡ホールディングス株式会社 | Carbon catalyst for decomposition of hazardous substance, hazardous-substance-decomposing material, and method for decomposition of hazardous substance |
| CN102802787A (en) * | 2009-11-26 | 2012-11-28 | 日清纺控股株式会社 | Carbon catalyst for decomposition of hazardous substance, hazardous-substance-decomposing material, and method for decomposition of hazardous substance |
| JP5192085B2 (en) * | 2009-11-26 | 2013-05-08 | 日清紡ホールディングス株式会社 | Carbon catalyst for decomposing toxic substances, decomposing substances and decomposing method |
| US8999280B2 (en) | 2009-11-26 | 2015-04-07 | Nisshinbo Holdings Inc. | Carbon catalyst for decomposition of hazardous substance, hazardous-substance-decomposing material, and method for decomposition of hazardous substance |
| CN114405267A (en) * | 2021-12-31 | 2022-04-29 | 北京市生态环境保护科学研究院 | Method for improving adsorption efficiency of industrial organic waste gas |
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|---|---|
| JP3776593B2 (en) | 2006-05-17 |
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