JPH0824819B2 - Exhaust gas pretreatment method - Google Patents
Exhaust gas pretreatment methodInfo
- Publication number
- JPH0824819B2 JPH0824819B2 JP63210567A JP21056788A JPH0824819B2 JP H0824819 B2 JPH0824819 B2 JP H0824819B2 JP 63210567 A JP63210567 A JP 63210567A JP 21056788 A JP21056788 A JP 21056788A JP H0824819 B2 JPH0824819 B2 JP H0824819B2
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- catalyst
- alumina
- pretreatment method
- pretreatment
- 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.)
- Expired - Lifetime
Links
- 238000002203 pretreatment Methods 0.000 title claims description 16
- 239000003054 catalyst Substances 0.000 claims description 65
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 47
- 239000002574 poison Substances 0.000 claims description 24
- 231100000614 poison Toxicity 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 63
- 239000000126 substance Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000003961 organosilicon compounds Chemical class 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 150000002903 organophosphorus compounds Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003915 air pollution Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は排ガスの前処理方法に関し、詳しくは触媒毒
を含有する排ガスを、その接触処理に先立ち、高活性化
アルミナ充填層に通して、排ガス中の触媒毒を除去する
排ガスの前処理方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for pretreatment of exhaust gas, more specifically, an exhaust gas containing a catalyst poison is passed through a highly activated alumina packed bed prior to its catalytic treatment, The present invention relates to an exhaust gas pretreatment method for removing catalyst poisons in exhaust gas.
（従来の技術） 近年、大気汚染防止あるいは悪臭除去のために、排ガ
スを接触的に処理して大気汚染あるいは悪臭の原因とな
る排ガス中の有害物質、例えば有機酸製造プラントから
の排ガスに含まれる有機酸、塗装焼付乾燥炉からの排ガ
スに含まれるアルデヒドなどを除去して排ガスを浄化す
る排ガス浄化方法が広く採用されている。(Prior Art) In recent years, in order to prevent air pollution or remove odors, the exhaust gas is treated catalytically to be contained in harmful substances in exhaust gas that cause air pollution or odor, for example, exhaust gas from an organic acid production plant. BACKGROUND ART Exhaust gas purification methods for purifying exhaust gas by removing organic acids, aldehydes and the like contained in exhaust gas from a coating baking drying furnace are widely adopted.
しかし、一般に、排ガス中には有害物質のほかにダス
ト、タール状物質、有機金属化合物、シリコン化合物、
リン化合物などが含有され、これらは排ガスの接触処理
に使用する酸化触媒（以下、「排ガス処理触媒」とい
う）にとって、触媒毒として作用し、触媒性能ひいては
触媒寿命を著しく低下させる原因となっている。特に、
有機金属化合物、有機シリコン化合物、有機リン化合物
などは触媒毒としての影響が著しい。例えば、有機シリ
コン化合物および有機リン化合物は、塗料、インキなど
の化学製品製造時の消泡剤またはこれら製品の添加剤と
して、あるいはプラスチックなどの難燃剤として広く使
用されているので、これらを取り扱う発生源からの排ガ
ス中には微量の有機シリコン化合物および有機リン化合
物が含有されていることが多い。排ガス中のこれらの化
合物は、排ガス処理触媒上で酸化分解して触媒活性表面
を被覆し、その触媒活性を著しく低下させる。However, in general, in the exhaust gas, in addition to harmful substances, dust, tar-like substances, organometallic compounds, silicon compounds,
Phosphorus compounds, etc. are contained, and these act as a catalyst poison for the oxidation catalyst used for catalytic treatment of exhaust gas (hereinafter referred to as “exhaust gas treatment catalyst”), which causes the catalyst performance and eventually the catalyst life to be significantly reduced. . In particular,
Organometallic compounds, organosilicon compounds, organophosphorus compounds, etc. have significant effects as catalyst poisons. For example, organosilicon compounds and organophosphorus compounds are widely used as defoaming agents during the production of chemical products such as paints and inks, or additives for these products, or as flame retardants for plastics. Exhaust gas from the source often contains trace amounts of organosilicon compounds and organophosphorus compounds. These compounds in the exhaust gas oxidatively decompose on the exhaust gas-treating catalyst to coat the catalytically active surface, and significantly reduce the catalytic activity.
このような触媒毒の除去方法として、例えば特開昭52
−138054号公報には吸着剤として活性炭、シリカゲル、
活性アルミナ、ゼオライトを用いる前処理方法が、また
特公昭61−20333号公報には、排ガスを予め150℃以上の
温度でアルミナ充填層に通す前処理方法が提案されてい
る。As a method of removing such a catalyst poison, for example, Japanese Patent Laid-Open No.
No. 138048 discloses activated carbon, silica gel,
A pretreatment method using activated alumina and zeolite has been proposed, and Japanese Patent Publication No. 61-20333 proposes a pretreatment method in which exhaust gas is passed through an alumina packed bed at a temperature of 150 ° C. or higher in advance.
（発明が解決しようとする課題） しかし、本発明者らの研究によれば、上記吸着剤を用
いる前処理方法およびアルミナ充填層を用いた前処理方
法のいずれによっても触媒毒を充分に除去できず、排ガ
ス処理触媒の劣化ひいては触媒寿命の低下を来し、実用
化にはなお問題があることが判明した。(Problems to be Solved by the Invention) However, according to the study by the present inventors, the catalyst poison can be sufficiently removed by both the pretreatment method using the adsorbent and the pretreatment method using the alumina packed bed. However, it was found that the exhaust gas treatment catalyst was deteriorated and the catalyst life was shortened, and there was still a problem in practical use.
また、アルミナ充填層を用いた前処理方法において
は、排ガス中に含まれるタール状物質のアルミナ充填層
における酸化分解が不十分であるため、これらタール状
物質がアルミナ充填層に吸着されて重合し、更には炭化
してカーボンとして蓄積されるため、上記のような触媒
毒、特に有機金属化合物、有機シリコン化合物および有
機リン化合物のアルミナ充填層における吸着、除去が著
しく低下し、アルミナ充填層の触媒毒除去効果が著しく
損なわれることになる。更に、蓄積したカーボンは、発
火点が比較的低いため、排ガス処理触媒層からの伝熱、
装置停止などによる蓄熱などによってアルミナ充填層が
昇温すると急激に発火、燃焼して、排ガス処理触媒の熱
劣化、装置の損傷など種々の問題を起こし、また安全上
も好ましくないことが判明した。Further, in the pretreatment method using the alumina-filled layer, since the tar-like substances contained in the exhaust gas are not sufficiently oxidized and decomposed in the alumina-filled layer, these tar-like substances are adsorbed in the alumina-filled layer and polymerized. Moreover, since it is carbonized and accumulated as carbon, the above-mentioned catalyst poisons, particularly the adsorption and removal of organometallic compounds, organosilicon compounds and organophosphorus compounds in the alumina packed bed are significantly reduced, and the catalyst in the alumina packed bed is reduced. The detoxification effect will be significantly impaired. Furthermore, since the accumulated carbon has a relatively low ignition point, heat transfer from the exhaust gas treatment catalyst layer,
It has been found that when the temperature of the alumina packed bed rises due to heat storage due to equipment stoppage, etc., it suddenly ignites and burns, causing various problems such as heat deterioration of the exhaust gas treatment catalyst and equipment damage, and it is also unfavorable for safety.
本発明は、上記問題点を解決し、排ガス処理触媒の触
媒毒となる有機金属化合物、有機シリコン化合物、有機
リン化合物などのほかタール状物質なども効率よく除去
する排ガスの前処理方法を提供することを目的とするも
のである。The present invention solves the above problems, and provides a pretreatment method for exhaust gas, which efficiently removes tar-like substances as well as organometallic compounds, organosilicon compounds, and organophosphorus compounds that are catalyst poisons of exhaust gas treatment catalysts. That is the purpose.
（課題を解決するための手段） 本発明者らの研究によれば、触媒毒を含有する排ガス
を接触処理して浄化する際に、排ガスを予め、貴金属お
よび重金属酸化物から選ばれた少なくとも１種の触媒成
分をアルミナに担持して得られる高活性化アルミナ充填
層に通すことによって、上記目的が達成できることを知
り、この知見に基づいて本発明を完成するに到った。(Means for Solving the Problems) According to the research conducted by the present inventors, when the exhaust gas containing a catalyst poison is catalytically treated and purified, the exhaust gas is at least 1 selected in advance from a noble metal and a heavy metal oxide. Based on this finding, the present invention has been completed based on the knowledge that the above object can be achieved by passing a catalyst layer of various species on alumina to pass through a highly activated alumina packed bed.
即ち、本発明は、触媒毒を含有する排ガスを接触処理
して浄化するに当り、該排ガスを予め金、銀、ルテニウ
ム、パラジウム、オスミウム、イリジウムおよび白金か
ら選ばれる少なくとも１種および／または鉄、マンガ
ン、クロム、銅、ニッケルおよびコバルトの酸化物から
選ばれる少なくとも１種の触媒成分を比表面積が50〜50
0m2/gの範囲の活性アルミナに担持してなる触媒の充填
層に通して触媒毒を除去することを特徴とする排ガスの
前処理方法を提供するものである。That is, the present invention, in purifying an exhaust gas containing a catalyst poison by contact treatment, the exhaust gas is preliminarily at least one selected from gold, silver, ruthenium, palladium, osmium, iridium and platinum and / or iron, At least one catalyst component selected from the oxides of manganese, chromium, copper, nickel and cobalt has a specific surface area of 50 to 50.
The present invention provides a method for pretreatment of exhaust gas, which comprises removing a catalyst poison by passing through a packed bed of a catalyst supported on activated alumina in the range of 0 m 2 / g.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明で使用する高活性化アルミナとは、排ガスの接
触処理用酸化触媒として一般に使用されている、白金、
パラジウム、銀などの貴金属および鉄、マンガン、クロ
ム、銅、ニッケル、コバルトなどの貴金属の酸化物、例
えばFe2O3、CuO、MnO2、Mn2O3、Cr2O3、NiO、CoO、Co3O
4などから選ばれた少なくとも１種の触媒成分をアルミ
ナに担持させたものである。アルミナとしては、一般に
使用されているアルミナ、例えばα−アルミナ、γ−ア
ルミナなどの活性アルミナを使用することができるが比
表面積が10m2/g以上、特に50〜500m2/gの範囲の活性ア
ルミナの使用が好適である。触媒成分の担持量は、アル
ミナの重量基準で0.05〜２重量％、好ましくは0.1〜１
重量％である。触媒成分の担持量が0.05重量％未満では
触媒毒およびタール状物質を充分に除去できない。な
お、排ガスに含有される触媒毒およびタール状物質は微
量であることから、触媒成分を２重量％を超えて使用す
る必要はなく、逆に高価な触媒成分の使用によって高活
性化アルミナの価格が上がって経済的に不利になる。The highly activated alumina used in the present invention is generally used as an oxidation catalyst for catalytic treatment of exhaust gas, platinum,
Palladium, oxides of precious metals such as silver and precious metals such as iron, manganese, chromium, copper, nickel and cobalt, for example Fe 2 O 3 , CuO, MnO 2 , Mn 2 O 3 , Cr 2 O 3 , NiO, CoO, Co 3 O
At least one catalyst component selected from 4, etc. is supported on alumina. The alumina, generally alumina is used, for example α- alumina, .gamma.-alumina activated alumina such as may be used, but a specific surface area of 10 m 2 / g or more, particularly active in the range of 50 to 500 m 2 / g The use of alumina is preferred. The supported amount of the catalyst component is 0.05 to 2% by weight, preferably 0.1 to 1 based on the weight of alumina.
% By weight. If the supported amount of the catalyst component is less than 0.05% by weight, catalyst poisons and tar-like substances cannot be sufficiently removed. Since the amount of catalyst poisons and tar-like substances contained in the exhaust gas is very small, it is not necessary to use the catalyst components in excess of 2% by weight, and conversely, the cost of highly activated alumina can be increased by using expensive catalyst components. Goes up and becomes economically disadvantageous.
上記高活性化アルミナの調製方法には特に制限はな
く、この種触媒の調製に一般に使用されている方法によ
って調製することができる。なお、その形状は、球状、
円柱状、ハニカム状などのいずれでもよく、またその大
きさは、例えば球状の場合には２〜8mm（粒径）程度、
円柱状の場合には１〜5mm（直径）×３〜8mm（高さ）程
度でよい。The method for preparing the highly activated alumina is not particularly limited, and it can be prepared by a method generally used for preparing this type of catalyst. The shape is spherical,
It may be cylindrical, honeycomb-shaped, or the like, and its size is, for example, about 2 to 8 mm (particle diameter) in the case of a spherical shape,
In the case of a cylindrical shape, it may be about 1 to 5 mm (diameter) x 3 to 8 mm (height).
なお、本発明で使用する高活性化アルミナとしては、
アルミナ粒子全てに上記範囲内の量の触媒成分を担持さ
せたものが均一な触媒毒除去反応を達成できるという点
において好ましいが、許容し得る程度の均一な触媒毒除
去反応が行える限り、触媒成分高濃度担持アルミナと触
媒成分低濃度担持アルミナもしくは触媒成分無担持アル
ミナとを全体としての触媒成分担持量が上記範囲内にな
るように均一に混合して使用することもできる。As the highly activated alumina used in the present invention,
It is preferable that all the alumina particles carry the catalyst component in an amount within the above range in that a uniform catalyst poison removal reaction can be achieved, but as long as an acceptable uniform catalyst poison removal reaction can be carried out, the catalyst component It is also possible to uniformly mix and use the high-concentration supported alumina and the low-concentration supported alumina of the catalyst component or the non-supported alumina of the catalyst component so that the total amount of the catalyst component supported falls within the above range.
本発明の前処理方法によれば、触媒毒を含有する排ガ
スを接触処理して浄化する前に、上記高活性化アルミナ
の充填層に通して触媒毒を除去する。According to the pretreatment method of the present invention, before the exhaust gas containing the catalyst poison is catalytically treated and purified, the catalyst poison is removed by passing through the packed bed of the highly activated alumina.
この高活性アルミナ充填層を用いた前処理条件は、排
ガス中に含有された有害物質の種類および濃度、排ガス
中の触媒毒の種類および濃度などによって変わるので、
前処理の実施に際して、これら要因を考慮して適宜決定
すればよいが、通常、温度が130〜500℃程度、常圧下、
空間速度（SV）が10,000〜50,000hr-1程度の条件下に実
施するのがよい。なお、本発明の前処理方法は、一般の
排ガス接触処理におけると同様、触媒毒の酸化、燃焼に
よる除去を促進するために酸素源として分子状酸素、一
般的には空気の存在下に実施するのがよい。The pretreatment conditions using this highly active alumina packed bed vary depending on the type and concentration of harmful substances contained in the exhaust gas, the type and concentration of catalyst poisons in the exhaust gas, etc.
When carrying out the pretreatment, it may be appropriately determined in consideration of these factors, but usually, the temperature is about 130 to 500 ° C., under normal pressure,
The space velocity (SV) is preferably 10,000 to 50,000 hr −1 . Incidentally, the pretreatment method of the present invention is carried out in the presence of molecular oxygen as an oxygen source, generally air, in order to accelerate the removal of the catalyst poison by oxidation and combustion, as in the case of the general exhaust gas contact treatment. Is good.
本発明の前処理方法は種々の排ガスに適用可能であ
り、具体例としては、塗装焼付乾燥炉からの有機溶媒、
アルデヒドなどを含有した排ガス、金属印刷、カラー鉄
板製造乾燥炉からのキシレンなどを含有する排ガス、接
着剤塗布乾燥炉からのトルエンなどを含有する排ガス、
粘着テープ製造などの乾燥炉からの酢酸エステルなどを
含有する排ガス、オフセット印刷乾燥炉からのナフサな
どを含有する排ガス、難燃性樹脂製造工程あるいは石炭
−重油混合燃料製造工程からの排ガスなどを挙げること
ができる。The pretreatment method of the present invention is applicable to various exhaust gases, as a specific example, an organic solvent from a coating baking drying oven,
Exhaust gas containing aldehyde etc., metal printing, exhaust gas containing xylene etc. from color iron plate manufacturing drying furnace, exhaust gas containing toluene etc. from adhesive coating drying furnace,
Exhaust gas containing acetic acid ester etc. from a drying furnace such as adhesive tape manufacturing, exhaust gas containing naphtha etc. from an offset printing drying furnace, exhaust gas from a flame retardant resin manufacturing process or a coal-heavy oil mixed fuel manufacturing process etc. be able to.
本発明の前処理方法によれば、従来の方法に比較し
て、触媒毒を効率よく除去できるので、排ガス処理触媒
の被毒が防止され、その性能を長時間保持することが可
能となる。また、タール状物質も効率よく除去できるの
で、その燃焼による触媒の劣化、装置の損傷などを防止
することができる。According to the pretreatment method of the present invention, the catalyst poison can be removed more efficiently than in the conventional method, so that the exhaust gas treatment catalyst can be prevented from being poisoned and its performance can be maintained for a long time. Further, since the tar-like substance can be efficiently removed, it is possible to prevent the catalyst from being deteriorated and the device from being damaged due to the combustion.
（実施例） 以下、本発明を実施例を挙げて更に詳細に説明する。(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
なお、この実施例においては、試験用排ガス処理反応
器を５個並列に設置し、これら反応器に排ガスとして石
油製品製造排ガスを流して実施例１〜４、比較例１を同
時に行った。In this example, five test exhaust gas treatment reactors were installed in parallel, and petroleum product manufacturing exhaust gas was flown as exhaust gas into these reactors to perform Examples 1 to 4 and Comparative Example 1 at the same time.
実施例１ 排ガス処理触媒として、平均粒径5mmφの粒状γ−ア
ルミナ（比表面積250m2/g）に白金を0.25重量％担持さ
せた酸化触媒を使用し、反応器に充填して排ガス処理触
媒充填層を形成した。この排ガス処理触媒充填層の前段
に、平均粒径3.2mmφのγ−アルミナ（比表面積250m2/
g）にパラジウムを0.2重量％担持させた高活性化アルミ
ナを充填して、前処理層としての高活性化アルミナ充填
層を形成した。Example 1 As an exhaust gas treatment catalyst, an oxidation catalyst in which 0.25% by weight of platinum was supported on granular γ-alumina having an average particle diameter of 5 mmφ (specific surface area 250 m 2 / g) was used, and the exhaust gas treatment catalyst was filled in the reactor. Layers were formed. In front of this exhaust gas treatment catalyst packed bed, γ-alumina (specific surface area 250 m 2 /
g) was filled with highly activated alumina supporting 0.2% by weight of palladium to form a highly activated alumina filled layer as a pretreatment layer.
石油製品製造排ガス（シリコン含量0.13mg/Nm3、炭化
水素含量1700ppm）を反応器に下記の条件下に導入し
た。Exhaust gas from petroleum product manufacturing (silicon content 0.13 mg / Nm 3 , hydrocarbon content 1700 ppm) was introduced into the reactor under the following conditions.
前処理層入口温度:300℃ 空間速度（SV）：前処理層および排ガス処理触媒充填層
ともに20,000hr-1 1,500時間通ガス後、排ガス処理触媒および高活性化
アルミナを取り出し、排ガス処理触媒についてはシリカ
の蓄積量のほかに、250℃、300℃および350℃での触媒
活性を測定し、また高活性化アルミナについては炭素お
よびシリカの蓄積量を測定した。Pretreatment layer inlet temperature: 300 ° C. space velocity (SV): pretreatment layer and exhaust gas treatment catalyst-packed layer both to 20,000hr -1 1,500 hours through after gas removed exhaust gas treatment catalyst and highly active alumina, the exhaust gas treatment catalyst In addition to the amount of silica accumulated, the catalytic activity at 250, 300 and 350 ° C was measured, and for highly activated alumina, the amounts of carbon and silica were measured.
なお、炭素蓄積量はCHNコーダにより、またシリカ蓄
積量は蛍光Ｘ線分析により測定した。また、触媒活性
は、トルエン1,000ppmの空気バランスのモデルガスを使
用し、空間速度（SV）20,000hr-1の条件下に流して、各
温度でのテストを行い処理効率を求めた。The carbon storage amount was measured by CHN coder, and the silica storage amount was measured by fluorescent X-ray analysis. Regarding catalytic activity, a model gas with 1,000 ppm of toluene in air balance was used, flowed under the condition of space velocity (SV) of 20,000 hr −1 , and tested at each temperature to obtain treatment efficiency.
結果を表１に示す。 Table 1 shows the results.
実施例２ 実施例１において高活性化アルミナのパラジウム担持
量を0.1重量％に変更した以外は、実施例１と同様にし
て排ガス処理試験を行った。Example 2 An exhaust gas treatment test was conducted in the same manner as in Example 1 except that the amount of palladium carried on the highly activated alumina was changed to 0.1% by weight.
結果を表１に示す。 Table 1 shows the results.
実施例３ 実施例１において高活性化アルミナのパラジウム担持
量を0.05重量％に変更した以外は、実施例１と同様にし
て排ガス処理試験を行った。Example 3 An exhaust gas treatment test was conducted in the same manner as in Example 1 except that the amount of palladium carried on the highly activated alumina was changed to 0.05% by weight.
結果を表１に示す。 Table 1 shows the results.
実施例４ 実施例１で使用したと同じγ−アルミナを硫酸マンガ
ン水溶液中に浸漬し、風乾した後、150℃で４時間乾燥
し、更に450℃で空気雰囲気中で２時間焼成して酸化マ
ンガンの担持量が１重量％の高活性化アルミナを調製し
た。Example 4 The same γ-alumina used in Example 1 was immersed in an aqueous solution of manganese sulfate, air-dried, dried at 150 ° C. for 4 hours, and further calcined at 450 ° C. in an air atmosphere for 2 hours to obtain manganese oxide. A highly activated alumina having a supported amount of 1% by weight was prepared.
実施例１において、高活性化アルミナとして上記酸化
マンガン担持アルミナを使用し、また前処理層入口温度
を350℃とした以外は、実施例１と同様にして排ガス処
理試験を行った。An exhaust gas treatment test was conducted in the same manner as in Example 1 except that the above manganese oxide-supported alumina was used as the highly activated alumina and the pretreatment layer inlet temperature was 350 ° C.
結果を表１に示す。 Table 1 shows the results.
比較例１ 実施例１において、前処理層として平均粒径3.2mmφ
のγ−アルミナの充填層を使用した以外は実施例１と同
様にして排ガス処理試験を行った。Comparative Example 1 In Example 1, the pretreatment layer had an average particle size of 3.2 mmφ.
An exhaust gas treatment test was conducted in the same manner as in Example 1 except that the packed bed of γ-alumina was used.
結果を表１に示す。 Table 1 shows the results.
なお、排ガス処理試験を行った後、γ−アルミナの示
差熱分析を行った結果、その発火点は約430℃と推定さ
れた。実際に空気流通下で燃焼試験を行ったところ、ほ
ぼ同温度で急激な燃焼、発熱が発生することが確認され
た。After conducting the exhaust gas treatment test, the ignition point was estimated to be about 430 ° C. as a result of performing a differential thermal analysis of γ-alumina. When a combustion test was actually conducted under air circulation, it was confirmed that rapid combustion and heat generation occurred at approximately the same temperature.
表１の結果から、本発明の高活性化アルミナ充填層を
用いて前処理を行うと、触媒毒としての有機シリコン化
合物およびタール状物質が効率よく除去され、排ガス処
理触媒の触媒活性が高水準に維持されることが理解され
る。 From the results of Table 1, when the pretreatment is performed using the highly activated alumina packed bed of the present invention, the organosilicon compound as a catalyst poison and the tar-like substance are efficiently removed, and the catalytic activity of the exhaust gas treatment catalyst is at a high level. Is understood to be maintained at.
（発明の効果） 本発明の前処理方法によれば、排ガス中に含有された
触媒毒が効率よく除去することができるので、排ガス処
理触媒の被毒を防止し、その性能を長時間維持すること
ができる。この触媒寿命の増加によって、排ガス処理触
媒の取替え間隔を大幅に延長できるという大きな経済的
利益を得ることができる。(Effect of the invention) According to the pretreatment method of the present invention, the catalyst poison contained in the exhaust gas can be efficiently removed, so that the exhaust gas treatment catalyst is prevented from being poisoned and its performance is maintained for a long time. be able to. Due to this increase in catalyst life, it is possible to obtain a great economic advantage that the replacement interval of the exhaust gas treatment catalyst can be greatly extended.
また、本発明の前処理方法によれば、タール状物質を
効率よく除去することができるので、このタール状物質
の激しい発熱を伴った燃焼による触媒の劣化、装置の損
傷などの問題を解決することができる。Further, according to the pretreatment method of the present invention, since the tar-like substance can be efficiently removed, problems such as deterioration of the catalyst due to combustion accompanied by intense heat generation of the tar-like substance and damage to the device are solved. be able to.
従って、本発明の前処理方法は排ガス処理技術分野で
極めて有用なものである。Therefore, the pretreatment method of the present invention is extremely useful in the technical field of exhaust gas treatment.
───────────────────────────────────────────────────── フロントページの続き 審査官 石井 良夫 (56)参考文献 特開 昭62−68542（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page Examiner Yoshio Ishii (56) References JP 62-68542 (JP, A)
Claims (1)
て浄化するに当たり、該排ガスを金、銀、ルテニウム、
パラジウム、オスミウム、イリジウムおよび白金から選
ばれる少なくとも１種および／または鉄、マンガン、ク
ロム、銅、ニッケルおよびコバルトの酸化物から選ばれ
る少なくとも１種の触媒成分を比表面積が50〜500m2/g
の範囲の活性アルミナに担持してなる触媒の充填層に通
して触媒毒を除去することを特徴とする排ガスの前処理
方法。1. When purifying industrial exhaust gas containing a catalyst poison by catalytic treatment, the exhaust gas is treated with gold, silver, ruthenium,
A specific surface area of at least one selected from palladium, osmium, iridium and platinum and / or at least one catalyst selected from oxides of iron, manganese, chromium, copper, nickel and cobalt having a specific surface area of 50 to 500 m 2 / g.
A pretreatment method for exhaust gas, which comprises removing a catalyst poison by passing through a packed bed of a catalyst supported on activated alumina in the range of
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63210567A JPH0824819B2 (en) | 1988-08-26 | 1988-08-26 | Exhaust gas pretreatment method |
| KR1019890012208A KR950006516B1 (en) | 1988-08-26 | 1989-08-26 | Method for purifying exhaust gas and apparatus therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63210567A JPH0824819B2 (en) | 1988-08-26 | 1988-08-26 | Exhaust gas pretreatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0259020A JPH0259020A (en) | 1990-02-28 |
| JPH0824819B2 true JPH0824819B2 (en) | 1996-03-13 |
Family
ID=16591462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63210567A Expired - Lifetime JPH0824819B2 (en) | 1988-08-26 | 1988-08-26 | Exhaust gas pretreatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0824819B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1764201A (en) * | 1999-11-24 | 2001-06-04 | General Electric Company | Method of cleaning industrial waste gases |
| CN114100669B (en) * | 2021-11-25 | 2024-03-08 | 青岛华世洁环保科技有限公司 | Pretreatment agent for silicon-containing VOCs, and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5515622A (en) * | 1978-07-20 | 1980-02-02 | Nikki Universal Co Ltd | Exhaust gas pretreating method |
| JPS6268542A (en) * | 1985-09-20 | 1987-03-28 | Cataler Kogyo Kk | Three-component catalyst for purifying exhaust gas |
-
1988
- 1988-08-26 JP JP63210567A patent/JPH0824819B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0259020A (en) | 1990-02-28 |
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