JPH0780248A - Purification of formaldehyde-containing gas - Google Patents
Purification of formaldehyde-containing gasInfo
- Publication number
- JPH0780248A JPH0780248A JP5230405A JP23040593A JPH0780248A JP H0780248 A JPH0780248 A JP H0780248A JP 5230405 A JP5230405 A JP 5230405A JP 23040593 A JP23040593 A JP 23040593A JP H0780248 A JPH0780248 A JP H0780248A
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde
- exhaust gas
- zeolite
- concentration
- rotor
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 238000000746 purification Methods 0.000 title abstract description 14
- 239000010457 zeolite Substances 0.000 claims abstract description 55
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 52
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 26
- 239000002904 solvent Substances 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 72
- 238000001179 sorption measurement Methods 0.000 description 25
- 239000003463 adsorbent Substances 0.000 description 19
- 239000013078 crystal Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000003973 paint Substances 0.000 description 10
- 238000003795 desorption Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000012013 faujasite Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 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
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ホルムアルデヒド含有
ガスの浄化処理方法に関するもので、より詳細には、塗
装排ガス等に含有され、従来捕捉の困難であったホルム
アルデヒドを有効に捕捉し、浄化する方法に関する。特
に、本発明は、低濃度のホルムアルデヒドを含む有機溶
剤排ガスを疎水性ゼオライトを担持したフィルターを用
いて効果的に浄化する方法を提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying formaldehyde-containing gas, and more specifically, it effectively traps and purifies formaldehyde contained in coating exhaust gas, which has been difficult to capture in the past. Regarding the method. In particular, the present invention provides a method for effectively purifying an organic solvent exhaust gas containing a low concentration of formaldehyde by using a filter carrying a hydrophobic zeolite.
【０００２】[0002]
【従来の技術】工場等から排出される炭化水素類は、光
化学スモッグの発生要因である。また、それらの多くは
有臭であり、工場が住宅地に隣接している場合にはしば
しば悪臭公害として捉えられることがある。2. Description of the Related Art Hydrocarbons discharged from factories are a cause of photochemical smog. Also, many of them are odorous and can often be perceived as odor pollution when the factory is adjacent to a residential area.
【０００３】これら炭化水素類を含む排ガスの浄化方法
としては、吸着式溶剤回収法（吸着剤に吸着させて回収
する方法）、酸化分解法（高温に加熱し酸化分解させる
方法）等が広範に行われてきた。これらの方法が急速に
普及したのは排ガスを浄化するという目的と同時に、炭
化水素類を溶剤またはエネルギーとして回収できるとい
う経済的なメリットがあったためと考えられる。As a method for purifying exhaust gas containing these hydrocarbons, an adsorption solvent recovery method (a method of adsorbing and collecting on an adsorbent), an oxidative decomposition method (a method of heating at a high temperature for oxidative decomposition) and the like are widely used. Has been done. It is considered that these methods have spread rapidly because they have the economical advantage of being able to recover hydrocarbons as a solvent or energy, as well as purifying exhaust gas.
【０００４】しかし、近年環境保全の立場から、こうい
った経済的なメリットを期待出来ない排ガスに対して
も、その浄化に取り組まなければならない状況になって
いる。すなわち、低濃度の排ガス浄化が、特に臭気対策
として必要になっている。なかでも、化学工場、塗装工
場、飼料工場などの排ガスに数ｐｐｍ〜数十ｐｐｍ含ま
れるホルムアルデヒドについてはこれまで有効な対策が
なかった。However, in recent years, from the standpoint of environmental protection, it has become necessary to work on the purification of exhaust gas for which such economic advantages cannot be expected. That is, low-concentration exhaust gas purification is particularly required as a measure against odor. In particular, there has been no effective countermeasure against formaldehyde contained in exhaust gas of chemical plants, coating plants, feed plants, etc. in the range of several ppm to several tens of ppm.
【０００５】炭化水素濃度がメタン換算で５０００ｐｐ
ｍ以下の場合は、多量の補助燃料が必要となるため経済
性が失われる。Hydrocarbon concentration is 5000 pp in terms of methane
If it is less than m, a large amount of auxiliary fuel is required, and the economical efficiency is lost.
【０００６】この様な低濃度の炭化水素排ガスを経済的
に浄化する方法として、ハニカム式濃縮装置により連続
的に排ガス中の炭化水素を濃縮し、濃縮された小風量の
排ガスを小型の回収装置或いは酸化分解装置で処理する
方式がある。しかし、炭化水素排ガス中にホルムアルデ
ヒドが含まれる場合には、その沸点が−１９．５℃と低
く吸着剤に補足されにくいためその処理が困難であっ
た。As a method for economically purifying such low-concentration hydrocarbon exhaust gas, the hydrocarbon in the exhaust gas is continuously concentrated by a honeycomb type concentrator, and the concentrated exhaust gas with a small air volume is collected in a small size. Alternatively, there is a method of treating with an oxidative decomposition device. However, when formaldehyde is contained in the hydrocarbon exhaust gas, the boiling point thereof is as low as -19.5 ° C, and it is difficult to capture it by the adsorbent, which makes the treatment difficult.
【０００７】従来、溶剤を含む排ガスの浄化には吸着剤
として活性炭が広範に使用されてきた。しかし、活性炭
自体は可燃性の物質であり活性炭を吸着剤として使用す
る排ガス浄化装置には潜在的に火災や爆発などの危険が
あった。Conventionally, activated carbon has been widely used as an adsorbent for purification of exhaust gas containing a solvent. However, activated carbon itself is a flammable substance, and an exhaust gas purification apparatus that uses activated carbon as an adsorbent has a potential risk of fire or explosion.
【０００８】この様な排ガス浄化装置の潜在的な危険を
回避する方法として、不燃性の吸着剤を使用することが
考えられ、新しい吸着剤として疎水性を高めたゼオライ
トが使用され始めている（特表昭６０−５０１４９５号
公報および特開昭６４−８５１１３号公報）。As a method of avoiding such a potential danger of the exhaust gas purifying apparatus, it is considered to use a non-combustible adsorbent, and zeolite having an increased hydrophobicity is beginning to be used as a new adsorbent (special feature: Table 60-501495 and JP 64-85113).
【０００９】ケトン系有機溶剤含有ガスの浄化に際して
再生過程で触媒性を示さないゼオライト系吸着剤とし
て、特開平４−２１０２３５号公報では、水熱処理した
疎水性ゼオライトを、特開平４−２４４２３０号公報で
はアルカリ金属イオン型の疎水性ゼオライトを提供して
いる。また、特開平５−２３５８６号公報は、高沸点成
分を含む排ガスの浄化に対して、吸着剤として固体酸量
０．１mmol/g以下でＳｉＯ2 ／ＡＩ2 Ｏ3 モル比５０以
上のゼオライトを提供している。As a zeolite-based adsorbent which does not exhibit catalytic properties in the regeneration process when purifying a gas containing a ketone-based organic solvent, in JP-A-4-210235, a hydrothermally treated hydrophobic zeolite is disclosed in JP-A-4-244230. Offers alkali metal ion type hydrophobic zeolites. Further, JP-A-5-23586 discloses a zeolite having a solid acid amount of 0.1 mmol / g or less and a SiO 2 / AI 2 O 3 molar ratio of 50 or more as an adsorbent for purification of exhaust gas containing a high boiling point component. providing.
【００１０】[0010]
【発明が解決しようとする課題】しかし、疎水性ゼオラ
イトの排ガス浄化装置への適用に関する応用研究は始ま
ったばかりであり、特にその吸着特性については未だ十
分に解明されているとは言い難い。However, applied research on the application of hydrophobic zeolite to an exhaust gas purifying apparatus has just started, and it is hard to say that its adsorption characteristics have been sufficiently elucidated.
【００１１】一般的には、空気中の有機物は疎水性ゼオ
ライト結晶内の細孔に補足されるので、ゼオライト結晶
単位容積当たりの細孔の占める容積（以下、空隙率とい
う）の大きいものほど有機化合物を多く吸着すると考え
られる。実際に大部分の有機溶剤排ガスについてこのこ
とが確認され、通常は空隙率が０．２６８ｍｌ／ｇとゼ
オライトの中でも最も大きいフォージャサイト型ゼオラ
イトが最も一般的に使用されている。Generally, since the organic matter in the air is captured by the pores in the hydrophobic zeolite crystal, the larger the volume occupied by the pores per unit volume of the zeolite crystal (hereinafter referred to as the porosity), the more the organic matter. It is considered to adsorb a large amount of compounds. In fact, this was confirmed for most organic solvent exhaust gases, and the faujasite-type zeolite, which has the highest porosity of 0.268 ml / g, is the most commonly used zeolite.
【００１２】そこで本発明者らも、疎水性のフォージャ
サイト型ゼオライトを吸着剤としたハニカム式濃縮装置
でホルムアルデヒドを含む排ガスの浄化を試みた。しか
しホルムアルデヒドの濃度が５０ｐｐｍ以下領域ではホ
ルムアルデヒドは吸着されず、ホルムアルデヒドを含む
排ガスの浄化がまったく行われないことが判明した。Therefore, the present inventors also tried to purify the exhaust gas containing formaldehyde by a honeycomb type concentrator using a hydrophobic faujasite type zeolite as an adsorbent. However, it was found that formaldehyde was not adsorbed in a region where the concentration of formaldehyde was 50 ppm or less, and exhaust gas containing formaldehyde was not purified at all.
【００１３】本発明者らは、ホルムアルデヒドを含む有
機溶剤排ガスの最適な疎水性ゼオライトを用いたハニカ
ム式濃縮装置による浄化方法を提供すべく鋭意検討を重
ねた。The inventors of the present invention have made extensive studies to provide a method for purifying an exhaust gas of an organic solvent containing formaldehyde by a honeycomb type concentrator using an optimum hydrophobic zeolite.
【００１４】その結果、ＳｉＯ2 ／ＡＩ2 Ｏ3 モル比１
００以上のＺＳＭ−５型ゼオライトを５０ｋｇ／ｍ3
以上の量で有するハニカム構造フィルターが、ホルムア
ルデヒドの吸着に有効であることを見いだした。As a result, the SiO 2 / AI 2 O 3 molar ratio was 1
00 or more ZSM-5 type zeolite 50 kg / m 3
It was found that the honeycomb structure filter having the above amount is effective for adsorbing formaldehyde.
【００１５】即ち、本発明の目的は、低濃度のホルムア
ルデヒドを含む有機溶剤排ガスを疎水性ゼオライトのフ
ィルターを用いて効果的に浄化する方法を提供するにあ
る。That is, an object of the present invention is to provide a method for effectively purifying an organic solvent exhaust gas containing a low concentration of formaldehyde by using a hydrophobic zeolite filter.
【００１６】[0016]
【課題を解決するための手段】本発明は、ホルムアルデ
ヒドを含有するガスの浄化に最適な、ＳｉＯ2 ／Ａｌ 2
Ｏ3 モル比１００以上のＺＳＭ−５型ゼオライトを５０
ｋｇ／ｍ3 以上の量で有するハニカム構造フィルターに
０．２〜０．５秒間接触させる方法を提供するものであ
る。SUMMARY OF THE INVENTION The present invention is a Holmuarde
SiO that is most suitable for purification of gas containing sulfide2 / Al 2
O3 ZSM-5 type zeolite with a molar ratio of 100 or more is 50
kg / m3 For honeycomb structure filters with the above amount
A method of contacting for 0.2 to 0.5 seconds is provided.
It
【００１７】[0017]
【作用】ゼオライト結晶の基本構造は、ＳｉＯ4 とその
置換体のＡｌＯ4 それぞれの四面体で、それらがお互い
に頂点の酸素原子を共有し、３次元方向に発達した結晶
構造を形成している。その結果、ゼオライト結晶は他の
鉱物にみられないような非常に大きな空洞や孔路を有し
ている。これらの細孔の入口径はゼオライトによってこ
となるが、通常３〜９オングストロームであり、種々の
分子を細孔内部に捕捉することができる。また、結晶内
部にはＡｌＯ4 の負電荷を補うために陽イオンが存在し
ている。この陽イオンによって形成された静電場の影響
により極性分子や分極性分子を選択的に吸着する。汎用
の吸着剤として一般的に使用されているＡ型ゼオライ
ト、Ｘ型ゼオライト等のＳｉＯ2 ／ＡＩ2 Ｏ3 モル比は
２〜５と低く、これらのゼオライトは有機化合物よりも
水を選択的に吸着する。したがって、有機溶剤を含む排
ガスの浄化用吸着剤としては適当ではない。[Function] The basic structure of a zeolite crystal is SiO 4 and its substituted AlO 4 tetrahedrons, each of which shares an apex oxygen atom and forms a crystal structure developed in a three-dimensional direction. . As a result, zeolite crystals have very large cavities and channels that are not found in other minerals. The entrance diameter of these pores varies depending on the zeolite, but is usually 3 to 9 angstrom, and various molecules can be trapped inside the pores. Further, cations are present inside the crystal to supplement the negative charge of AlO 4 . Polar molecules and polarizable molecules are selectively adsorbed by the influence of the electrostatic field formed by the cations. The SiO 2 / AI 2 O 3 molar ratio of A-type zeolite, X-type zeolite, etc., which are generally used as a general-purpose adsorbent, is as low as 2 to 5, and these zeolites selectively select water over organic compounds. Adsorb. Therefore, it is not suitable as an adsorbent for purifying exhaust gas containing an organic solvent.
【００１８】ゼオライトはＳｉＯ2 ／ＡＩ2 Ｏ3 モル比
２０以上で親水性を失い、次第に疎水性を示すようにな
る。このように疎水性を示すゼオライトは、有機溶剤を
含む排ガスの浄化に対して、活性炭と同様に疎水性吸着
剤として有用である。特に、水分が共存する系でも有機
溶剤に対する吸着容量の低下が小さく一定の吸着性能を
示すため気象条件によってその性能が低下する事はな
い。Zeolite loses hydrophilicity at a SiO 2 / AI 2 O 3 molar ratio of 20 or more and gradually becomes hydrophobic. Like the activated carbon, the zeolite having hydrophobicity is useful as a hydrophobic adsorbent for purification of exhaust gas containing an organic solvent. In particular, even in a system in which water coexists, the adsorption capacity for an organic solvent does not decrease so much that the adsorption performance is constant, so that the performance does not deteriorate depending on weather conditions.
【００１９】本発明者らは、前述のごとくホルムアルデ
ヒドを含む有機溶剤排ガスの浄化という課題に対して、
当初疎水性のフォージャサイト型ゼオライトを吸着剤と
したハニカム式溶剤濃縮装置を使用して検討を重ねた。
しかし、一般的な有機溶剤は吸着できるのに、ホルムア
ルデヒドだけは全く吸着されず、十分な排ガス浄化がで
きなかった。The present inventors have addressed the problem of purifying exhaust gas of organic solvent containing formaldehyde as described above.
Initially, studies were repeated using a honeycomb-type solvent concentrator using hydrophobic faujasite-type zeolite as an adsorbent.
However, although general organic solvents can be adsorbed, formaldehyde alone is not adsorbed and exhaust gas cannot be sufficiently purified.
【００２０】そこで、種々の結晶構造を有する疎水性ゼ
オライトについてホルムアルデヒドの吸着等温線を測定
した。その結果、これまでの知見では予測できなかった
ことであるが、ＺＳＭ−５型の結晶構造を有する疎水性
ゼオライトのみが特異的に高いホルムアルデヒドの吸着
特性を示すことがわかった。Therefore, the adsorption isotherms of formaldehyde were measured for hydrophobic zeolites having various crystal structures. As a result, it was found that only hydrophobic zeolite having a ZSM-5 type crystal structure exhibits a specifically high formaldehyde adsorption property, which was unexpectedly unpredictable.
【００２１】有機化合物の疎水性ゼオライトにおける吸
着サイトは、結晶内の細孔であるが、その表面は結晶構
造に関係なく酸素原子で形成されている。従って、この
ＺＳＭ−５型に対するホルムアルデヒドの特異的な吸着
はその特殊な細孔構造によるものではないかと推定され
る。The adsorption site in the hydrophobic zeolite of the organic compound is a pore in the crystal, but its surface is formed of oxygen atoms regardless of the crystal structure. Therefore, it is presumed that the specific adsorption of formaldehyde on this ZSM-5 type is due to its special pore structure.
【００２２】ちなみに、一例として、フォージャサイト
型のゼオライト結晶の空孔率は０．２６８ｍｌ／ｇであ
り、ＺＳＭ−５型の場合は０．１９９ｍｌ／ｇである。
また、窒素吸着法により求めた比表面積はフォージャサ
イト型で約７００ｍ2 ／ｇ、ＺＳＭ−５型で約３００ｍ
2 ／ｇである。疎水性ゼオライトは実質的に珪素と酸素
から形成されており、吸着剤の表面状態によって吸着力
が決まるならば、低濃度でもＺＳＭ−５型に対してフォ
ージャサイト型の疎水性ゼオライトは常に高い吸着量を
示すはずである。しかし、フォージャサイト型の疎水性
ゼオライトは５０ｐｐｍ以下の濃度域でホルムアルデヒ
ドを全く吸着しないにもかかわらず、ＺＳＭ−５型のそ
れは常温でたしかにホルムアルデヒドを吸着する。たと
えば、５０ｐｐｍのホルムアルデヒドを、３０℃におい
て、疎水性のＺＳＭ−５型ゼオライトは約１．５ｇ／１
００ｇ吸着するが、疎水性のフォージャサイト型は０．
１ｇ／１００ｇ以下の吸着量しか示さない。Incidentally, as an example, the porosity of the faujasite-type zeolite crystal is 0.268 ml / g, and that of the ZSM-5 type is 0.199 ml / g.
The specific surface area determined by the nitrogen adsorption method is about 700 m 2 / g for the faujasite type and about 300 m for the ZSM-5 type.
2 / g. Hydrophobic zeolite is substantially composed of silicon and oxygen, and if the adsorptive power is determined by the surface condition of the adsorbent, the faujasite type hydrophobic zeolite is always higher than the ZSM-5 type even if the concentration is low. It should indicate the amount of adsorption. However, although the faujasite type hydrophobic zeolite does not adsorb formaldehyde in the concentration range of 50 ppm or less, the ZSM-5 type does adsorb formaldehyde at room temperature. For example, 50 ppm formaldehyde at 30 ° C. is about 1.5 g / 1 for the hydrophobic ZSM-5 type zeolite.
Although it adsorbs 00 g, the hydrophobic faujasite type adsorbs 0.
It only shows an adsorption amount of 1 g / 100 g or less.
【００２３】この様に、ＺＳＭ−５ゼオライトはホルム
アルデヒドに対して格段に優れた吸着性を示すことが判
明したので、さらにハニカム式濃縮装置への適用につい
て検討を行った。As described above, since it was found that ZSM-5 zeolite exhibits remarkably excellent adsorptivity to formaldehyde, its application to a honeycomb type concentrator was further investigated.
【００２４】ハニカム式濃縮装置は、一例として、ハニ
カム構造を有するセラミック繊維のローターに疎水性ゼ
オライトを担持した主要部からなり、このローターは、
吸着部と再生部とにシールで区分され、ローターの各部
分は吸着部と再生部とに交互に出入りする構造になって
いる。ローターは低速で回転し、疎水性ゼオライトに吸
着されたホルムアルデヒドや有機溶剤は再生部で熱風に
より連続的に脱着される。このため、吸着部のローター
は常にホルムアルデヒドや有機溶剤を吸着することがで
きる。As an example, the honeycomb type concentrating device is composed of a main part in which a hydrophobic zeolite is supported on a rotor of ceramic fibers having a honeycomb structure.
The adsorption section and the regeneration section are divided by a seal, and each part of the rotor has a structure in which it enters and leaves the adsorption section and the regeneration section alternately. The rotor rotates at a low speed, and formaldehyde and organic solvent adsorbed on the hydrophobic zeolite are continuously desorbed by hot air in the regeneration section. Therefore, the rotor of the adsorption unit can always adsorb formaldehyde and the organic solvent.
【００２５】このハニカム式濃縮装置のローターとし
て、疎水性ＺＳＭ−５型ゼオライトを担持したものを製
作し、ホルムアルデヒドを含む有機溶剤排ガスの浄化に
適用した。As the rotor of this honeycomb type concentrator, a rotor carrying a hydrophobic ZSM-5 type zeolite was manufactured and applied to purification of exhaust gas of an organic solvent containing formaldehyde.
【００２６】ハニカムローターにおける疎水性ゼオライ
トの量、即ちローター単位容積当たりの重量（ｋｇ／ｍ
3 ）は、ローターの有機溶剤保持量および濃縮倍率を決
定する因子であり、特に重要である。ローターに吸着さ
れた有機溶剤は、再生部においてローターから脱着され
るが、このとき熱風とローターの間で熱交換が行われる
ので、吸着された有機溶剤あたりの再生に必要な熱風量
はゼオライトの容積あたりの量が多いほど少なくてす
み、濃縮倍率も高く取れる。実際には、５０ｋｇ／ｍ3
以上の量があれば、十分な浄化性能及び経済的な有機溶
剤濃縮性能が達成される。The amount of hydrophobic zeolite in the honeycomb rotor, that is, the weight per unit volume of the rotor (kg / m
3 ) is a factor that determines the amount of organic solvent retained and the concentration ratio of the rotor, and is particularly important. The organic solvent adsorbed on the rotor is desorbed from the rotor in the regeneration section, but at this time heat exchange is performed between the hot air and the rotor, so the amount of hot air required for regeneration per adsorbed organic solvent is The larger the volume, the smaller the volume, and the higher the concentration ratio. Actually, 50 kg / m 3
With the above amount, sufficient purification performance and economical organic solvent concentration performance can be achieved.
【００２７】また、疎水性ＺＳＭ−５型ゼオライトを担
持したローターにおいて、排ガスのローター内における
滞留時間、すなわち接触時間が０．２〜０．５秒の条件
で、最も効率良くホルムアルデヒドが除去された。接触
時間が０．２秒以下の場合は、ローター部におけるホル
ムアルデヒド分子の拡散過程が律速となり、ホルムアル
デヒドの吸着が十分に行われなかったと考えられる。一
方、０．５秒以上の場合は排ガスの浄化は申し分なく達
成されるものであるが、接触時間を長くするということ
は一定の処理ガス量に対して大型のローターを必要とす
ることであり、過大な設備投資につながるので好ましく
ない。Further, in the rotor supporting the hydrophobic ZSM-5 type zeolite, formaldehyde was most efficiently removed under the condition that the residence time of exhaust gas in the rotor, that is, the contact time was 0.2 to 0.5 seconds. . When the contact time is 0.2 seconds or less, it is considered that the diffusion process of formaldehyde molecules in the rotor part is rate-determining and formaldehyde is not sufficiently adsorbed. On the other hand, in the case of 0.5 seconds or more, purification of exhaust gas can be achieved satisfactorily, but lengthening the contact time means that a large rotor is required for a certain amount of treated gas. However, it is not preferable because it leads to excessive capital investment.
【００２８】ローターの再生温度は、共存する有機溶剤
の種類にもよるが、ホルムアルデヒドだけであれば１０
０℃以上の温度で行えば良い。The regeneration temperature of the rotor depends on the kinds of coexisting organic solvents, but it is 10 if formaldehyde is the only solvent.
It may be performed at a temperature of 0 ° C. or higher.
【００２９】[0029]
【発明の好適態様】本発明において、ホルムアルデヒド
含有ガスとしては、ホルムアルデヒドを比較的低濃度で
含む任意のガス、例えば、化学工場、塗装工場、飼料工
場などの排ガスに適用することができる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the formaldehyde-containing gas can be applied to any gas containing formaldehyde in a relatively low concentration, for example, exhaust gas from a chemical factory, a coating factory, a feed factory or the like.
【００３０】本発明は、これらのガスの内でも、全有機
溶剤濃度がメタン換算で５００〜５０００ｐｐｍであ
り、かつホルムアルデヒド濃度が５〜１００ｐｐｍであ
る排ガス、特に塗料やインクの乾燥乃至焼き付け排ガス
の処理に有用である。Among these gases, the present invention treats an exhaust gas having a total organic solvent concentration of 500 to 5000 ppm in terms of methane and a formaldehyde concentration of 5 to 100 ppm, particularly for drying or baking exhaust gas of paint or ink. Useful for.
【００３１】塗料やインクの樹脂分としては、各種樹脂
が使用されているが、樹脂の主成分や樹脂の硬化剤成分
として、或いは樹脂の変性剤成分として、フェノール−
ホルムアルデヒド樹脂や、メラミン−ホルムアルデヒド
樹脂、尿素−ホルムアルデヒド樹脂が使用されているこ
とが多い。Various resins have been used as the resin component of paints and inks. As a main component of the resin, a curing agent component of the resin, or a modifier component of the resin, phenol-
Formaldehyde resin, melamine-formaldehyde resin, urea-formaldehyde resin are often used.
【００３２】塗料乃至インクの乾燥乃至焼き付け工程で
は、樹脂の重縮合により、或いは樹脂の熱分解により、
樹脂中のホルムアルデヒドが発生する。このホルムアル
デヒドは、濃度が比較的低いものであるが、本発明によ
れば、このホルムアルデヒドを有効に除去することがで
きる。In the process of drying or baking the paint or ink, polycondensation of the resin or thermal decomposition of the resin causes
Formaldehyde in resin is generated. Although this formaldehyde has a relatively low concentration, the formaldehyde can be effectively removed according to the present invention.
【００３３】また、有機溶剤成分の含有量の低い排ガス
としては、水性塗料乃至インクの乾燥乃至焼き付け排ガ
スや、無溶剤型乃至低溶剤型の塗料乃至インクからの排
ガスが挙げられる。水性塗料乃至インクの場合、溶剤の
主たるものは勿論水であるが、樹脂分の水に対する溶解
性や分散性を向上させ、塗料等に造膜性を付与するた
め、極性有機溶媒等が必ず含有されている。無溶剤型乃
至低溶剤型の塗料乃至インクでは、液状の樹脂分が、紫
外線、放射線、触媒等の作用により硬化して、緻密な被
覆となるものであるが、基体への濡れ性や塗装性等を高
めるために、若干の溶剤が希釈剤として含まれている場
合がほとんどである。また、無溶剤型乃至低溶剤型の塗
料では、塗膜の硬化は紫外線等により行われるとして
も、塗膜の硬化を完結させ、塗膜の歪を取り除くため、
熱処理を行うのが一般的である。従って、排出される排
ガスには、低濃度の有機溶剤成分が含有されているが、
本発明によれば、この様な塗料乃至インクの処理時の付
排ガスから、低濃度の有機溶剤成分をも同時に除去する
ことができる。Examples of the exhaust gas having a low content of the organic solvent component include exhaust gas from drying or baking of water-based paint or ink, and exhaust gas from solvent-free or low-solvent paint or ink. In the case of water-based paints and inks, the main solvent is of course water, but in order to improve the solubility and dispersibility of the resin component in water and to impart film-forming properties to paints, etc., polar organic solvents, etc. must be contained Has been done. In solvent-free or low-solvent type paints or inks, the liquid resin component is hardened by the action of ultraviolet rays, radiation, catalysts, etc. to form a dense coating. In most cases, a small amount of solvent is contained as a diluent in order to improve the above. Further, in the case of solvent-free or low-solvent type paint, even if the coating film is cured by ultraviolet rays or the like, in order to complete the curing of the coating film and remove the distortion of the coating film,
Generally, heat treatment is performed. Therefore, although the exhaust gas discharged contains a low-concentration organic solvent component,
According to the present invention, a low-concentration organic solvent component can be simultaneously removed from the exhaust gas attached during the treatment of such a paint or ink.
【００３４】本発明で用いるＺＳＭ−５型ゼオライト
は、ＳｉＯ2 ／ＡＩ2 Ｏ3 のモル比が１００以上、特に
２００乃至５０００の範囲にあるのがよい。このＺＳＭ
−５型ゼオライトは、上記シリカ分及びアルミナ分に加
えて、ナトリウム等のアルカリ金属分を含有していても
よく、またアルカリ金属分が水素に置換された水素型ゼ
オライトであってもよい。The ZSM-5 type zeolite used in the present invention preferably has a SiO 2 / AI 2 O 3 molar ratio of 100 or more, particularly in the range of 200 to 5,000. This ZSM
The -5 type zeolite may contain an alkali metal component such as sodium in addition to the silica component and the alumina component, and may be a hydrogen type zeolite in which the alkali metal component is replaced with hydrogen.
【００３５】このＺＳＭ−５型ゼオライトのＢＥＴ法比
表面積は、一般に３００乃至４００ｍ2 ／ｇの範囲にあ
り、一方細孔容積は、０．１８〜０．２１ｃｃ／ｇの範
囲にあることが望ましい。また、その粒子径は、一般に
１乃至５μｍの範囲内にある。The BET specific surface area of this ZSM-5 type zeolite is generally in the range of 300 to 400 m 2 / g, while the pore volume is preferably in the range of 0.18 to 0.21 cc / g. . The particle size is generally in the range of 1 to 5 μm.
【００３６】ＺＳＭ−５型ゼオライトは、それ自体公知
の方法、例えば、シリカ源、アルミナ源、アルカリ金属
成分及び水を、塩基性有機窒素化合物をテンプレートと
して水熱処理する方法や、テンプレートを用いることな
く、水性コロイドシリカゾル、アルミン酸アルカリ、及
び水酸化アルカリを水熱処理する方法等により得られ
る。The ZSM-5 type zeolite can be obtained by a method known per se, for example, a method of hydrothermally treating a silica source, an alumina source, an alkali metal component and water with a basic organic nitrogen compound as a template, or without using a template. , An aqueous colloidal silica sol, an alkali aluminate, and an alkali hydroxide are hydrothermally treated.
【００３７】ＺＳＭ−５型ゼオライトのハニカム式フィ
ルターとしては、既に指摘した通り、ハニカム構造を有
するセラミック繊維のローターに疎水性ゼオライトを担
持させたものが有利に使用されるが、これに限定される
ことなく、他のハニカム基体にＺＳＭ−５型ゼオライト
を担持させたものや、ＺＳＭ−５型ゼオライトを、必要
によりクレイ等の無機成形助剤や樹脂等の有機成形助剤
と共に、ハニカムに成形したものを用いることもでき
る。As already mentioned, the ZSM-5-type zeolite honeycomb filter is preferably a ceramic fiber rotor having a honeycomb structure and hydrophobic zeolite supported thereon, but is not limited thereto. Without supporting, ZSM-5 type zeolite supported on another honeycomb substrate, or ZSM-5 type zeolite was formed into a honeycomb together with an inorganic forming aid such as clay and an organic forming aid such as resin, if necessary. A thing can also be used.
【００３８】ＺＳＭ−５型ゼオライトのハニカムへの充
填量は、５０ｋｇ／ｍ3 以上、特に７０乃至１５０ｋｇ
／ｍ3 の範囲にあることが好ましい。ＺＳＭ−５型ゼオ
ライトの充填量が余り大きくなりすぎると、ガスの圧損
が増大し、コストも高くなるので好ましくない。The filling amount of ZSM-5 type zeolite into the honeycomb is 50 kg / m 3 or more, particularly 70 to 150 kg.
It is preferably in the range of / m 3 . If the filling amount of the ZSM-5 type zeolite is too large, the gas pressure loss increases and the cost also increases, which is not preferable.
【００３９】ハニカム式ローターの径は、特に制限はな
いが、一般に４００乃至６０００ｍｍ程度のものが適当
であり、吸着部と脱着部との面積比率は、一般に７：１
乃至３：１の範囲にあるのがよい。ローターの回転速度
は、１．５乃至８回転／時間、特に２乃至５回転／分の
範囲で変化させることができる。The diameter of the honeycomb rotor is not particularly limited, but a diameter of 400 to 6000 mm is generally suitable, and the area ratio of the adsorption portion and the desorption portion is generally 7: 1.
It should be in the range of 3: 1. The rotation speed of the rotor can be varied in the range of 1.5 to 8 revolutions / hour, in particular 2 to 5 revolutions / minute.
【００４０】処理ガスは、ホルムアルデヒドや有機溶剤
の吸着性の点で、ハニカムフィルターに、６０℃以下、
特に４０℃以下の温度で供給することが好ましい。勿
論、排ガスが上記温度よりも高温である場合には、冷却
し、または排ガス中にタール分や粉塵が含有されている
場合には集塵操作を行うことができる。The processing gas is adsorbed to formaldehyde and an organic solvent, and is applied to the honeycomb filter at 60 ° C. or lower,
It is particularly preferable to supply at a temperature of 40 ° C. or lower. Of course, when the exhaust gas is higher than the above temperature, it can be cooled, or when the exhaust gas contains tar and dust, dust collection operation can be performed.
【００４１】本発明において、この処理により、全有機
溶剤濃度を１００ｐｐｍ以下となし、かつ同時にホルム
アルデヒド濃度を５ｐｐｍ以下とすることが望ましい。In the present invention, it is desirable that the total organic solvent concentration be 100 ppm or less and at the same time the formaldehyde concentration be 5 ppm or less by this treatment.
【００４２】脱着は１００℃以上、特に１３０乃至２５
０℃の温度で、また吸着剤の吸着平衡特性によっても相
違するが、脱着−吸着の温度差が３０乃至４５０℃、特
に８０乃至２００℃となるように、吸着処理を行うこと
が好ましい。脱着用高温キャリアーガスは、処理用ガス
の一部を、上記温度に加熱して、用いるのが好ましい。Desorption is performed at 100 ° C. or higher, especially 130 to 25
Although it depends on the temperature of 0 ° C. and the adsorption equilibrium characteristics of the adsorbent, it is preferable to carry out the adsorption treatment so that the desorption-adsorption temperature difference is 30 to 450 ° C., particularly 80 to 200 ° C. The high temperature carrier gas for desorption is preferably used by heating a part of the processing gas to the above temperature.
【００４３】吸着工程からの脱着ガスは、有機成分が高
濃度に濃縮されており、有機成分の濃度は、一般に爆発
下限界値の３０％以下の範囲であり、濃縮の程度は、５
乃至１５倍のオーダーである。このため、この濃縮ガス
は、少ない燃料での混燃で、或いは触媒との接触による
酸化で容易に処理を行えるという利点を与える。The desorption gas from the adsorption step has a high concentration of organic components, and the concentration of the organic components is generally in the range of 30% or less of the lower explosive limit value, and the concentration level is 5%.
To the order of 15 times. Therefore, this concentrated gas has an advantage that it can be easily treated by mixed combustion with a small amount of fuel or by oxidation by contact with a catalyst.
【００４４】[0044]
【実施例】以下に、本発明の実施例を説明する。EXAMPLES Examples of the present invention will be described below.
【００４５】（ハニカム式濃縮試験装置）装置の概略図
を図１に示す。本実施例で使用するローター式吸着装置
１は、吸着剤ローター２からなっており、この吸着剤ロ
ーター２は、吸着域３、脱着域４及び冷却域５をこの順
序に横切るように設けられている。(Honeycomb type concentration test device) A schematic view of the device is shown in FIG. The rotor type adsorption device 1 used in the present embodiment is composed of an adsorbent rotor 2, and the adsorbent rotor 2 is provided so as to cross the adsorption region 3, the desorption region 4 and the cooling region 5 in this order. There is.
【００４６】ホルムアルデヒド及び有機溶剤含有ガス６
を、吸着域３に供給して、有機成分を吸着剤ローター２
に吸着させ、前記ガスの一部を冷却域５に供給し、この
ガス７を熱交換器８により高温に加熱し、この高温ガス
９を、前記吸着装置の脱着域４に供給し、有機成分を脱
着して、有機成分の濃縮ガス１０を生成させる。Formaldehyde and organic solvent-containing gas 6
To the adsorption zone 3 to add organic components to the adsorbent rotor 2
Is adsorbed onto the cooling zone 5, a part of the gas is supplied to the cooling zone 5, the gas 7 is heated to a high temperature by the heat exchanger 8, and the high temperature gas 9 is supplied to the desorption zone 4 of the adsorbing device. Are desorbed to generate a concentrated gas 10 of an organic component.
【００４７】この有機成分の濃縮ガス１０を、接触式排
気処理装置１１に供給し、濃縮ガス中の有機成分を酸化
燃焼させることにより、大気中に放出可能なガスに転化
する。このガスは高温であるので、前述した熱交換器８
に供給し、脱着用高温ガスへの加熱に利用する。The concentrated gas 10 of the organic component is supplied to the contact type exhaust treatment device 11, and the organic component in the concentrated gas is oxidized and burned to be converted into a gas that can be released into the atmosphere. Since this gas has a high temperature, the heat exchanger 8
It is used for heating to desorption hot gas.
【００４８】試験装置ハニカムローター２の直径は６０
０ｍｍφであった。ローター２の約７５％は吸着部であ
り、残り約２５％は再生部（脱着域４及び冷却域５）で
ある。ローターは４ｒｐｍで回転し、再生部には１８０
℃の熱風が供給され、ホルムアルデヒド及び有機溶剤を
吸着した部分は連続的に再生される。Test apparatus Honeycomb rotor 2 has a diameter of 60
It was 0 mmφ. About 75% of the rotor 2 is an adsorption section, and the remaining about 25% is a regeneration section (desorption zone 4 and cooling zone 5). The rotor rotates at 4 rpm and the playback section is 180
The hot air of ℃ is supplied, and the part adsorbing formaldehyde and organic solvent is continuously regenerated.
【００４９】実施例１ ＳｉＯ2 ／ＡＩ2 Ｏ3 モル比が１０００のＺＳＭ−５型
ゼオライトを１００ｋｇ／ｍ3 で担持したハニカムロー
ターを用い有機溶剤排ガスの浄化試験を行った。排ガス
の温度、組成を表１に示す。Example 1 An organic solvent exhaust gas purification test was conducted using a honeycomb rotor carrying 100 kg / m 3 of ZSM-5 type zeolite having a SiO 2 / AI 2 O 3 molar ratio of 1000. Table 1 shows the temperature and composition of the exhaust gas.
【００５０】ローターへの排ガス接触時間を変えたとき
の排ガス中のＴＨＣおよびホルムアルデヒド濃度を表２
に示す。この結果から、接触時間が０．２秒以上であれ
ば、ホルムアルデヒドを含む排ガスの浄化が有効に行わ
れることがわかる。Table 2 shows THC and formaldehyde concentrations in the exhaust gas when the exhaust gas contact time with the rotor was changed.
Shown in. From this result, it is understood that the exhaust gas containing formaldehyde is effectively purified when the contact time is 0.2 seconds or more.
【００５１】比較例１ ＳｉＯ2 ／ＡＩ2 Ｏ3 モル比が５０００のフォージャサ
イト型ゼオライトを１００ｋｇ／ｍ3 で担持したハニカ
ムローターを用い、実施例１と同様に有機溶剤排ガスの
浄化実験を行った。結果を表３に示す。ＴＨＣ低下して
いるがホルムアルデヒドはほとんど除去されていないこ
とがわかる。Comparative Example 1 Using a honeycomb rotor carrying 100 kg / m 3 of faujasite-type zeolite having a SiO 2 / AI 2 O 3 molar ratio of 5000, a purification experiment of organic solvent exhaust gas was conducted in the same manner as in Example 1. It was The results are shown in Table 3. It can be seen that although THC is lowered, formaldehyde is hardly removed.
【００５２】[0052]
【表１】 [Table 1]
【００５３】[0053]
【表２】 [Table 2]
【００５４】[0054]
【表３】 [Table 3]
【００５５】[0055]
【発明の効果】この発明により、従来困難であったホル
ムアルデヒド含有ガスの浄化が可能になった。特に、ホ
ルムアルデヒドの濃度が５０ｐｐｍ以下である有機溶剤
排ガスがハニカム式濃縮装置において可能になった意義
は大きい。すなわち、人体に有害なホルムアルデヒドの
放出が抑制するため経済的で、装置の発火などの危険性
のない方法が提供された。According to the present invention, it has become possible to purify formaldehyde-containing gas, which has been difficult in the past. In particular, it is significant that an organic solvent exhaust gas having a formaldehyde concentration of 50 ppm or less has become possible in the honeycomb type concentrator. That is, a method is provided that is economical because it suppresses the release of formaldehyde, which is harmful to the human body, and that does not pose a risk of ignition of the device.
【図１】本発明の実施例に用いた装置の概略配置図であ
る。FIG. 1 is a schematic layout diagram of an apparatus used in an example of the present invention.
【符号の説明】 １ ローター式吸着装置 ２ 吸着剤ローター ３ 吸着域 ４ 脱着域 ５ 冷却域 ６ ホルムアルデヒド及び有機溶剤含有ガス ７ 冷却域からのガス ８ 熱交換器 ９ 高温ガス １０ 有機成分の濃縮ガス １１ 接触式排気処理装置[Explanation of symbols] 1 rotor type adsorption device 2 adsorbent rotor 3 adsorption region 4 desorption region 5 cooling region 6 gas containing formaldehyde and organic solvent 7 gas from cooling region 8 heat exchanger 9 high temperature gas 10 concentrated gas of organic components 11 Contact type exhaust treatment device
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｄ 53/34 ＺＡＢ Ｂ０１Ｊ 20/18 Ｂ 7202−4Ｇ 20/28 Ａ 7202−4Ｇ (72)発明者 森下 悟 神奈川県綾瀬市寺尾台４丁目２番15号 (72)発明者 野田 志知 神奈川県座間市入谷４−3011−６東建座間 ハイツ２−510 (72)発明者 小峰 高吉 神奈川県横浜市泉区新橋1029−19Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI Technical indication location B01D 53/34 ZAB B01J 20/18 B 7202-4G 20/28 A 7202-4G (72) Inventor Satoru Morishita Kanagawa 2-2-1 Teraodai, Ayase City, Aichi Prefecture (72) Inventor Shichi Noda 4-3011-6 Iriya, Zama City, Zanagawa, Kanagawa Prefecture 2-510 Heights, Zakama, Token Zama (72) Inventor Takayoshi Komine, Shinbashi, Izumi-ku, Yokohama 1029-19
Claims (2)
ＡＩ2 Ｏ3 モル比１００以上のＺＳＭ−５型ゼオライト
を５０ｋｇ／ｍ3 以上の量で有するハニカム構造フィル
ターに０．２〜０．５秒間接触させることを特徴とする
ホルムアルデヒド含有ガスの浄化方法。1. A formaldehyde-containing gas containing SiO 2 /
A method for purifying a formaldehyde-containing gas, which comprises bringing a ZSM-5 type zeolite having an AI 2 O 3 molar ratio of 100 or more into a honeycomb structure filter having an amount of 50 kg / m 3 or more for 0.2 to 0.5 seconds.
５０００ｐｐｍであり、かつホルムアルデヒド濃度が５
〜１００ｐｐｍであるホルムアルデヒド含有ガスを、前
記接触により、全有機溶剤濃度を１００ｐｐｍ以下とな
し、かつ同時にホルムアルデヒド濃度を５ｐｐｍ以下と
する請求項１記載の方法。2. The total organic solvent concentration is 500 to methane conversion.
5000 ppm and formaldehyde concentration of 5
The method according to claim 1, wherein the formaldehyde-containing gas having a concentration of -100 ppm is brought to a total organic solvent concentration of 100 ppm or less and at the same time a formaldehyde concentration of 5 ppm or less by the contact.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23040593A JP3526892B2 (en) | 1993-09-16 | 1993-09-16 | Method for purifying formaldehyde-containing gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23040593A JP3526892B2 (en) | 1993-09-16 | 1993-09-16 | Method for purifying formaldehyde-containing gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0780248A true JPH0780248A (en) | 1995-03-28 |
| JP3526892B2 JP3526892B2 (en) | 2004-05-17 |
Family
ID=16907374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23040593A Expired - Fee Related JP3526892B2 (en) | 1993-09-16 | 1993-09-16 | Method for purifying formaldehyde-containing gas |
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| Country | Link |
|---|---|
| JP (1) | JP3526892B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11226342A (en) * | 1997-04-22 | 1999-08-24 | Johannes Schedler | Method and apparatus for cleaning gas |
| JP2009082797A (en) * | 2007-09-28 | 2009-04-23 | Toyobo Co Ltd | Organic solvent-containing gas treatment system |
| JP2010524628A (en) * | 2007-04-23 | 2010-07-22 | エンビオン、インコーポレイテッド | Air purifier having a regenerated deodorizing filter and a method for regenerating the deodorizing filter of the air purifier |
| JP2010201316A (en) * | 2009-03-02 | 2010-09-16 | Jg Environmental Technology Co Ltd | Method of and apparatus for optimizing operation control used for concentration rotor system |
| FR2953153A1 (en) * | 2009-11-27 | 2011-06-03 | Irma | HYDROPHOBIC ZEOLITHE EXCHANGED WITH A TRANSITION METAL AS ALDEHYDESE ADSORBENT |
| JP2012115721A (en) * | 2010-11-29 | 2012-06-21 | Honda Motor Co Ltd | Exhaust gas treating apparatus |
| CN107952289A (en) * | 2016-10-17 | 2018-04-24 | 秦素洁 | A kind of filter screen with purifying formaldehyde and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108905559A (en) * | 2018-07-18 | 2018-11-30 | 浙江柯迈环境建设有限公司 | A kind of finishing formaldehyde remover and preparation method thereof |
-
1993
- 1993-09-16 JP JP23040593A patent/JP3526892B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11226342A (en) * | 1997-04-22 | 1999-08-24 | Johannes Schedler | Method and apparatus for cleaning gas |
| JP2010524628A (en) * | 2007-04-23 | 2010-07-22 | エンビオン、インコーポレイテッド | Air purifier having a regenerated deodorizing filter and a method for regenerating the deodorizing filter of the air purifier |
| JP2009082797A (en) * | 2007-09-28 | 2009-04-23 | Toyobo Co Ltd | Organic solvent-containing gas treatment system |
| JP2010201316A (en) * | 2009-03-02 | 2010-09-16 | Jg Environmental Technology Co Ltd | Method of and apparatus for optimizing operation control used for concentration rotor system |
| FR2953153A1 (en) * | 2009-11-27 | 2011-06-03 | Irma | HYDROPHOBIC ZEOLITHE EXCHANGED WITH A TRANSITION METAL AS ALDEHYDESE ADSORBENT |
| WO2011064371A1 (en) * | 2009-11-27 | 2011-06-03 | Institut Regional Des Materiaux Avances (Irma) | Hydrophobic zeolite exchanged with a transition metal as an aldehyde adsorbent |
| JP2012115721A (en) * | 2010-11-29 | 2012-06-21 | Honda Motor Co Ltd | Exhaust gas treating apparatus |
| CN107952289A (en) * | 2016-10-17 | 2018-04-24 | 秦素洁 | A kind of filter screen with purifying formaldehyde and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3526892B2 (en) | 2004-05-17 |
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