JP5994079B2 - Decomposition method of volatile organic gas - Google Patents
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- JP5994079B2 JP5994079B2 JP2012055125A JP2012055125A JP5994079B2 JP 5994079 B2 JP5994079 B2 JP 5994079B2 JP 2012055125 A JP2012055125 A JP 2012055125A JP 2012055125 A JP2012055125 A JP 2012055125A JP 5994079 B2 JP5994079 B2 JP 5994079B2
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- 238000000034 method Methods 0.000 title claims description 65
- 238000000354 decomposition reaction Methods 0.000 title claims description 9
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 37
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 33
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
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- 238000006243 chemical reaction Methods 0.000 description 19
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 238000009841 combustion method Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229950011008 tetrachloroethylene Drugs 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 150000002830 nitrogen compounds Chemical class 0.000 description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000010801 sewage sludge Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004045 organic chlorine compounds Chemical class 0.000 description 2
- -1 phosphoric acid compound Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000791 photochemical oxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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Description
本発明は、自動車や化学工場から排出されるガス中に含まれる揮発性有機物質を燃焼触媒法によって分解する方法に関するものであり、特に低濃度の揮発性有機物質を効率良く分解除去できる方法に関するものである。 The present invention relates to a method for decomposing a volatile organic substance contained in a gas discharged from an automobile or a chemical factory by a combustion catalyst method, and particularly to a method capable of efficiently decomposing and removing a low concentration volatile organic substance. Is.
自動車や化学工場から排出されるガス中には、トルエン、酢酸エチル、イソプロパノール等、各種の揮発性有機物質（ＶＯＣ：ｖｏｌａｔｉｌｅ ｏｒｇａｎｉｃ ｃｏｍｐｏｕｎｄｓ）が含まれており、人体に影響のある浮遊粒子状物質や光化学オキシダントの原因となる。このようなＶＯＣの多くは、大気汚染防止法によってその排出量が規制され、様々なＶＯＣ排出削減の取り組みが行なわれている。 Gases emitted from automobiles and chemical factories contain various volatile organic compounds (VOC) such as toluene, ethyl acetate, isopropanol, and so on. Causes photochemical oxidants. Many of these VOCs have their emissions regulated by the Air Pollution Control Act, and various efforts to reduce VOC emissions are being made.
ガス中の有害成分の分解方法としては、燃焼法（直接燃焼法、触媒燃焼法）、吸着法、プラズマ分解法、光触媒法等、様々な方法が知られている。これらの方法のうち、燃焼法は、基本的に対象とするガスを加熱・燃焼させることによって有害成分を分解除去する方法である。 Various methods such as a combustion method (direct combustion method, catalytic combustion method), an adsorption method, a plasma decomposition method, and a photocatalytic method are known as methods for decomposing harmful components in gas. Of these methods, the combustion method is basically a method of decomposing and removing harmful components by heating and burning a target gas.
この燃焼法は、直接燃焼法、触媒燃焼法に大別される。直接燃焼法は、対象とするガス中成分を約８００℃以上の高温雰囲気で直接的に加熱分解するものである。しかしながら、この方法では、有害成分を分解するための装置が大型化するばかりか、窒素化合物が生成する懸念がある。 This combustion method is roughly classified into a direct combustion method and a catalytic combustion method. The direct combustion method directly heats and decomposes a target gas component in a high temperature atmosphere of about 800 ° C. or higher. However, in this method, there is a concern that not only the apparatus for decomposing harmful components is enlarged, but also nitrogen compounds are generated.
これに対し、触媒燃焼法では、触媒を用いることによって、比較的低温の加熱（例えば５００℃以下）であっても分解が進行するので、窒素化合物が生成することがなく、直接燃焼法を実施する装置と比べて小規模になるという利点がある。また、吸着剤を用いた吸着法での吸着剤の交換頻度よりも、触媒燃焼法における触媒の交換頻度が低いという利点もある。 On the other hand, in the catalytic combustion method, by using a catalyst, decomposition proceeds even at relatively low temperature heating (for example, 500 ° C. or less), so that a direct combustion method is performed without generating nitrogen compounds. There is an advantage that it becomes small-scale as compared with the device to do. There is also an advantage that the replacement frequency of the catalyst in the catalytic combustion method is lower than the replacement frequency of the adsorbent in the adsorption method using the adsorbent.
これまでの触媒燃焼法で用いられている触媒は、基本的に高価な貴金属元素が用いられており、こうした元素を、ゼオライトやジルコニアを主成分とする担体に担持させたものが一般的である。このような技術として、例えば特許文献１には、「白金族元素を少なくとも１種以上含有した金属酸化物を前段に、白金族元素を少なくとも１種以上含有した金属酸化部およびゼオライトの混合物を後段に配置した有機化合物燃焼除去触媒。」について開示されている。 Catalysts used in conventional catalytic combustion methods basically use expensive noble metal elements, and these elements are generally supported on a support mainly composed of zeolite or zirconia. . As such a technique, for example, Patent Document 1 discloses that “a metal oxide containing at least one platinum group element at the front stage and a mixture of a metal oxide part containing at least one platinum group element and a zeolite at the rear stage. The organic compound combustion removal catalyst arranged in the above.
しかしながら、上記のような触媒では、高価な金属元素を含有するものであるので、コストが高くなるばかりか、触媒使用後に再利用することは困難な状況である。また、触媒として使用した後に、使用済み触媒をそのまま廃棄することは環境に悪影響を及ぼすことになる。 However, since the catalyst as described above contains an expensive metal element, the cost becomes high and it is difficult to reuse the catalyst after using the catalyst. Further, discarding the used catalyst as it is after being used as a catalyst has an adverse effect on the environment.
触媒を用いてガスを処理する方法として、光触媒を用いる方法（光触媒法）も知られている。この方法は、光触媒作用を有する金属酸化物を利用して、加熱することなくガスを処理するものである。このような技術で用いる光触媒として、例えば特許文献２には、「光触媒作用を有する金属酸化物および抗菌性を有する金属イオンがアパタイト結晶構造中に組み込まれている光触媒アパタイトからなる光触媒アパタイト組成物。」が開示されている。 As a method of treating a gas using a catalyst, a method using a photocatalyst (photocatalytic method) is also known. This method uses a metal oxide having a photocatalytic action to treat a gas without heating. As a photocatalyst used in such a technique, for example, Patent Document 2 discloses “a photocatalytic apatite composition comprising a photocatalytic apatite in which a metal oxide having a photocatalytic action and a metal ion having antibacterial properties are incorporated in an apatite crystal structure. Is disclosed.
しかしながら、こうした光触媒においても、上記触媒燃焼法で用いる触媒と同様に、触媒使用後に再利用することは困難な状況であり、また触媒として使用した後に、そのまま廃棄することは環境に悪影響を及ぼすという問題がある。 However, in such a photocatalyst as well as the catalyst used in the above catalytic combustion method, it is difficult to reuse after using the catalyst, and discarding it as it is after using it as a catalyst has an adverse effect on the environment. There's a problem.
一方、環境への影響を考慮し、水酸アパタイトを触媒として用いる技術も提案されている。こうした技術として、例えば特許文献３には、「トリクロロエチレンガスまたはテトラクロロエチレンガスを水酸アパタイトと加熱状態で接触反応させるトリクロロエチレンガスまたはテトラクロロエチレンガスの分解除去方法。」が提案されている。この技術は、基本的にトリクロロエチレンやテトラクロロエチレン等の有機系塩素化合物を除去するための技術であり、ＶＯＣに対する除去効果については確認されていない。 On the other hand, in consideration of the influence on the environment, a technique using hydroxyapatite as a catalyst has also been proposed. As such a technique, for example, Patent Document 3 proposes “a method for decomposing and removing trichloroethylene gas or tetrachloroethylene gas in which trichloroethylene gas or tetrachloroethylene gas is contacted with hydroxyapatite in a heated state”. This technique is basically a technique for removing organic chlorine compounds such as trichlorethylene and tetrachloroethylene, and its removal effect on VOC has not been confirmed.
また、水酸アパタイトに関する技術として、下水汚泥焼却灰から回収されたリン資源を有効利用することが報告されている（例えば、非特許文献１）。この文献では、下水汚泥焼却灰には、水酸アパタイトとリン酸水素カルシウムが含まれることが開示されており、これらの物質の有効な再利用が期待されている。 In addition, as a technique related to hydroxyapatite, it has been reported that phosphorus resources recovered from sewage sludge incineration ash are effectively used (for example, Non-Patent Document 1). In this document, it is disclosed that sewage sludge incineration ash contains hydroxyapatite and calcium hydrogen phosphate, and effective reuse of these substances is expected.
本発明は上記の様な事情に着目してなされたものであって、その目的は、環境に悪影響を及ぼすことなく、再使用が可能な触媒を用い、低濃度の揮発性有機物質を含むガスを触媒燃焼法によって効率良く分解できる揮発性有機ガスの分解方法を提供することにある。 The present invention has been made paying attention to the circumstances as described above, and its purpose is to use a reusable catalyst without adversely affecting the environment, and a gas containing a low concentration volatile organic substance. Another object of the present invention is to provide a method for decomposing volatile organic gas that can be efficiently decomposed by catalytic combustion.
上記目的を達成することのできた本発明方法とは、ガス中の揮発性有機物質を触媒燃焼法によって分解する方法であって、触媒として水酸アパタイトを用いる点に要旨を有するものである。 The method of the present invention that has achieved the above object is a method for decomposing volatile organic substances in a gas by a catalytic combustion method, and has a gist in that hydroxyapatite is used as a catalyst.
本発明方法で用いる水酸アパタイトは、ＣａとＰのモル比（Ｃａ／Ｐ）が、１．６７〜２．５０であるものが好ましい。また、このモル比（Ｃａ／Ｐ）は、１．７１〜２．５０であることがより好ましい。 The hydroxyapatite used in the method of the present invention preferably has a Ca to P molar ratio (Ca / P) of 1.67 to 2.50. The molar ratio (Ca / P) is more preferably 1.71 to 2.50.
本発明方法において、揮発性有機物質の分解時の加熱温度は３００〜５００℃程度であることが好ましい。また本発明で対象とする揮発性有機ガス中の揮発性有機物質の含有量は、１〜２０００ｐｐｍ程度を想定したものである。 In the method of the present invention, the heating temperature at the time of decomposition of the volatile organic substance is preferably about 300 to 500 ° C. The content of the volatile organic substance in the volatile organic gas targeted in the present invention is assumed to be about 1 to 2000 ppm.
本発明では、触媒燃焼法で用いる触媒として水酸アパタイトを用いるようにしたので、触媒自体が環境に悪影響を及ぼすことなく、再使用が可能であり、しかも低濃度のＶＯＣを含むガスであっても触媒燃焼法によって効率良く分解でき、ＶＯＣを含むガスの分解方法として極めて有用である。 In the present invention, since hydroxyapatite is used as the catalyst used in the catalytic combustion method, the catalyst itself can be reused without adversely affecting the environment, and it is a gas containing a low concentration of VOC. Can be efficiently decomposed by the catalytic combustion method, and is extremely useful as a method for decomposing a gas containing VOC.
本発明者らは、前記課題を解決するために、様々な角度から検討を重ねた。そして、触媒燃焼法で用いる触媒として水酸アパタイトを用いれば、触媒燃焼法によってＶＯＣを効率的に分解できることを見出し、本発明を完成した。 In order to solve the above-mentioned problems, the present inventors have repeatedly studied from various angles. And when hydroxyapatite was used as a catalyst used by a catalytic combustion method, it discovered that VOC could be decomposed | disassembled efficiently by a catalytic combustion method, and completed this invention.
水酸アパタイト（ヒドロキシアパタイト：ＨＡＰ）は、リン酸カルシウムと水酸化カルシウムの複合体であり、一般式［Ｃａ10（ＨＰＯ4）6（ＯＨ）2］で示され化合物である。この水酸アパタイトは、製造方法等の条件の違いによって、ＣａとＰのモル比（Ｃａ／Ｐ）が１．５５〜２．５の範囲で様々異なるものが生成することは知られている。 Hydroxyapatite (hydroxyapatite: HAP) is a complex of calcium phosphate and calcium hydroxide, and is a compound represented by the general formula [Ca 10 (HPO 4 ) 6 (OH) 2 ]. It is known that various hydroxyapatites are produced in a molar ratio of Ca to P (Ca / P) in the range of 1.55 to 2.5 depending on the conditions such as the production method.
本発明者らは、触媒燃焼法でＶＯＣを分解するために用いる触媒について鋭意研究を重ねた。その結果、ＣａとＰのモル比（Ｃａ／Ｐ）によってもその能力（触媒活性）が異なるとしても、触媒燃焼法でＶＯＣを分解するための触媒として、水酸アパタイトは十分にその機能を発揮し得ることが判明したのである。 The inventors of the present invention have made extensive studies on a catalyst used for decomposing VOC by a catalytic combustion method. As a result, even if the capacity (catalytic activity) differs depending on the molar ratio of Ca to P (Ca / P), hydroxyapatite exhibits its function sufficiently as a catalyst for decomposing VOC by the catalytic combustion method. It turns out that it can be done.
水酸アパタイトを、触媒燃焼法で用いる触媒とする技術は既に提案されている（前記特許文献３）。しかしながら、これまで提案されている技術は、基本的にトリクロロエチレンやテトラクロロエチレン等の有機系塩素化合物を除去するためのものであり、ＶＯＣに対する除去効果については確認されていない。また、この技術において例示されている水酸アパタイトは、ＣａとＰのモル比（Ｃａ／Ｐ）が１．５〜１．６７程度のものである。即ち、水酸アパタイトにおけるＣａとＰのモル比（Ｃａ／Ｐ）は、化学量論的には１．６７程度となるが、触媒としての効果が発揮されるのは、ＣａとＰのモル比（Ｃａ／Ｐ）が１．５〜１．６７のものが示されているのである。以下では、このような水酸アパタイトを、「Ｃａ欠損型ＨＡＰ」と略記することがある。 A technique of using hydroxyapatite as a catalyst used in the catalytic combustion method has already been proposed (Patent Document 3). However, the techniques proposed so far are basically for removing organic chlorine compounds such as trichlorethylene and tetrachloroethylene, and the removal effect on VOC has not been confirmed. Further, the hydroxyapatite exemplified in this technique has a Ca to P molar ratio (Ca / P) of about 1.5 to 1.67. That is, the molar ratio of Ca and P (Ca / P) in hydroxyapatite is about 1.67 in terms of stoichiometry, but the molar ratio of Ca and P is effective as a catalyst. Those with (Ca / P) of 1.5 to 1.67 are shown. Hereinafter, such hydroxyapatite may be abbreviated as “Ca-deficient HAP”.
水酸アパタイトの物性は、ＣａとＰのモル比（Ｃａ／Ｐ）によっても異なるものとなる。本発明者らが検討したところでは、本発明方法で用いる水酸アパタイトは、ＣａとＰのモル比（Ｃａ／Ｐ）が、むしろ１．６７〜２．５０であるものが触媒機能をより有効に発揮し得るものとなる。このモル比（Ｃａ／Ｐ）は、１．７１〜２．５０であることがより好ましい。以下では、このような水酸アパタイトを、「Ｃａリッチ型ＨＡＰ」と略記することがある。但し、上記モル比（Ｃａ／Ｐ）が、２．５０を超えると、水酸アパタイトとしての結晶構造を維持できず、触媒としての機能を発揮しにくくなる。 The physical properties of hydroxyapatite vary depending on the molar ratio of Ca and P (Ca / P). As a result of studies by the present inventors, the hydroxyapatite used in the method of the present invention has a more effective catalytic function when the molar ratio of Ca to P (Ca / P) is rather 1.67 to 2.50. It will be able to demonstrate. The molar ratio (Ca / P) is more preferably 1.71 to 2.50. Hereinafter, such hydroxyapatite may be abbreviated as “Ca-rich HAP”. However, when the molar ratio (Ca / P) exceeds 2.50, the crystal structure as the hydroxyapatite cannot be maintained, and the function as the catalyst is hardly exhibited.
揮発性有機物質（ＶＯＣ）は、基本的に炭素と水素（或は炭素と水素と酸素）の化合物であり、分解することによって一酸化炭素（ＣＯ）、二酸化炭素（ＣＯ2）および水が生成されることになる。また、環境への影響を考慮すれば、より無害である二酸化炭素（ＣＯ2）への変換率が高い方がより安全と言える。本発明方法では、水酸アパタイトを触媒燃焼法の触媒として用いることによって、ＶＯＣが効果的に分解され、しかも二酸化炭素（ＣＯ2）への変換率が高くなり（後記実施例参照）、より安全な方法である。 Volatile organic substances (VOCs) are basically compounds of carbon and hydrogen (or carbon, hydrogen, and oxygen) that produce carbon monoxide (CO), carbon dioxide (CO 2 ), and water by decomposition. Will be. In view of the influence on the environment, it can be said that it is safer to have a higher conversion rate to carbon dioxide (CO 2 ), which is more harmless. In the method of the present invention, by using hydroxyapatite as a catalyst for the catalytic combustion method, VOC is effectively decomposed, and the conversion rate to carbon dioxide (CO 2 ) is increased (see Examples below), which is safer. It is a simple method.
触媒燃焼法では、基本的に５００℃以下の温度で分解が進むものであるが、本発明方法においては、揮発性有機物質の分解時の加熱温度は３００〜５００℃程度であることが好ましい。また、分解をより促進する（変換率を高める）ためには、加熱温度は上記温度範囲内でより高温であることが好ましく、具体的には４００℃以上がより好ましく、更に好ましくは４５０℃以上である。但し、加熱温度が５００℃を超えると、空気中の窒素と反応して窒素化合物が生成し易くなる。 In the catalytic combustion method, decomposition proceeds basically at a temperature of 500 ° C. or lower, but in the method of the present invention, the heating temperature at the time of decomposition of the volatile organic material is preferably about 300 to 500 ° C. In order to further promote decomposition (increase the conversion rate), the heating temperature is preferably higher within the above temperature range, specifically 400 ° C. or higher, more preferably 450 ° C. or higher. It is. However, when the heating temperature exceeds 500 ° C., it reacts with nitrogen in the air and a nitrogen compound is easily generated.
本発明で対象とする揮発性有機ガス中の揮発性有機物質（ＶＯＣ）の含有量は、１〜２０００ｐｐｍ程度を想定したものである。即ち、揮発性有機物質の含有量（濃度）が２０００ｐｐｍから４００ｐｐｍまでの比較的高濃度のガスは勿論のこと、揮発性有機物質（ＶＯＣ）の含有量（濃度）が１ｐｐｍから４００ｐｐｍ未満までの比較的低濃度のものであっても、効果的にＶＯＣを分解処理できる。 The content of the volatile organic substance (VOC) in the volatile organic gas targeted in the present invention is assumed to be about 1 to 2000 ppm. That is, not only comparatively high concentration gas with volatile organic substance content (concentration) from 2000ppm to 400ppm, but also comparison with volatile organic substance (VOC) content (concentration) from 1ppm to less than 400ppm. Even if the concentration is low, VOC can be effectively decomposed.
本発明方法を実施するための設備については、従来から触媒燃焼法に適用されているものを用いれば良い。即ち、触媒を配置する容器を加熱できる構成とすると共に、被処理ガス（揮発性有機化合物含有ガス）の導入口、および処理後のガスの排出口を備え、容器内で被処理ガスと触媒とを接触できるような構造のものであれば良い。また、被処理ガスと触媒との接触条件（ガスと触媒との比率、ガス導入量等）は適宜設定すればよい。更に、触媒として用いる水酸アパタイトの形態についても何等限定するものではなく、例えば粉末状、顆粒状、塊状等様々なものが使用できる。 As equipment for carrying out the method of the present invention, those conventionally applied to the catalytic combustion method may be used. In other words, the container in which the catalyst is disposed can be heated, and is provided with an inlet for a gas to be treated (volatile organic compound-containing gas) and a gas outlet for the gas to be treated. Any structure can be used as long as it can be contacted. Further, the contact conditions between the gas to be treated and the catalyst (ratio of gas to catalyst, gas introduction amount, etc.) may be set as appropriate. Further, the form of the hydroxyapatite used as the catalyst is not limited at all, and various forms such as powder, granules, and lumps can be used.
本発明では、触媒燃焼法で用いる触媒として水酸アパタイトを用いるものであり、金属元素や金属酸化物を含まないものであるので、環境に悪影響を及ぼすことはない。また、このような水酸アパタイトは、触媒活性が低下したときには酸および水による洗浄を行なうことによって、容易に触媒機能を回復するものであり、再使用が可能である。 In the present invention, hydroxyapatite is used as a catalyst used in the catalytic combustion method and does not include a metal element or a metal oxide, so that it does not adversely affect the environment. Such hydroxyapatite can be easily reused by washing with acid and water when the catalytic activity is reduced, and can be reused.
尚、水酸アパタイトのモル比（Ｃａ／Ｐ）を調整するには、反応条件におけるＣａとＰの配合比量を変えるだけで実現できる。本発明のおいても、このような方法を用いて製造した。例えば、湿式法において、水酸化カルシウムスラリー（石化乳）にリン酸をゆっくり滴下していき、任意の時点でリン酸の滴下を止めて熟成すると、モル比（Ｃａ／Ｐ）＞１．６７であればＣａリッチ型ＨＡＰとなり、モル比（Ｃａ／Ｐ）＝１．６７であれば両論水酸アパタイトとなり、モル比（Ｃａ／Ｐ）＜１．６７であればＣａ欠損型ＨＡＰとなる。 The molar ratio of hydroxyapatite (Ca / P) can be adjusted by simply changing the blending ratio of Ca and P under the reaction conditions. In the present invention, it was also manufactured using such a method. For example, in a wet method, when phosphoric acid is slowly dropped into a calcium hydroxide slurry (fossilized milk) and ripening is stopped at any point in time, the molar ratio (Ca / P)> 1.67. If it exists, it will become Ca rich type HAP, if it is molar ratio (Ca / P) = 1.67, it will become amphatic hydroxyapatite, and if molar ratio (Ca / P) <1.67, it will become Ca deficient type HAP.
また、触媒原料にリン酸カルシウムを使用し、その中の一部として下水汚泥焼却灰から回収されたリン酸化合物も利用できる（前記非特許文献１）。このリン酸化合物には、水酸アパタイトとリン酸水素カルシウムが含まれることが報告されており、また水酸アパタイトとしてＣａリッチ型ＨＡＰが比較的多く含まれることが判明している。 Moreover, the phosphoric acid compound collect | recovered from the sewage sludge incineration ash can be utilized as a catalyst raw material which uses calcium phosphate as a part of it (the said nonpatent literature 1). This phosphate compound has been reported to contain hydroxyapatite and calcium hydrogen phosphate, and it has been found that Ca-rich HAP is relatively contained as hydroxyapatite.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
ＣａとＰのモル比（Ｃａ／Ｐ）［Ｃａ／Ｐモル比］が異なる各種水酸アパタイトを準備し、ＶＯＣを含むガスと加熱条件下で接触させた。このとき、水酸アパタイトは３ｇとし、これを充填した容器内に、各種ＶＯＣ（トルエン、酢酸エチル、イソプロパノール）を夫々５０，２５，２５（ｐｐｍ）に調整した単成分ガスを連続的に導入して接触させた。また、加熱温度は１５０〜５００℃の範囲（１５０℃、２００℃、３００℃、４００℃、４５０℃、５００℃の５段階）で変化させた。そして、反応前・後におけるＶＯＣ濃度、および生成したガス量（ＣＯ2量、ＣＯ量、ＣＯ＋ＣＯ2量）に基づき、各ＶＯＣ成分から夫々の生成ガスへの変換率（ＣＯ2変換率、ＣＯ変換率、ＣＯ＋ＣＯ2変換率）を測定した。このときの分析には、ＣＯ計（光明理化学工業株式会社製 「ＵＭ−２８０Ｌ」）とＣＯ2計（理研計器株式会社製 「ＲＩ−２５０Ｄ」）を用いた。 Various hydroxyapatites having different molar ratios of Ca and P (Ca / P) [Ca / P molar ratio] were prepared and contacted with a gas containing VOC under heating conditions. At this time, the hydroxyapatite is 3 g, and a single component gas in which various VOCs (toluene, ethyl acetate, isopropanol) are adjusted to 50, 25, and 25 (ppm), respectively, is continuously introduced into a container filled with the hydroxyapatite. Touched. The heating temperature was changed in the range of 150 to 500 ° C. (5 steps of 150 ° C., 200 ° C., 300 ° C., 400 ° C., 450 ° C., and 500 ° C.). Based on the VOC concentration before and after the reaction, and the amount of gas produced (CO 2 amount, CO amount, CO + CO 2 amount), the conversion rate (CO 2 conversion rate, CO conversion) from each VOC component to the respective product gas Rate, CO + CO 2 conversion rate). For the analysis at this time, a CO meter (“UM-280L” manufactured by Komyo Chemical Co., Ltd.) and a CO 2 meter (“RI-250D” manufactured by Riken Keiki Co., Ltd.) were used.
その結果を、被処理ガス成分（ＶＯＣ成分）の種類、加熱温度、Ｃａ／Ｐモル比と共に、下記表１〜６に示す。尚、表１、２は、被処理ガス成分（ＶＯＣ成分）としてトルエンを含有するガスを処理したときの結果を示したものであり、表３、４は、被処理ガス成分（ＶＯＣ成分）として酢酸エチルを含有するガスを処理したときの結果を示したものであり、表５、６は、被処理ガス成分（ＶＯＣ成分）としてイソプロパノールを含有するガスを処理したときの結果を示したものである。 The results are shown in Tables 1 to 6 below together with the type of gas component to be treated (VOC component), the heating temperature, and the Ca / P molar ratio. Tables 1 and 2 show the results when a gas containing toluene as a gas component to be processed (VOC component) is processed. Tables 3 and 4 show the results of a gas component to be processed (VOC component). The results when the gas containing ethyl acetate was treated are shown. Tables 5 and 6 show the results when the gas containing isopropanol as the gas component to be treated (VOC component) was treated. is there.
上記表１、２の結果に基づき、水酸アパタイトのモル比（Ｃａ／Ｐ）および加熱温度が、トルエンの変換率に与える影響を図１に示す。上記表３、４の結果に基づき、水酸アパタイトのモル比（Ｃａ／Ｐ）および加熱温度が、酢酸エチルの変換率に与える影響を図２に示す。上記表５、６の結果に基づき、水酸アパタイトのモル比（Ｃａ／Ｐ）および加熱温度が、イソプロパノールの変換率に与える影響を図３に示す。 Based on the results of Tables 1 and 2, the influence of the molar ratio of hydroxyapatite (Ca / P) and the heating temperature on the conversion rate of toluene is shown in FIG. Based on the results of Tables 3 and 4, the influence of the molar ratio of hydroxyapatite (Ca / P) and the heating temperature on the conversion rate of ethyl acetate is shown in FIG. Based on the results of Tables 5 and 6, the influence of the molar ratio of hydroxyapatite (Ca / P) and the heating temperature on the conversion rate of isopropanol is shown in FIG.
これらの結果から、次のように考察できる。いずれの場合においても、加熱温度が高くなるにつれて変換率は高くなる傾向を示すが、水酸アパタイト中のＣａ／Ｐモル比が高くなるにつれて、変換率が相対的に高くなっていることが分かる。特に、Ｃａ欠損型ＨＡＰを用いる場合に比べて、Ｃａリッチ型ＨＡＰを用いた場合の方が、各ＶＯＣ成分が効果的に分解されていることが分かる。またいずれの条件であっても、ＣＯ変換率よりもＣＯ2変換率が高くなっており、本発明方法が安全性の高い触媒燃焼法であることを示している。 From these results, it can be considered as follows. In any case, the conversion rate tends to increase as the heating temperature increases, but it can be seen that the conversion rate increases relatively as the Ca / P molar ratio in the hydroxyapatite increases. . In particular, it can be seen that each VOC component is more effectively decomposed when Ca-rich HAP is used than when Ca-deficient HAP is used. In any of the conditions, the CO 2 conversion rate is higher than the CO conversion rate, indicating that the method of the present invention is a highly safe catalytic combustion method.
Claims (3)
触媒として金属元素および金属酸化物を用いず、ＣａとＰのモル比（Ｃａ／Ｐ）が、１．７１〜２．５０である水酸アパタイトを用いることを特徴とする揮発性有機ガスの分解方法。 A method for decomposing volatile organic substances in gas by catalytic combustion,
Decomposition of volatile organic gas characterized in that hydroxyapatite having a Ca to P molar ratio (Ca / P) of 1.71 to 2.50 is used without using a metal element or metal oxide as a catalyst. Method.
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