JPH01224337A - Catalyst for disproportionating and decomposing reaction of chlorofluoromethane - Google Patents
Catalyst for disproportionating and decomposing reaction of chlorofluoromethaneInfo
- Publication number
- JPH01224337A JPH01224337A JP63049075A JP4907588A JPH01224337A JP H01224337 A JPH01224337 A JP H01224337A JP 63049075 A JP63049075 A JP 63049075A JP 4907588 A JP4907588 A JP 4907588A JP H01224337 A JPH01224337 A JP H01224337A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- chlorofluoromethane
- substance
- platinum group
- group element
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 title claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims abstract 2
- 238000007323 disproportionation reaction Methods 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 239000004338 Dichlorodifluoromethane Substances 0.000 abstract description 4
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 abstract description 4
- 235000019404 dichlorodifluoromethane Nutrition 0.000 abstract description 4
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910052703 rhodium Inorganic materials 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 4
- 229940029284 trichlorofluoromethane Drugs 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、ジクロロジフルオロメタンやトリクロロフル
オロメタン等のクロロフルオロメタンの不均化及び分解
反応用触媒及び方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a catalyst and method for disproportionation and decomposition reactions of chlorofluoromethanes such as dichlorodifluoromethane and trichlorofluoromethane.
クロロフルオロメタンは、大気中に放出された場合の環
境影響のためにその使用量及び生産量が制限されている
が、低温用冷媒、ウレタンフオーム用発泡剤、エアゾー
ルの噴霧剤として重要であり、使用量及び生産量の削減
は社会的、経済的活動に大きな影響を与える。クロロフ
ルオロメタンの使用量及び生産量の削減の影響をできる
限り小さくし、ざらに大気中への放出を防ぐためにはク
ロロフルオロメタンをほかの物質に変換あるいは分解し
除去することなどが必要である。Chlorofluoromethane is important as a low-temperature refrigerant, a blowing agent for urethane foam, and a spray agent for aerosols, although its usage and production are limited due to the environmental impact if it is released into the atmosphere. Reductions in usage and production have a major impact on social and economic activities. In order to minimize the impact of reducing the amount of chlorofluoromethane used and produced, and to prevent its release into the atmosphere, it is necessary to remove chlorofluoromethane by converting it into other substances or decomposing it. .
また、クロロフルオロメタンの不均化反応は、高次フッ
素化クロロフルオロメタンの製造法としても用いられる
。Furthermore, the disproportionation reaction of chlorofluoromethane is also used as a method for producing higher-order fluorinated chlorofluoromethane.
これまでクロロフルオロメタンの不均化反応用触媒とし
ては、塩化アルミニウム等のフリーデルクラフト系触媒
（特公昭４９−１６４号公報、特開昭５１−１６６０２
号各公報参照）、フッ化クロムを主体とする触媒（特公
昭４Ｂ−３４００９号公報）、各種担体にニッケル塩あ
るいはチタン塩を担持させた触媒（特願昭５１−６６３
０号明細書）などが知られている。Up until now, as a catalyst for the disproportionation reaction of chlorofluoromethane, Friedel-Crafts catalysts such as aluminum chloride (Japanese Patent Publication No. 49-164, Japanese Unexamined Patent Publication No. 51-16602)
(see each publication), catalysts mainly containing chromium fluoride (Japanese Patent Publication No. 4B-34009), catalysts with nickel salts or titanium salts supported on various carriers (Japanese Patent Application No. 1983-663)
No. 0 Specification) etc. are known.
しかしフリーデルクラフト系触媒は活性に十分な持続性
がない欠点を持ち、他の触媒は比較的高温を必要とする
欠点を持つ。また、これらはいずれもクロロフルオロメ
タンの除去用触媒としての利用は考えられていない。さ
らに、分解反応が促進された場合、触媒表面へ炭素質が
沈着することによって触媒活性あるいは活性持続性が低
下する欠点を持つ。However, Friedel-Crafts catalysts have the disadvantage of not having sufficient sustainability of activity, and other catalysts have the disadvantage of requiring relatively high temperatures. Further, none of these is considered to be used as a catalyst for removing chlorofluoromethane. Furthermore, when the decomposition reaction is accelerated, carbonaceous substances are deposited on the catalyst surface, resulting in a decrease in catalyst activity or activity sustainability.
１ 本発明者は、クロロフルオロメタンの金属酸化物に
よる不均化及び分解反応について種々研究を行ったとこ
ろ、白金族元素を担持した二酸化チタンによってクロロ
フルオロメタンが室温付近の低温であっても４００ ｒ
ｖ以下の波長成分を含む光の照射によって不均化及び分
解することを見いだし、これをクロロフルオロメタンの
不均化及び分解反応用触媒として使用し得る点に着目し
て本発明をなすに至った。光照射効果の理由ははっきり
とはわからないが、白金族元素の担持により二酸化チタ
ンが高い光触媒作用を持つことから、クロロフルオロメ
タンが分解される一方、触媒表面に吸着した水が光照射
により分解され除去されることや、触媒表面へクロロフ
ルオロメタンの分解により沈着した炭素質が光照射によ
って酸化されて除去されることによって、水や沈着した
炭素質による触媒活性あるいは活性持続性の低下を防ぐ
ことができるためと考えられる。1 The present inventor conducted various studies on the disproportionation and decomposition reactions of chlorofluoromethane caused by metal oxides, and found that titanium dioxide supporting platinum group elements can reduce chlorofluoromethane to 400% even at low temperatures near room temperature. r
The present invention was developed based on the discovery that chlorofluoromethane can be disproportionated and decomposed by irradiation with light containing a wavelength component of V or less, and that it can be used as a catalyst for the disproportionation and decomposition reaction of chlorofluoromethane. Ta. Although the reason for the light irradiation effect is not clear, titanium dioxide has a high photocatalytic effect due to the support of platinum group elements, so while chlorofluoromethane is decomposed, water adsorbed on the catalyst surface is decomposed by light irradiation. Preventing a decrease in catalytic activity or activity sustainability due to water and deposited carbon by removing the carbon deposited on the catalyst surface by decomposition of chlorofluoromethane and oxidizing it by light irradiation. This is thought to be due to the ability to
本発明の方法に従えば、トリクロロフルオロメタンを４
００ｎｍ以下の波長成分を含む光の存在下、白金族元素
を担持した二酸化チタンに気体状で接触させることによ
り、不均化反応により四塩化炭素、ジクロロジフルオロ
メタンを生成し、トリクロロフルオロメタンを直接にあ
るいは四塩化炭素などを経て二酸化炭素に分解させるこ
とができる。According to the method of the present invention, trichlorofluoromethane is
By contacting titanium dioxide carrying a platinum group element in gaseous form in the presence of light containing a wavelength component of 00 nm or less, carbon tetrachloride and dichlorodifluoromethane are produced by a disproportionation reaction, and trichlorofluoromethane is directly produced. It can be decomposed into carbon dioxide through carbon or carbon tetrachloride.
本発明においては、二酸化チタン表面に白金族元素を金
属状態で分散、担持して用いる。この担持は、例えば実
施例で示す方法で行われる。白金族元素は、二酸化チタ
ン表面に５ｗｔ％以下担持することが望ましい。この場
合、白金族元素としては、白金の他、ルテニウム、ロジ
ウム、パラジウム、オスミウム、イリジウムが用いられ
る。In the present invention, a platinum group element is dispersed and supported in a metallic state on the surface of titanium dioxide. This loading is carried out, for example, by the method shown in the Examples. It is desirable that the platinum group element be supported on the surface of titanium dioxide in an amount of 5 wt % or less. In this case, as the platinum group element, in addition to platinum, ruthenium, rhodium, palladium, osmium, and iridium are used.
このようにして得られる白金族元素を担持した二酸化チ
タン触媒は、４００ ｎｍ以下の波長成分を含む光の存
在下、室温付近の温度においてもクロロフルオロメタン
の不均化反応または分解反応を進行させ、触媒活性は比
較的長期にわたり保たれる。The titanium dioxide catalyst supporting platinum group elements obtained in this way allows the disproportionation reaction or decomposition reaction of chlorofluoromethane to proceed even at temperatures around room temperature in the presence of light containing wavelength components of 400 nm or less. , the catalytic activity is maintained for a relatively long period of time.
本発明により得られるクロロフルオロメタンの不均化及
び分解反応用触媒は、クロロフルオロメタンの除去用触
媒として好適である。The catalyst for disproportionation and decomposition of chlorofluoromethane obtained by the present invention is suitable as a catalyst for removing chlorofluoromethane.
次に実施例によって本発明をさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
市販の“Ｔｉｔａｎｉｕｍ ０ｘｉｄｅ Ｐ２５”
（日本アエロジル株式会社製品）（平均粒径的２１ ｎ
ｍ）をヘリウム雰囲気とした蒸留水に懸濁させ、重量比
で２％となるよう秤量した塩化白金酸を加える。メタノ
ールを少量加えた後、懸濁液をかくはんしながら、キセ
ノンランプで光照射し、白金金属を二酸化チタン表面に
析出、担持した。この白金担持二酸化チタン粉末−水混
合物を濾過、水洗いし、室温で乾燥した。Commercially available “Titanium Oxide P25”
(Nippon Aerosil Co., Ltd. product) (average particle size 21 n
m) is suspended in distilled water in a helium atmosphere, and chloroplatinic acid weighed to give a weight ratio of 2% is added. After adding a small amount of methanol, the suspension was stirred and irradiated with light using a xenon lamp to precipitate and support platinum metal on the surface of titanium dioxide. This platinum-supported titanium dioxide powder-water mixture was filtered, washed with water, and dried at room temperature.
この触媒を２５０ｍｇ秤量し、閉鎖式循環反応装置（内
容ｆ！２．３１）に設置して、温度２５℃で、光照射を
行わずに５４時間トリクロロフルオロメタン（ｉｏ＋ｐ
ｐｍ、空気希釈）を反応させた。引き続き、ｌｋＷキセ
ノンショートアークランプ（フィルターに竪
［−
得た。Weighed 250 mg of this catalyst, placed it in a closed circulation reactor (content f! 2.31), and kept it at 25°C for 54 hours without light irradiation using trichlorofluoromethane (io+p
pm, air dilution) was reacted. This was followed by an IkW xenon short arc lamp (vertical to the filter).
Claims (1)
特徴とするクロロフルオロメタンの不均化及び分解反応
用触媒。 ２、白金族元素を担持した二酸化チタンの存在下、光照
射することを特徴とするクロロフルオロメタンの不均化
及び分解方法。[Scope of Claims] 1. A catalyst for the disproportionation and decomposition reaction of chlorofluoromethane, characterized by using titanium dioxide supporting a platinum group element. 2. A method for disproportionation and decomposition of chlorofluoromethane, which comprises irradiating light in the presence of titanium dioxide carrying a platinum group element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63049075A JPH01224337A (en) | 1988-03-02 | 1988-03-02 | Catalyst for disproportionating and decomposing reaction of chlorofluoromethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63049075A JPH01224337A (en) | 1988-03-02 | 1988-03-02 | Catalyst for disproportionating and decomposing reaction of chlorofluoromethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01224337A true JPH01224337A (en) | 1989-09-07 |
Family
ID=12820965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63049075A Pending JPH01224337A (en) | 1988-03-02 | 1988-03-02 | Catalyst for disproportionating and decomposing reaction of chlorofluoromethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01224337A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0866635A (en) * | 1993-12-14 | 1996-03-12 | Toto Ltd | Photocatalytic thin film and its formation |
| CN113117672A (en) * | 2021-04-13 | 2021-07-16 | 福州大学 | Branched alkane reforming photo-thermal catalyst and preparation method and application thereof |
-
1988
- 1988-03-02 JP JP63049075A patent/JPH01224337A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0866635A (en) * | 1993-12-14 | 1996-03-12 | Toto Ltd | Photocatalytic thin film and its formation |
| CN113117672A (en) * | 2021-04-13 | 2021-07-16 | 福州大学 | Branched alkane reforming photo-thermal catalyst and preparation method and application thereof |
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