JPH059138A - Method for producing trifluoroethylene - Google Patents
Method for producing trifluoroethyleneInfo
- Publication number
- JPH059138A JPH059138A JP3230088A JP23008891A JPH059138A JP H059138 A JPH059138 A JP H059138A JP 3230088 A JP3230088 A JP 3230088A JP 23008891 A JP23008891 A JP 23008891A JP H059138 A JPH059138 A JP H059138A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- silicon oxide
- oxide
- trifluoroethylene
- hydrogen
- 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
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】
【構成】 １,１,２−トリクロロ−１,２,２−トリフル
オロエタンと水素とを触媒存在下に反応させることによ
ってトリフルオロエチレンを製造する方法において、触
媒として、活性炭、酸化けい素、酸化アルミニウム、酸
化けい素／酸化アルミニウムおよび酸化けい素／酸化マ
グネシウムから成る群から選択された担体に担持された
ニッケルを使用することを特徴とする製造方法。
【効果】 本発明によれば、トリフルオロエチレンを良
好な選択率で得ることができる。(57) [Summary] [Structure] In a method for producing trifluoroethylene by reacting 1,1,2-trichloro-1,2,2-trifluoroethane with hydrogen in the presence of a catalyst, A method for producing nickel characterized by using nickel supported on a carrier selected from the group consisting of activated carbon, silicon oxide, aluminum oxide, silicon oxide / aluminum oxide and silicon oxide / magnesium oxide. According to the present invention, trifluoroethylene can be obtained with a good selectivity.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フロン１１３ (１,１,
２−トリクロロ−１,２,２−トリフルオロエタン、ＣＦ
Ｃ−１１３) から、トリフルオロエチレン (ＣＦ2＝Ｃ
ＦＨ、ＣＦＣ−１１２３) を製造する方法に関する。BACKGROUND OF THE INVENTION The present invention relates to Freon 113 (1, 1,
2-trichloro-1,2,2-trifluoroethane, CF
C-113) to trifluoroethylene (CF 2 = C
FH, CFC-1123).
【０００２】[0002]
【発明が解決しようとする課題】本発明の目的は、１,
１,２−トリクロロ−１,２,２−トリフルオロエタンか
らトリフルオロエチレンを高選択率で製造する方法を提
供することにある。The object of the present invention is to:
An object of the present invention is to provide a method for producing trifluoroethylene from 1,2-trichloro-1,2,2-trifluoroethane with high selectivity.
【０００３】[0003]
【課題を解決するための手段】本発明の要旨は、１,１,
２−トリクロロ−１,２,２−トリフルオロエタンと水素
とを触媒存在下に反応させることによってトリフルオロ
エチレンを製造する方法において、触媒として、活性
炭、酸化けい素、酸化アルミニウム、酸化けい素／酸化
アルミニウムおよび酸化けい素／酸化マグネシウムから
成る群から選択された担体に担持されたニッケルを使用
することを特徴とする製造方法に存する。The gist of the present invention is 1, 1,
In a method for producing trifluoroethylene by reacting 2-trichloro-1,2,2-trifluoroethane and hydrogen in the presence of a catalyst, as a catalyst, activated carbon, silicon oxide, aluminum oxide, silicon oxide / A process for producing nickel characterized by using nickel supported on a carrier selected from the group consisting of aluminum oxide and silicon oxide / magnesium oxide.
【０００４】本発明の方法で使用される触媒は、担体に
担持されたニッケルである。担体は、活性炭、酸化けい
素、酸化アルミニウム、酸化けい素／酸化アルミニウム
および酸化けい素／酸化マグネシウムから成る群から選
択されたものである。酸化けい素／酸化アルミニウムに
おいて、酸化けい素と酸化アルミニウムの重量比は、好
ましくは１０：９０〜９０：１０である。また、酸化け
い素／酸化マグネシウムにおいて、酸化けい素と酸化マ
グネシウムの重量比は、好ましくは１０：９０〜９０：
１０、より好ましくは１０：９０〜５０：５０である。
触媒に占めるニッケルの重量は好ましくは０.１〜５０
重量％である。触媒の粒度は特に限定されないが、好ま
しくは８〜２００メッシュ、より好ましくは３２〜６０
メッシュである。触媒は、例えば、硝酸ニッケルの水溶
液に担体の粉末を加え、蒸発乾固し、さらに乾燥するこ
とによって製造することができる。The catalyst used in the method of the present invention is nickel supported on a carrier. The carrier is selected from the group consisting of activated carbon, silicon oxide, aluminum oxide, silicon oxide / aluminum oxide and silicon oxide / magnesium oxide. In silicon oxide / aluminum oxide, the weight ratio of silicon oxide and aluminum oxide is preferably 10:90 to 90:10. In the case of silicon oxide / magnesium oxide, the weight ratio of silicon oxide and magnesium oxide is preferably 10:90 to 90 :.
10, more preferably 10:90 to 50:50.
The weight of nickel in the catalyst is preferably 0.1 to 50.
% By weight. The particle size of the catalyst is not particularly limited, but is preferably 8 to 200 mesh, more preferably 32 to 60 mesh.
It is a mesh. The catalyst can be produced, for example, by adding a carrier powder to an aqueous solution of nickel nitrate, evaporating to dryness, and further drying.
【０００５】１,１,２−トリクロロ−１,２,２−トリフ
ルオロエタンと水素との反応モル比は特に限定されるも
のではないが、通常、水素が２〜２０倍モル、好ましく
は２〜１０倍モルである。水素の量が２倍モルよりも少
ないと選択性が低下し、水素の量が２０倍モルよりも多
いと水素の利用率が低下する。The reaction molar ratio of 1,1,2-trichloro-1,2,2-trifluoroethane and hydrogen is not particularly limited, but usually hydrogen is 2 to 20 times mol, preferably 2 times. It is 10 times the molar amount. When the amount of hydrogen is less than 2 times the mole, the selectivity is lowered, and when the amount of hydrogen is more than 20 times the mole, the utilization rate of hydrogen is lowered.
【０００６】本発明の反応は、連続式で行うことが好ま
しい。原料ガスの供給速度（ＳＶ）は好適には１００〜
１００００（ｈ-1）である。ここで、ＳＶは、（単位時
間当たりの供給ガス体積(反応温度下））／（触媒の見
かけ充填体積)で定義される。反応圧力は特に制限な
く、あらゆる実用的な反応圧力下で実施可能である。圧
力は、通常０.１〜１００kg/cm2、好ましくは１〜２０k
g/cm2である。反応温度は、常圧の場合、３００〜５５
０℃、好ましくは３５０〜５００℃である。３００℃よ
り低温では転化率が低く、逆に、５５０℃より高温では
選択率の低下や触媒の劣化を招く。反応ガスは希釈せず
にそのまま用いてもよいし、Ｎ2、Ａr、Ｈeなど反応に
影響を与えないガスで希釈して用いてもよい。The reaction of the present invention is preferably carried out continuously. The feed rate (SV) of the raw material gas is preferably 100 to
It is 10000 (h -1 ). Here, SV is defined by (volume of supply gas per unit time (under reaction temperature)) / (apparent filling volume of catalyst). The reaction pressure is not particularly limited, and it can be carried out under any practical reaction pressure. The pressure is usually 0.1 to 100 kg / cm 2 , preferably 1 to 20 k.
It is g / cm 2 . The reaction temperature is 300 to 55 at atmospheric pressure.
The temperature is 0 ° C, preferably 350 to 500 ° C. When the temperature is lower than 300 ° C, the conversion rate is low, and conversely, when the temperature is higher than 550 ° C, the selectivity is lowered and the catalyst is deteriorated. The reaction gas may be used as it is without being diluted, or may be diluted with a gas such as N 2 , Ar or He that does not affect the reaction.
【０００７】[0007]
【発明の好ましい態様】製造例１触媒の調製 以下に示す各触媒（粒径：３２〜６０メッシュ、ニッケ
ルの担持量：１重量％（Ｎi／ＭgＯ触媒のみ３重量
％））を調製した。 （１）Ｎi／Ｃ ３２〜６０メッシュの活性炭に硝酸ニッケル水溶液を加
え蒸発乾固させた。これを１２０℃で一昼夜乾燥した。
これを高温焼成せずに反応に用いた。 （２）Ｎi／ＳiＯ2 硝酸ニッケルの水溶液に３２〜６０メッシュのシリカ
エアロジルを加え、蒸発乾固させ、１２０℃で１日乾燥
した。Preferred Embodiment of the Invention Production Example 1Preparation of catalyst Each catalyst (particle size: 32-60 mesh, nickel
Supported amount: 1% by weight (3% by weight only for Ni / MgO catalyst)
%)) Was prepared. (1) Add nickel nitrate solution to Ni / C 32-60 mesh activated carbon.
Evaporated to dryness. This was dried overnight at 120 ° C.
This was used for the reaction without firing at high temperature. (2) Ni / SiO2 32-60 mesh silica in nickel nitrate solution
Add Aerosil, evaporate to dryness and dry at 120 ° C for 1 day
did.
【０００８】（３）Ｎi／Ａl2Ｏ3 硝酸ニッケルの水溶液に３２〜６０メッシュの酸化ア
ルミニウムの粉末を加え、蒸発乾固させ、１２０℃で１
日乾燥した。 （４）Ｎi／ＳiＯ2-Ａl2Ｏ3 硝酸ニッケルの水溶液にＳiＯ2-Ａl2Ｏ3混合物（重量
比７１：２９）の粉末（３２〜６０メッシュ）を加え、
蒸発乾固させ、１２０℃で１日乾燥した。 （５）Ｎi／ＳiＯ2-ＭgＯ 硝酸ニッケルの水溶液にＳiＯ2-ＭgＯ混合物（重量比５
０：５０）の粉末（３２〜６０メッシュ）を加え、蒸発
乾固させ、１２０℃で１日乾燥した。(3) Ni / Al2O3 Aqueous nickel nitrate solution with 32-60 mesh oxide
Luminium powder was added, evaporated to dryness, and 1 at 120 ° C.
Sun dried. (4) Ni / SiO2-Al2O3 An aqueous solution of nickel nitrate containing SiO2-Al2O3Mixture (weight
71:29 ratio powder (32-60 mesh) is added,
It was evaporated to dryness and dried at 120 ° C. for 1 day. (5) Ni / SiO2-MgO Addition to nickel nitrate aqueous solution2-MgO mixture (weight ratio 5
0:50) powder (32-60 mesh) was added and evaporated
It was dried to dryness and dried at 120 ° C. for 1 day.
【０００９】（６）Ｎi／ＭgＯ 硝酸ニッケルの水溶液に３２〜６０メッシュのＭgＯを
加え、蒸発乾固させ、１２０℃で１日乾燥した。続いて
６００℃で５分間、空気中で焼成した。 （７）Ｎi／ＴiＯ2 硝酸ニッケルの水溶液に３２〜６０メッシュのＴiＯ2
を加え、蒸発乾固させ、１２０℃で１日乾燥した。(6) Ni / MgO 32-60 mesh MgO is added to an aqueous solution of nickel nitrate.
In addition, it was evaporated to dryness and dried at 120 ° C. for 1 day. continue
It was calcined in air at 600 ° C. for 5 minutes. (7) Ni / TiO2 32-60 mesh TiO in nickel nitrate solution2
Was added, evaporated to dryness, and dried at 120 ° C. for 1 day.
【００１０】実施例１〜５ならびに比較例１および２ 常圧固定床パルス反応装置を用いた。触媒として製造例
１で得られたものを用い、触媒量は１gとした。触媒を
予め水素気流中４５０℃で２時間の還元処理を行った。
フロン１１３（１０cm3／分）、Ａr（５６cm3／分）、
Ｈ2（２９cm3／分）から成る原料ガスを流速９５cm3／
分で供給し、４５０℃で反応を行った。反応により生成
するハロゲン化水素は酸化カルシウムに吸収させ、生成
ガスをガスクロマトグラフィーで分析した。また、少量
の生成物の同定にはＧＣ−質量分析装置を用いた。２時
間後のフロン１１３の転化率および得られた生成物の選
択率を表１に示す。Examples 1-5 and Comparative Examples 1 and 2 Atmospheric fixed bed pulse reactors were used. The catalyst obtained in Production Example 1 was used as the catalyst, and the catalyst amount was 1 g. The catalyst was previously subjected to reduction treatment in a hydrogen stream at 450 ° C. for 2 hours.
Freon 113 (10 cm 3 / min), Ar (56 cm 3 / min),
A raw material gas composed of H 2 (29 cm 3 / min) was flown at a flow rate of 95 cm 3
It was supplied in minutes and the reaction was carried out at 450 ° C. The hydrogen halide produced by the reaction was absorbed in calcium oxide, and the produced gas was analyzed by gas chromatography. A GC-mass spectrometer was used to identify a small amount of product. Table 1 shows the conversion rate of Freon 113 after 2 hours and the selectivity of the obtained product.
【００１１】[0011]
【表１】 触媒 転化率 選択率(％) (％) 1113 1123 1132 123a 133 実施例１ Ｎi／Ｃ 43.0 71.7 19.9 2.3 1.1 1.5 実施例２ Ｎi／ＳiＯ2 65.2 64.2 16.0 4.5 0.5 2.1 実施例３ Ｎi／Ａl2Ｏ3 21.6 23.0 17.7 5.2 1.9 2.1 実施例４ Ｎi／SiO2-Al2O3 17.8 14.2 61.5 4.5 0.9 4.5 実施例５ Ｎi／SiO2-MgO 54.8 64.4 17.8 8.0 1.1 1.5 比較例１ Ｎi／ＭgＯ 1.9 14.7 2.7 0.5 3.1 0比較例２ Ｎi／ＴiＯ2 66.2 22.6 8.1 0.2 0.6 2.1 [Table 1] Catalyst conversion rateSelectivity (%) (%) 1113 1123 1132 123a 133 Example 1 Ni / C 43.0 71.7 19.9 2.3 1.1 1.5 Example 2 Ni / SiO2 65.2 64.2 16.0 4.5 0.5 2.1 Example 3 Ni / Al2O3 21.6 23.0 17.7 5.2 1.9 2.1 Example 4 Ni / SiO2-Al2O3 17.8 14.2 61.5 4.5 0.9 4.5 Example 5 Ni / SiO2-MgO 54.8 64.4 17.8 8.0 1.1 1.5 Comparative Example 1 Ni / MgO 1.9 14.7 2.7 0.5 3.1 0Comparative Example 2 Ni / TiO 2 66.2 22.6 8.1 0.2 0.6 2.1
【００１２】[0012]
【発明の効果】本発明によれば、トリフルオロエチレン
を良好な選択率で得ることができる。According to the present invention, trifluoroethylene can be obtained with a good selectivity.
Claims (1)
フルオロエタンと水素とを触媒存在下に反応させること
によってトリフルオロエチレンを製造する方法におい
て、触媒として、活性炭、酸化けい素、酸化アルミニウ
ム、酸化けい素／酸化アルミニウムおよび酸化けい素／
酸化マグネシウムから成る群から選択された担体に担持
されたニッケルを使用することを特徴とする製造方法。Claim: What is claimed is: 1. A method for producing trifluoroethylene by reacting 1,1,2-trichloro-1,2,2-trifluoroethane with hydrogen in the presence of a catalyst. As activated carbon, silicon oxide, aluminum oxide, silicon oxide / aluminum oxide and silicon oxide /
A method for manufacturing, characterized in that nickel supported on a carrier selected from the group consisting of magnesium oxide is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3230088A JP2630127B2 (en) | 1990-09-11 | 1991-09-10 | Method for producing trifluoroethylene |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24168890 | 1990-09-11 | ||
| JP2-241688 | 1990-09-11 | ||
| JP3230088A JP2630127B2 (en) | 1990-09-11 | 1991-09-10 | Method for producing trifluoroethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH059138A true JPH059138A (en) | 1993-01-19 |
| JP2630127B2 JP2630127B2 (en) | 1997-07-16 |
Family
ID=26529134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3230088A Expired - Fee Related JP2630127B2 (en) | 1990-09-11 | 1991-09-10 | Method for producing trifluoroethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2630127B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716590A (en) * | 1993-12-17 | 1998-02-10 | Wacker-Chemie Gmbh | Catalytic hydrodehalogenation of halogen-containing compounds of group IV elements |
| US6940159B2 (en) | 2001-08-22 | 2005-09-06 | Sony Corporation | Method and apparatus for molding, module electronic devices and a module electronic device molded thereby |
| JP2025078705A (en) * | 2023-11-07 | 2025-05-20 | Ａｇｃ株式会社 | Method for producing halogenated alkenes |
-
1991
- 1991-09-10 JP JP3230088A patent/JP2630127B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716590A (en) * | 1993-12-17 | 1998-02-10 | Wacker-Chemie Gmbh | Catalytic hydrodehalogenation of halogen-containing compounds of group IV elements |
| US6940159B2 (en) | 2001-08-22 | 2005-09-06 | Sony Corporation | Method and apparatus for molding, module electronic devices and a module electronic device molded thereby |
| JP2025078705A (en) * | 2023-11-07 | 2025-05-20 | Ａｇｃ株式会社 | Method for producing halogenated alkenes |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2630127B2 (en) | 1997-07-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |