JPS60185734A - Preparation of trifluorochloroethylene - Google Patents
Preparation of trifluorochloroethyleneInfo
- Publication number
- JPS60185734A JPS60185734A JP59041223A JP4122384A JPS60185734A JP S60185734 A JPS60185734 A JP S60185734A JP 59041223 A JP59041223 A JP 59041223A JP 4122384 A JP4122384 A JP 4122384A JP S60185734 A JPS60185734 A JP S60185734A
- Authority
- JP
- Japan
- Prior art keywords
- active carbon
- catalyst
- hydrogen
- activated carbon
- reaction
- 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はヤシガラ活性炭触媒を用いた３弗化塩化エチレ
ンの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing ethylene trifluorochloride using a coconut shell activated carbon catalyst.
３弗化塩化エチレン（以下０ＴＦＥと略記する）の製法
については、従来から種り提案されており、代表的なも
のとして、１．１．２− ）ジクロロ−１，２，２−）
リフルオロエタン（以下Ｒ−１１３という）を亜鉛を用
いて脱塩素する液相法（特公昭４７−４５３２２号公報
、特公昭５７−５２０７〜８号公報等参照）又は、ジク
ロロモノフルオロメタンとクロロジフルオロメタン七の
集熱分解法（％公昭４０−２１３２号公報等参照〕ある
いはある種の触媒の存在下にＲ−１１３を水素を用いて
脱塩素する気相法（特公昭４７−２６４８４号公報等参
照）等が知られている。Various methods for producing ethylene trifluorochloride (hereinafter abbreviated as 0TFE) have been proposed in the past, and a typical method is 1.1.2-)dichloro-1,2,2-).
A liquid phase method in which refluoroethane (hereinafter referred to as R-113) is dechlorinated using zinc (see Japanese Patent Publication No. 47-45322, Japanese Patent Publication No. 57-5207-8, etc.) or dichloromonofluoromethane and chloromethane A concentrative decomposition method for difluoromethane (see Japanese Patent Publication No. 40-2132, etc.) or a gas phase method in which R-113 is dechlorinated using hydrogen in the presence of a certain type of catalyst (Japanese Patent Publication No. 26484-1984) etc.) are known.
亜鉛を用いた液相法は比較的高収率で０ＴＦＥを得るこ
とができるが、副生ずる塩化亜鉛の処理等に問題があり
、集熱分解法は収率が低く、又気相法では触媒が比較的
短期間で失活する等の問題がある。The liquid phase method using zinc can obtain 0TFE in a relatively high yield, but there are problems with the treatment of zinc chloride produced as a by-product, the yield of the concentrating cracking method is low, and the gas phase method There are problems such as deactivation in a relatively short period of time.
本発明者等は、スケールアップするに際しメリットのあ
る気相法に着目し、高い収率で０ＴＩＣを与えるととも
に活性を長期間持続し得る触媒の探索を進めた結果、活
性炭触媒、特にヤシガラ活性炭触媒が優れていることを
見い出すことができた。すなわち本発明はＲ−１１３と
水素とをヤシガラ活性炭触媒の存在下に反応せしめるこ
とを特徴とする０ＴＦＩの製造方法に関するものである
。The present inventors focused on the gas phase method, which has advantages in scaling up, and as a result of searching for a catalyst that can provide 0 TIC with a high yield and maintain activity for a long period of time, the inventors found that activated carbon catalysts, especially coconut husk activated carbon catalysts, I was able to find out that it is excellent. That is, the present invention relates to a method for producing 0TFI, which is characterized by reacting R-113 and hydrogen in the presence of a coconut shell activated carbon catalyst.
本発明における反応は以下の通りである。The reaction in the present invention is as follows.
ｃｃｌ、ｙａａＩＦ＝ （Ｒ１１３）＋ ）ｈ−ＯＣＩ
Ｆ＝ＯＦ２（ＯＴＦＫ）＋２ＨＯＩＲ−１１３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、Ｒ−
１１３１モルに対し水素１に０．２〜４モル、好ましく
は９．５〜２モルであればよい。反応温度は常圧におい
て４００〜６００℃、好ましくは４５０〜５５０℃であ
ればよく、これ以下の温度では収率７５監悪く、これ以
上の温度では熱分解等に伴う副反応力；起りやすくなり
好ましくない。反応圧力は、特に限定な〈実施可能であ
り、常圧又は自圧で充分に進行する。触媒に対する接触
時間は、通常５〜１２０秒、好ましくは１０〜６０秒の
範囲カムら選定すればよい。反応は、過剰の温度Ｅ昇を
防ぐために、窒素等の不活性ガスで稀釈しな力；ら実施
してもよい。ccl, yaaIF= (R113)+ )h-OCI
The reaction molar ratio between F=OF2(OTFK)+2HOIR-113 and hydrogen is not particularly limited, but R-
The amount may be 0.2 to 4 moles, preferably 9.5 to 2 moles per 1131 moles of hydrogen. The reaction temperature may be 400 to 600°C, preferably 450 to 550°C at normal pressure. If the temperature is lower than this, the yield will be 75% lower, and if the temperature is higher than this, side reactions due to thermal decomposition etc. will be more likely to occur. Undesirable. The reaction pressure is particularly limited (practicable), and the reaction proceeds satisfactorily at normal pressure or autogenous pressure. The contact time with the catalyst is usually selected from a range of 5 to 120 seconds, preferably 10 to 60 seconds. The reaction may be carried out without diluting with an inert gas such as nitrogen in order to prevent an excessive rise in temperature.
本発明に用いる触媒は、ヤシガラ活性炭触媒である。活
性炭触媒の原料には、木材、鋸屑。The catalyst used in the present invention is a coconut shell activated carbon catalyst. Raw materials for activated carbon catalysts include wood and sawdust.
木材乾留物、木炭、果実ガラ、ヤシガラ、胡桃ガラ、リ
グニン、パルプ廃液、せ贋搾り滓を廃糖蜜、泥炭、亜炭
２石炭、ピッチ、コークス等種々知られているが、鉱物
質の原料よりも植物質の原料が好ましく、％にヤシガラ
を原料としたヤシガラ活性炭触媒が最適である。ヤシガ
ラ活性炭触媒の形状は、直径約２〜５１＋ＩＩＩ＋程度
の成型炭、約４〜５０メツシユ程度の破砕炭７粒状炭、
砂状炭等各種の形状を採用し得るが、４〜３０メツシユ
前後の破砕炭、成型炭が好ましい。Wood carbonized distillate, charcoal, fruit husk, coconut husk, walnut husk, lignin, pulp waste liquid, slag, molasses, peat, lignite, coal, pitch, coke, etc. are known, but they are used more than mineral raw materials. Vegetable raw materials are preferred, and coconut shell activated carbon catalysts made from coconut shells are most suitable. The shapes of the coconut shell activated carbon catalyst are: shaped coal with a diameter of about 2 to 51+III+, crushed coal with a diameter of about 4 to 50 mesh, 7 granular charcoal,
Although various shapes such as sandy charcoal can be employed, crushed charcoal and briquette charcoal of around 4 to 30 meshes are preferable.
又、環化亜鉛、塩化マグネシウム等の金属塩化物や生石
灰、リン酸カルシウム、硫酸、ホウ酸等の薬品により付
活されたものでもよいが、本発明におけるヤシガラ活性
炭触媒は水蒸気で付活されたものが好ましい。Additionally, catalysts activated with metal chlorides such as cyclized zinc and magnesium chloride, or chemicals such as quicklime, calcium phosphate, sulfuric acid, and boric acid may be used, but the coconut shell activated carbon catalyst of the present invention is activated with water vapor. preferable.
以下、本発明の実施例について、さらに具体的に説明す
るが、本発明に従えばＯＴＦＫ１の初期の収率ばかりで
なく、長期間経過後の収率も極めて優れていることがわ
かる。Examples of the present invention will be described in more detail below, and it can be seen that according to the present invention, not only the initial yield of OTFK1 but also the yield after a long period of time are extremely excellent.
実施例１
８〜３０メツシユの破砕ヤシガラ活性炭触媒２００ｄを
インコネル６００製Ｕ字型反応器（管径１７２ｉｎｃｈ
＋長さＩＷＩ）に充填し、これを塩浴炉に侵して外部よ
り加熱し４８０℃に保持した。これにＲ−１１３を０．
３モル／ｈｒ＋ 水素を０．６モル／ｈｒ の速度で供
給して反応を行なった。Example 1 200 d of crushed coconut shell activated carbon catalyst of 8 to 30 meshes was placed in a U-shaped reactor made of Inconel 600 (tube diameter 172 inches).
+ length IWI), and this was placed in a salt bath furnace and heated from the outside and maintained at 480°C. Add 0.0% R-113 to this.
The reaction was carried out by supplying 3 mol/hr+ hydrogen at a rate of 0.6 mol/hr.
４８時間後反応器出ロガスをガスクロマトグラフで分析
した結果は次の通りであった。After 48 hours, the log gas discharged from the reactor was analyzed by gas chromatography, and the results were as follows.
第 １ 表
実施例２
４〜６メツシユのヤシガラ粒状活性炭触媒２００ｄを実
施例１と同じ反応器に充填し、温度を５００℃に保持し
てＲ−１１３，水素をそれぞれ０．４モル／時、０．６
モル／時の流速で供給して反応を行なった。４８時間後
反応器出ロガスをガスクロマトグラフで分析した結果、
Ｒ−１１３反応率５８チ、３弗化塩化エチレンの選択率
は８３％であった。Table 1 Example 2 200 d of coconut shell granular activated carbon catalyst of 4 to 6 meshes was packed in the same reactor as in Example 1, the temperature was maintained at 500°C, and R-113 and hydrogen were each 0.4 mol/hour. 0.6
The reaction was carried out by feeding at a flow rate of mol/hour. As a result of analyzing the log gas from the reactor after 48 hours using a gas chromatograph,
The R-113 reaction rate was 58%, and the trifluorochloroethylene selectivity was 83%.
実施例３
４〜６メツシユのヤシガラ粒状活性炭触媒４００ｄ’に
、−ステロイＣ製のＵ字型反応器（管径１１ｎｏｂ＋長
さ１１Ｒ）に充填し、これを塩浴炉に侵して外部より加
熱して５００℃に保持した。Example 3 A U-shaped reactor (pipe diameter 11 nob + length 11 R) made of -steroy C was filled with 400 d' of coconut shell granular activated carbon catalyst of 4 to 6 meshes, and heated from the outside in a salt bath furnace. and maintained at 500°C.
これにＲ１１３＋水素をそれぞれ０．５モル／時、０．
５モル／時の速度で供給して反応を行なった。To this, R113 + hydrogen was added at 0.5 mol/hour and 0.5 mol/hour, respectively.
The reaction was carried out by feeding at a rate of 5 mol/hour.
３日後反応器出ロガスを分析した結果、Ｒ−１１３の反
応率３弗化塩化エチレンの選択率はそれぞれ６１ｉ ８
２％であった。また３週間後は５９％、８５％であり、
さらに７週間後は５６．５チ、８８チであった。As a result of analyzing the log gas from the reactor after 3 days, the reaction rate of R-113 and the selectivity of ethylene fluoride and chloride were 61i and 8, respectively.
It was 2%. Also, after 3 weeks, it was 59% and 85%,
After another 7 weeks, it was 56.5 inches and 88 inches.
実施例４
４〜６メツシユの成型ヤシガラ炭系活性炭触媒２００ｄ
を実施例１と同じ反応器に充填し、実施例３と同じ条件
下で反応を行ない、３日後反応器出ロガスを分析した結
果、Ｒ−１１３反応率は６４．５％であり、３弗化塩化
エチレンの選択率は７９．８％であった。また１チ月後
の性能はＲ−１１３反応率５９％、３弗化塩化工チレン
選択率は８７．５％であった。Example 4 Molded coconut shell carbon-based activated carbon catalyst with 4 to 6 meshes 200d
was charged into the same reactor as in Example 1, and the reaction was carried out under the same conditions as in Example 3. After 3 days, the log gas from the reactor was analyzed. As a result, the R-113 reaction rate was 64.5%, and 3 The selectivity of ethylene chloride was 79.8%. The performance after one month was as follows: R-113 reaction rate was 59% and trifluorochlorinated tyrene selectivity was 87.5%.
比較例１
１０〜３２メツシユの石炭系活性炭触媒２００ｄｏｔ実
施例１と同じ反応器に充填し、実施例１と同じ条件下で
反応を行ない、２４時間後反応器出ロガスをガスクロマ
トグラフで分析した結果、Ｒ−１１３反応率は２８．３
％でおり、３弗化塩化エチレンの選択率は５９．２％で
あった。Comparative Example 1 200 dots of a coal-based activated carbon catalyst of 10 to 32 meshes were packed into the same reactor as in Example 1, the reaction was carried out under the same conditions as in Example 1, and after 24 hours, the log gas output from the reactor was analyzed by gas chromatography. , R-113 reaction rate is 28.3
%, and the selectivity of trifluorochloroethylene was 59.2%.
比較例２
４〜６メツシユのビート炭活性炭触媒４００ｄを実施例
３と同じ反応器に充填し、実施例３と同じ条件下で反応
全行ない、２４時間後反応器出ロガスを分析した結果、
Ｒ−１１３の反応率は３９％であり、３弗化塩化エチレ
ンの選択ＷＩ−は６３．５％であった。Comparative Example 2 The same reactor as in Example 3 was filled with 400 d of beet carbon activated carbon catalyst of 4 to 6 meshes, the entire reaction was carried out under the same conditions as in Example 3, and the log gas output from the reactor was analyzed after 24 hours.
The reaction rate of R-113 was 39%, and the selection WI- of trifluorochloroethylene was 63.5%.
Claims (1)
オロエタンと水素とを触媒の存在下に反応せしめる３弗
化塩化エチレンを製造する方法において、触媒としてヤ
シガラ活性炭触媒を用いることを特徴とする３弗化塩化
エチレンの製造方法。1. In a method for producing ethylene trifluorochloride, which involves reacting 2-trichloro-1,2,2-trifluoroethane with hydrogen in the presence of a catalyst, it is possible to use a coconut shell activated carbon catalyst as a catalyst. Characteristic method for producing ethylene trifluorochloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59041223A JPS60185734A (en) | 1984-03-06 | 1984-03-06 | Preparation of trifluorochloroethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59041223A JPS60185734A (en) | 1984-03-06 | 1984-03-06 | Preparation of trifluorochloroethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60185734A true JPS60185734A (en) | 1985-09-21 |
| JPS6346049B2 JPS6346049B2 (en) | 1988-09-13 |
Family
ID=12602398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59041223A Granted JPS60185734A (en) | 1984-03-06 | 1984-03-06 | Preparation of trifluorochloroethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60185734A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4876405A (en) * | 1986-07-18 | 1989-10-24 | Ausimont S.P.A. | Process for preparing fluoroethylenes and chlorofluoro-ethylenes from chlorofluoroethanes |
| US5564532A (en) * | 1994-03-25 | 1996-10-15 | Aisin Seiki Kabushiki Kaisha | Mounting member for disk brake |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993016023A1 (en) * | 1992-02-06 | 1993-08-19 | Daikin Industries, Ltd. | 1,1,1,2,2,5,5,5-octafluoropentane and production thereof |
-
1984
- 1984-03-06 JP JP59041223A patent/JPS60185734A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4876405A (en) * | 1986-07-18 | 1989-10-24 | Ausimont S.P.A. | Process for preparing fluoroethylenes and chlorofluoro-ethylenes from chlorofluoroethanes |
| US5564532A (en) * | 1994-03-25 | 1996-10-15 | Aisin Seiki Kabushiki Kaisha | Mounting member for disk brake |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6346049B2 (en) | 1988-09-13 |
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