JP2751401B2 - Method for producing 1,1-dichloro-1,2,2,2-tetrafluoroethane - Google Patents
Method for producing 1,1-dichloro-1,2,2,2-tetrafluoroethaneInfo
- Publication number
- JP2751401B2 JP2751401B2 JP1128683A JP12868389A JP2751401B2 JP 2751401 B2 JP2751401 B2 JP 2751401B2 JP 1128683 A JP1128683 A JP 1128683A JP 12868389 A JP12868389 A JP 12868389A JP 2751401 B2 JP2751401 B2 JP 2751401B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- catalyst
- hydrogen fluoride
- tetrafluoroethane
- producing
- 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.)
- Expired - Fee Related
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Classifications
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- 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)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は1,1−ジクロロ−1,2,2,2−テトラフルオロエ
タン（R-114a）の製造方法に関するものである。R-114a
は、冷媒、発泡剤としての用途のほかに、ジクロロジフ
ルオロエタン（R-12）の代替フロンとしての使用が検討
されている1,1,1,2−テトラフルオロエタン（R-134a）
製造の中間体として有用である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing 1,1-dichloro-1,2,2,2-tetrafluoroethane (R-114a). R-114a
Is being considered for use as a refrigerant instead of dichlorodifluoroethane (R-12) in addition to its use as a refrigerant and blowing agent. 1,1,1,2-Tetrafluoroethane (R-134a)
Useful as an intermediate in production.
［従来の技術及び発明が解決しようとする課題］ 従来より、1,1,1−トリクロロ−2,2,2−トリフルオロ
エタン（R-113a）の気相フッ素化反応に、ハロゲン化ク
ロムなどが、触媒として有効であることが知られてい
る。しかるに従来の触媒では、目的反応生成物であるR-
114aが選択的に得にくいという難点がある。すなわちR-
114aがさらにフッ素化された１−クロロ−1,1,2,2,2−
ペンタフルオロエタン（R-115）の副生を抑制するのが
困難である。[Problems to be Solved by the Prior Art and the Invention] Conventionally, chromium halides and the like have been Is known to be effective as a catalyst. However, in the conventional catalyst, the target reaction product, R-
It is difficult to obtain 114a selectively. That is, R-
1-chloro-1,1,2,2,2- in which 114a is further fluorinated
It is difficult to suppress the by-product of pentafluoroethane (R-115).
［課題を解決するための手段］ 本発明者は、Fe、Ni、Co、およびMnからなる群から選
ばれる少なくとも１種の元素を主成分とし、Crを含む酸
化物触媒について鋭意検討を重ねた結果、これらの複合
酸化物および、アルカリ金属およびアルカリ土類金属か
ら選ばれる少なくとも１種の元素をさらに含んだ複合酸
化物が、耐久性を損なうことなしに目的とする生成物の
選択率を向上させることができることを見いだした。す
なわち、R-113aを気相フッ素化するにあたり、ハロゲン
化クロムまたは酸化クロムのみからなる触媒に比べ1,1
−ジクロロ−1,2,2,2−テトラフルオロエタン（R-114
a）への選択性が著しく向上することを見い出した。本
発明はFe、Ni、Co、およびMnからなる群から選ばれる少
なくとも１種の元素を主成分とし、Crを含む酸化物から
なるフッ素化触媒の存在下、R-113aとフッ化水素とを反
応せしめることを特徴とするR-114aの製造方法、及びフ
ッ素化触媒中に、助触媒としてアルカリ金属およびアル
カリ土類金属から選ばれる少なくとも１種の元素を含む
酸化物からなるフッ素化触媒の存在下、R-113aとフッ化
水素とを反応せしめることを特徴とするR-114aの製造方
法である。フッ素化触媒の選択性についてさらに詳しく
言えば、ハロゲン化クロム／アルミニウムおよび酸化ク
ロム／アルミナ触媒でのR-114a選択率が70％程度であ
り、更にフッ素化された、R-115の副生が避けられない
のに対し、本触媒の使用によりR-114a選択率が95％以上
となり、R-115の副生を大幅に抑制することが可能とな
った。[Means for Solving the Problems] The present inventors have made intensive studies on an oxide catalyst containing at least one element selected from the group consisting of Fe, Ni, Co, and Mn as a main component and containing Cr. As a result, these composite oxides and a composite oxide further containing at least one element selected from alkali metals and alkaline earth metals improve the selectivity of a target product without impairing durability. I found something that could be done. That is, in the gas-phase fluorination of R-113a, compared to a catalyst comprising only chromium halide or chromium oxide, 1,1
-Dichloro-1,2,2,2-tetrafluoroethane (R-114
It was found that the selectivity to a) was significantly improved. The present invention has at least one element selected from the group consisting of Fe, Ni, Co, and Mn as a main component, and in the presence of a fluorination catalyst comprising an oxide containing Cr, R-113a and hydrogen fluoride. A method for producing R-114a, characterized by reacting, and the presence of, in the fluorination catalyst, a fluorination catalyst comprising an oxide containing at least one element selected from alkali metals and alkaline earth metals as a co-catalyst The following is a method for producing R-114a, which comprises reacting R-113a with hydrogen fluoride. More specifically, the selectivity of the fluorination catalyst is as follows. The selectivity of R-114a is about 70% for the chromium halide / aluminum and chromium oxide / alumina catalysts, and the fluorinated by-product of R-115 is reduced. On the other hand, the use of this catalyst increased the selectivity of R-114a to 95% or more, making it possible to significantly suppress the by-product of R-115.
以下、反応の詳細について説明する。 Hereinafter, the details of the reaction will be described.
本発明におけるフッ素化触媒は、Fe、Ni、Co、および
Mnからなる群から選ばれる少なくとも１種の元素を主成
分とし、Crを含む酸化物、およびこれらの構成元素に加
えてNa、Ｋ等のアルカリ金属およびMg、Ca等のアルカリ
土類金属を含む酸化物である。上記のあらゆる触媒は、
反応に供せられる前にフッ化水素やトリクロロフルオロ
エタン（R-11）、1,1,2−トリクロロ−1,2,2−トリフル
オロエタン（R-113）など、少なくともフッ素原子を１
個含むハロゲン化メタン、ハロゲン化エタン等により活
性化しておくことが望ましい。The fluorination catalyst in the present invention is Fe, Ni, Co, and
Oxides containing at least one element selected from the group consisting of Mn and containing Cr, and alkali metals such as Na and K and alkaline earth metals such as Mg and Ca in addition to these constituent elements It is an oxide. All of the above catalysts are
Before being subjected to the reaction, at least one fluorine atom such as hydrogen fluoride, trichlorofluoroethane (R-11), 1,1,2-trichloro-1,2,2-trifluoroethane (R-113) is used.
It is desirable to activate with halogenated methane, halogenated ethane or the like.
反応温度は気相中常圧もしくは加圧下で、好ましくは
200℃〜550℃、特に好ましくは、250℃〜400℃の温度範
囲で行なうことが適当である。反応温度が高すぎると触
媒寿命が短くなり、反応温度が低すぎるとR-113a転化率
が低下する。The reaction temperature is normal pressure or under pressure in the gas phase, preferably
It is suitable to carry out the reaction at a temperature in the range of 200 ° C to 550 ° C, particularly preferably 250 ° C to 400 ° C. If the reaction temperature is too high, the catalyst life will be shortened, and if the reaction temperature is too low, the conversion of R-113a will decrease.
接触時間は、通常0.1〜300秒、特に好ましくは５〜60
秒である。The contact time is usually 0.1 to 300 seconds, particularly preferably 5 to 60 seconds.
Seconds.
反応は液相加圧下で行なってもよく、反応温度は50〜
550℃、好ましくは50〜450℃、接触時間は0.1〜10000
分、好ましくは10〜1000分が適当である。The reaction may be performed under liquid pressure, and the reaction temperature is 50 to
550 ° C, preferably 50-450 ° C, contact time 0.1-10000
Minutes, preferably 10-1000 minutes.
フッ化水素とR-113aの割合は大幅に変動させ得る。し
かしながら通常、化学量論量からその３倍量までのフッ
化水素を使用して塩素原子を置換する。出発物質の全モ
ル数に対して、化学量論量よりかなり多い量、例えば５
モルまたはそれ以上のフッ化水素を使用し得る。The ratio between hydrogen fluoride and R-113a can vary widely. However, usually stoichiometric up to three times its amount is used to replace the chlorine atoms. With respect to the total number of moles of the starting material, an amount which is considerably larger than the stoichiometric amount, for example,
Molar or more hydrogen fluoride may be used.
また触媒活性維持のため酸素または塩素をR-113aに対
して0.1〜10Vol.％共存させることが好ましい。Further, in order to maintain the catalytic activity, it is preferable that oxygen or chlorine coexist with R-113a in an amount of 0.1 to 10% by volume.
［実施例］ 以下、本発明の実施例を示す。EXAMPLES Examples of the present invention will be described below.
調製例１ Fe(NO3)3・9H2Oの600g、Cr(NO3)3・9H2Oの150gを2.5
リットルの水に溶解し、これと28％の水酸化アンモニウ
ムの水溶液2000gを攪拌しながら、加熱した４リットル
の水に添加して水酸化物の沈殿を得た。これを別し、
純水による洗浄、および乾燥を行なった後、450℃で５
時間焼成して酸化物の粉末を得た。これを打錠成型機を
用いて直径5mm、高さ5mmの円筒状に成型した。こうして
得た触媒を反応前にフッ化水素／窒素の混合ガス気流
中、300〜400℃でフッ素化して、活性化した。Preparation Example 1 Fe (NO 3) 3 · 9H 2 O in 600 g, Cr and (NO 3) 3 · 9H 2 O in 150 g 2.5
This was dissolved in 1 liter of water, and 2,000 g of a 28% aqueous solution of ammonium hydroxide was added to 4 liters of heated water with stirring to obtain a hydroxide precipitate. Apart from this,
After washing with pure water and drying, 5 minutes at 450 ° C
After firing for an hour, an oxide powder was obtained. This was molded into a cylinder having a diameter of 5 mm and a height of 5 mm using a tableting machine. The catalyst thus obtained was activated by fluorination at 300 to 400 ° C. in a hydrogen fluoride / nitrogen mixed gas stream before the reaction.
調製例２ Fe(NO3)3・9H2Oのかわりに、Ni(NO3)2・6H2Oの800g、
KNO3・2H2Oの100gを用いる他は、調製例１と同様にして
触媒を調製した。Instead of Preparation 2 Fe (NO 3) 3 · 9H 2 O, Ni (NO 3) 2 · 6H 2 O in 800 g,
A catalyst was prepared in the same manner as in Preparation Example 1, except that 100 g of KNO 3 .2H 2 O was used.
調製例３ Fe(NO3)3・9H2Oのかわりに、Co(NO3)2・6H2Oの800g、
およびMg(NO3)2・6H2Oの100gを用いる他は、調製例１と
同様にして触媒を調製した。Preparation Example 3 Fe in place of (NO 3) 3 · 9H 2 O, Co (NO 3) 2 · 6H 2 O in 800 g,
A catalyst was prepared in the same manner as in Preparation Example 1, except that 100 g of Mg (NO 3 ) 2 .6H 2 O was used.
調製例４ Fe(NO3)3・9H2Oのかわりに、Co(NO3)2・6H2Oの800g、
およびMn(NO3)2・6H2Oの100gを用いる他は、調製例１と
同様にして触媒を調製した。Preparation Example 4 800 g of Co (NO 3 ) 2 .6H 2 O instead of Fe (NO 3 ) 3 .9H 2 O,
A catalyst was prepared in the same manner as in Preparation Example 1, except that 100 g of Mn (NO 3 ) 2 .6H 2 O was used.
調製例５ Fe(NO3)3・9H2Oの600gのかわりに、Fe(NO3)3・9H2Oの
400g、およびCo(NO3)2・6H2Oの200g、を用いる他は、調
製例１と同様にして触媒を調製した。Instead of Preparation 5 Fe (NO 3) 3 · 9H 2 O in 600g, Fe (NO 3) 3 · 9H 2 O in
A catalyst was prepared in the same manner as in Preparation Example 1, except that 400 g and 200 g of Co (NO 3 ) 2 .6H 2 O were used.
比較調製例 1100gのAl(NO3)3・9H2O、125gのCr(NO3)3・9H2O、お
よび40gのMg(NO3)2・6H2Oを2.5リットルの水に溶解し、
これと28％の水酸化アンモニウムの水溶液2000gを攪拌
しながら、加熱した４リットルの水に添加して水酸化物
の沈殿を得た。これを別し、純水による洗浄、および
乾燥を行なった後、450℃で５時間焼成して酸化物の粉
末を得た。これを打錠成型機を用いて直径5mm、高さ5mm
の円筒状に成型した。こうして得た触媒を反応前にフッ
化水素／窒素の混合ガス気流中、300〜400℃でフッ素化
して、活性化した。Al of Comparative Preparation Example 1100g (NO 3) 3 · 9H 2 O, 125g of Cr (NO 3) 3 · 9H 2 O, and 40g of Mg (NO 3) was dissolved 2 · 6H 2 O 2.5 liters of water ,
This and 2,000 g of a 28% aqueous solution of ammonium hydroxide were added to 4 liters of heated water with stirring to obtain a hydroxide precipitate. This was separated, washed with pure water and dried, and then calcined at 450 ° C. for 5 hours to obtain an oxide powder. This is 5mm in diameter and 5mm in height using a tableting machine.
Into a cylindrical shape. The catalyst thus obtained was activated by fluorination at 300 to 400 ° C. in a hydrogen fluoride / nitrogen mixed gas stream before the reaction.
実施例１ 内径2.54cm、長さ100cmのインコネル600製Ｕ字型反応
管に調製例１で示したように調製した触媒を200ml充填
し反応させた。ガス化させたR-113aを200ml/分で、酸素
を2ml/分で、フッ酸を400ml/分で供給し、320℃に保持
した。酸分を除去した後のガス組成をガスクロを用いて
分析した。反応成績を表１に示す。Example 1 A U-shaped reaction tube made of Inconel 600 having an inner diameter of 2.54 cm and a length of 100 cm was filled with 200 ml of the catalyst prepared as shown in Preparation Example 1 and reacted. The gasified R-113a was supplied at a rate of 200 ml / min, oxygen was supplied at a rate of 2 ml / min, and hydrofluoric acid was supplied at a rate of 400 ml / min. The gas composition after removing the acid was analyzed using a gas chromatograph. The reaction results are shown in Table 1.
実施例２ 調製例２で調製した触媒を使用して、反応温度を350
℃とする他は実施例１と同様の条件で反応を行なった。
反応成績をまとめて表２に示す。 Example 2 Using the catalyst prepared in Preparation Example 2, the reaction temperature was 350
The reaction was carried out under the same conditions as in Example 1 except that the temperature was changed to ° C.
Table 2 summarizes the reaction results.
実施例３ 調製例３で調製した触媒を使用して、反応温度を300
℃とする他は実施例１と同様の条件で反応を行なった。
反応成績をまとめて表３に示す。 Example 3 Using the catalyst prepared in Preparation Example 3, the reaction temperature was 300
The reaction was carried out under the same conditions as in Example 1 except that the temperature was changed to ° C.
Table 3 summarizes the reaction results.
実施例４ 調製例４で調製した触媒を使用して、反応温度を300
℃とする他は実施例１と同様の条件で反応を行なった。
反応成績をまとめて表４に示す。 Example 4 The reaction temperature was set to 300 using the catalyst prepared in Preparation Example 4.
The reaction was carried out under the same conditions as in Example 1 except that the temperature was changed to ° C.
Table 4 summarizes the reaction results.
実施例５ 調製例５で調製した触媒を使用して、反応温度を350
℃とする他は実施例１と同様の条件で反応を行なった。
反応成績をまとめて表５に示す。 Example 5 Using the catalyst prepared in Preparation Example 5, the reaction temperature was 350
The reaction was carried out under the same conditions as in Example 1 except that the temperature was changed to ° C.
Table 5 summarizes the reaction results.
比較例 比較調製例で調製した触媒を使用して、反応温度を33
0℃とする他は実施例１と同様の条件で反応を行なっ
た。反応成績をまとめて表６に示す。 Comparative Example Using the catalyst prepared in Comparative Preparation Example,
The reaction was carried out under the same conditions as in Example 1 except that the temperature was changed to 0 ° C. Table 6 summarizes the reaction results.
［発明の効果］ 本発明は、実施例に示した如く、R-113aのフッ素化
を、従来知られているクロム系触媒より高選択的に行な
うことが可能となり、高効率でR-114aを製造し得るとい
う効果を有する。 [Effects of the Invention] As shown in the examples, the present invention makes it possible to carry out the fluorination of R-113a more selectively than conventionally known chromium-based catalysts, and to convert R-114a with high efficiency. It has the effect that it can be manufactured.
Claims (3)
れる少なくとも１種の元素を主成分とし、Crを含む酸化
物からなるフッ素化触媒の存在下、1,1,1−トリクロロ
−2,2,2−トリフルオロエタンとフッ化水素とを反応せ
しめることを特徴とする1,1−ジクロロ−1,2,2,2−テト
ラフルオロエタンの製造方法。1. The method according to claim 1, wherein the main component is at least one element selected from the group consisting of Fe, Ni, Co, and Mn, and 1,1,1-trichloroform is present in the presence of a fluorination catalyst comprising an oxide containing Cr. A method for producing 1,1-dichloro-1,2,2,2-tetrafluoroethane, comprising reacting 2,2,2-trifluoroethane with hydrogen fluoride.
れる少なくとも１種の元素を主成分とし、アルカリ金属
およびアルカリ土類金属から選ばれる少なくとも１種の
元素およびCrを含む酸化物からなるフッ素化触媒の存在
下、1,1,1−トリクロロ−2,2,2−トリフルオロエタンと
フッ化水素とを反応せしめることを特徴とする1,1−ジ
クロロ−1,2,2,2−テトラフルオロエタンの製造方法。2. An oxide containing at least one element selected from the group consisting of Fe, Ni, Co, and Mn as a main component, and at least one element selected from alkali metals and alkaline earth metals and Cr. Characterized in that 1,1,1-trichloro-2,2,2-trifluoroethane is reacted with hydrogen fluoride in the presence of a fluorination catalyst consisting of 1,1-dichloro-1,2,2 For producing 1,2-tetrafluoroethane.
エタンとフッ化水素との反応を気相中常圧もしくは加圧
下で、200℃〜550℃の温度範囲で行なう請求項１〜２の
いずれか１項に記載の製造方法。3. The method according to claim 1, wherein the reaction of 1,1,1-trichloro-2,2,2-trifluoroethane with hydrogen fluoride is carried out in a gas phase at normal pressure or under pressure at a temperature in the range of 200 ° C. to 550 ° C. Item 3. The method according to any one of Items 1 to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1128683A JP2751401B2 (en) | 1989-05-24 | 1989-05-24 | Method for producing 1,1-dichloro-1,2,2,2-tetrafluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1128683A JP2751401B2 (en) | 1989-05-24 | 1989-05-24 | Method for producing 1,1-dichloro-1,2,2,2-tetrafluoroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02311429A JPH02311429A (en) | 1990-12-27 |
| JP2751401B2 true JP2751401B2 (en) | 1998-05-18 |
Family
ID=14990849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1128683A Expired - Fee Related JP2751401B2 (en) | 1989-05-24 | 1989-05-24 | Method for producing 1,1-dichloro-1,2,2,2-tetrafluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2751401B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9104775D0 (en) * | 1991-03-07 | 1991-04-17 | Ici Plc | Fluorination catalyst and process |
| FR2684567B1 (en) * | 1991-12-09 | 1994-11-04 | Atochem | MASS CATALYSTS BASED ON CHROME AND NICKEL OXIDES AND THEIR APPLICATION TO THE FLUORINATION OF HALOGENATED HYDROCARBONS. |
-
1989
- 1989-05-24 JP JP1128683A patent/JP2751401B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02311429A (en) | 1990-12-27 |
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