JPH11140002A - Production of 1,3,3,3-tetrafluoropropene - Google Patents
Production of 1,3,3,3-tetrafluoropropeneInfo
- Publication number
- JPH11140002A JPH11140002A JP30854197A JP30854197A JPH11140002A JP H11140002 A JPH11140002 A JP H11140002A JP 30854197 A JP30854197 A JP 30854197A JP 30854197 A JP30854197 A JP 30854197A JP H11140002 A JPH11140002 A JP H11140002A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- tetrafluoropropene
- pentafluoropropane
- activated carbon
- temperature
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、トリフルオロメチル基
の導入試剤、医農薬、ポリマー、機能性材料の中間原料
あるいは冷媒等として有用な１，３，３，３−テトラフ
ルオロプロペンの製造方法に関する。The present invention relates to a process for producing 1,3,3,3-tetrafluoropropene useful as a reagent for introducing a trifluoromethyl group, an intermediate material for medicines and agrochemicals, polymers, functional materials or as a refrigerant. About.
【０００２】[0002]
【従来技術】１，３，３，３−テトラフルオロプロペン
の製造方法としては、従来、１，３，３，３−テトラフ
ルオロ−１−ヨウ化プロパンをアルコール性水酸化カリ
ウムにより脱ヨウ化水素する方法（Ｒ．Ｎ．Ｈａｓｚｅ
ｌｄｉｎｅら，Ｊ．Ｃｈｅｍ．Ｓｏｃ．１９５３，１１
９９−１２０６； ＣＡ ４８ ５７８７ｆ）または
１，１，１，３，３−ペンタフルオロプロパンをジブチ
ルエーテル中で水酸化カリウムにより脱フッ化水素する
方法（Ｉ．Ｌ．Ｋｎｕｎｙａｎｔｓら，Ｉｚｖｅｓｔ．
Ａｋａｄ．Ｎａｕｋ Ｓ．Ｓ．Ｓ．Ｒ．，Ｏｔｄｅｌ．
Ｋｈｉｍ．Ｎａｕｋ．１９６０，１４１２−１８；ＣＡ
５５，３４９ｆ）等が知られている。2. Description of the Related Art As a method for producing 1,3,3,3-tetrafluoropropene, conventionally, 1,3,3,3-tetrafluoro-1-propane iodide is dehydroiodated with alcoholic potassium hydroxide. Method (RN Hasze)
ldine et al. Chem. Soc. 1953, 11
99-4206; CA 48 5787f) or a method of dehydrofluorinating 1,1,1,3,3-pentafluoropropane with potassium hydroxide in dibutyl ether (IL Kunyanants et al., Izvest.
Akad. Nauk S.D. S. S. R. , Otdel.
Khim. Nauk. 1960, 1412-18; CA
55, 349f) and the like are known.
【０００３】また、含フッ素プロパンから脱フッ化水素
させて含フッ素プロペンを製造する方法としては、２，
２−ジフルオロロプロパンを７３１℃に加熱してして１
ｔ−フルオロプロペンを製造する方法（Austin et al.,
J. Am. Chem. Soc 75[1953]4834)、１，１，１−トリ
フルオロプロパンを８３０〜８５０℃に加熱して１，１
−ジフルオロプロペンを製造する方法（Kinetic Chemic
al. Inc., U.S.P.2480560[1945]）が知られている。[0003] Further, as a method for producing fluorinated propene by dehydrofluorination from fluorinated propane, there are two methods:
Heat 2-difluoropropane to 731 ° C. to give 1
Method for producing t-fluoropropene (Austin et al.,
J. Am. Chem. Soc 75 [1953] 4834), 1,1,1-trifluoropropane was heated to 830 to 850 ° C.
-Method for producing difluoropropene (Kinetic Chemic
al. Inc., USP2480560 [1945]).
【０００４】[0004]
【発明が解決しようとする課題】上記のような水酸化カ
リウムにより脱ハロゲン化水素する方法は、反応率およ
び選択率に優れた方法ではあるが、水酸化カリウムが化
学量論量以上必要であること、また原料である１，３，
３，３−テトラフルオロ−１−ヨウ化プロパンを予め調
製しなければならず、工業的に適用するには困難な点が
多い。The above-mentioned method of dehydrohalogenating with potassium hydroxide is excellent in the reaction rate and selectivity, but requires a stoichiometric amount of potassium hydroxide. And the raw materials 1,3
3,3-Tetrafluoro-1-propane iodide must be prepared in advance, and there are many difficulties for industrial application.
【０００５】一方、脱フッ化水素による方法は原料以外
の反応試剤を特に必要とせず、工業的に好ましいが、前
記のように７００℃以上という高温度を必要とするとい
う問題点があった。[0005] On the other hand, the method using dehydrofluorination does not require a reaction reagent other than the raw material, and is industrially preferable. However, there is a problem that a high temperature of 700 ° C or more is required as described above.
【０００６】[0006]
【課題を解決するための具体的手段】本発明者らは、工
業的規模で入手できるかもしくは工業的規模で入手でき
る原料から比較的容易に製造可能な物質を原料とする
１，３，３，３−テトラフルオロプロペンの製造法につ
いて検討したところ、１，１，１，３，３−ペンタフル
オロプロペンを原料とし、これを気相中で特定の温度以
上にすることで１，３，３，３−テトラフルオロプロペ
ンが得られ、また、触媒として活性炭またはクロム化合
物等の金属化合物を担持した活性炭を用いることが特に
好適であることも併せて見いだし、本発明に到達した。SUMMARY OF THE INVENTION The present inventors have made 1,3,3 a starting material which can be obtained on an industrial scale or which can be relatively easily produced from raw materials available on an industrial scale. A study was conducted on a method for producing 1,3,3-tetrafluoropropene. As a result, 1,1,1,3,3-pentafluoropropene was used as a raw material, and the temperature was raised to a specific temperature or higher in a gaseous phase. , 3-tetrafluoropropene was obtained, and it was also found that it is particularly preferable to use activated carbon or activated carbon carrying a metal compound such as a chromium compound as a catalyst, and have reached the present invention.
【０００７】すなわち、本発明は、１，１，１，３，３
−ペンタフルオロプロパンを気相中で高められた温度の
反応領域に通じることからなる１，３，３，３−テトラ
フルオロプロペンの製造法である。That is, the present invention relates to 1,1,1,3,3
A process for producing 1,3,3,3-tetrafluoropropene, which comprises passing pentafluoropropane in a gas phase to a reaction zone at an elevated temperature.
【０００８】本発明に使用する１，１，１，３，３−ペ
ンタフルオロプロパンの製造方法は特に限定されない。
例えば、一般式ＣＦYＣｌ3-YＣＨ2ＣＨＦWＣｌ2-W（式
中、Ｗは０または１、Ｙは０〜３の整数を表す。）で表
されるプロパン類を触媒の存在下液相においてフッ化水
素でフッ素化する方法、特に１，１，１，３，３−ペン
タクロロプロパンをフッ化水素により液相フッ素化して
製造する方法であって、触媒としてアンチモン化合物を
使用する方法、または１，１，１，３，３−ペンタクロ
ロプロパンあるいは１−クロロ−３，３，３−トリフル
オロプロペンをクロム触媒の存在下気相においてフッ化
水素でフッ素化する方法によって製造したものを挙げる
ことができる。[0008] The method for producing 1,1,1,3,3-pentafluoropropane used in the present invention is not particularly limited.
For example, propane represented by the general formula CF Y Cl 3-Y CH 2 CHF W Cl 2-W (where W represents 0 or 1, and Y represents an integer of 0 to 3) in the presence of a catalyst. A method of fluorinating with hydrogen fluoride in a liquid phase, particularly a method of producing 1,1,1,3,3-pentachloropropane by liquid-phase fluorination with hydrogen fluoride, wherein an antimony compound is used as a catalyst Or 1,1,1,3,3-pentachloropropane or 1-chloro-3,3,3-trifluoropropene produced by a method of fluorinating with hydrogen fluoride in the gas phase in the presence of a chromium catalyst. Can be mentioned.
【０００９】本発明の方法は、フッ化水素に対して実質
的に不活性な材質で造られた反応器の温度を高めた反応
領域へ１，１，１，３，３−ペンタフルオロプロパンを
導入することでおこなわれる。容器は通常、管状であっ
てステンレス鋼、ハステロイ、モネル、白金、炭素また
はこれらをライニングした材質が用いられる。この反応
器は中空であってもよく、またフッ化水素に対して実質
的に不活性な材質で造られた各種の形状の充填剤を有し
ていてもよい。充填剤としては、白金、ニッケル、金、
銀、炭素などが用いられるが、炭素からなるものが特に
好ましい。 この充填剤として用いられる炭素は通常活
性炭であり、木材、のこくず、木炭、椰子殻炭、パーム
核炭、素灰などを原料とする植物質系、泥炭、亜炭、褐
炭、瀝青単、無煙炭などを原料とする石炭系、石油残
渣、硫酸スラッジ、オイルカーボンなどを原料とする石
油系あるいは合成樹脂を原料とするものなどがある。こ
のような活性炭は、各種のものが市販されているのでそ
れらのうちから選んで使用すればよい。例えば、瀝青炭
から製造された活性炭（例えば、カルゴン粒状活性炭Ｃ
ＡＬ（東洋カルゴン（株）製）、椰子殻炭（例えば、武
田薬品工業（株）製）などを挙げることができるが、当
然これらの種類、製造業者に限られることはない。ま
た、これらの活性炭は通常粒状で使用するが、その形
状、大きさは特に限定されず、通常の知識をもって反応
器の大きさを基準に決定することができる。The process of the present invention comprises the steps of: adding 1,1,1,3,3-pentafluoropropane to an elevated temperature reaction zone of a reactor made of a material substantially inert to hydrogen fluoride. It is done by introducing. The container is usually tubular and made of stainless steel, Hastelloy, Monel, platinum, carbon or a material lined with these. The reactor may be hollow or may have various shapes of fillers made of a material that is substantially inert to hydrogen fluoride. Fillers include platinum, nickel, gold,
Silver, carbon and the like are used, and those made of carbon are particularly preferable. The carbon used as the filler is usually activated carbon, and is a plant based on wood, sawdust, charcoal, coconut husk charcoal, palm kernel charcoal, ash, etc., peat, lignite, lignite, bituminous, anthracite And the like, and petroleum based on petroleum residue, sulfuric acid sludge, oil carbon or the like as a raw material or synthetic resin as a raw material. Since various types of such activated carbons are commercially available, they may be selected and used. For example, activated carbon produced from bituminous coal (for example, granular activated carbon C
AL (manufactured by Toyo Calgon Co., Ltd.), coconut shell charcoal (eg, manufactured by Takeda Pharmaceutical Co., Ltd.) and the like can be cited, but are not limited to these types and manufacturers. These activated carbons are usually used in the form of granules, but their shape and size are not particularly limited, and can be determined based on the size of the reactor with ordinary knowledge.
【００１０】また、この活性炭は、アルミニウム、クロ
ム、マンガン、ニッケル、コバルト、チタンの中から選
ばれる１種または２種以上の金属の酸化物、フッ化物、
塩化物、フッ化塩化物、オキシフッ化物、オキシ塩化
物、オキシフッ化塩化物等を担持した活性炭であっても
よい。[0010] The activated carbon may be an oxide, a fluoride of one or more metals selected from aluminum, chromium, manganese, nickel, cobalt and titanium.
Activated carbon carrying chloride, fluoride chloride, oxyfluoride, oxychloride, oxyfluoride chloride or the like may be used.
【００１１】これらの金属担持活性炭触媒を調製する方
法は限定されないが、活性炭そのまま、または予めフッ
化水素、塩化水素、塩素化フッ素化炭化水素などにより
ハロゲンで修飾された活性炭にクロム、チタン、マンガ
ン、ニッケル、コバルトの中から選ばれる１種または２
種以上の金属の可溶性化合物を溶解した溶液を含浸する
か、スプレーすることで調製される。The method of preparing these metal-supported activated carbon catalysts is not limited, but chromium, titanium, manganese can be added to activated carbon as it is or to activated carbon previously modified with halogen such as hydrogen fluoride, hydrogen chloride, or chlorinated fluorinated hydrocarbon. One or two selected from nickel, nickel and cobalt
It is prepared by impregnating or spraying a solution of a soluble compound of one or more metals.
【００１２】金属担持量は０．１〜８０ｗｔ％、好まし
くは１〜４０ｗｔ％が適当である。活性炭に担持させる
金属の可溶性化合物としては、水、エタノール、アセト
ンなどの溶媒に溶解する該当金属の硝酸塩、塩化物、酸
化物などが挙げられる。具体的には、硝酸クロム、三塩
化クロム、三酸化クロム、重クロム酸カリウム、三塩化
チタン、硝酸マンガン、塩化マンガン、二酸化マンガ
ン、硝酸ニッケル、塩化ニッケル、硝酸コバルト、塩化
コバルトなどを用いることができる。The amount of the metal carried is 0.1 to 80% by weight, preferably 1 to 40% by weight. Examples of the soluble compound of the metal supported on the activated carbon include nitrates, chlorides and oxides of the metal dissolved in a solvent such as water, ethanol and acetone. Specifically, chromium nitrate, chromium trichloride, chromium trioxide, potassium dichromate, titanium trichloride, manganese nitrate, manganese chloride, manganese dioxide, nickel nitrate, nickel chloride, cobalt nitrate, cobalt chloride, etc. may be used. it can.
【００１３】何れの方法で金属を担持した触媒も、使用
の前に所定の反応温度以上の温度で予めフッ化水素、フ
ッ素化（および塩素化）炭化水素などのフッ素化剤で処
理し、反応中の触媒の組成変化を防止することが有効で
ある。また、反応中に酸素、塩素、フッ素化または塩素
化炭化水素などを反応器中に供給することは触媒寿命の
延長、反応率、反応収率の向上に有効である。[0013] The catalyst supporting the metal by any method is treated with a fluorinating agent such as hydrogen fluoride or fluorinated (and chlorinated) hydrocarbon at a temperature higher than a predetermined reaction temperature before use. It is effective to prevent a change in the composition of the catalyst inside. Supplying oxygen, chlorine, fluorinated or chlorinated hydrocarbons, etc. into the reactor during the reaction is effective for extending the life of the catalyst, improving the reaction rate, and improving the reaction yield.
【００１４】本発明の方法の反応温度は２００〜６００
℃、好ましくは２５０〜５００℃であり、反応温度２０
０℃よりも低ければ反応は遅く実用的ではない。反応温
度が６００℃を超えても特に反応率は向上せず、分解生
成物、二量化物等が生成し、１，３，３，３−テトラフ
ルオロプロペンの選択率が低下するので好ましくない。The reaction temperature of the process according to the invention is between 200 and 600.
C., preferably 250-500.degree.
If it is lower than 0 ° C., the reaction is slow and not practical. If the reaction temperature exceeds 600 ° C., the reaction rate is not particularly improved, and decomposition products and dimers are formed, and the selectivity of 1,3,3,3-tetrafluoropropene decreases, which is not preferable.
【００１５】本発明の方法において、反応領域へ供給す
る１，１，１，３，３−ペンタフルオロプロパンは、窒
素、ヘリウム、アルゴンなどの不活性ガスを同時に供給
してもよい。また、フッ化水素を共存させてもよい。In the method of the present invention, the 1,1,1,3,3-pentafluoropropane supplied to the reaction zone may be supplied simultaneously with an inert gas such as nitrogen, helium or argon. Further, hydrogen fluoride may be allowed to coexist.
【００１６】反応圧力は特に限定されないが、装置の面
から０．１〜１０ｋｇ／ｃｍ2で行うのが好ましい。系
内に存在する原料有機物とフッ化水素が、反応系内で液
化しないような条件を選ぶことが望ましい。接触時間
は、通常０．１〜３００秒、好ましくは５〜２００秒で
ある。The reaction pressure is not particularly limited, but is preferably 0.1 to 10 kg / cm 2 from the viewpoint of the apparatus. It is desirable to select conditions so that the raw material organic matter and hydrogen fluoride present in the system do not liquefy in the reaction system. The contact time is usually 0.1 to 300 seconds, preferably 5 to 200 seconds.
【００１７】本発明の方法により処理されて反応器より
流出する１，３，３，３−テトラフルオロプロペンを含
む生成物は、公知の方法で精製されて製品となる。精製
方法は限定されないが、例えば、生成物を最初に水また
は／およびアルカリ性溶液で洗浄して塩化水素、フッ化
水素などの酸性物質を除去し、乾燥の後、蒸留に付して
有機不純物を除くことで行うことができる。The product containing 1,3,3,3-tetrafluoropropene which is treated by the method of the present invention and flows out of the reactor is purified by a known method to obtain a product. The purification method is not limited. For example, the product is first washed with water or / and an alkaline solution to remove acidic substances such as hydrogen chloride and hydrogen fluoride, and after drying, subjected to distillation to remove organic impurities. It can be done by removing.
【００１８】本発明の方法においては、生成物の１，
３，３，３−テトラフルオロプロペンはトランス体とシ
ス体の混合物として得られるが、シス体は原料の１，
１，１，３，３−ペンタフルオロプロパンと沸点が近
く、しかも共沸様の挙動を示すので容易に分離できな
い。そこで、１，３，３，３−テトラフルオロプロペン
のトランス体およびシス体並びに１，１，１，３，３−
ペンタフルオロプロパンからなる混合物（生成物）を蒸
留してトランス体のみを回収し、残りのシス体と１，
１，１，３，３−ペンタフルオロプロパンを分離するこ
となく、再び本発明の反応に供することができる。すな
わち、分離回収の困難なシス体を敢えて分離することな
く、トランス体として回収することで高純度の１，３，
３，３−テトラフルオロプロペンを製造することができ
る。In the process of the present invention, the product 1,
3,3,3-Tetrafluoropropene can be obtained as a mixture of a trans form and a cis form, and the cis form is 1,1,
The boiling point is close to that of 1,1,3,3-pentafluoropropane, and it exhibits an azeotropic behavior, so that it cannot be easily separated. Thus, trans and cis forms of 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-
The mixture (product) consisting of pentafluoropropane was distilled to recover only the trans form, and the remaining cis form and 1,1
Without separating 1,1,3,3-pentafluoropropane, it can be used again for the reaction of the present invention. In other words, the cis-isomer, which is difficult to separate and recover, is not deliberately separated, but is recovered as a trans-isomer, so that 1,3,
3,3-tetrafluoropropene can be produced.
【００１９】[0019]
【実施例】［調製例１］３００ｇの特級試薬Ｃｒ（ＮＯ
3）3・９Ｈ2Ｏを１リットルの純水に溶かした溶液に、
直径４〜６ｍｍ、表面積１２００ｍ2／ｇ、細孔径１８
Ａの粒状活性炭（武田薬品工業、粒状白鷺ＧＸ）１．８
リットルを浸漬し、一昼夜放置した。次に濾過して活性
炭を取り出し、熱風循環式乾燥器中で１００℃に保ち、
さらに一昼夜乾燥した。得られたクロム担持活性炭を加
熱装置を備えた直径３．５ｃｍ長さ１５０ｃｍの円筒形
ＳＵＳ３１６Ｌ製反応管に充填し、窒素ガスを流しなが
ら３００℃まで昇温し、水の排出が見られなくなった時
点で、窒素ガスにフッ化水素を同伴させその濃度を徐々
に高め、反応器温度を３５０℃に上げ、その状態を１時
間保ち触媒の調製を行った。 ［実施例１］外部加熱装置により加熱する円筒形反応管
からなる気相反応装置（ＳＵＳ３１６Ｌ製、直径２．５
ｃｍ・長さ４０ｃｍ）に気相フッ素化触媒として調製例
１で調製した触媒を１５０ミリリットル充填した。約５
０ｍｌ／分の流量で窒素ガスを流しながら反応管の温度
を３８０℃に上げ、フッ化水素を約０．３ｇ／分の速度
で１時間にわたり導入し続けた。フッ化水素の導入を停
止し、窒素ガスの流量を２０ｍｌ／分に減らし、原料有
機物として１，１，１，３，３−ペンタフルオロプロペ
ンを予め気化させて０．４４ｇ／分の速度で反応器へ供
給開始した。EXAMPLES [Preparation Example 1] 300 g of a special grade reagent Cr (NO
3) the 3 · 9H 2 O to a solution of pure water 1 liter,
Diameter 4-6 mm, surface area 1200 m 2 / g, pore size 18
A granular activated carbon (Takeda Pharmaceutical Co., Ltd., granular Shirasagi GX) 1.8
Liters were immersed and left overnight. Next, the activated carbon was filtered out and kept at 100 ° C. in a hot-air circulation dryer.
It was dried all day and night. The obtained chromium-supported activated carbon was filled into a cylindrical SUS316L reaction tube having a diameter of 3.5 cm and a length of 150 cm equipped with a heating device, and heated to 300 ° C. while flowing a nitrogen gas. At this time, the concentration of hydrogen fluoride was gradually increased by entraining hydrogen gas into the nitrogen gas, the reactor temperature was raised to 350 ° C., and the state was maintained for 1 hour to prepare a catalyst. [Example 1] A gas phase reactor (made of SUS316L, having a diameter of 2.5) comprising a cylindrical reaction tube heated by an external heater.
cm./length 40 cm) was filled with 150 ml of the catalyst prepared in Preparation Example 1 as a gas phase fluorination catalyst. About 5
The temperature of the reaction tube was raised to 380 ° C. while flowing nitrogen gas at a flow rate of 0 ml / min, and hydrogen fluoride was continuously introduced at a rate of about 0.3 g / min for 1 hour. The introduction of hydrogen fluoride was stopped, the flow rate of nitrogen gas was reduced to 20 ml / min, and 1,1,1,3,3-pentafluoropropene was vaporized as a raw material organic material in advance and reacted at a rate of 0.44 g / min. Supply to the vessel started.
【００２０】反応開始１時間後には反応は安定したの
で、反応器から排出する生成ガスを水中に吹き込み酸性
ガスを除去した後、ドライアイス−アセトン−トラップ
で捕集した。捕集した有機物をガスクロマトグラフィー
で分析した結果を表１に示した。One hour after the start of the reaction, the reaction was stable. The product gas discharged from the reactor was blown into water to remove acidic gas, and then collected by a dry ice-acetone trap. The results of analyzing the collected organic matter by gas chromatography are shown in Table 1.
【００２１】[0021]
【表１】 [Table 1]
【００２２】［実施例２］外部加熱装置により加熱する
円筒形反応管からなる気相反応装置（ＳＵＳ３１６Ｌ
製、直径２．５ｃｍ・長さ４０ｃｍ）に気相フッ素化触
媒として調製例１で調製した触媒を１５０ミリリットル
充填した。約５０ｍｌ／分の流量で窒素ガスを流しなが
ら反応管の温度を３８０℃に上げ、フッ化水素を約０．
３ｇ／分の速度で１時間にわたり導入し続けた。次に反
応管の温度を３５０℃に下げ、フッ化水素の供給を停止
し、窒素ガスの流量を２０ｍｌ／分に減らし、原料有機
物として１，１，１，３，３−ペンタフルオロプロパン
を予め気化させて０．４８ｇ／分の速度で反応器へ供給
開始した。Example 2 A gas phase reactor (SUS316L) comprising a cylindrical reaction tube heated by an external heater
(Diameter: 2.5 cm, length: 40 cm) was charged with 150 ml of the catalyst prepared in Preparation Example 1 as a gas phase fluorination catalyst. The temperature of the reaction tube was raised to 380 ° C. while flowing nitrogen gas at a flow rate of about 50 ml / min, and about 0.2 ml of hydrogen fluoride was added.
The introduction was continued at a rate of 3 g / min for 1 hour. Next, the temperature of the reaction tube was lowered to 350 ° C., the supply of hydrogen fluoride was stopped, the flow rate of nitrogen gas was reduced to 20 ml / min, and 1,1,1,3,3-pentafluoropropane was previously used as a raw material organic substance. It was vaporized and started feeding to the reactor at a rate of 0.48 g / min.
【００２３】反応開始１時間後には反応は安定したの
で、反応器から流出する生成ガスを水中に吹き込み酸性
ガスを除去した後、ドライアイス−アセトン−トラップ
で捕集した。捕集した有機物をガスクロマトグラフィー
で分析した結果を表１に示した。Since the reaction was stable one hour after the start of the reaction, the product gas flowing out of the reactor was blown into water to remove the acidic gas, and then collected with a dry ice-acetone trap. The results of analyzing the collected organic matter by gas chromatography are shown in Table 1.
【００２４】［実施例３］１，１，１，３，３−ペンタ
フルオロプロパンを反応温度３００℃で反応させる以外
実施例２と同様に反応を行った。結果を表１に示す。Example 3 A reaction was carried out in the same manner as in Example 2 except that 1,1,1,3,3-pentafluoropropane was reacted at a reaction temperature of 300 ° C. Table 1 shows the results.
【００２５】［実施例４］外部加熱装置により加熱する
円筒形反応管からなる気相反応装置（ＳＵＳ３１６Ｌ
製、直径２．５ｃｍ・長さ４０ｃｍ）に気相フッ素化触
媒として調製例１で調製した触媒を１５０ミリリットル
充填した。約１５０ｍｌ／分の流量で窒素ガスを流しな
がら反応管の温度を３８０℃に上げ、フッ化水素を約
０．２８ｇ／分の速度で１時間にわたり導入し続けた。
反応管の温度を２５５℃に下げ、フッ化水素の供給量、
窒素ガスの流量をそのままにして、原料有機物として
１，１，１，３，３−ペンタフルオロプロパンを予め気
化させて０．２１ｇ／分の速度で反応器へ供給開始し
た。Example 4 A gas phase reactor (SUS316L) comprising a cylindrical reaction tube heated by an external heater
(Diameter: 2.5 cm, length: 40 cm) was charged with 150 ml of the catalyst prepared in Preparation Example 1 as a gas phase fluorination catalyst. The temperature of the reaction tube was raised to 380 ° C. while flowing nitrogen gas at a flow rate of about 150 ml / min, and hydrogen fluoride was continuously introduced at a rate of about 0.28 g / min for 1 hour.
Reduce the temperature of the reaction tube to 255 ° C.,
With the flow rate of the nitrogen gas kept as it was, 1,1,1,3,3-pentafluoropropane was vaporized in advance as a raw material organic substance, and supply to the reactor was started at a rate of 0.21 g / min.
【００２６】反応開始１時間後には反応は安定したの
で、反応器から排出する生成ガスを水中に吹き込み酸性
ガスを除去した後、ドライアイス−アセトン−トラップ
で捕集した。捕集した有機物をガスクロマトグラフィー
で分析した結果を表１に示した。One hour after the start of the reaction, the reaction was stable. The product gas discharged from the reactor was blown into water to remove the acidic gas, and then collected with a dry ice-acetone trap. The results of analyzing the collected organic matter by gas chromatography are shown in Table 1.
【００２７】[0027]
【発明の効果】本発明の１，３，３，３−テトラフルオ
ロプロペンの製造法は、１，１，１，３，３−ペンタフ
ルオロプロパンを原料とし、連続的に１，３，３，３−
テトラフルオロプロペンを製造できるので、工業的な製
造法として有用である。According to the process for producing 1,3,3,3-tetrafluoropropene of the present invention, 1,1,1,3,3-pentafluoropropane is used as a raw material and 3-
Since tetrafluoropropene can be produced, it is useful as an industrial production method.
Claims (3)
パンを気相中で高められた温度の反応領域に通じること
からなる１，３，３，３−テトラフルオロプロペンの製
造法。1. A process for producing 1,3,3,3-tetrafluoropropene, which comprises passing 1,1,1,3,3-pentafluoropropane in a gas phase to a reaction zone at an elevated temperature.
れた炭素である請求項１記載の１，３，３，３−テトラ
フルオロプロペンの製造法。2. The method for producing 1,3,3,3-tetrafluoropropene according to claim 1, wherein the reaction region is carbon or carbon carrying a metal compound.
がトランス体およびシス体からなる１，３，３，３−テ
トラフルオロプロペンである請求項１記載の１，３，
３，３−テトラフルオロプロペンの製造法。3. The 1,3,3,3-tetrafluoropropene according to claim 1, wherein the 1,3,3,3-tetrafluoropropene is a 1,3,3,3-tetrafluoropropene comprising a trans form and a cis form.
A method for producing 3,3-tetrafluoropropene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30854197A JP3886229B2 (en) | 1997-11-11 | 1997-11-11 | Method for producing 1,3,3,3-tetrafluoropropene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30854197A JP3886229B2 (en) | 1997-11-11 | 1997-11-11 | Method for producing 1,3,3,3-tetrafluoropropene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11140002A true JPH11140002A (en) | 1999-05-25 |
| JP3886229B2 JP3886229B2 (en) | 2007-02-28 |
Family
ID=17982277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30854197A Expired - Fee Related JP3886229B2 (en) | 1997-11-11 | 1997-11-11 | Method for producing 1,3,3,3-tetrafluoropropene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3886229B2 (en) |
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