JP3886229B2 - Method for producing 1,3,3,3-tetrafluoropropene - Google Patents
Method for producing 1,3,3,3-tetrafluoropropene Download PDFInfo
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- JP3886229B2 JP3886229B2 JP30854197A JP30854197A JP3886229B2 JP 3886229 B2 JP3886229 B2 JP 3886229B2 JP 30854197 A JP30854197 A JP 30854197A JP 30854197 A JP30854197 A JP 30854197A JP 3886229 B2 JP3886229 B2 JP 3886229B2
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- tetrafluoropropene
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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【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。
【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.Haszeldineら,J.Chem.Soc.1953,1199−1206; 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。
【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1t−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 Chemical. Inc., U.S.P.2480560[1945])が知られている。
【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。
【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。
【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、気相中クロム化合物を担持した活性炭触媒の存在下、350〜600℃の反応領域に通じることで、好適に1,3,3,3−テトラフルオロプロペンが製造できることを見出し、本発明に到達した。
【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クロム化合物を担持した活性炭触媒の存在下、350〜600℃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。
【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。
【0009】
本発明の方法は、気相中、クロム化合物を担持した活性炭触媒の存在下、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350〜600℃にした反応領域へ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。この反応器は充填剤として活性炭を有している。活性炭としては、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CAL(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。
【0010】
この活性炭は、クロム金属の酸化物、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ている。
【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。
【0012】
金属の担持量は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、三酸化クロムなどを用いることができる。
【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。
【0014】
本発明の方法の反応温度は350〜600℃である。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。
【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。
【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。
【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。
【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。
【0019】
【実施例】
[調製例1]
300gの特級試薬Cr(NO3)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18A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2.5cm・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。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。
【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。
【0021】
【表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。
【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。
【0024】
[比較例1]
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。
【0025】
[比較例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。
【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。
【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。[0001]
[Industrial application fields]
The present invention relates to a method for producing 1,3,3,3-tetrafluoropropene useful as an agent for introducing a trifluoromethyl group, a pharmaceutical or agricultural chemical, a polymer, an intermediate raw material for a functional material, a refrigerant, or the like.
[0002]
[Prior art]
As a method for producing 1,3,3,3-tetrafluoropropene, a conventional method in which 1,3,3,3-tetrafluoro-1-iodopropane is dehydroiodized with alcoholic potassium hydroxide (R N. Haszeldine et al., J. Chem. Soc. 1953, 1199-1206; CA 48 5787f) or 1,1,1,3,3-pentafluoropropane is dehydrofluorinated with potassium hydroxide in dibutyl ether. The method (IL Knunants et al., Izbest. Akad. Nauk SSR, Otdel. Khim. Nauk. 1960, 1412-18; CA 55, 349f) and the like are known.
[0003]
As a method for producing a fluorine-containing propene by dehydrofluorination a fluorinated propane, 2,2-difluoro b propane a method of manufacturing a heated 1t- tetrafluoropropene to 731 ℃ (Austin et al., J. Am. Chem. Soc 75 [1953] 4834), 1,1,1-trifluoropropane heated to 830-850 ° C. to produce 1,1-difluoropropene (Kinetic Chemical. Inc., USP2480560 [1945]) is known.
[0004]
[Problems to be solved by the invention]
The method of dehydrohalogenating with potassium hydroxide as described above is a method having excellent reaction rate and selectivity, but potassium hydroxide is required to be a stoichiometric amount or more, and 1,3 which is a raw material. , 3,3-tetrafluoro-1-iodopropane has to be prepared in advance, which is difficult to apply industrially.
[0005]
On the other hand, the method using dehydrofluorination does not particularly require a reaction reagent other than the raw material and is industrially preferable, but has a problem that it requires a high temperature of 700 ° C. or higher as described above.
[0006]
[Specific means for solving the problem]
The present inventors have studied a method for producing 1,3,3,3-tetrafluoropropene using as a raw material a material that can be obtained on an industrial scale or can be produced relatively easily from a raw material available on an industrial scale. As a result, 1,1,1,3,3-pentafluoropropene was used as a raw material, and in the presence of an activated carbon catalyst supporting a chromium compound in the gas phase, the reaction region at 350 to 600 ° C. led to 1, The inventors have found that 3,3,3-tetrafluoropropene can be produced and have reached the present invention.
[0007]
That is, the present invention consists in passing 1,1,1,3,3-pentafluoropropane through a reaction region of 350 to 600 ° C. in the presence of an activated carbon catalyst carrying a chromium compound in the gas phase. , 3,3-tetrafluoropropene.
[0008]
The method for producing 1,1,1,3,3-pentafluoropropane used in the present invention is not particularly limited. For example, propanes represented by the general formula CF Y Cl 3 -Y CH 2 CHF W Cl 2 -W (wherein W represents 0 or 1, Y represents an integer of 0 to 3) in the presence of a catalyst. 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, using an antimony compound as a catalyst Or 1,1,1,3,3-pentachloropropane or 1-chloro-3,3,3-trifluoropropene produced by fluorination with hydrogen fluoride in the gas phase in the presence of a chromium catalyst Can be mentioned.
[0009]
The method of the present invention is a reaction in which the temperature of a reactor made of a material substantially inert to hydrogen fluoride is 350 to 600 ° C. in the presence of an activated carbon catalyst supporting a chromium compound in the gas phase. This is done by introducing 1,3,3-pentafluoropropane into the region . The container is usually tubular and is made of stainless steel, hastelloy, monel, platinum, carbon or a material lined with these. This reactor has activated carbon as a filler. The activated carbon includes vegetation based on wood, sawdust, charcoal, coconut shell charcoal, palm kernel charcoal, and raw ash, coal based on peat, lignite, lignite, bituminous and anthracite, petroleum There are those using petroleum-based or synthetic resin as a raw material, such as residue, sulfuric acid sludge, oil carbon and the like. Since such activated carbon is commercially available, it can be selected from among them. For example, activated carbon produced from bituminous coal (for example, Calgon granular activated carbon CAL (manufactured by Toyo Calgon Co., Ltd.), coconut shell charcoal (eg, manufactured by Takeda Pharmaceutical Co., Ltd.), etc. can be mentioned. However, these activated carbons are usually used in granular form, but the shape and size are not particularly limited, and can be determined based on the size of the reactor with ordinary knowledge. it can.
[0010]
The activated carbon, oxides of chromium metal, fluoride, chloride, fluoride chloride, oxyfluoride, oxychloride, and carries oxyfluoride chlorides.
[0011]
The method for preparing these metal-supported activated carbon catalysts is not limited. However, the soluble compound of chromium metal is dissolved in the activated carbon as it is, or in activated carbon modified in advance with halogen such as hydrogen fluoride, hydrogen chloride, chlorinated fluorinated hydrocarbon or the like. Prepared by impregnating or spraying the solution.
[0012]
Supported amount of metal is 0.1~80wt%, preferably is 1-40 wt% suitable. Examples of the soluble compound of the metal supported on the activated carbon include nitrates, chlorides, oxides, and the like of the corresponding metal that dissolves in a solvent such as water, ethanol, and acetone. Specifically, chromium nitrate, chromium trichloride, chromium trioxide, or the like can be used.
[0013]
A catalyst carrying a metal by any method is treated with a fluorinating agent such as hydrogen fluoride, fluorinated (and chlorinated) hydrocarbon in advance at a temperature equal to or higher than a predetermined reaction temperature before use, and the catalyst in the reaction It is effective to prevent changes in the composition. In addition, supplying oxygen, chlorine, fluorinated or chlorinated hydrocarbons into the reactor during the reaction is effective for extending the catalyst life, improving the reaction rate, and the reaction yield.
[0014]
The reaction temperature of the process of the present invention is Ru 350 to 600 ° C. der. Even if the reaction temperature exceeds 600 ° C., the reaction rate is not particularly improved, decomposition products, dimerization products and the like are generated, and the selectivity for 1,3,3,3-tetrafluoropropene is lowered, which is not preferable.
[0015]
In the method of the present invention, 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 coexist.
[0016]
Although reaction pressure is not specifically limited, It is preferable to carry out at 0.1-10 kg / cm < 2 > from the surface of an 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]
The product containing 1,3,3,3-tetrafluoropropene treated by the method of the present invention and discharged from the reactor is purified to a product by a known method. 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]
In the method of the present invention, the product 1,3,3,3-tetrafluoropropene is obtained as a mixture of the trans isomer and the cis isomer, but the cis isomer is the starting 1,1,1,3,3-penta Since it has a boiling point close to that of fluoropropane and exhibits an azeotropic behavior, it cannot be easily separated. Therefore, the trans form and cis form of 1,3,3,3-tetrafluoropropene and the mixture (product) consisting of 1,1,1,3,3-pentafluoropropane were distilled to recover only the trans form. The remaining cis-isomer and 1,1,1,3,3-pentafluoropropane can be subjected to the reaction of the present invention again without separation. That is, a high-purity 1,3,3,3-tetrafluoropropene can be produced by recovering the cis form, which is difficult to separate and recover, as a trans form without intentional separation.
[0019]
【Example】
[Preparation Example 1]
In a solution obtained by dissolving 300 g of the special grade reagent Cr (NO 3 ) 3 · 9H 2 O in 1 liter of pure water, granular activated carbon (Takeda Pharmaceutical, granular white rabbit with a diameter of 4 to 6 mm, a surface area of 1200 m 2 / g, and a pore diameter of 18A GX) 1.8 liters were immersed and left overnight. Next, the activated carbon was taken out by filtration, kept at 100 ° C. in a hot air circulation dryer, and further dried overnight. The obtained chromium-supported activated carbon was filled in a cylindrical SUS316L reaction tube having a diameter of 3.5 cm and a length of 150 cm equipped with a heating device, and the temperature was raised to 300 ° C. while flowing nitrogen gas, and water discharge was not observed. At that time, the concentration of hydrogen fluoride was gradually increased with nitrogen gas, the reactor temperature was raised to 350 ° C., and this state was maintained for 1 hour to prepare a catalyst.
[Example 1]
A gas phase reactor (made of SUS316L, diameter 2.5 cm, length 40 cm) composed of a cylindrical reaction tube heated by an external heating device was filled 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 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 in advance as a raw material organic material and reacted at a rate of 0.44 g / min. Supply to the vessel started.
[0020]
Since the reaction was stable 1 hour after the start of the reaction, the product gas discharged from the reactor was blown into water to remove acidic gas, and then collected with a dry ice-acetone trap. Table 1 shows the results of analyzing the collected organic matter by gas chromatography.
[0021]
[Table 1]
[0022]
[Example 2]
A gas phase reactor (made of SUS316L, diameter 2.5 cm, length 40 cm) composed of a cylindrical reaction tube heated by an external heating device was filled 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 hydrogen fluoride was continuously introduced at a rate of about 0.3 g / min for 1 hour. Next, the temperature of the reaction tube is lowered to 350 ° C., the supply of hydrogen fluoride is stopped, the flow rate of nitrogen gas is reduced to 20 ml / min, and 1,1,1,3,3-pentafluoropropane is preliminarily used as a raw material organic substance. Vaporization was started and feeding to the reactor was started at a rate of 0.48 g / min.
[0023]
Since the reaction was stable 1 hour after the start of the reaction, the product gas flowing out from the reactor was blown into water to remove the acidic gas, and then collected with a dry ice-acetone trap. Table 1 shows the results of analyzing the collected organic matter by gas chromatography.
[0024]
[ Comparative Example 1 ]
The reaction was conducted 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. The results are shown in Table 1.
[0025]
[ Comparative Example 2 ]
A gas phase reactor (made of SUS316L, diameter 2.5 cm, length 40 cm) composed of a cylindrical reaction tube heated by an external heating device was filled with 150 ml of the catalyst prepared in Preparation Example 1 as a gas phase fluorination catalyst. While flowing nitrogen gas at a flow rate of about 150 ml / min, the temperature of the reaction tube was raised to 380 ° C., and hydrogen fluoride was continuously introduced at a rate of about 0.28 g / min for 1 hour. The temperature of the reaction tube is lowered to 255 ° C., and the supply amount of hydrogen fluoride and the flow rate of nitrogen gas are left as they are. Feeding to the reactor was started at a rate of / min.
[0026]
Since the reaction was stable 1 hour after the start of the reaction, the product gas discharged from the reactor was blown into water to remove acidic gas, and then collected with a dry ice-acetone trap. Table 1 shows the results of analyzing the collected organic matter by gas chromatography.
[0027]
【The invention's effect】
The method for producing 1,3,3,3-tetrafluoropropene according to the present invention comprises 1,1,1,3,3-pentafluoropropane as a raw material, and is continuously 1,3,3,3-tetrafluoropropene. Is useful as an industrial production method.
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