JP3821514B2 - Method for producing 1,3,3,3-tetrafluoropropene - Google Patents
Method for producing 1,3,3,3-tetrafluoropropene Download PDFInfo
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- JP3821514B2 JP3821514B2 JP15999996A JP15999996A JP3821514B2 JP 3821514 B2 JP3821514 B2 JP 3821514B2 JP 15999996 A JP15999996 A JP 15999996A JP 15999996 A JP15999996 A JP 15999996A JP 3821514 B2 JP3821514 B2 JP 3821514B2
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Description
【０００１】
【産業上の利用分野】
本発明は、医農薬、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】
【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−ヨウ化プロパンまたは１，１，１，３，３−ペンタフルオロ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。
【０００４】
【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−ペンタクロロプロパンを原料とし、これをフッ化水素で気相フッ素化することで１，３，３，３−テトラフルオロプロペンが得られ、また、該気相フッ素化にあたって、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。
【０００５】
すなわち、本発明は、気相中においてフッ素化触媒存在下、１，１，１，３，３−ペンタクロロプロパンをフッ化水素と反応させることを特徴とする１，３，３，３−テトラフルオロプロペンの製造法であり、また、該フッ素化触媒が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であることを特徴とする１，３，３，３−テトラフルオロプロペンの製造法である。
【０００６】
本発明に使用する１，１，１，３，３−ペンタクロロプロパンは、塩化ビニリデンとクロロホルムとを銅アミン触媒存在下に反応させる方法（Ｍ．Ｋｏｔｏｒａら，Ｒｅａｃｔ．Ｋｉｎｅｔ．Ｃａｔａｌ．Ｌｅｔｔ．，１９９１，４４，２，４１５）、四塩化炭素と塩化ビニルとを銅アミン触媒存在下に反応させる方法（Ｍ．Ｋｏｔｏｒａら，Ｊ．Ｍｏｌ．Ｃａｔａｌ．，１９９２，７７，５１）、四塩化炭素と塩化ビニルを塩化第一鉄触媒の存在下反応させる方法（Ｊ．Ｏｒｇ．Ｃｈｅｍ．，ＵＳＳＲ，１９６９，３，２１０１）等で得ることができる。
【０００７】
本発明にかかる活性炭は、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。
【０００８】
また、本発明にかかる活性炭は、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。
【０００９】
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。
【００１０】
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。
【００１１】
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。
【００１２】
反応温度は２００〜６００℃、好ましくは３００〜５００℃であり、反応温度２００℃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℃を超えると触媒寿命が短くなり、また、反応は速く進行するが分解生成物等が生成し、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。
【００１３】
本発明の方法において、反応領域へ供給する１，１，１，３，３−ペンタクロロプロパン／フッ化水素のモル比は反応温度により変わりうるが、１／４〜１／３０、好ましくは１／４〜１／１０である。フッ化水素が１，１，１，３，３−ペンタクロロプロパンの３０モル倍を超えると同一反応器における有機物処理量の減少ならびに反応系から排出された未反応フッ化水素と生成物との混合物の分離に支障をきたし、一方、フッ化水素が４モル倍よりも少ないと反応率が低下し、選択率が低下するので好ましくない。
【００１４】
本発明の方法においては、過剰量のフッ化水素を使用することが好ましいので、未反応のフッ化水素は未反応有機物および生成物から分離し、反応系へリサイクルする。フッ化水素と有機物の分離は、公知の手段で行うことができる。
【００１５】
反応圧力は特に限定されないが、装置の面から１〜１０ｋｇ／ｃｍ2で行うのが好ましい。系内に存在する原料有機物、中間物質およびフッ化水素が、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５〜６０秒である。
【００１６】
反応器は、耐熱性とフッ化水素、塩化水素等に対する耐食性を有する材質で作られれば良く、ステンレス鋼、ハステロイ、モネル、白金などが好ましい。また、これらの金属でライニングされた材料で作ることもできる。
【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、予め回収されるべきフッ化水素を分離した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】
【実施例】
［調製例１］
東洋カルゴン製椰子殻破砕炭１００ｇ（ＰＣＢ ４×１０メッシュ）を純水１５０ｇに浸漬し、別途４０ｇの特級試薬ＣｒＣｌ3・６Ｈ2Ｏを１００ｇの純水に溶かし調製した溶液と混合攪拌し、一昼夜放置した。次に濾過して活性炭を取り出し、電気炉中で２００℃に保ち、２時間焼成した。得られたクロム担持活性炭を電気炉を備えた直径５ｃｍ長さ３０ｃｍの円筒形ＳＵＳ３１６Ｌ製反応管に充填し、窒素ガスを流しながら２００℃まで昇温し、水の流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た。充填されたクロム担持活性炭へのフッ化水素の吸着によるホットスポットが反応管出口端に達したところで反応器温度を４００℃に上げ、その状態を２時間保ち触媒の調製を行った。
【００１９】
［調製例２］
東洋カルゴン製椰子殻破砕炭１００ｇ（ＰＣＢ ４×１０メッシュ）を純水１５０ｇに浸漬し、別途２００ｇの２０％ＴｉＣｌ3水溶液と混合攪拌し、一昼夜放置した。次に濾過して活性炭を取り出し、電気炉中で２００℃に保ち、２時間焼成した。得られたチタン担持活性炭を電気炉を備えた直径５ｃｍ長さ３０ｃｍの円筒形ＳＵＳ３１６Ｌ製反応管に充填し、窒素ガスを流しながら２００℃まで昇温し、水の流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た。充填されたチタン担持活性炭へのフッ化水素の吸着によるホットスポットが反応管出口端に達したところで反応器温度を４００℃に上げ、その状態を２時間保ち触媒の調製を行った。
【００２０】
［調製例３］
３３６ｇの特級試薬ＣｒＣｌ3・６Ｈ2Ｏを純水に溶かして１Ｌとした。この溶液に直径５ｍｍ、表面積３４０ｍ2の粒状γ−アルミナ２５０ｍｌを浸漬し、一昼夜放置した。次に濾過してγ−アルミナを取り出し、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アルミナを電気炉を備えた直径５ｃｍ長さ３０ｃｍ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、水の流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た。充填されたクロム担持アルミナのフッ素化によるホットスポットが反応管出口端に達したところで反応器温度を４５０℃に上げ、その状態を１時間保ち触媒の調製を行った。
【００２１】
［実施例１］
電気炉を備えた円筒形反応管からなる気相反応装置（ＳＵＳ３１６Ｌ製、直径１インチ・長さ３０ｃｍ）に気相フッ素化触媒として調製例１で調製した触媒を１５０ｍｌ充填した。約１００ｍｌ／分の流量で窒素ガスを流しながら反応管の温度を２００℃に上げ、フッ化水素を約０．１０ｇ／分の速度で窒素ガスに同伴させた。そのまま反応管の温度を５００℃まで昇温し１時間保った。次に反応管の温度を４００℃に下げ、フッ化水素を０．１０ｇ／分の供給速度とし、１，１，１，３，３−ペンタクロロプロパンを予め気化させて０．３２ｇ／分の速度で反応器へ供給開始した。
【００２２】
反応開始１時間後には反応は安定したので、その時から２時間にわたって、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２１．２ｇの有機物を捕集した。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。
【００２３】
【表１】
［実施例２］
調製例２で調製した触媒を用い、実施例１と同様の準備段階の後、表１に示す条件で実施例１と同様の反応操作、回収操作、分析を行った。結果を表１に示す。
【００２５】
［実施例３、４］
活性炭を単独で用い、表１に示す条件で実施例１と同様の反応操作、回収操作、分析を行った。結果を表１に示す。
【００２６】
［参考例］
触媒として、調製例３のクロム担持アルミナ触媒を用いた他は実施例１と同様の準備段階の後、表１に示す条件で実施例１と同様の反応操作、回収操作、分析を行った。結果を表１に示す。
【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−ペンタクロ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 intermediate raw material for medicines and agricultural chemicals, functional materials, or a refrigerant.
[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]
[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 or 1,1,1,3,3-pentafluoropropane must be prepared in advance, which is difficult to apply industrially.
[0004]
[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-pentachloropropane was used as a raw material, and by gas phase fluorination with hydrogen fluoride, 1,3,3,3-tetrafluoropropene was obtained. It has also been found that it is particularly preferable to use activated carbon carrying activated carbon or a metal compound such as a chromium compound as a catalyst in the gas phase fluorination, and the present invention has been achieved.
[0005]
That is, the present invention relates to 1,3,3,3-tetrafluoro characterized by reacting 1,1,1,3,3-pentachloropropane with hydrogen fluoride in the presence of a fluorination catalyst in the gas phase. A method for producing propene, and a method for producing 1,3,3,3-tetrafluoropropene, wherein the fluorination catalyst is activated carbon or activated carbon carrying a metal compound such as a chromium compound.
[0006]
1,1,1,3,3-Pentachloropropane used in the present invention is a method in which vinylidene chloride and chloroform are reacted in the presence of a copper amine catalyst (M. Kotora et al., React. Kinet. Catal. Lett., 1991). , 44, 2, 415), a method of reacting carbon tetrachloride and vinyl chloride in the presence of a copper amine catalyst (M. Kotora et al., J. Mol. Catal., 1992, 77, 51), carbon tetrachloride and chloride. It can be obtained by a method of reacting vinyl in the presence of a ferrous chloride catalyst (J. Org. Chem., USSR, 1969, 3, 2101).
[0007]
The activated carbon according to the present invention is a plant based on wood, sawdust, charcoal, coconut shell charcoal, palm kernel charcoal, raw ash, etc., coal based on peat, lignite, lignite, bituminous, anthracite, etc. Oil, petroleum residue, sulfuric acid sludge, oil carbon and the like as raw materials, and those using synthetic resin as raw materials. Since such activated carbon is commercially available, it can be selected from among them. For example, activated carbon manufactured 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.
[0008]
The activated carbon according to the present invention is an oxide, fluoride, chloride, fluorinated chloride, or oxyfluoride of one or more metals selected from aluminum, chromium, manganese, nickel, cobalt, and titanium. Further, activated carbon carrying oxychloride, oxyfluoride chloride, or the like may be used.
[0009]
The method for preparing these metal-supported activated carbon catalysts is not limited, but the activated carbon itself, or activated carbon modified in advance with a halogen such as hydrogen fluoride, hydrogen chloride, chlorinated fluorinated hydrocarbon, chromium, titanium, manganese, nickel, It is prepared by impregnating or spraying a solution in which a soluble compound of one or more metals selected from cobalt is dissolved.
[0010]
The metal loading is 0.1-80 wt%, preferably 1-40 wt%. 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, potassium dichromate, titanium trichloride, manganese nitrate, manganese chloride, manganese dioxide, nickel nitrate, nickel chloride, cobalt nitrate, cobalt chloride, etc. may be used. it can.
[0011]
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.
[0012]
The reaction temperature is 200 to 600 ° C., preferably 300 to 500 ° C. If the reaction temperature is lower than 200 ° C., the reaction is slow and not practical. When the reaction temperature exceeds 600 ° C., the catalyst life is shortened, and the reaction proceeds rapidly, but decomposition products and the like are generated, and the selectivity for 1,3,3,3-tetrafluoropropene is decreased, which is not preferable. .
[0013]
In the method of the present invention, the molar ratio of 1,1,1,3,3-pentachloropropane / hydrogen fluoride fed to the reaction zone may vary depending on the reaction temperature, but it is 1/4 to 1/30, preferably 1 / 4 to 1/10. When hydrogen fluoride exceeds 30 moles of 1,1,1,3,3-pentachloropropane, the amount of organic matter treated in the same reactor is reduced and the mixture of unreacted hydrogen fluoride discharged from the reaction system and product On the other hand, if the amount of hydrogen fluoride is less than 4 mole times, the reaction rate is lowered and the selectivity is lowered, which is not preferable.
[0014]
In the method of the present invention, since it is preferable to use an excessive amount of hydrogen fluoride, unreacted hydrogen fluoride is separated from unreacted organic substances and products and recycled to the reaction system. Separation of hydrogen fluoride and organic matter can be performed by known means.
[0015]
Although reaction pressure is not specifically limited, It is preferable to carry out by 1-10 kg / cm < 2 > from the surface of an apparatus. It is desirable to select conditions so that the raw organic substances, intermediate substances 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 60 seconds.
[0016]
The reactor may be made of a material having heat resistance and corrosion resistance to hydrogen fluoride, hydrogen chloride and the like, and stainless steel, hastelloy, monel, platinum and the like are preferable. It can also be made from materials lined with these metals.
[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.
Although the purification method is not limited, for example, the product from which hydrogen fluoride to be recovered in advance is separated is first washed with water or / and an alkaline solution to remove acidic substances such as hydrogen chloride and hydrogen fluoride, and then dried. Then, it can be performed by subjecting it to distillation to remove organic impurities.
[0018]
【Example】
[Preparation Example 1]
100 g of coconut shell crushed charcoal (PCB 4 × 10 mesh) made by Toyo Calgon is immersed in 150 g of pure water, and 40 g of special grade reagent CrCl 3 · 6H 2 O is separately dissolved in 100 g of pure water and mixed and stirred for a whole day and night. I left it alone. Next, it filtered and took out activated carbon, it maintained at 200 degreeC in the electric furnace, and baked for 2 hours. When the obtained chromium-supported activated carbon was filled in a cylindrical SUS316L reaction tube having a diameter of 5 cm and a length of 30 cm equipped with an electric furnace, the temperature was raised to 200 ° C. while flowing nitrogen gas, and when no water was seen to flow out. Nitrogen gas was accompanied by hydrogen fluoride, and the concentration was gradually increased. When a hot spot due to adsorption of hydrogen fluoride on the packed chromium-supported activated carbon reached the outlet end of the reaction tube, the reactor temperature was raised to 400 ° C., and this state was maintained for 2 hours to prepare a catalyst.
[0019]
[Preparation Example 2]
100 g of coconut shell crushed charcoal (PCB 4 × 10 mesh) manufactured by Toyo Calgon was immersed in 150 g of pure water, separately mixed with 200 g of 20% TiCl 3 aqueous solution, and allowed to stand overnight. Next, it filtered and took out activated carbon, it maintained at 200 degreeC in the electric furnace, and baked for 2 hours. When the obtained titanium-supported activated carbon was filled into a cylindrical SUS316L reaction tube having a diameter of 5 cm and a length of 30 cm equipped with an electric furnace, the temperature was raised to 200 ° C. while flowing nitrogen gas, and when no outflow of water was observed. Nitrogen gas was accompanied by hydrogen fluoride, and the concentration was gradually increased. When a hot spot by adsorption of hydrogen fluoride on the packed titanium-supported activated carbon reached the outlet end of the reaction tube, the reactor temperature was raised to 400 ° C., and the state was maintained for 2 hours to prepare a catalyst.
[0020]
[Preparation Example 3]
336 g of special grade reagent CrCl 3 .6H 2 O was dissolved in pure water to make 1 L. In this solution, 250 ml of granular γ-alumina having a diameter of 5 mm and a surface area of 340 m 2 was immersed and allowed to stand overnight. Next, γ-alumina was taken out by filtration, kept at 100 ° C. in a hot air circulating dryer, and further dried overnight. When the obtained chromium-supported alumina was filled into a cylindrical SUS316L reaction tube having a diameter of 5 cm and a length of 30 cm equipped with an electric furnace, the temperature was raised to 300 ° C. while flowing nitrogen gas, and when no outflow of water was observed. Nitrogen gas was accompanied by hydrogen fluoride, and the concentration was gradually increased. When the hot spot by fluorination of the packed chromium-supported alumina reached the outlet end of the reaction tube, the reactor temperature was raised to 450 ° C., and the state was maintained for 1 hour to prepare a catalyst.
[0021]
[Example 1]
A gas phase reactor (made of SUS316L, diameter 1 inch, length 30 cm) composed of a cylindrical reaction tube equipped with an electric furnace was charged 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 100 ml / min, the temperature of the reaction tube was raised to 200 ° C., and hydrogen fluoride was entrained with nitrogen gas at a rate of about 0.10 g / min. The temperature of the reaction tube was raised to 500 ° C. and kept for 1 hour. Next, the temperature of the reaction tube is lowered to 400 ° C., hydrogen fluoride is supplied at a rate of 0.10 g / min, and 1,1,1,3,3-pentachloropropane is vaporized in advance to a rate of 0.32 g / min. Then, the supply to the reactor was started.
[0022]
Since the reaction was stable 1 hour after the start of the reaction, the product gas flowing out from the reactor was blown into the water for 2 hours to remove the acidic gas, and then 21.2 g of organic matter was captured with a dry ice-acetone trap. Gathered. Table 1 shows the results of analyzing the collected organic matter by gas chromatography.
[0023]
[Table 1]
[Example 2]
Using the catalyst prepared in Preparation Example 2, the same reaction operation, recovery operation, and analysis as in Example 1 were performed under the conditions shown in Table 1 after the same preparation steps as in Example 1. The results are shown in Table 1.
[0025]
[Examples 3 and 4]
The same reaction operation, recovery operation, and analysis as in Example 1 were performed under the conditions shown in Table 1 using activated carbon alone. The results are shown in Table 1.
[0026]
[Reference example]
The same reaction operation, recovery operation, and analysis as in Example 1 were performed under the conditions shown in Table 1 after the same preparation steps as in Example 1 except that the chromium-supported alumina catalyst of Preparation Example 3 was used as the catalyst. The results are shown in Table 1.
[0027]
【The invention's effect】
The process for producing 1,3,3,3-tetrafluoropropene according to the present invention continuously produces 1,3,3,3-tetrafluoropropene from 1,1,1,3,3-pentachloropropane as a raw material. Therefore, it is useful as an industrial production method.
Claims (2)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15999996A JP3821514B2 (en) | 1996-06-20 | 1996-06-20 | Method for producing 1,3,3,3-tetrafluoropropene |
| US08/764,496 US6111150A (en) | 1996-06-20 | 1996-12-12 | Method for producing 1,1,1,3,3,-pentafluoropropane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15999996A JP3821514B2 (en) | 1996-06-20 | 1996-06-20 | Method for producing 1,3,3,3-tetrafluoropropene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH107605A JPH107605A (en) | 1998-01-13 |
| JP3821514B2 true JP3821514B2 (en) | 2006-09-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15999996A Expired - Lifetime JP3821514B2 (en) | 1996-06-20 | 1996-06-20 | Method for producing 1,3,3,3-tetrafluoropropene |
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| Country | Link |
|---|---|
| JP (1) | JP3821514B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9017571B2 (en) | 2010-07-12 | 2015-04-28 | Central Glass Company, Limited | Dry etching agent and dry etching method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE69909860T2 (en) * | 1998-02-26 | 2004-05-27 | Central Glass Co., Ltd., Ube | Process for the production of fluorinated propanes |
| US7279451B2 (en) * | 2002-10-25 | 2007-10-09 | Honeywell International Inc. | Compositions containing fluorine substituted olefins |
| US7880040B2 (en) | 2004-04-29 | 2011-02-01 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US7592494B2 (en) * | 2003-07-25 | 2009-09-22 | Honeywell International Inc. | Process for the manufacture of 1,3,3,3-tetrafluoropropene |
| JP4864879B2 (en) | 2004-04-29 | 2012-02-01 | ハネウェル・インターナショナル・インコーポレーテッド | Method for synthesizing 1,3,3,3-tetrafluoropropene |
| US8383867B2 (en) | 2004-04-29 | 2013-02-26 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
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| US8058486B2 (en) * | 2004-04-29 | 2011-11-15 | Honeywell International Inc. | Integrated process to produce 2,3,3,3-tetrafluoropropene |
| US7674939B2 (en) | 2004-04-29 | 2010-03-09 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| EP2336102A1 (en) * | 2005-11-03 | 2011-06-22 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US8513473B2 (en) | 2007-10-10 | 2013-08-20 | Central Glass Company, Limited | Method for producing trans-1,3,3,3-tetrafluoropropene |
| JP2009279522A (en) * | 2008-05-22 | 2009-12-03 | Kobe Steel Ltd | Oxide catalyst and method for preparing oxide catalyst, as well as deodorant and deodorizing filter |
| US7829748B1 (en) | 2009-09-21 | 2010-11-09 | Honeywell International Inc. | Process for the manufacture of 1,3,3,3-tetrafluoropropene |
| US8293954B2 (en) * | 2010-03-10 | 2012-10-23 | Honeywell International Inc. | Catalyst life improvement for the vapor phase manufacture of 1-chloro-3,3,3-trifluoropropene |
| WO2013187489A1 (en) | 2012-06-13 | 2013-12-19 | セントラル硝子株式会社 | Method for producing 1-chloro-3, 3, 3-trifluoro-1-propene and 1, 3, 3, 3-tetrafluoropropene |
| CN103880589B (en) | 2012-12-19 | 2015-07-29 | 中化蓝天集团有限公司 | The technique of HFO-1234ze and HFC-245fa is prepared in a kind of coproduction |
-
1996
- 1996-06-20 JP JP15999996A patent/JP3821514B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9017571B2 (en) | 2010-07-12 | 2015-04-28 | Central Glass Company, Limited | Dry etching agent and dry etching method |
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|---|---|
| JPH107605A (en) | 1998-01-13 |
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