JP2004043410A - Method for producing 1,3,3,3-tetrafluoropropene - Google Patents
Method for producing 1,3,3,3-tetrafluoropropene Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
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】
【従来の技術】
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、本出願人はクロム、チタニウム、アルミニウム、マンガン、コバルト等の金属の酸化物、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を活性炭に担持した触媒を用いて、１，３，３，３−テトラフルオロプロペンを製造する方法を開示している（特開平１０−００７６０４号公報）。
【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。
【０００５】
【課題を解決するための手段】
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方法として、フッ素化触媒の存在下、１−クロロ−３，３，３−トリフルオロプロペンを原料に、これをフッ化水素で気相フッ素化して１，３，３，３−テトラフルオロプロペンを製造する方法について検討したところ、フッ素化触媒として特定の金属を用いることが好適であることを見いだし、本発明に到達した。
【０００６】
すなわち、本発明は、気相中でフッ素化触媒存在下、１−クロロ−３，３，３−トリフルオロプロペンをフッ化水素と反応させて１，３，３，３−テトラフルオロプロペンの製造する方法において、フッ素化触媒としてチタニウムまたはクロムの少なくとも一つを用い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方法である。
【０００７】
１−クロロ−３，３，３−トリフルオロプロペンをフッ化水素と反応させる反応においては、反応条件等により１，３，３，３−テトラフルオロ−１−クロロプロパンや１，１，１，３，３−ペンタフルオロプロパンを副生するが、これらの副生成物の生成を抑えて、１，３，３，３−テトラフルオロプロパンのみを製造することが望ましい。本発明の製造方法を用いることにより、副生成物の顕著な生成は抑えられ、特に１，３，３，３−テトラフルオロ−１−クロロプロパンの生成は認められなくなる。
【０００８】
本発明に使用する１−クロロ−３，３，３−トリフルオロプロペンは、３−ブロモ−３−クロロ−１，１，１−トリフルオロプロパンをアルコール性水酸化カリウムにより脱塩化水素する方法（Ｒ．Ｎ．Ｈａｓｚｅｌｄｉｎｅ，Ｊ．Ｃｈｅｍ．Ｓｏｃ．，１９５１、２４９５）、３，３，３−トリフルオロプロピンに塩化水素を付加させる方法（Ｊ．Ｃｈｅｍ．Ｓｏｃ．，１９５２，３４９０）、３−クロロ−１，１，１−トリフルオロ−３−ヨード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（Ｊ．Ｃｈｅｍ．Ｓｏｃ．，１９５３、１１９９．）または１，３，３，３−テトラクロロロプロペンをアンチモン触媒でフッ素化する方法（ＵＳＰ２，７８７，６４６号公報）等で得ることができる。
【０００９】
また本出願人の出願にかかる特開平１０−７６０５号公報には、１，１，１，３，３−ペンタクロロプロパンをフッ化水素により気相フッ素化する方法を開示している。
【００１０】
本発明にかかる好適なフッ素化触媒は、クロムまたはチタニウムである。
触媒として用いるにあたり、表面積の大きいものが好ましく、例えば、チタニウムは、スポンジチタンであることが好ましい。スポンジチタンは例えば東邦チタニウム（株）で種種の組成のグレード品が得られる。また、これらの金属と他の金属化合物を混合したものを触媒として用いることができ、例えば、クロムと銅化合物との両者を混合し、ペレット化したものが使用できる。
【００１１】
また、触媒として使用するにあたり、それぞれの金属に加え、その表面の一部または全部が、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となったものを混合することも可能である。
【００１２】
何れの触媒も、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】
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。
【００１４】
本発明の方法において、反応領域へ供給する１−クロロ−３，３，３−トリフルオロプロペン／フッ化水素のモル比は反応温度により変わりうるが、１／１〜１／６０、好ましくは１／１〜１／３０である。フッ化水素が１−クロロ−３，３，３−トリフルオロプロペンの６０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１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。
【００１５】
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。
【００１６】
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。
【００１７】
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あれば良く、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。
【００１８】
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。
【００１９】
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。
【００２０】
本発明の方法においては、触媒として金属を用いることより熱効率が良くなるため、温度調節を行う際にコントロールが容易であり、工業的に操作しやすいという利点もある。
【００２１】
【実施例】
［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２．５ｃｍ・長さ３０ｃｍ）に気相フッ素化触媒として銅／クロム（日揮化学製）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３００℃まで昇温し、１時間保った。次に反応管の温度を３００℃に下げ、フッ化水素を０．０７ｇ／分の供給速度とし、１−クロロ−３，３，３−トリフルオロプロペンを予め気化させて０．０６ｇ／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６．２ｇ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、１，３，３，３−テトラフルオロプロペン２６．４％、１，１，３，３，３−ペンタフルオロプロパン４．５％及び１−クロロ−３，３，３−トリフルオロプロペン６８．８％の生成物を得た。１，３，３，３−テトラフルオロ−１−クロロプロパンの生成は認められなかった。
【００２３】
［実施例２］
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２．５ｃｍ・長さ３０ｃｍ）に気相フッ素化触媒としてスポンジチタン（純正化学製、Ｔｉ純度＞９９％）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３００℃まで昇温し、１時間保った。次に反応管の温度を３６５℃に下げ、フッ化水素を０．０７ｇ／分の供給速度とし、１−クロロ−３，３，３−トリフルオロプロペンを予め気化させて０．０６ｇ／分の速度で反応器へ供給開始した。
【００２４】
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５．９ｇ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、１，３，３，３−テトラフルオロプロペン１４．４％、１，１，３，３，３−ペンタフルオロプロパン０．３％及び１−クロロ−３，３，３−トリフルオロプロペン８０．９％の生成物を得た。１，３，３，３−テトラフルオロ−１−クロロプロパンの生成は認められなかった。
【００２５】
【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方法は、１−クロロ−３，３，３−トリフルオロプロペンを原料とし、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、工業的な製造方法として有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing 1,3,3,3-tetrafluoropropene, which is useful as an intermediate material for pharmaceuticals and agricultural chemicals, intermediate materials for functional materials, refrigerants, and the like.
[0002]
[Prior art]
As a method for producing 1,3,3,3-tetrafluoropropene, conventionally, a method of dehydroiodinating 1,3,3,3-tetrafluoro-1-propane iodide 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. Methods (IL Knunyants et al., Izvest. Akad. Nauk SSRR, Otdel. Khim. Nauk. 1960, 1412-18; CA 55, 349f) and the like are known.
[0003]
In addition, the present applicant has developed a catalyst in which oxides, fluorides, chlorides, fluoride chlorides, oxyfluorides, oxychlorides, and oxyfluoride chlorides of metals such as chromium, titanium, aluminum, manganese, and cobalt are supported on activated carbon. Discloses a method for producing 1,3,3,3-tetrafluoropropene using the method (JP-A-10-007604).
[0004]
[Problems to be solved by the invention]
The method of dehydrohalogenating with potassium hydroxide as described above is a method excellent in the reaction rate and selectivity, but requires a stoichiometric amount of potassium hydroxide or more, and the raw material 1,3 , 3,3-Tetrafluoro-1-propane iodide or 1,1,1,3,3-pentafluoropropane must be prepared in advance, and there are many difficulties in industrial application.
[0005]
[Means for Solving the Problems]
The present inventors, as a method for producing 1,3,3,3-tetrafluoropropene from a material that can be obtained on an industrial scale or can be relatively easily produced from a raw material available on an industrial scale, Method for producing 1,3,3,3-tetrafluoropropene by subjecting 1-chloro-3,3,3-trifluoropropene as a raw material to gas-phase fluorination with hydrogen fluoride in the presence of a fluorination catalyst The present inventors have found that it is preferable to use a specific metal as the fluorination catalyst, and have reached the present invention.
[0006]
That is, the present invention provides a method for producing 1,3,3,3-tetrafluoropropene by reacting 1-chloro-3,3,3-trifluoropropene with hydrogen fluoride in a gas phase in the presence of a fluorination catalyst. A method for producing 1,3,3,3-tetrafluoropropene, wherein at least one of titanium and chromium is used as a fluorination catalyst.
[0007]
In the reaction of reacting 1-chloro-3,3,3-trifluoropropene with hydrogen fluoride, 1,3,3,3-tetrafluoro-1-chloropropane, 1,1,1,3 However, it is desirable to produce only 1,3,3,3-tetrafluoropropane by suppressing the production of these by-products. By using the production method of the present invention, remarkable generation of by-products is suppressed, and in particular, generation of 1,3,3,3-tetrafluoro-1-chloropropane is not recognized.
[0008]
1-chloro-3,3,3-trifluoropropene used in the present invention can be obtained by a method of dehydrochlorinating 3-bromo-3-chloro-1,1,1-trifluoropropane with alcoholic potassium hydroxide ( RN Haszeldine, J. Chem. Soc., 1951, 2495), a method of adding hydrogen chloride to 3,3,3-trifluoropropyne (J. Chem. Soc., 1952, 3490), 3-chloro -1,1,1-trifluoro-3-iodopropane by dehydroiodination with alcoholic potassium hydroxide (J. Chem. Soc., 1953, 1199.) or 1,3,3,3-tetrahydropropane It can be obtained by a method of fluorinating chlorolopropene with an antimony catalyst (US Pat. No. 2,787,646).
[0009]
Japanese Patent Application Laid-Open No. 10-7605, filed by the present applicant, discloses a method of fluorinating 1,1,1,3,3-pentachloropropane with hydrogen fluoride in the gas phase.
[0010]
A preferred fluorination catalyst according to the present invention is chromium or titanium.
When used as a catalyst, those having a large surface area are preferable. For example, titanium is preferably sponge titanium. As sponge titanium, for example, grade products having various compositions can be obtained from Toho Titanium Co., Ltd. A mixture of these metals and another metal compound can be used as a catalyst. For example, a mixture of both chromium and a copper compound and pelletized can be used.
[0011]
In addition, when used as a catalyst, in addition to each metal, a part or all of the surface is composed of oxide, fluoride, chloride, fluoride chloride, oxyfluoride, oxychloride, oxyfluoride chloride, etc. It is also possible to mix what is now.
[0012]
Before use, any catalyst is treated with a fluorinating agent such as hydrogen fluoride or fluorinated (and chlorinated) hydrocarbon at a temperature higher than a predetermined reaction temperature to prevent a change in the composition of the catalyst during the reaction. It is effective. Supplying oxygen, chlorine, fluorinated or chlorinated hydrocarbons, etc. into the reactor during the reaction is effective in extending the catalyst life, improving the reaction rate, and improving the reaction yield.
[0013]
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 life of the catalyst is shortened, and the reaction proceeds quickly, but decomposition products are generated, and the selectivity of 1,3,3,3-tetrafluoropropene decreases, which is not preferable. .
[0014]
In the method of the present invention, the molar ratio of 1-chloro-3,3,3-trifluoropropene / hydrogen fluoride supplied to the reaction zone can vary depending on the reaction temperature, but is 1/1 to 1/60, preferably 1 to 1. / 1 to 1/30. If the amount of hydrogen fluoride exceeds 60 times the molar amount of 1-chloro-3,3,3-trifluoropropene, the amount of organic substances to be treated in the same reactor decreases, and the amount of unreacted hydrogen fluoride discharged from the reaction system and the product decreases. The separation of the mixture is hindered. On the other hand, if the amount of hydrogen fluoride is less than 1 mol times, the reaction rate decreases, and the selectivity decreases, which is not preferable.
[0015]
In the method of the present invention, it is preferable to use an excess amount of hydrogen fluoride, so that unreacted hydrogen fluoride is separated from unreacted organic substances and products and recycled to the reaction system. Separation of hydrogen fluoride and organic substances can be performed by a known means.
[0016]
The reaction pressure is not particularly limited, but is preferably 1 to 10 kg / cm 2 from the viewpoint of the apparatus. It is desirable to select conditions so that the raw material organic substances, intermediate substances and hydrogen fluoride present in the system are not liquefied in the reaction system. The contact time is generally 0.1 to 300 seconds, preferably 5 to 60 seconds.
[0017]
The reactor may be made of any material having heat resistance and corrosion resistance to hydrogen fluoride, hydrogen chloride and the like, and is preferably stainless steel, Hastelloy, Monel, platinum or the like. It can also be made of materials lined with these metals.
[0018]
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.
[0019]
The purification method is not limited. For example, a 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. Thereafter, distillation can be performed to remove organic impurities.
[0020]
In the method of the present invention, since the thermal efficiency is improved by using a metal as a catalyst, there is also an advantage that the temperature can be easily controlled and industrially easy to operate.
[0021]
【Example】
[Example 1]
A gas-phase reactor (made of SUS316L, 2.5 cm in diameter, 30 cm in length) composed of a cylindrical reaction tube equipped with an electric furnace was charged with 150 ml of copper / chromium (manufactured by Nikki Chemical) as a gas-phase fluorination catalyst. The temperature of the reaction tube was raised to 200 ° C. while flowing nitrogen gas at a flow rate of about 100 ml / min, and hydrogen fluoride was entrained in the nitrogen gas at a rate of about 0.10 g / min. The temperature of the reaction tube was raised to 300 ° C. and kept for 1 hour. Next, the temperature of the reaction tube was lowered to 300 ° C., hydrogen fluoride was supplied at a supply rate of 0.07 g / min, and 1-chloro-3,3,3-trifluoropropene was previously vaporized to 0.06 g / min. Feeding to the reactor was started at a rate.
[0022]
One hour after the start of the reaction, the reaction was stable. For 2 hours from that time, the generated gas flowing out of the reactor was blown into water to remove the acidic gas, and then 6.2 g of organic matter was captured with a dry ice-acetone trap. Gathered. The collected organic matter was analyzed by gas chromatography. As a result, 26.4% of 1,3,3,3-tetrafluoropropene, 4.5% of 1,1,3,3,3-pentafluoropropane and 1-chloro A product of 68.8% of -3,3,3-trifluoropropene was obtained. No formation of 1,3,3,3-tetrafluoro-1-chloropropane was observed.
[0023]
[Example 2]
150 ml of titanium sponge (manufactured by Junsei Chemical Co., Ti purity> 99%) as a gas phase fluorination catalyst in a gas phase reaction device (made of SUS316L, diameter 2.5 cm, length 30 cm) comprising a cylindrical reaction tube equipped with an electric furnace. Filled. The temperature of the reaction tube was raised to 200 ° C. while flowing nitrogen gas at a flow rate of about 100 ml / min, and hydrogen fluoride was entrained in the nitrogen gas at a rate of about 0.10 g / min. The temperature of the reaction tube was raised to 300 ° C. and kept for 1 hour. Next, the temperature of the reaction tube was lowered to 365 ° C., the supply rate of hydrogen fluoride was set to 0.07 g / min, and 1-chloro-3,3,3-trifluoropropene was previously vaporized to 0.06 g / min. Feeding to the reactor was started at a rate.
[0024]
One hour after the start of the reaction, the reaction was stable. For 2 hours from that time, the generated gas flowing out of the reactor was blown into water to remove acidic gas, and then 5.9 g of organic matter was captured with a dry ice-acetone trap. Gathered. The collected organic matter was analyzed by gas chromatography. As a result, 14.4% of 1,3,3,3-tetrafluoropropene, 0.3% of 1,1,3,3,3-pentafluoropropane and 1-chloro A product of 80.9% of -3,3,3-trifluoropropene was obtained. No formation of 1,3,3,3-tetrafluoro-1-chloropropane was observed.
[0025]
【The invention's effect】
The process for producing 1,3,3,3-tetrafluoropropene according to the present invention uses 1-chloro-3,3,3-trifluoropropene as a raw material and continuously prepares 1,3,3,3-tetrafluoropropene. Is useful as an industrial production method.
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