JP4271415B2 - Method for producing 1,3,3,3-tetrafluoropropene - Google Patents
Method for producing 1,3,3,3-tetrafluoropropene Download PDFInfo
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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、銅 / クロム触媒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】
［参考例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]
BACKGROUND OF THE INVENTION
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]
In addition, the present applicant is a catalyst in which an oxide of metal such as chromium, titanium, aluminum, manganese, cobalt, fluoride, chloride, fluorinated chloride, oxyfluoride, oxychloride, oxyfluoride chloride is supported on activated carbon. Discloses a method for producing 1,3,3,3-tetrafluoropropene using 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 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.
[0005]
[Means for Solving the Problems]
As 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, Method for producing 1,3,3,3-tetrafluoropropene by using 1-chloro-3,3,3-trifluoropropene as a raw material and vapor-phase fluorination with hydrogen fluoride in the presence of a fluorination catalyst As a result, the 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 produces 1,3,3,3-tetrafluoropropene by reacting 1-chloro-3,3,3-trifluoropropene with hydrogen fluoride in the presence of a fluorination catalyst in the gas phase. In this method, a copper / chromium catalyst is used as the fluorination catalyst, which is a method for producing 1,3,3,3-tetrafluoropropene.
[0007]
In the reaction of reacting 1-chloro-3,3,3-trifluoropropene with hydrogen fluoride, 1,3,3,3-tetrafluoro-1-chloropropane or 1,1,1,3 depending on the reaction conditions However, it is desirable to produce only 1,3,3,3-tetrafluoropropane while suppressing the formation of these by-products. By using the production method of the present invention, significant production of by-products is suppressed, and in particular, production of 1,3,3,3-tetrafluoro-1-chloropropane is not recognized.
[0008]
1-chloro-3,3,3-trifluoropropene used in the present invention is 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 is dehydroiodinated with alcoholic potassium hydroxide (J. Chem. Soc., 1953, 1199.) or 1,3,3,3-tetra It can be obtained by a method of fluorinating chlorolopropene with an antimony catalyst (USP 2,787,646).
[0009]
Japanese Patent Application Laid-Open No. 10-7605 relating to the application of the present applicant discloses a method for vapor-phase fluorination of 1,1,1,3,3-pentachloropropane with hydrogen fluoride.
[0010]
The 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. Sponge titanium is available from Toho Titanium Co., Ltd., and grades with various compositions can be obtained. Moreover, what mixed these metals and other metal compounds can be used as a catalyst, for example, what mixed both the chromium and copper compounds and pelletized can be used.
[0011]
When used as a catalyst, in addition to each metal, part or all of its surface is made of oxide, fluoride, chloride, fluorinated chloride, oxyfluoride, oxychloride, oxyfluoride chloride, etc. It is also possible to mix what has become.
[0012]
Any catalyst is treated with a fluorinating agent such as hydrogen fluoride or fluorinated (and chlorinated) hydrocarbon in advance at a temperature equal to or higher than a predetermined reaction temperature before use to prevent changes in the composition of the catalyst during the reaction. It is effective. 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.
[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 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. .
[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 may vary depending on the reaction temperature, but is 1/1 to 1/60, preferably 1 / 1-1 / 30. When the hydrogen fluoride exceeds 60 moles of 1-chloro-3,3,3-trifluoropropene, the amount of organic matter treated in the same reactor is reduced, and the unreacted hydrogen fluoride discharged from the reaction system and the product On the other hand, the separation of the mixture is hindered. On the other hand, when the amount of hydrogen fluoride is less than 1 mole, the reaction rate is lowered and the selectivity is lowered, which is not preferable.
[0015]
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.
[0016]
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.
[0017]
The reactor may be any material that has 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.
[0018]
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.
[0019]
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.
[0020]
In the method of the present invention, heat efficiency is improved by using a metal as a catalyst. Therefore, there is an advantage that control is easy when temperature adjustment is performed, and industrial operation is easy.
[0021]
【Example】
[Example 1]
A gas phase reactor (made of SUS316L, diameter 2.5 cm, length 30 cm) composed of a cylindrical reaction tube equipped with an electric furnace was filled with 150 ml of copper / chromium (manufactured by JGC Chemical) 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 300 ° C. as it was and kept for 1 hour. Next, the temperature of the reaction tube is lowered to 300 ° C., the supply rate of hydrogen fluoride is 0.07 g / min, and 1-chloro-3,3,3-trifluoropropene is vaporized in advance to obtain 0.06 g / min. Feeding to the reactor at a rate began.
[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 acidic gas, and then 6.2 g of organic matter was trapped with a dry ice-acetone trap. Gathered. The collected organic substance was analyzed by gas chromatography. As a result, 1,3,3,3-tetrafluoropropene was 26.4%, 1,1,3,3,3-pentafluoropropane 4.5% and 1-chloro. A product of 68.8% -3,3,3-trifluoropropene was obtained. Formation of 1,3,3,3-tetrafluoro-1-chloropropane was not observed.
[0023]
[Reference Example 1]
150 ml of sponge titanium (made by Junsei Chemical, Ti purity> 99%) as a gas phase fluorination catalyst in a gas phase reactor (made of SUS316L, diameter 2.5 cm, length 30 cm) comprising a cylindrical reaction tube equipped with an electric furnace Filled. 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 300 ° C. as it was and kept for 1 hour. Next, the temperature of the reaction tube is lowered to 365 ° C., the supply rate of hydrogen fluoride is 0.07 g / min, and 1-chloro-3,3,3-trifluoropropene is vaporized in advance to 0.06 g / min. Feeding to the reactor at a rate began.
[0024]
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 5.9 g of organic matter was captured with a dry ice-acetone trap. Gathered. As a result of analyzing the collected organic substance by gas chromatography, it was found that 1,3,3,3-tetrafluoropropene was 14.4%, 1,1,3,3,3-pentafluoropropane 0.3% and 1-chloro. A product of 80.9% -3,3,3-trifluoropropene was obtained. Formation of 1,3,3,3-tetrafluoro-1-chloropropane was not 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 produces 1,3,3,3-tetrafluoropropene. Is useful as an industrial production method.
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| US7279451B2 (en) * | 2002-10-25 | 2007-10-09 | Honeywell International Inc. | Compositions containing fluorine substituted olefins |
| US7655610B2 (en) * | 2004-04-29 | 2010-02-02 | Honeywell International Inc. | Blowing agent compositions comprising fluorinated olefins and carbon dioxide |
| JP4864878B2 (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 | Synthesis method of 1,3,3,3-tetrafluoropropene |
| EP1837323A1 (en) | 2006-03-24 | 2007-09-26 | SOLVAY (Société Anonyme) | Process for the manufacture of 1,1,1,3,3-pentafluoropropane |
| US8563789B2 (en) | 2007-06-27 | 2013-10-22 | Arkema Inc. | Process for the manufacture of hydrofluoroolefins |
| WO2009003084A1 (en) | 2007-06-27 | 2008-12-31 | Arkema Inc. | Process for the manufacture of hydrofluoroolefins |
| JP2009132626A (en) * | 2007-11-28 | 2009-06-18 | Central Glass Co Ltd | Method for producing 1,3,3,3-tetrafluoropropene |
| JP2011525925A (en) * | 2008-06-26 | 2011-09-29 | アーケマ・インコーポレイテッド | Catalytic gas phase fluorination from 1230xa to 1234yf |
| JP5515555B2 (en) * | 2008-09-25 | 2014-06-11 | セントラル硝子株式会社 | Method for producing 1,3,3,3-tetrafluoropropene |
| JP5747684B2 (en) | 2010-09-14 | 2015-07-15 | セントラル硝子株式会社 | Method for dehydrating hydrofluorocarbon or hydrochlorofluorocarbon, and method for producing 1,3,3,3-tetrafluoropropene using the dehydration method |
| JP5817373B2 (en) * | 2010-11-10 | 2015-11-18 | セントラル硝子株式会社 | Process for producing trans-1,3,3,3-tetrafluoropropene |
| EP2807137B1 (en) | 2012-01-25 | 2017-04-26 | Daikin Industries, Ltd. | Process for producing fluorine-containing olefin |
| JP6233352B2 (en) | 2015-06-02 | 2017-11-22 | ダイキン工業株式会社 | Method for producing fluorine-containing olefin |
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