JPS6036411B2 - Method for producing 1,1,1,3,3,3-hexafluoro-propan-2-ol - Google Patents
Method for producing 1,1,1,3,3,3-hexafluoro-propan-2-olInfo
- Publication number
- JPS6036411B2 JPS6036411B2 JP55042808A JP4280880A JPS6036411B2 JP S6036411 B2 JPS6036411 B2 JP S6036411B2 JP 55042808 A JP55042808 A JP 55042808A JP 4280880 A JP4280880 A JP 4280880A JP S6036411 B2 JPS6036411 B2 JP S6036411B2
- Authority
- JP
- Japan
- Prior art keywords
- hexafluoroacetone
- catalyst
- nickel
- reaction
- hydrogen
- 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.)
- Expired
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims description 27
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 6
- NMFQPFSIPWZZMR-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropan-2-ol Chemical compound FC(F)C(F)(O)C(F)(F)F NMFQPFSIPWZZMR-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- -1 lithium aluminum hydride Chemical compound 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000005297 pyrex Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000209507 Camellia Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000750631 Takifugu chinensis Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- BGGJELJUYBEGKP-UHFFFAOYSA-N chromium(2+);oxygen(2-) Chemical compound [O-2].[Cr+2] BGGJELJUYBEGKP-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 235000018597 common camellia Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は１，１，１，３，３，３−へキサフルオロープ
ロパンー２−オールの改良された製造方法に関し、特に
へキサフルオロアセトンの接触水素化による１，１，１
，３，３，３ーヘキサフルオロープロパン−２ーオール
の製造における改良に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved process for the production of 1,1,1,3,3,3-hexafluoropropan-2-ol, in particular by catalytic hydrogenation of hexafluoroacetone. 1,1
, 3,3,3-hexafluoropropan-2-ol.
１，１，１，３，３，３ーヘキサフルオロープロパン−
２−オールは界面活性剤、乳化剤として（ベルギー特許
第６３４３６８号）、またカルボン酸ビニル重合体のよ
うな重合物質の溶媒として（米国特許第３１５３００４
号）、また麻酔性化合物の中間体としても（米国特許第
３３４６４４８号）有用であることが知られている。1,1,1,3,3,3-hexafluoropropane-
2-ol has been used as a surfactant, emulsifier (Belgium Patent No. 634368) and as a solvent for polymeric materials such as vinyl carboxylate polymers (U.S. Pat. No. 3,153,004).
It is also known to be useful as an intermediate for anesthetic compounds (US Pat. No. 3,346,448).
１，１，１，３，３，３ーヘキサフルオロープロパンー
２ーオールの製造法としては■へキサフルオロアセトン
の水素化ホウ素ナトリウム（ソ連特許第１３８６０４号
）あるいは水素化アルミニウムリチウム（米国特許第３
２２７６７４号）を用いた液相還元、■へキサフルオロ
アセトンの酸化白金触媒（米国特許第３６０７９５２号
）あるいはアルカリ金属無機塩基を助触媒とした金属パ
ラジウム触媒（独国特許第２１１３５５１号）を用いた
液相水素化、および■へキサフルオロアセトンの、金属
鋼一酸化クロム触媒（ベルギー特許第６３４３６８号）
、あるいは非担持酸化プラチナ触媒〔Ｊ．Ａｍ．Ｃｈｅ
ｍ，Ｓｏｃ．、第８鏡蓋：４９４８〜５２頁（１９６仏
苧）〕、あるいは酸化アルミニウムのべしット担椿パラ
ジウム触媒（オランダ特許出願第６６１０９３６号）、
更には炭素担持パラジウム触媒（独国特許第１９５６６
２ｙ烏）を用いた気相接触水素還元する方法等が知られ
ている。As a method for producing 1,1,1,3,3,3-hexafluoropropane-2-ol, ■ Sodium borohydride of hexafluoroacetone (USSR Patent No. 138604) or lithium aluminum hydride (US Pat. No. 3)
227674), and (2) hexafluoroacetone using a platinum oxide catalyst (US Pat. No. 3,607,952) or a metal palladium catalyst cocatalyzed with an alkali metal inorganic base (German Patent No. 2,113,551). Metallic steel chromium monoxide catalyst for liquid phase hydrogenation and hexafluoroacetone (Belgium patent no. 634368)
, or an unsupported platinum oxide catalyst [J. Am. Che
m, Soc. , No. 8 Mirror Cover: pp. 4948-52 (196 French)], or Aluminum Oxide Besit-supported Camellia Palladium Catalyst (Netherlands Patent Application No. 6610936),
Furthermore, carbon-supported palladium catalyst (German patent no. 19566
A method of gas-phase catalytic hydrogen reduction using 2y Karasu) is known.
これらの方法のうち工業的には■の液相水素化あるいは
■の気相接触水素化が適しているが、前者は一般に高価
な貴金属触媒を使用し、しかもかなりの高圧下で水素化
を行なわせしめる点で難点を有し、一方、後者は常圧下
で連続的に水素化を行なわせしめることが可能であるが
、例えば金属鋼と酸化クロム触媒を使用した場合は高温
、長接触時間の条件下でもへキサフルオロァセトンの１
，１，１，３，３，３ーヘキサフルオロープロパンー２
−オールへの転化率は低く、この転化率を上げるために
は高価な貴金属触媒を使用せざるを得ない点で必ずしも
満足できるものではなく、更にこれらの気相接触水素化
においては転イＧ率を上げるために１５０ｑｏ以上の高
温で反応を行うが、この場合には副生成物としてフッ素
および有機酸等の酸性化合物が発生することもあり、こ
れらの酸性化合物が触媒を失活させることから担体とし
て耐酸性物質を使用することを余儀なくされている。Among these methods, liquid-phase hydrogenation (①) or gas-phase catalytic hydrogenation (②) are industrially suitable, but the former generally uses expensive precious metal catalysts and hydrogenation is carried out under considerably high pressure. On the other hand, in the latter case, it is possible to carry out hydrogenation continuously under normal pressure, but for example, when metal steel and a chromium oxide catalyst are used, it is difficult to carry out hydrogenation under conditions of high temperature and long contact time. But hexafluoroacetone 1
,1,1,3,3,3-hexafluoropropane-2
- The conversion rate to ol is low, and in order to increase this conversion rate, expensive noble metal catalysts have to be used, which is not necessarily satisfactory. Furthermore, in these gas phase catalytic hydrogenations, conversion In order to increase the reaction rate, the reaction is carried out at a high temperature of 150 qo or more, but in this case, acidic compounds such as fluorine and organic acids may be generated as by-products, and these acidic compounds deactivate the catalyst. It is forced to use acid-resistant substances as carriers.
本発明者等はへキサフルオロアセトンの気相接触水素化
において、上記のような問題点を解決すべ〈研究を重ね
ていたが、副生成物の酸が発生しないような隠和な条件
下、ニッケル系触媒を用いることによって、１，１，１
，３，３，３ーヘキサフルオローブロパン−２ーオール
を定量的に得られることを見出し本発明に到達したもの
である。The present inventors have been conducting repeated research to solve the above-mentioned problems in gas-phase catalytic hydrogenation of hexafluoroacetone. By using a nickel-based catalyst, 1,1,1
, 3,3,3-hexafluoropropan-2-ol can be obtained quantitatively, and the present invention has been achieved.
即ち、本発明はへキサフルオロアセトンをニッケル触媒
の存在下、３０〜１４０００の反応温度において、水素
と気相接触反応させることを特徴とする１，１，１，３
，３，３ーヘキサフルオロープロバンー２−オールの製
造法に関するものである。That is, the present invention is characterized in that hexafluoroacetone is subjected to a gas phase catalytic reaction with hydrogen in the presence of a nickel catalyst at a reaction temperature of 30 to 14,000 °C.
, 3,3-hexafluoroproban-2-ol.
本発明において用いられるニッケル触媒としては炭酸ニ
ッケル、酸化ニッケル、水酸化ニッケル等を水素気体中
で還元して得られる還元ニッケル触媒、有機酸塩（例え
ば、ギ酸ニッケル、シュウ酸ニッケル、酢酸ニッケル等
）′を酸素の存在しない状態で加熱分解して得られる分
解還元ニッケル触媒、あるいはこれらのニッケル触媒を
活性炭、活性ァルミナ又は亜鉛等に担持させたニッケル
触媒、更には酸化マンガン、酸化ジルコニウムなどの助
触媒を添加し、ケィソウ士、白土などの支持物を使用し
成型して得られる広範囲のニッケル触媒の使用が可能で
ある。これら触媒の使用量は原料へキサフルオロアセト
ンに対し０．１〜５部が適当である。また工業的には広
く使用されているケィソゥ士付還元ニッケル触媒（例え
ば日揮化学社製）を使用した場合その触媒量は原料へキ
サフルオロアセトンに対し１部以下で充分である。本発
明における３０〜１４０午○という反応温度は、３０℃
未満では生成物が反応管中で凝縮するため好ましくなく
、また１４０ｑｏより高い温度では副反応が引き起こさ
れ酸性化合物が劉生するため収率の低下が著しいためで
ある。本発明において用いる水素はへキサフルオロアセ
トンに対し当モル量以上あればよいが、水素をキャリア
ーガスとして過剰に使用することは何ら支障ないｏ本発
明における接触時間は一般に３の砂以下で、反応温度が
高いほど短くてよく、通常は５秒程度で十分であり、ほ
ぼ定量的に所望の１，１，１，３，３，３−へキサフル
オロープロパン−２−オールを製造することができる。Examples of the nickel catalyst used in the present invention include reduced nickel catalysts obtained by reducing nickel carbonate, nickel oxide, nickel hydroxide, etc. in hydrogen gas, and organic acid salts (e.g., nickel formate, nickel oxalate, nickel acetate, etc.). Decomposition-reduction nickel catalysts obtained by thermally decomposing ’ in the absence of oxygen, or nickel catalysts in which these nickel catalysts are supported on activated carbon, activated alumina, zinc, etc., and co-catalysts such as manganese oxide and zirconium oxide. It is possible to use a wide range of nickel catalysts obtained by adding and molding using a support such as diatomaceous clay or white clay. The appropriate amount of these catalysts to be used is 0.1 to 5 parts based on the raw material hexafluoroacetone. In addition, when a reduced nickel catalyst with carbon dioxide (for example, manufactured by JGC Chemical Co., Ltd.), which is widely used in industry, is used, the amount of the catalyst is 1 part or less based on the raw material hexafluoroacetone. The reaction temperature of 30 to 140 pm in the present invention is 30°C
If the temperature is lower than 140 qo, the product will condense in the reaction tube, which is undesirable, and if the temperature is higher than 140 qo, side reactions will occur and acidic compounds will form, resulting in a significant drop in yield. The hydrogen used in the present invention may be used in an equimolar amount or more relative to hexafluoroacetone, but there is no problem in using hydrogen in excess as a carrier gas.The contact time in the present invention is generally less than 3 hours, and the reaction time is The higher the temperature, the shorter the time, usually about 5 seconds is sufficient, and it is possible to produce the desired 1,1,1,3,3,3-hexafluoropropan-2-ol almost quantitatively. can.
なお、上記の条件下においては酸性化合物が創生するこ
となく、水素化反応が選択的にほぼ定量的に進行するた
め安価なニッケル触媒の触媒寿命も顕著に長く、より安
価に所望の１，１，１，３，３，３ーヘキサフルオロー
プロパンー２オールが得られることは本発明の利点の１
つである。Note that under the above conditions, the hydrogenation reaction proceeds selectively and almost quantitatively without the formation of acidic compounds, so the lifetime of the inexpensive nickel catalyst is significantly longer, and the desired 1, One of the advantages of the present invention is that 1,1,3,3,3-hexafluoropropane-2ol is obtained.
It is one.
以下本発明を実施例について詳細に説明するが、本発明
はこれら特別な実施例のみに限定されるものではない。
実施例 １
約１８５ｑｏに加熱したパィレックス管（内径１３肋）
中に還元ニッケル触媒（５側めべレツト、日揮化学社製
、Ｎｉ４５〜４７重量％、ケィソウ士２７〜２９％、Ｃ
ｒ ２〜３％、Ｃｕ２〜３％、黒鉛４〜５％）４夕を充
填し、水素気流下で１８５℃で予備活性化した後、約６
０午０に冷却し、次いでへキサフルオロアセトン（１０
夕／Ｈｒ）と水素（８０の【／ｍｉｎ）の混合ガスを通
す。EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these specific Examples.
Example 1 Pyrex pipe heated to about 185 qo (inner diameter 13 ribs)
Reduced nickel catalyst (5-side plate, manufactured by JGC Chemical Co., Ltd., Ni 45-47% by weight, diatomite 27-29%, C
R2~3%, Cu2~3%, graphite 4~5%) and preactivated at 185°C under a hydrogen stream, then
Cool to 0:00 and then add hexafluoroacetone (100
A mixed gas of 80 m/h) and hydrogen (80 m/min) is passed through.
還元反応は速やかに進行し、反応温度は直ちに８０℃迄
上昇した後８０℃に保持する。この反応に於ける接触時
間は４秒である。反応温度が８ぴ０に上昇した時のへキ
サフルオロアセトンの転化率は９９．２％、１，１，１
，３，３，３−へキサフルオロ−プロパン−２−オール
の選択率は１００％であった。また、２畑時間後のへキ
サフルオロアセトンの転化率は９９．０％、１，１，１
，３，３，３−へキサフルオロープロ／ぐン−２ーオー
ルの選択率は１００％であり、長期にわたり触媒の失活
は認められなかった。比較例 １
実施例１に記載した反応装置及び触媒を使用し、反応温
度１５０℃、接触時間８秒の条件下でへキサフルオロア
セトンの気相接触還元を行った結果、生成物中には副生
した水及び酸が多量に認められた。The reduction reaction proceeds rapidly, and the reaction temperature immediately rises to 80°C and is then maintained at 80°C. The contact time in this reaction is 4 seconds. The conversion rate of hexafluoroacetone was 99.2% when the reaction temperature rose to 8.0%, 1,1,1
, 3,3,3-hexafluoro-propan-2-ol, the selectivity was 100%. In addition, the conversion rate of hexafluoroacetone after 2 field hours was 99.0%, 1,1,1
, 3,3,3-hexafluoropro/gun-2-ol was 100%, and no deactivation of the catalyst was observed over a long period of time. Comparative Example 1 Using the reaction apparatus and catalyst described in Example 1, gas phase catalytic reduction of hexafluoroacetone was carried out under conditions of a reaction temperature of 150°C and a contact time of 8 seconds. A large amount of water and acid were observed.
へキサフルオロアセトンの転化率は９９．２％、１，１
，１，３，３，３ーヘキサフルオ。−プロパン−２−オ
ールの選択率は７８．１％であった。実施例 ２
実施例１に記載した反応装置及び触媒を用いへキサフル
オロアセトン１モルに対し水素３モルの流量で、接触時
間４秒、反応温度７０ｑｏの条件下で気相接触還元を行
った結果、ヘキサフルオロアセトンの転化率は９７．５
％、１，１，１，３，３，３ーヘキサフルオロ−プロパ
ン−２−オールの選択率は１００％であった。The conversion rate of hexafluoroacetone is 99.2%, 1,1
, 1,3,3,3-hexafluor. The selectivity of -propan-2-ol was 78.1%. Example 2 Results of gas phase catalytic reduction performed using the reaction apparatus and catalyst described in Example 1 at a flow rate of 3 moles of hydrogen per mole of hexafluoroacetone, a contact time of 4 seconds, and a reaction temperature of 70 qo. , the conversion rate of hexafluoroacetone is 97.5
%, the selectivity for 1,1,1,3,3,3-hexafluoro-propan-2-ol was 100%.
実施例 ３
実施例１で用いたものと同じ組成の還元ニッケル触媒４
０夕と活性炭７０夕を混合し内径２５柵のパィレックス
管に充填し、接触時間７秒、反応温度４０℃でへキサフ
ルオロアセトン（４０夕／Ｈｒ）及び水素（ヘキサフル
オロアセトンに対し３当量）を供給したところ、ヘキサ
フルオロアセトンの転化率は９９．８％、１，１，１，
３，３，３ーヘキサフルオロープロパン−２−オールの
選択率は１００％であり、酸性化合物の創生は全く認め
られなかった。Example 3 Reduced nickel catalyst 4 with the same composition as that used in Example 1
A mixture of activated carbon and 70 hours of activated carbon was filled into a Pyrex tube with an inner diameter of 25 mm, and the contact time was 7 seconds and the reaction temperature was 40°C. Hexafluoroacetone (40 hours/Hr) and hydrogen (3 equivalents relative to hexafluoroacetone) were added. was supplied, the conversion rate of hexafluoroacetone was 99.8%, 1,1,1,
The selectivity of 3,3,3-hexafluoropropan-2-ol was 100%, and no generation of acidic compounds was observed.
比較例 ２
銅−酸化クロム触媒（Ｃｕｏ４４〜４６重量％、Ｃｒ２
０３４３〜４４％、Ｍが０２４〜５％）２０夕を内径１
３肌のパィレックス管に充填し、接触時間１現砂、反応
温度８０ｑｏでへキサフルオロアセトン（１０夕／Ｈｒ
）及び水素（ヘキサフルオロアセトンに対し３当量）を
供給したところ、水素化は殆んど進行せず、ヘキサフル
オロアセトンの転化率は０．５％であった。Comparative Example 2 Copper-chromium oxide catalyst (Cuo44-46% by weight, Cr2
0343~44%, M is 024~5%) 20mm inner diameter 1
Hexafluoroacetone (10 evenings/Hr) was filled into a Pyrex tube with a contact time of 1 hour and a reaction temperature of 80 qo.
) and hydrogen (3 equivalents relative to hexafluoroacetone), hydrogenation hardly proceeded and the conversion rate of hexafluoroacetone was 0.5%.
比較例 ３
炭素担特０．５％パラジウム触媒１０夕を内径１３肋の
パィレックス管に充填し、接触時間７秒、反応温度２０
０００でへキサフルオロアセトン（１０多／Ｈｒ）及び
水素（ヘキサフルオロアセトンに対し３当量）を供給し
たところ、ヘキサフルオロアセトンの転化率は９６．５
％であったが１，１，１，３，３，３−へキサフルオロ
ープロ／ぐン−２−オールの選択率は７０．４％と低く
、酸性化合物が多量副生した。Comparative Example 3 A Pyrex tube with an inner diameter of 13 ribs was filled with 10 sheets of carbon-supported 0.5% palladium catalyst, contact time was 7 seconds, and reaction temperature was 20.
When hexafluoroacetone (10/Hr) and hydrogen (3 equivalents to hexafluoroacetone) were supplied at 000, the conversion rate of hexafluoroacetone was 96.5.
%, but the selectivity of 1,1,1,3,3,3-hexafluoropro/gun-2-ol was as low as 70.4%, and a large amount of acidic compounds were produced as by-products.
Claims (1)
３０〜１４０℃の反応温度において、水素と気相接触反
応させることを特徴とする、１，１，１，３，３，３−
ヘキサフルオロ−プロパン−２−オールの製造法。1 Hexafluoroacetone in the presence of a nickel catalyst,
1,1,1,3,3,3-, characterized by carrying out a gas phase contact reaction with hydrogen at a reaction temperature of 30 to 140°C.
A method for producing hexafluoro-propan-2-ol.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55042808A JPS6036411B2 (en) | 1980-04-03 | 1980-04-03 | Method for producing 1,1,1,3,3,3-hexafluoro-propan-2-ol |
| GB8108711A GB2073181B (en) | 1980-04-03 | 1981-03-19 | Preparation of 1,1,1,3,3,3-hexafluoropropane-2-ol by vapour phase hydrogenation of hexafluoroacetone with nickel catalyst |
| DE3111817A DE3111817C2 (en) | 1980-04-03 | 1981-03-25 | Process for the preparation of 1,1,1,3,3,3-hexafluoropropan-2-ol by vapor phase hydrogenation of hexafluoroacetone with nickel catalysts |
| IT20854/81A IT1136832B (en) | 1980-04-03 | 1981-03-31 | PREPARATION OF 1,1,1,3,3,3-ESAFLOUROPROPANO-2-OL FOR HYDROGENATION IN THE STEAM PHASE OF ESAFLUORACETONE WITH NICKEL CATALYST |
| FR8106654A FR2479803A1 (en) | 1980-04-03 | 1981-04-02 | PROCESS FOR THE PREPARATION OF 1,1,1,3,3,3-HEXAFLUOROPROPANE-2-OL BY VAPOR HYDROGENATION OF HEXAFLUOROACETONE WITH A NICKEL CATALYST |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55042808A JPS6036411B2 (en) | 1980-04-03 | 1980-04-03 | Method for producing 1,1,1,3,3,3-hexafluoro-propan-2-ol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56139433A JPS56139433A (en) | 1981-10-30 |
| JPS6036411B2 true JPS6036411B2 (en) | 1985-08-20 |
Family
ID=12646252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55042808A Expired JPS6036411B2 (en) | 1980-04-03 | 1980-04-03 | Method for producing 1,1,1,3,3,3-hexafluoro-propan-2-ol |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6036411B2 (en) |
| DE (1) | DE3111817C2 (en) |
| FR (1) | FR2479803A1 (en) |
| GB (1) | GB2073181B (en) |
| IT (1) | IT1136832B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6041647B2 (en) * | 1980-11-11 | 1985-09-18 | セントラル硝子株式会社 | Method for producing 1,1,1,3,3,3-hexafluoropropan-2-ol |
| JPS6059219B2 (en) * | 1981-11-18 | 1985-12-24 | セントラル硝子株式会社 | Method for producing 2-trifluoromethylpropanol |
| JPH075490B2 (en) * | 1990-03-14 | 1995-01-25 | セントラル硝子株式会社 | Process for producing 1,1,1,3,3,3-hexafluoropropan-2-d-2-ol-d |
| US7524995B1 (en) | 2008-06-12 | 2009-04-28 | E.I. Du Pont De Nemours And Company | Continuous process to produce hexafluoroisopropanol |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB621654A (en) * | 1947-02-24 | 1949-04-13 | Eric Richard Wallsgrove | Improvements in or relating to the production of 1, 1, 1-trifluoropropan-2-ol |
| US2824897A (en) * | 1955-06-24 | 1958-02-25 | Minnesota Mining & Mfg | Perchlorofluoro alcohols |
| FR1190705A (en) * | 1957-12-11 | 1959-10-14 | Minnesota Mining & Mfg | Polychlorofluoro alcohols |
| US3418337A (en) * | 1961-05-03 | 1968-12-24 | Du Pont | Hexafluoro-2-propanol and its complex with tetrahydrofuran |
| GB963269A (en) * | 1961-07-08 | 1964-07-08 | Distillers Co Yeast Ltd | Production of ketones and secondary alkanols |
| US3449435A (en) * | 1963-05-31 | 1969-06-10 | Kyowa Hakko Kogyo Kk | Process for the catalytic vapor phase hydrogenation of an beta-unsaturated carbonyl compound with a gaseous mixture of hydrogen and a lower alkane |
| DE1277232B (en) * | 1967-03-18 | 1968-09-12 | Basf Ag | Process for the preparation of saturated aliphatic alcohols |
| FR1595013A (en) * | 1968-01-17 | 1970-06-08 | ||
| JPS5550704B2 (en) * | 1972-06-08 | 1980-12-19 |
-
1980
- 1980-04-03 JP JP55042808A patent/JPS6036411B2/en not_active Expired
-
1981
- 1981-03-19 GB GB8108711A patent/GB2073181B/en not_active Expired
- 1981-03-25 DE DE3111817A patent/DE3111817C2/en not_active Expired
- 1981-03-31 IT IT20854/81A patent/IT1136832B/en active
- 1981-04-02 FR FR8106654A patent/FR2479803A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3111817A1 (en) | 1982-02-18 |
| FR2479803A1 (en) | 1981-10-09 |
| IT1136832B (en) | 1986-09-03 |
| GB2073181A (en) | 1981-10-14 |
| FR2479803B1 (en) | 1984-12-21 |
| GB2073181B (en) | 1984-08-08 |
| JPS56139433A (en) | 1981-10-30 |
| DE3111817C2 (en) | 1985-06-05 |
| IT8120854A0 (en) | 1981-03-31 |
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