GB2073181A - Preparation of 1,1,1,3,3,3- hexafluoropropane-2-ol by Vapor Phase Hydrogenation of Hexafluoroacetone with Nickel Catalyst - Google Patents
Preparation of 1,1,1,3,3,3- hexafluoropropane-2-ol by Vapor Phase Hydrogenation of Hexafluoroacetone with Nickel Catalyst Download PDFInfo
- Publication number
- GB2073181A GB2073181A GB8108711A GB8108711A GB2073181A GB 2073181 A GB2073181 A GB 2073181A GB 8108711 A GB8108711 A GB 8108711A GB 8108711 A GB8108711 A GB 8108711A GB 2073181 A GB2073181 A GB 2073181A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- hexafluoroacetone
- process according
- vapor phase
- hydrogenation
- 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.)
- Granted
Links
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 title claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 26
- 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 claims abstract description 19
- 239000012808 vapor phase Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 abstract description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000005297 pyrex Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007524 organic acids Chemical class 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
- 239000000047 product Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004063 acid-resistant material Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- -1 lithium aluminum hydride Chemical compound 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 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
- 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
- 235000005985 organic acids Nutrition 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
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Abstract
A process of preparing 1,1,1,3,3,3-hexafluoropropane-2-ol by vapor phase catalytic hydrogenation of hexafluoroacetone with hydrogen gas, characterized by the employment of a catalyst containing metallic nickel as its essential component. Because of high effectiveness of this catalyst the hydrogenation reaction can proceed even at relatively low temperature, so that the reaction temperature is maintained within the range from 30 DEG C to 140 DEG C to avoid formation of acidic compounds by side reactions. In this process nearly theoretical conversion of hexafluoroacetone can be achieved with 100% selectivity for 1,1,1,3,3,3-hexafluoropropane-2-ol.
Description
SPECIFICATION
Preparation of 1,1,1 ,3,3,3-Hexafluoropropane- 2-ol by Vapor Phase Hydrogenation of
Hexafluoroacetone with Nickel Catalyst
This invention relates to a process of preparing 1,1,1 ,3,3,3-hexafluoropropane-2-ol by vapor phase catalytic hydrogenation of hexafl uoroacetone.
It has been reported that 1,1,1,3,3,3hexafluoropropane-2-ol is a compound useful as either a surface active agent or an emulsifying agent (according to Belgian Patent No. 634,368), as a solvent for some polymers such as vinyl polymers of carboxylic acids (according to U.S.
Patent No. 3,153,004) and as an intermediate of some anesthetic compounds (according to U.S.
Patent No. 3,346,448).
Usually 1,1,1 ,3,3,3-hexafluoropropane-2-ol is prepared from hexafluoroacetone, and various kinds of reduction or hydrogenation methods for this purpose have heretofore been proposed.
Typical examples of such proposals are: liquid phase reduction by using sodium boron hydride (U.S.S.R. Patent No. 138,604) or lithium aluminum hydride (U.S. Patent No. 3,227,674); liquid phase hydrogenation by using platinum oxide catalyst (U.S. Patent No. 3,607,952) or metallic palladium catalyst together with an inorganic basic salt of an alkali metal effective as a promoter (German Patent No.2,113,551); and vapor phase hydrogenation by using metallic copper-chromium oxide catalyst (Belgian Patent
No. 634,368), platinum oxide catalyst without carrier (J. Am. Chem. Soc., Vol. 86(1964), 494852), palladium catalyst carried by aluminium oxide pellets (Dutch Patent Application No.
6610936) or palladium catalyst carried by carbon (German Patent No. 1,956,629).
among these methods, the liquid phase hydrogenation method and the vapor phase hydrogenation method are considered to be more suitable to industrial practice than the initially mentioned liquid phase reduction method.
However, the liquid phase hydrogenation method is rather disadvantageous in the necessity of using an expensive noble-metal catalyst and also in the need of performing the hydrogenation at a considerably high pressure.
The vapor phase catalytic hydrogenation method is advantageous in the possibility of accomplishing continuous hydrogenation of hexafluoroacetone at atmospheric pressures.
However, in the case of using a relatively economical catalyst such as a metallic copperchromium oxide catalyst in this method, the conversion of hexafluoroacetone to 1,1,1,3,3,3hexafluoropropane-2-ol remains at an unsatisfactory low level even when the reaction temperature is raised considerably and the contact time is prolonged. To raise the conversion factor to an industrially satisfactory level, it becomes necessary to employ a noble-metai catalyst though it is undesirable from the economical viewpoint. Moreover, the catalytic hydrogenation reaction must be performed at a temperature above 1 5000 to realize a satisfactorily high conversion factor.However, the employment of such a high reaction temperature often results in formation of acidic compounds such as hydrofluoric acid and/or some organic acids as by-products of the intended hydrogenation reaction, and in that case the acidic compounds tend to deactiveate the catalyst. Therefore, it becomes a requisite to employ an acid-resistant material for the carrier of the catalyst.
It is an object of the present invention to provide an improved process of preparing 1,1,1 ,3,3,3-hexafluoropropane-2-ol by vapor phase catalytic hydrogenation of hexafluoroacetone, which process can be performed under mild reaction conditions by using an economical catalyst but nevertheless can realize a very high rate conversion of hexafluoroacetone with an extremely high selectivity factor for 1,1,1,3,3,3- hexafluoropropane-2-ol, without forming any acidic by-products detrimental to the activity of the catalyst.
According to the present invention, vapor phase catalytic hydrogenation of hexafluoroacetone with hydrogen to form 1,1,1 ,3,3,3-hexafluoropropane-2-ol is performed by the employment of a catalyst which comprises metallic nickel as an essential component thereof, and the hydrogenation reaction temperature is maintained within the range from 300C to 1400C.
The process according to the invention can be performed at atmospheric pressures, and a relatively short contact time suffices to complete the hydrogenation reaction.
The catalyst is not required to be nickel alone and can be prepared in various forms and compositions as will later be described.
By this process it is easy to achieve nearly complete conversion of hexafluoroacetone introduced into the reaction apparatus, and the selectivity factor for 1,1 ,1 ,3,3,3- hexafloropropane-2-ol becomes 100%. Since no acidic compounds are formed as byproducts, the nickel catalyst in the reaction apparatus has a very long service life with only very small loss in its activity.
A catalyst used in the present invention comprises metallic nickel, which is preferably a reduced nickel obtained, for example, by reduction of a suitable nickel compound such as nickel oxide, nickel carbonate or nickel hydroxide in a hydrogen gas atmosphere or by thermal decomposition reduction of a nickel salt of an organic acid such as nickel formate, oxalate or acetate in the absence of oxygen. Of course it is possible to employ a catalyst substantially wholly consisting of metallic nickel, but it is also possible to use a catalyst in which metallic nickel is carried by a conventional carrier the material of which is exemplified by activated carbon or charcoal, activated alumina and zinc oxide.Furthermore, metallic nickel may be mixed with at least one kind of catalytic metal oxide such as cupric oxide and/or chromic oxide, and/or promoter(s) such as manganese dioxide and/or zirconium dioxide, and a resultant mixture may be shaped into granules or pellets by using a familiar support material such as diatomite (kieselguhr) or terra alba.
Usually it suffices to use 0.1 to 5 parts by weight of nickel for 100 parts by weight of hexafluoroacetone to be hydrogenated.
By using such a nickel catalyst it becomes possible to realize the intended hydrogenation reaction at a relatively low temperature which is required by the present invention to be within the range from 300C to 1 400C. If the reaction temperature is made to be lower than 300C, the product of the hydrogenation reaction tends to condense within the reaction tube. If the reaction temperature is raised beyond 1 400C, there arises the possibility of side reactions that will form acidic compounds as undesirable by-products of the process, with natural decrease in the yield of the intended compound.
Insofar as a nickel cayalyst is used and the reaction temperature is maintained within the specified range, theprocess according to the invention can be performed similarly to a known vapor phase catalytic hydrogenation of hexafluoroacetone by using a known apparatus.
As to the quantity of hydrogen gas used in the process of the invention, the minimum requirement is the mole equivalent to hexafluoroacetone to be hydrogenated. However, there arises no problem by using excess quantity of hydrogen gas to serve the function of carrier gas for hexafluoroacetone.
Usually the contact time in the hydrogenation reaction according to the invention is made shorter than about 30 seconds and can be made shorter as the reaction temperature is made higher. In most cases a relatively short contact time such as 5-10 seconds is sufficient to achieve nearly theoretical conversion of hexafluoroacetone to 1,1,1,3,3,3hexafluoropropane-2-ol.
The invention will be illustrated by the following non-limitative examples. Some references are also presented for the sake of comparison.
Example 1
Use was made of a reduced nickel catalyst which was in the form of pellets 5 mm in diameter and contained 45 47% of Ni, 27- 29% of diatomite, 2-3% of Cr, 2-3% of Cu and 4-5% of graphite by weight. 4 g of this catalyst was packed in a Pyrex tube having an inner diameter of 13 mm and preliminarily activated by heating at 185do in a hydrogen gas stream passed through the tube and then cooled to about 600C.
Thereafter a mixed gas of hexafluoroacetone (10 g/hr) and hydrogen (4800 ml/hr) was continuously passed through the tube packed with the activated catalyst to cause hydrogenation of hexafluoroacetone by vapor phase catalytic reaction. The hydrogenation
reaction proceeded so rapidly that the reaction temperature in the tube soon rose to 800C, and thereafter the reaction temperature was maintained constantly at 8O0C. The length of the catalyst column in the tube and the flow rate of the mixed gas were such that the contact time in this hydrogenation reaction was 4 seconds.
At an initial stage soon after the rise of the reaction temperature to 800C, the conversion of the supplied hexafluoroacetone was 99.2%, and the selectivity factor for 1 , 1 .1,3,3,3- hexafluoropropane-2-ol was 100%. After continuation of the reaction for 20 hours, the conversion of hexafluoroacetone was 99.0%, and the selectivity factor for 1 ,1 ,1 ,3,3,3- hexafluoropropane-2-ol was 100%, meaning that the catalyst in the reaction tube exhibited no loss in its activity during the time period of 20 hours.
Reference 1
The materials, catalyst and apparatus of
Example 1 were employed with no alteration. In this case, however, the reaction temperature in the vapor phase hydrogenation of hexafluoroacetone was raised up to and
maintained at 1 500C, and the contact time was extended to 8 seconds.
The product of this hydrogenation process contained considerable amounts of water and acids as by-products. The conversion of
hexafluoroacetone was 99.2%, but the selectivity factor for 1,1,1 ,3,3,3hexafluoropropane-2-ol was
only 78.1%.
Example 2
Using the same catalyst and apparatus as in
Example 1, hexafluoroacetone and hydrogen in
the proportion of 1:3 by mole were passed
through the reaction tube to undergo vapor phase
contact reaction. In this example the reaction temperature was maintained at a relatively low
level of 700C, but the contact time was 4 seconds similarly to the process of Example 1.
The conversion of hexafluoroacetone in this example was 97.5%, and the selectivity factor for 1,1,1,3,3,3-hexafluoropropane-2-ol was 100%.
Example 3
A mixture of 40 g of the reduced nickel catalyst used in Example 1 and 70 g of activated charcoal was packed in a Pyrex tube having an inner diameter of 25 mm. Hexafluoroacetone (40 g/hr) and hydrogen (three times the mole equivalent to the hexafluoroacetone were continuously passed through the thus prepared reaction tube to undergo vapor phase hydrogenation reaction with control of the reaction temperature to a very low level of 40dC and the contact time to 7 seconds.
In this case the conversion of hexafluoroacetone was 99.870, and the selectivity factor for 1,1,1 ,3,3,3-hexafluoropropane-2-ol was 100%. It was confirmed that no acidic compounds were formed as by-products of this reaction.
Reference 2
Use was made of a copper-chromium oxide catalyst containing 4446% of CuO, 43-44% of Cr2O3 and 45% of MnO2 by weight. 20 g of this catalyst was packed in a Pyrex tube having an inner diameter of 1 3 mm, and hexafluoroacetone (10 g/hr) and hydrogen (three times the mole equivalent to the hexafluoroacetone) were continuously passed through the tube. The reaction temperature was maintained at 800C, and the contact time was made to be 10 seconds.
In this experiment, however, hexafluoroacetone scarcely underwent hydrogenation: numerically, the conversion of hexafluoroacetone was only 0.5%.
Reference 3
The catalyst in Reference 2 was replaced by 10 g of a catalyst containing 0.5% of palladium supported on carbon, using the same Pyrex tube as in Reference 2. Hexafluoroacetone and hydrogen were passed through the tube at the same flow rates and molar ratio as in Reference 2.
In this case the reaction temperature was maintained at 2000 C, and the contact time was made to be 7 seconds.
As the result the conversion of hexafluoroacetone reached 96.5%, but the selectivity factor for 1,1,1,3,3,3hexafluoropropane-2-ol was as low as 70.4% since large amounts of acidic compounds were formed as by-products.
Claims (11)
1. A process of preparing 1,1,1,3,3,3hexafluoropropane-2-ol by vapor phase rection of hexafluoroacetone with hydrogen in the presence of a hydrogenation catalyst, characterized in that said catalyst comprises metallic nickel as an essential component thereof and that the reaction temperature is maintained within the range from 30into 14O0C.
2. A process according to Claim 1, wherein said metallic nickel is a reduced nickel.
3. A process according to Claim 1, wherein the catalytic component of said catalyst is entirely metallic nickel.
4. A process according to Claim 1, wherein said catalyst further comprises a metal oxide having a catalytic activity on vapor phase hydrogenation of hexafluoroacetone.
5. A process according to Claim 3 or 4, wherein said catalyst further comprises a carrier.
6. A process according to Claim 5, wherein the material of said carrier is selected from the group consisting of carbon, alumina and zinc oxide
7. A process according to Claim 3 or 4, wherein said catalyst further comprises a metal oxide effective as a catalytic activity promoter.
8. A.process according to Claim 7, wherein said catalyst further comprises a support material selected from the group consisting of diatomite and terra alba and takes the form of pellets.
9. A process according to Claim 1, wherein said catalyst further comprises a support material selected from the group consisting of diatomite and terra alba, at least a portion of said catalyst taking the form of pellets each of which contains said metallic nickel and said support material.
1 0. A process according to Claim 1 , wherein said vapor phase reaction is caused by continuouslypassing hexafluoroacetone and hydrogen through a reaction chamber in which is disposed said catalyst.
11. A process according to Claim 10, wherein hexafluoroacetone, hydrogen and said catalyst are allowed to contact with each other for a time period not longer than 30 seconds.
1 2. A process according to Claim 11, wherein said time period is in the range from 5 to 10 seconds.
1 3. A process of preparing 1,1,1,3,3,3hexafluoropropane-2-ol as claimed in Claim 1, substantially as herein described in any one of
Example 1 to 3.
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 |
|---|---|
| GB2073181A true GB2073181A (en) | 1981-10-14 |
| GB2073181B GB2073181B (en) | 1984-08-08 |
Family
ID=12646252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8108711A Expired 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 |
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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3242618A1 (en) * | 1981-11-18 | 1983-06-01 | Central Glass Co., Ltd., Ube, Yamaguchi | PRODUCTION OF 2-TRIFLUORMETHYL PROPANOL BY VAPOR PHASE HYDRATION OF 2-TRIFLUORMETHYL PROPANAL |
| US7524995B1 (en) | 2008-06-12 | 2009-04-28 | E.I. Du Pont De Nemours And Company | Continuous process to produce hexafluoroisopropanol |
Families Citing this family (2)
| 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 |
| 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 |
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
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3242618A1 (en) * | 1981-11-18 | 1983-06-01 | Central Glass Co., Ltd., Ube, Yamaguchi | PRODUCTION OF 2-TRIFLUORMETHYL PROPANOL BY VAPOR PHASE HYDRATION OF 2-TRIFLUORMETHYL PROPANAL |
| US4540835A (en) * | 1981-11-18 | 1985-09-10 | Central Glass Company Limited | Preparation of 2-trifluoromethylpropanol by vapor phase hydrogenation of 2-trifluoromethylpropanal |
| US7524995B1 (en) | 2008-06-12 | 2009-04-28 | E.I. Du Pont De Nemours And Company | Continuous process to produce hexafluoroisopropanol |
| WO2009152006A2 (en) | 2008-06-12 | 2009-12-17 | E. I. Du Pont De Nemours And Company | Continuous process to produce hexafluoroisopropanol |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2479803B1 (en) | 1984-12-21 |
| JPS6036411B2 (en) | 1985-08-20 |
| IT1136832B (en) | 1986-09-03 |
| JPS56139433A (en) | 1981-10-30 |
| GB2073181B (en) | 1984-08-08 |
| FR2479803A1 (en) | 1981-10-09 |
| IT8120854A0 (en) | 1981-03-31 |
| DE3111817C2 (en) | 1985-06-05 |
| DE3111817A1 (en) | 1982-02-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20000319 |