A METHOD FOR PRODUCING COMPOUNDS HAVING A DOUBLE BOND AT THE TERMINAL

Abstract: A method for producing a compound having a double bond at the terminal which comprises dehydrating a compound rep­ resented by the formula (I), R - - CH₃ (I) wherein R is a C₃ - C₂₀ hydrocarbon group which may have one or more double bonds, by contacting with zirconium oxide as a catalyst. According to the method described above, ter­ minal olefins which are useful as a material for heat-resistant polymers, a comonomer for polyolefins, a raw material for de­ tergents, etc. are provided at low costs and with safety.

Description: A.METHOD FOR PRODUCING COMPOUNDS HAVING A DOUBLE .BOND AT THE TERMINAL The present invention relates to a method for producing a compound having a double bond at the terminal (hereinafter referred to as terminal olefin). More particularly, the present invention relates to a method for producing the terminal olefin by dehydration of a compound represented by the formula (I), EMI1.1 wherein R is a C3 - C20 hydrocarbon group which may have one or more double bonds. It is hitherto well known that an olefin can be produced by dehydration of a compound represented by the formula (I). The details of the method can be known, for example, from J. Am. Chem. Soc., 85, 2180 (1963), Oil Chemistry, 17, 236 (1968), etc. But, dehydration with the usual solid acid catalyst mainly produced the internal olefin to fail to selectively produce the terminal olefin. Thorium oxide is known as a catalyst for the selective production of the terminal olefin, but its use in industry is difficult because thorium is a radioactive element so that there occurs a serious problem of safety in handling thorium oxide as a catalyst. The present inventors extensively studied to overcome the defects of the conventionally well-known catalyst, i.e., (1) the internal olefin is mainly produced and the selectivity of the terminal olefin is low, (2) the catalyst contains a radioactive element so that there is a problem of safety, and thereby to find a method which can produce the terminal olefin with good selectivity and safety. As a result, the present inventors found the followings: In producing a compound having a double bond at the terminal by dehydration of a compound represented by the foregoing formula (I), said compound having a double bond at the terminal can be produced at low costs as well as with good efficiency and safety by using zirconium oxide as a catalyst. The present inventors thus completed the present invention. An object of the present invention is to provide a method for producing terminal olefinsat low costs and with safety which is useful as a material for heatresistant polymers, a comonomer for polyolefins, a raw material for detergents and the like. The accompanying drawing shows the relationsp between the total content of silicon dioxide and titanium dioxide and the selectivity of vinylcyclohexane. The starting material used in the method of the present invention is a compound represented by the formula (I), EMI3.1 wherein R is a C3 - C20 hydrocarbon group which may have one or more double bonds. R is not particularly limited so far as it is a C3 - C20 hydrocarbon group, but it is preferably a C3 - C10 hydrocarbon group and more preferably a C3 - C10 saturated hydrocarbon group. Among them 4methyl-2-pentanol and l-cyclohexylethanol are most preferred. In the practice of the present invention with this material, the OH group and the hydrogen atom of the methyl group in the formula (I) are released in the form of water to selectively produce the terminal olefin. Generally, zirconium compounds are produced by various methods using Zircon, Baddeleyite, etc. as a raw material, but complete removal of silicon, titanium, aluminum, iron, etc. contained in raw ores is so difficult that it is usual for zircornium products to contain these impurities in trace amounts. It is preferred that the zirconium nndP used in the present invention is of high purity, and that it does not contain particularly silicon and titanium among these impurities so far as possible. When the total content, as oxide, of the both metals is 0.3 wt.% or less, a sufficient selectivity is obtained in the production of the terminal olefin, and when the total content is 0.1 wt.% or less, a more preferred selectivity is obtained. Zirconium oxide used in the present invention is obtained by various methods, and particularly, one obtained by calcination of zirconium compounds at 3000 to 15000C is preferred. In this case, preferred examples of zirconium compound used for calcination include for example zirconium hydroxide, zirconyl hydroxide, zirconium nitrate, zirconyl nitrate, zirconyl carbonate, zirconium alkoxide and the like, These compounds may be calcined in a state wherein they are supported on suitable carriers, or zirconium oxide after calcination may be supported on suitable carriers. Of course, it is also a preferred example of use to use zirconium oxide itself after calcination as a catalyst without using carriers. It is also possible to prepare the catalyst in the coexistence of a second component such as yttrium, etc. if necessary. The calcination temperature is generally 3000 to 15000C, but preferably, a temperature of 5000 to 11000C is employed. The calcination time is generally 0.1 to 50 hours, but preferably, a period of time of 1 to 10 hours is employed. Generally, the activity tends to lower as the calcination temperature becomes high, and sufficient activity comes to fail to appear when the temperature exceeds 15000C. Next, a method for practicing the present invention will be explained. A method of reaction is not particularly limited, but generally, a gas-phase reaction of fixed-bed form or fluidized-bed form is employed. The reaction temperature is generally 2000 to 500 C, but preferably, a temperature of 3000 to 4000C is employed. The reaction pressure is not particularly limited, and the reaction may be carried out at atmospheric pressure or under pressure a little higher than that. If necessary, a method may also be employed in which the starting material (I) is reacted in dilution with an inert gas such as nitrogen, etc. The reaction under a reduced pressure also gives a good result. For the feed rate of the starting material, a rate of 0.1 to 15 her 1, preferably 0.5 to 5 her 1, as expressed by LHSV, is employed. The present invention will be explained in more detail with reference to the following examples, but it is not limited to these examples. EXAMPLE 1 A hard glass tubular reactor of 12.5 mm in internal diameter having at the center a tubular sheath of .4 mm in external diameter for temperature measurement was packed with 12 ml of a zirconia catalyst, which had been prepared by calcination of zirconium hydroxide hring a ptrticle size of 0,7 to 1,7mm at 10000C for 2 hours, and Generally heated in an electric furnace. To this tubular reactor were supplied 8.6 ml/hr (LHSV=0.72 hr-1) of 4-methyl-2-pentanol and 3.2 l/min of nitrogen gas at atmospheric pressure through a gasificater heated by an electric furnace to contact with the catalyst. The reaction gas from the tubular reactor was analyzed by gas chromatography. As a result, the followings were found: Conversion of the starting material, 89%; selectivity of 4-methylpenten-l, 90%; selectivity of 4-methylpenten-2, 58; and selctivity of methyl isobutyl ketone, 5%. The temperature of the electric furnace at that time was 363 C. The SiO2 and TiO2 contents of the catalyst were 0.05 wt.% or less and 0.01 wt.% or less, respectively. The result is shown in Table 1. EXAMPLES 2 to 4 Experiments with various kinds of alcohol were carried out in the same manner as in Example 1 except that the amount of catalyst used was 4 ml; the alcohol, a starting material, was supplied together with 0.4 l/min of nitrogen gas; and the zirconium oxide catalyst used was prepared by calcining zirconyl nitrate [ZrO(NO3)2 2H2OI at 10000C for 2 hours, and its SiO2 and TiO2 contents were 0.05 wt.% or less and 0.01 wt.% or less, respectively. The results are shown in Table 1. Table 1 EMI8.1 Catalyst <SEP> Reaction <tb> Impurity <SEP> Reaction <tb> Example <SEP> Calcination <tb> Material <SEP> for <SEP> (wt.%) <SEP> Starting <SEP> temperature <SEP> ( C) <tb> condition <tb> catalyst <SEP> material <SEP> (furnace <tb> ( C <SEP> x <SEP> hr) <tb> SiO2 <SEP> TiO2 <SEP> temperature) <tb> Zirconium <SEP> 4-Methyl-21000 <SEP> x <SEP> 2 <SEP> #0.05 <SEP> #0.01 <SEP> 363 <tb> hydroxide <SEP> pentanol <tb> Zirconyl <tb> 2 <SEP> nitrate, <SEP> 1000 <SEP> x <SEP> 2 <SEP> #0.05 <SEP> #0.01 <SEP> 2-Hexanol <SEP> 360 <tb> ZrO(NO3)2.2H2O <tb> 3 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 2-Octanol <SEP> 370 <tb> 2-Nonyl4 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 368 <tb> alcohol <tb> - Cont'd - Table 1 (Cont'd) EMI9.1 Feed <SEP> rate <SEP> of <tb> Selectivity <SEP> Selectivity <SEP> Selectivity <tb> starting <SEP> Conversion <tb> of <SEP> terminal <SEP> of <SEP> other <SEP> of <SEP> ketone <tb> material <SEP> (%) <tb> olefin <SEP> (%) <SEP> olefins <SEP> (%) <SEP> (%) <tb> (ml/hr) <tb> 8.6 <SEP> 89 <SEP> 90 <SEP> 5 <SEP> 5 <tb> 8 <SEP> 90 <SEP> 90 <SEP> 4 <SEP> 6 <tb> 7 <SEP> 93 <SEP> 89 <SEP> 6 <SEP> 5 <tb> 8 <SEP> 90 <SEP> 89 <SEP> 6 <SEP> 5 <tb> EXAMPLES 5 to 8 Experiments were carried out using catalysts prepared by changing the calcination temperature of zirconyl nitrate. The experimental condition was the same as in Example 1 except that 4-Methyl-2-pentanol was used as a starting material; 2 1/mien of nitrogen gas was supplied at the same time; and the amount of every catalyst used was 4 ml. The results are shown in Table 2. Table 2 (Effect of calcination temperature of catalyst) EMI11.1 Catalyst <SEP> Reaction <tb> Impurity <SEP> Reaction <tb> Example <SEP> Calcination <tb> Material <SEP> for <SEP> (wt.%) <SEP> Starting <SEP> temperature <SEP> ( C) <tb> condition <tb> catalyst <SEP> material <SEP> (furnace <tb> ( C <SEP> x <SEP> hr) <tb> SiO2 <SEP> TiO2 <SEP> temperature) <tb> Zirconyl <tb> 4-Methyl-25 <SEP> nitrate, <SEP> 400 <SEP> x <SEP> 2 <SEP> #0.05 <SEP> #0.01 <SEP> 285 <tb> pentanol <tb> ZrO(NO3)2.2H2O <tb> 6 <SEP> Ditto <SEP> 600 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 299 <tb> 7 <SEP> Ditto <SEP> 800 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 314 <tb> 8 <SEP> Ditto <SEP> 1000 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 350 <tb> - Cont'd - Table 2 (Cont'd) EMI12.1 Feed <SEP> rate <SEP> of <SEP> Selectivity <SEP> Selectivity <SEP> Selectivity <tb> Conversion <tb> material <SEP> of <SEP> terminal <SEP> of <SEP> other <SEP> of <SEP> ketone <tb> (%) <tb> (ml/hr) <SEP> olefin <SEP> (%) <SEP> olefins <SEP> (%) <SEP> (%) <tb> 3 <SEP> 89 <SEP> 87 <SEP> 6 <SEP> 7 <tb> 3 <SEP> 89 <SEP> 90 <SEP> 5 <SEP> 5 <tb> 3 <SEP> 90 <SEP> 91 <SEP> 3 <SEP> 6 <tb> 3 <SEP> 93 <SEP> 87 <SEP> 3 <SEP> 10 <tb> EXAMPLE 9 A hard glass tubular reactor of 19 mm in internal diameter having at the center a tubular sheath of 6 mm in external diameter for temperature measurement was packed with 27 ml of a zirconia catalyst, which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 10000C for 2hours,and ex-tennaUy,.heated in an electric furnace. To this tubular reactor were supplied 28 ml/hr (LHSV=1.04 hr 1) of l-cyclohexylethanol and 1.5 1/mien of nitrogen gas at atmospheric pressure through a gasificater heated by an electric furnace. The reaction gas from the tubular reactor was trapped and analyzed by gas chromatography. At the point when the activity of the catalyst reached a stationary state, the followings were found: Conversion of the starting material, 90%; selectivity of vinylcyclohexane, 90%; selectivity of ethylidenecyclohexane, 4.5%; and selectivity of methyl cyclohexyl ketone, 5.5%. The central temperature of the catalyst at that time was 3760C. An about 100-hour continuous run was made but with little change in the activity and selectivity. The SiO2 and TiO2 contents of the catalyst were 0.05 wt.% or less and 0.01 wt.% or less, respectively. The results are collectively shown in Table 3. EXAMPLES 10 to 17 Experiments were carried out with various catalysts and under various conditions according to Exmmple 1. The results are shown in Table 3. Table 3 Effects of catalyst (including calcination temperature) and reaction condition EMI14.1 Catalyst <SEP> Reaction <tb> Impurity <tb> Example <SEP> Calcination <SEP> Reaction <tb> Material <SEP> for <SEP> (wt.%) <SEP> Starting <tb> condition <SEP> temperacatalyst <SEP> material <tb> ( C <SEP> x <SEP> hr) <SEP> ture*3 <SEP> ( C) <tb> SiO2 <SEP> TiO2 <tb> Zirconium <tb> 9 <SEP> hydroxide, <SEP> 1000 <SEP> x <SEP> 2 <SEP> #0.05 <SEP> #0.01 <SEP> CHE <SEP> 376 <tb> Zr(OH)4 <tb> 10 <SEP> Ditto <SEP> 360 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 326 <tb> 11 <SEP> Ditto <SEP> 405 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 332 <tb> 12 <SEP> Ditto <SEP> 510 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 332 <tb> 13 <SEP> Ditto <SEP> 610 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 329 <tb> 14 <SEP> Ditto <SEP> 800 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 351 <tb> 15 <SEP> Ditto <SEP> 900 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 372 <tb> 16 <SEP> ZrO(NO3)2.2H2O <SEP> 400 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 345 <tb> ZrO(NO3)2.2H2O <tb> 17 <SEP> 400 <SEP> x <SEP> 2 <SEP> Ditto <SEP> Ditto <SEP> Ditto <SEP> 350 <tb> supported <SEP> on <tb> alumina*2 <tb> <RTI ID=14.2> -Cont'd Note: * Reaction was carried out using a Pyrex glass tubular reactor of 28 mm in internal diameter packed with 100 ml of the cytalyst. *2 Zirconyl nitrate was supported on an &alpha;-alumina in an amount of 20 wt.%, as converted to anhydrous basis, of the &alpha;-alumina. *3 Central temperature of catalyst. Table 3 (Cont'd) EMI15.1 Feed <SEP> rate <SEP> of <SEP> Selectivity <SEP> Selectivity <tb> Feed <SEP> rate <SEP> Selectivity <tb> starting <SEP> Conversion <SEP> of <SEP> terminal <SEP> of <SEP> other <tb> of <SEP> N2 <SEP> of <SEP> ketone <tb> material <SEP> (%) <SEP> olefin(VCH) <SEP> olefins <tb> (1/min) <SEP> (MCK) <SEP> (%) <tb> LHSV <SEP> (hr-1) <SEP> (%) <SEP> (EDC) <SEP> (%) <tb> 1.04 <SEP> 1.5 <SEP> 90 <SEP> 90 <SEP> 4.5 <SEP> 5.5 <tb> 2.7 <SEP> 1.5 <SEP> 94 <SEP> 78 <SEP> 15 <SEP> 7 <tb> 2.7 <SEP> 1.5 <SEP> 93 <SEP> 79 <SEP> 15 <SEP> 5 <tb> 2.8 <SEP> 1.5 <SEP> 87 <SEP> 80 <SEP> 16 <SEP> 4 <tb> 2.9 <SEP> 1.5 <SEP> 83 <SEP> 80 <SEP> 15 <SEP> 5 <tb> 1.4 <SEP> 1.5 <SEP> 81 <SEP> 85 <SEP> 9 <SEP> 5 <tb> 1.3 <SEP> 1.5 <SEP> 93 <SEP> 87 <SEP> 4 <SEP> 9 <tb> 1.6 <SEP> 5.3* <SEP> 90 <SEP> 81 <SEP> 13 <SEP> 5 <tb> 2.2 <SEP> 1.5 <SEP> 92 <SEP> 81 <SEP> 15 <SEP> 4 <tb> CHE 1-Cyclohexylethanol EDC Ethylidenecyclohexane VCH Vinylcyclohexane MCK Methyl cyclohexyl ketone EXAMPLE 18 A stainless steel tubular reactor of 16 mm in internal diameter having at the center a tubular sheath of 4 mm in external diameter for temperature measurement was packed with 30 ml of zInxnium oxide having a particle size of 0,7 - to 1,7 mm and externally heated in an electric furnace. To this tubular reactor were supplied 29 ml/hr (LHSV=0.98 hr-1) of l-cyclohexylethanol and 1.4 1/min of nitrogen gas at atmospheric pressure through a gasificater heated by an electric furnace. The reaction gas from the reactor was trapped and analyzed by gas chromatography. As a result, the followings were found: Conversion of the starting material, 90%; selectivity of vinylcyclohexane, 84%; selectivity of ethylidenecyclohexane, 10%; and selectivity of methyl cyclohexyl ketone, 6%. The central temperature of the catalyst at that time was 3650C. The SiO2 and TiO2 contents of the catalyst were 0.05 wt.% or less and 0.01 wt.% or less, respectively. The results are collectively shown in Table 4. EXAMPLE 19 A stainless steel tubular reactor of 4 mm in internal diameter was packed with 7.4 ml of a zirconia catalyst prepared by calcination of zirconium hydoxide having a parLicle size of 0,7 to 1,7 mm at 500 C for 2 bours, and externally heated in an electric furnace. To this tubular reactor was supplied 54 ml/hr (LHSV=7.3 hr-1) of l-cyclohexylethanol at atmospheric pressure. The reaction gas from the reactor was analyzed by gas chromatography. As a result, the followings were found: Conversion of the material, 85%; selectivity of vinylcyclohexane, 81%; selectivity of ethylidenecyclohexane, 6%; and selectivity of methyl cyclohexyl ketone, 13%. The temperature of the electric furnace at that time was 4090C. The silicon and titanium contents, as converted to dioxide basis, of the zirconium oxide catalyst used in this example were 0.03 wt.% or less and 0.001 wt.% or less, respectively. The results are collectively shown in Table 4. EXAMPLE 20 A stainless steel tubular reactor of 8 mm in internal diameter was packed with 50 ml of a zirconia catalyst which had been prepared by calcination of zirconium hydoxide having a particle size of 0,7 to 1,7 my at 4000C for 2 hours, and externally heated in an electric furnace. To this tubular reactor was supplied 90 ml/hr (LHSV=1.8 hr 1) of 4methyl-2-pentanol at atmospheric pressure. The reaction gas from the reactor was analyzed by gas chromatography. As a result, the followings were found: Conversion of the starting material, 90%; selectivity of 4-methyl-lpentene, 81%; selectivity of 4-methyl-2-pentene, 10%; and selectivity of methyl isobutyl ketone, 9%. The temperature of the electric furnace at that time was 4000C. The silicon and titanium contents of the zirconia catalyst used in this example were the same as in Example 19. The results are collectively shown in Table 4. Table 4 EMI18.1 Catalyst <SEP> Reaction <tb> Impurity <tb> Example <SEP> Calcination <SEP> Reaction <tb> Material <SEP> for <SEP> (wt.%) <SEP> Starting <tb> condition <SEP> temperature <tb> catalyst <SEP> material <tb> ( C <SEP> x <SEP> hr) <SEP> ( C) <tb> SiO2 <SEP> TiO2 <tb> Zirconium <SEP> Not <tb> 18 <SEP> #0.05 <SEP> #0.01 <SEP> CHE <SEP> 365* <tb> oxide <SEP> calcined <tb> Zirconium <tb> 19 <SEP> hydroxide <SEP> 500 <SEP> x <SEP> 2 <SEP> #0.03 <SEP> #0.001 <SEP> Ditto <SEP> 409* <tb> Zr(OH)4 <tb> 20 <SEP> Ditto <SEP> 400 <SEP> x <SEP> 2 <SEP> #0.05 <SEP> #0.01 <SEP> MPOH <SEP> 400** <tb> -Cont'd Note: * Central temperature of catalyst. **Furnace temperature. CHE 1-Cyclohexylethanol MPEÚ 4-Methylpenten-1 VCH Vinylcyclohexane MPEê 4-Methylpenten-2 EDC Ethylidenecyclohexane MIBK Methyl isobutyl ketone MCK Methyl cyclohexyl ketone MPOH 4-Methyl-2-petanol Table 4 (Cont'd) EMI19.1 Feed <SEP> rate <SEP> of <SEP> Selectivity <SEP> Selectivity <tb> Feed <SEP> rate <SEP> Selectivity <tb> starting <SEP> Conversion <SEP> of <SEP> terminal <SEP> of <SEP> other <tb> of <SEP> N2 <SEP> of <SEP> ketone <tb> material <SEP> (%) <SEP> olefin <SEP> olefins <tb> (1/min) <tb> LHSV <SEP> (hr-1) <SEP> (%) <SEP> (%) <SEP> (%) <tb> 0.98 <SEP> 1.4 <SEP> 990 <SEP> VCH <SEP> 84 <SEP> EDC <SEP> 10 <SEP> MDK <SEP> 6 <tb> 7.3 <SEP> 0 <SEP> 85 <SEP> VCH <SEP> 81 <SEP> EDC <SEP> 6 <SEP> MCK <SEP> 13 <tb> 1.8 <SEP> 0 <SEP> 90 <SEP> MPEÚ <SEP> 81 <SEP> MPEê <SEP> 10 <SEP> MIBK <SEP> 9 <tb> COMPARATIVE EXAMPLES 1 to 3 Reaction was carried out in the same manner as in Example 18 except that the SiO2 and TiO2 contents of the catalyst used were different from those in Example 18. The results are shown in Table 5. A relationship between, on the one hand, the selectivity of vinylcyclohexane and, on the other hand, the SiO2 and TiO2 contents of the catalysts used in Example 18 and Comparative Examples 1 to 3, is as shown in Fig. 1 (the total content of sio2 and TiO2 of the catalyst used in Example 18 was 0.06 wt.%). Table 5 EMI21.1 Catalyst <SEP> Reaction <tb> Compara Impurity <tb> tive <SEP> Material <SEP> Calcination <SEP> Reaction <tb> (wt.%) <SEP> Starting <tb> example <SEP> for <SEP> condition <SEP> temperature <tb> catalyst <SEP> ( C <SEP> x <SEP> hr) <SEP> material <SEP> ( C)* <tb> SiO2 <SEP> TiO2 <tb> Zirconium <tb> Not <tb> 1 <SEP> oxide <SEP> 0.30 <SEP> 0.08 <SEP> CHE <SEP> 381 <tb> calcined <tb> ZrO2 <tb> 2 <SEP> Ditto <SEP> Ditto <SEP> 0.20 <SEP> 0.30 <SEP> Ditto <SEP> 319 <tb> 3 <SEP> Ditto <SEP> Ditto <SEP> 0.30 <SEP> 0.30 <SEP> Ditto <SEP> 324 <tb> Note: *Central temperature of the catalyst. CHE 1-Cyclohexylethanol VCH Vinylyclohexane Table 5 (Cont'd) EMI22.1 Feed <SEP> rate <SEP> of <SEP> Selectivity <tb> starting <SEP> Conversion <SEP> of <SEP> terminal <tb> material <SEP> (%) <SEP> olefin <SEP> (VCH) <tb> LHSV <SEP> (hr-1) <SEP> (%) <tb> 0.63 <SEP> 95 <SEP> 60 <tb> 0.98 <SEP> 92 <SEP> 50 <tb> 0.98 <SEP> 93 <SEP> 43 <tb>

Claims: WHAT IS CLAIMED IS: 1. A method for producing a compound having a double bond at the terminal which comprises dehydrating a compound represented by the general formula (I), EMI23.1 wherein R is a C3 - C20 hydrocarbon group which may have one or more double bonds, by contacting it with zirconium oxide as a catalyst. 2. A method according to Claim 1, wherein a highpurity zirconium oxide in which the total content of silicon and titanium converted to dioxide basis is 0.3% by weight or less is used as a catalyst. 3. A method according to Claim 2, wherein the total content of silicon and titanium converted to dioxide basis is 0.18 by weight or less in the high purity zirconium oxide. 4. A method according to Claim 1, wherein the zirconium oxide is one prepared by the calcination of a zirconium compound at 300C to 15000C. 5. A method according to Claim 4, wherein the zirconium oxide is one prepared by the calcination of a zirconium compound at 5000 to 10000C. 6. A method according to Claim 1, wherein the C3 - C20 hydrocarbon group in the general formula (I) is a C3 - C10 saturated hydrocarbon group. 7. A method according to Claim 6, wherein the compound of the general formula (I) is 4-methyl-2-pentanol or 1-cyclohexylethanol. 8. A method according to Claim 1, wherein the dehydration is conducted at 2000 to 5000C. 9. A method according to Claim 8, wherein the dehydration is conducted at 3000 to 4000C.

Inventors: ARAKI, MASASHI, HIBI, TAKUO, TAKAHASHI, KAZUTERU
Applicants: SUMITOMO CHEMICAL COMPANY, LIMITED
Application year: 1985
Main classification: C07C1
IPC codes: C07C1