Method for producing alcohol

Abstract

A method for producing an alcohol having 8 or more and 22 or less carbon atoms includes the following steps: step 1: forming a porous layer on a surface of a porous material having a pore size mode of 30 nm or more and 200 nm or less to obtain a bimodal carrier; step 2: supporting cobalt on the bimodal carrier obtained in step 1 to obtain a catalyst having peaks of pore distribution in a range of 1 nm or more and 25 nm or less and a range of 30 nm or more and 200 nm or less, respectively; and step 3: reacting carbon monoxide with hydrogen at a gauge pressure of 2 MPa or more and 100 MPa or less in the presence of the catalyst obtained in step 2.

Claims

1. A method for producing an alcohol having 8 or more and 22 or less carbon atoms comprising the following steps: step 1: forming a porous layer on a surface of a porous material having a pore size mode of 30 nm or more and 200 nm or less to obtain a bimodal carrier, step 2: supporting cobalt on the bimodal carrier obtained in step 1 to obtain a catalyst having peaks of pore distribution in a range of 1 nm or more and 25 nm or less and a range of 30 nm or more and 200 nm or less, respectively; and step 3: reacting carbon monoxide with hydrogen at a gauge pressure of 2 MPa or more and 100 MPa or less in the presence of the catalyst obtained in step 2.

2. The method for producing an alcohol having 8 or more and 22 or less carbon atoms according to claim 1, wherein the porous layer contains one or two or more selected from a silicate, silicon oxide, aluminum oxide, and zirconium oxide.

3. The method for producing an alcohol having 8 or more and 22 or less carbon atoms according to claim 1, wherein step 1 comprises the following steps: step 1-1: supporting a dispersion or a solution containing a raw material of the porous layer on the porous material; and step 1-2: calcining the porous material with the dispersion or the solution supported thereon obtained in step 1-1.

4. The method for producing an alcohol having 8 or more and 22 or less carbon atoms according to claim 1, wherein the porous material contains silicon oxide.

5. The method for producing an alcohol having 8 or more and 22 or less carbon atoms according to claim 1, wherein the reaction temperature in step 3 is 100 C. or more and 300 C. or less.

6. The method for producing an alcohol having 8 or more and 22 or less carbon atoms according to claim 1, wherein in the pore distribution of the catalyst, the peak position of pore distribution is in the range of 4 nm or more and 14 nm or less.

7. The method for producing an alcohol having 8 or more and 22 or less carbon atoms according to claim 1, wherein in the pore distribution of the catalyst, the peak position of pore distribution in the range of 40 nm or more and 200 nm or less.

8. The method for producing an alcohol having 8 or more and 22 or less carbon atoms according to claim 1, wherein the gauge pressure in the reaction in step 3 is 4 MPa or more.

9. A method for producing an alcohol having 8 or more and 22 or less carbon atoms comprising a step of reacting carbon monoxide with hydrogen at a gauge pressure of 2 MPa or more and 100 MPa or less in the presence of the catalyst obtained by forming a porous layer on a surface of a porous material having a pore size mode of 50 nm or more and 100 nm or less to obtain a bimodal carrier and supporting cobalt on said bimodal carrier to obtain a catalyst having peaks of pore distribution in a range of 3 nm or more to 15 nm or less and a range of 50 nm or more to 100 nm or less, respectively.

10. The method for producing an alcohol having 8 or more and 22 or less carbon atoms according to claim 9, wherein a temperature to react carbon monoxide with hydrogen is 100 C. or more and 300 C. or less.

11. The method for producing an alcohol having 8 or more and 22 or less carbon atoms according to claim 9, wherein the gauge pressure in the reaction between carbon monoxide and hydrogen is 4 MPa or more.

Description

EXAMPLES

1. Evaluation Method

(1) (1) Reactivity and Selectivity

(2) (i) Method for Analyzing Gas Component During Reaction

(3) A gas component during a reaction was introduced into a gas chromatograph (also referred to as GC) equipped with a thermal conductivity detector (also referred to as TCD) or a hydrogen flame ionization detector (also referred to as FID) through an outlet pipe from a reaction apparatus for every hour, to subject the gas component to GC analysis using argon as an internal standard substance.

(4) The volume concentration of carbon monoxide in the gas component was calculated with an internal reference method using argon as an internal standard substance from a GC peak area % derived from carbon monoxide and a GC peak area % derived from argon. A calibration curve was prepared by measuring gases obtained by mixing standard gas containing carbon monoxide, methane, and carbon dioxide with argon, and plotting the peak area ratio of carbon monoxide and argon against the volume concentration ratio of carbon monoxide and argon at each mixing ratio.

(5) The volume concentration of methane in the gas component was calculated with an internal reference method using argon as an internal standard substance from a GC peak area % derived from methane and a GC peak area % derived from argon. A calibration curve was prepared by measuring gases obtained by mixing standard gas containing carbon monoxide, methane, and carbon dioxide with argon at various mixing ratios, and plotting the peak area ratio of methane and argon against the volume concentration ratio of methane and argon at each mixing ratio.

(6) The volume concentration of olefin in the gas component was obtained by the following equation.

(7) $\begin{array}{cc}\mathrm{Volume}\mathrm{concentration}\mathrm{of}\mathrm{olefin}\%=\mathrm{Volume}\mathrm{concentration}\mathrm{of}\mathrm{methane}\%\frac{\begin{array}{c}\mathrm{GC}\mathrm{peak}\mathrm{area}\mathrm{derived}\mathrm{from}\mathrm{detected}\mathrm{olefins}\\ \mathrm{having}\mathrm{all}\mathrm{numbers}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\end{array}}{\mathrm{GC}\mathrm{peak}\mathrm{area}\mathrm{derived}\mathrm{from}\mathrm{detected}\mathrm{methane}}& \left[\mathrm{Equation}1\right]\end{array}$

(8) The volume concentration of paraffin in the gas component was obtained by the following equation.

(9) $\begin{array}{cc}\mathrm{Volume}\mathrm{concentration}\mathrm{of}\mathrm{paraffin}\%=\mathrm{Volume}\mathrm{concentration}\mathrm{of}\mathrm{methane}\%\frac{\begin{array}{c}\mathrm{GC}\mathrm{peak}\mathrm{area}\mathrm{derived}\mathrm{from}\mathrm{detected}\mathrm{paraffins}\\ \mathrm{having}\mathrm{all}\mathrm{numbers}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\end{array}}{\mathrm{GC}\mathrm{peak}\mathrm{area}\mathrm{derived}\mathrm{from}\mathrm{detected}\mathrm{methane}}& \left[\mathrm{Equation}2\right]\end{array}$
GC Measurement Conditions
(a) In the case of concentration analysis for carbon monoxide and methane
Amount of sample introduced: 1 mL
Gas chromatograph: GC-320 (manufactured by GL Sciences Inc.)
Detector: TCD (embedded in the gas chromatograph)
Column: Active Carbon (manufactured by GL Sciences Inc., 60 to 80 mesh, column length: 3 m, column inner diameter: 2 mm)
Column temperature condition: 80 C.
Carrier gas: N.sub.2
Inlet pressure: 200 kPa
Temperature of sample introduction part: 110 C.
Temperature of detector: 80 C.
(b) In the Case of Concentration Analysis for Olefin and Paraffin
Amount of sample introduced: 0.8 mL
Gas chromatograph: GC-14B (manufactured by Shimadzu Corporation)
Detector: FID (embedded in the gas chromatograph)
Column: Porapak Q (manufactured by GL Sciences Inc., filler mesh size: 80/100, column length: 3 m, column inner diameter: 2 mm)
Column temperature condition: 70 C. (0 min)->2 C./min->230 C. (0 min)
Carrier gas: N.sub.2
Inlet pressure: 200 kPa
Temperature of sample introduction part: 200 C.
Temperature of detector: 230 C.
(ii) Analysis of Liquid Component of Reaction Product at End of Reaction

(10) After the end of the reaction, the reaction apparatus was cooled to 25 C., and a reactor and an ice trap each containing a product were then removed. The product in the ice trap was mixed in the reactor, and deionized water was added into the mixed solution to separate the mixed solution into an organic layer and a water layer.

(11) To the organic layer, 0.1 g of 1-octanol (manufactured by Kanto Chemical Co., Inc.), 0.1 g of dodecane (manufactured by Kanto Chemical Co., Inc.) as internal standard substances were added, and to the water layer, 0.05 g of tertiary butanol (manufactured by Kanto Chemical Co., Inc.) was added, followed by sufficient stirring to obtain solutions. The solutions were then subjected to GC analysis. 0.2 L of each sample was directly introduced to a GC to subject the sample to GC analysis.

(12) The mass concentrations of alcohols in the organic layer were calculated with an internal reference method using 1-octanol as an internal standard substance from the sum of GC peak areas % derived from detected alcohols. A calibration curve was prepared by measuring a sample obtained by mixing a standard sample of each alcohol with 1-octanol, and plotting the peak area ratio of each alcohol and 1-octanol against the mass concentration ratio of each alcohol and 1-octanol.

(13) The mass concentrations of olefins in the organic layer were calculated with an internal reference method using dodecane as an internal standard substance from the sum of GC peak areas % derived from detected olefins and a GC peak area % derived from dodecane. A calibration curve was prepared by measuring a sample obtained by mixing a standard sample of each olefin with dodecane, and plotting the peak area ratio of each olefin and dodecane against the mass concentration ratio of each olefin and dodecane.

(14) The mass concentrations of paraffins in the organic layer were calculated with an internal reference method using dodecane as an internal standard substance from the sum of GC peak areas % derived from detected paraffins and a GC peak area % derived from dodecane. A calibration curve was prepared from the peak area ratio of each paraffin having a known concentration and dodecane having a known concentration and the concentration ratio of each paraffin and dodecane.

(15) The mass concentrations of alcohols in the water layer were calculated with an internal reference method using tertiary butanol as an internal standard substance from the sum of GC peak areas % derived from detected alcohols and a GC peak area % derived from tertiary butanol. A calibration curve was prepared from the peak area ratio of each alcohol having a known concentration and tertiary butanol having a known concentration and the concentration ratio of each alcohol and tertiary butanol.

(16) GC Measurement Conditions

(17) Amount of sample introduced: 0.2 L

(18) Gas chromatograph: GC-2014 (manufactured by Shimadzu Corporation)

(19) Detector: FID (embedded in the gas chromatograph)

(20) Column: InertCap 5 (manufactured by GL Sciences Inc., column length: 30 m, column inner diameter: 0.25 mm)

(21) Column temperature condition: 40 C. (5 min)->8 C./min->70 C. (1 min)->8 C./min->260 C. (5 min)->10 C./min->310 C. (20 min)->10 C./min->320 C. (9 min)

(22) Carrier gas: N.sub.2 45 mL/min

(23) Temperature of sample introduction part: 310 C.

(24) Temperature of detector: 310 C.

(25) (iii) Method for Calculating CO Conversion, ROH Selectivity, Olefin Selectivity, Paraffin Selectivity, and Number of Carbon Atoms of ROH

(26) The CO conversion, the ROH selectivity, the olefin selectivity, the paraffin selectivity, and the number of carbon atoms of ROH were calculated according to the following equations, respectively.

(27) In the following equations, c-mol (also referred to as number of moles of carbon atoms) is the number of moles of carbon atoms in each component, and is represented by the following equations. c-mol % (also referred to as carbon mol %) is the proportion of the number of moles of carbon atoms of each product to the number of moles of carbon atoms of all products, and is represented by the following equations. The total amount of olefins generated, the total amount of paraffins generated, the total amount of HC generated, the total amount of ROH generated, the CO conversion, the ROH selectivity, the olefin selectivity, the paraffin selectivity, and the number of carbon atoms of ROH were calculated from the following equations.

(28) $\begin{array}{cc}\mathrm{Number}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{carbon}\mathrm{atoms}=\mathrm{Number}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{each}\mathrm{component}\mathrm{Number}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\mathrm{in}\mathrm{each}\mathrm{component}\mathrm{Carbon}\mathrm{mol}\%=\frac{\begin{array}{c}\mathrm{Number}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{carbon}\\ \mathrm{atoms}\mathrm{of}\mathrm{each}\mathrm{product}\end{array}}{\begin{array}{c}\mathrm{Number}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{carbon}\\ \mathrm{atoms}\mathrm{of}\mathrm{all}\mathrm{products}\end{array}}100\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{olefin}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)=\mathrm{Sum}\mathrm{of}\mathrm{the}\mathrm{numbers}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\mathrm{of}\mathrm{generated}\mathrm{olefins}\mathrm{having}\mathrm{all}\mathrm{numbers}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{paraffin}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)=\mathrm{Sum}\mathrm{of}\mathrm{the}\mathrm{numbers}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\mathrm{of}\mathrm{generated}\mathrm{paraffins}\mathrm{having}\mathrm{all}\mathrm{numbers}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{HC}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)=\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{olefin}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)+\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{paraffin}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{ROH}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)=\mathrm{Sum}\mathrm{of}\mathrm{the}\mathrm{numbers}\mathrm{of}\mathrm{moles}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\mathrm{of}\mathrm{generated}\mathrm{alcohols}\mathrm{having}\mathrm{all}\mathrm{numbers}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\text{.Math.}\mathrm{CO}\mathrm{Conversion}\left(\mathrm{mol}\%\right)=(1-\left(\frac{\begin{array}{c}\mathrm{Concentration}\mathrm{of}\mathrm{carbon}\mathrm{monoxide}\\ \mathrm{in}\mathrm{gas}\mathrm{component}\mathrm{at}\\ \mathrm{outlet}\mathrm{of}\mathrm{reactor}\left(\mathrm{mol}\%\right)\end{array}}{\begin{array}{c}\mathrm{Concentration}\mathrm{of}\mathrm{carbon}\mathrm{monoxide}\mathrm{in}\\ \mathrm{gas}\mathrm{supplied}\mathrm{to}\mathrm{reactor}\left(\mathrm{mol}\%\right)\end{array}}\right)100\mathrm{ROH}\mathrm{selectivity}\left(c\text{-}\mathrm{mol}\%\right)=\frac{\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{ROH}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)}{\begin{array}{c}\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{ROH}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)+\\ \mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{HC}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)\end{array}}100\mathrm{Olefin}\mathrm{selectivity}\left(c\text{-}\mathrm{mol}\%\right)=\frac{\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{olefin}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)}{\begin{array}{c}\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{ROH}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)+\\ \mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{HC}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)\end{array}}100\mathrm{Paraffin}\mathrm{selectivity}\left(c\text{-}\mathrm{mol}\%\right)=\frac{\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{paraffin}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)}{\begin{array}{c}\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{ROH}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)+\\ \mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{HC}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)\end{array}}100\mathrm{Number}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\mathrm{of}\mathrm{ROH}\left(c\text{-}\mathrm{mol}\%\right)=\frac{\begin{array}{c}\mathrm{Amount}\mathrm{generated}\mathrm{ROH}\mathrm{having}\\ \mathrm{each}\mathrm{number}\mathrm{of}\mathrm{carbon}\mathrm{atoms}\left(c\text{-}\mathrm{mol}\right)\end{array}}{\mathrm{Total}\mathrm{amount}\mathrm{of}\mathrm{ROH}\mathrm{generated}\left(c\text{-}\mathrm{mol}\right)}100& \left[\mathrm{Equation}3\right]\end{array}$
(2) Composition of Catalyst

(29) After 0.1 g of a catalyst and 2 g of an alkali flux were collected in a platinum crucible, the platinum crucible was heated to 950 C. to melt the content. After the platinum crucible was naturally cooled at 25 C., 10 mL of a mixed solution of hydrochloric acid and ultrapure water was added into the platinum crucible, and the platinum crucible was then heated to 70 C. or more and 80 C. or less to dissolve the content. After the platinum crucible was naturally cooled at 25 C., the volume of the content was set to 100 mL by ultrapure water. An aqueous solution obtained by setting the volume was used as a sample.

(30) A solution for preparing a calibration curve was prepared by adding hydrochloric acid, an alkali flux, and ultrapure water to a cobalt standard solution so that the concentration of hydrogen chloride was set to 0.6 mol/L, and the concentration of an alkali flux was set to 2% by mass.

(31) The sample and the solution for preparing a calibration curve were measured with ICP-AEP, and the content of cobalt in the catalyst was calculated from the concentration of cobalt in the obtained sample.

(32) An ICP emission spectrometer iCAP6500Duo (manufactured by Thermo Fisher Scientific K.K.) was used for measurement of the concentration of cobalt by ICP-AEP.

(33) The alkali flux used was obtained by mixing sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., special grade) with boric acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade) at sodium carbonate: boric acid (mass ratio)=1:0.4. The mixed solution of hydrochloric acid and ultrapure water used was obtained by mixing hydrochloric acid with ultrapure water at hydrochloric acid: ultrapure water (volume ratio)=1:1. The hydrochloric acid used was hydrochloric acid (manufactured by Kanto Chemical Co., Inc., for atomic absorption spectrometry). The cobalt standard solution used was 1000 mg/L of a standard solution for atomic absorption spectrometry (manufactured by Kanto Chemical Co., Inc.).

(34) (3) Method for Measuring Pore Structure

(35) The pore size modes, the pore distributions, the specific surface areas, and the pore volumes of the catalyst and the bimodal carrier were calculated from an adsorption-desorption isotherm obtained by a nitrogen adsorption method performed at 119 points at a relative pressure P/P.sub.0 of 0 to 0.995 using an automatic gas adsorption apparatus AUTOSORB-1 (manufactured by Quantachrome Corporation) at 197 C. The catalyst and the bimodal carrier were dried under reduced pressure at 200 C. for 2 hours, and then measured. Herein, P is an adsorption equilibrium pressure during measurement, and P.sub.0 is the saturated vapor pressure of nitrogen at a measurement temperature.

2. Production Example of Bimodal Carrier

(36) (1) Porous Material

(37) In the production example of the bimodal carrier according to the present invention, the porous material used was a silica carrier CARiACT Q-50 (pore size mode: 65 nm, manufactured by Fuji Silysia Chemical Ltd.).

(38) (2) Raw Material of Porous Layer

(39) In the production example of the bimodal carrier according to the present invention, as the raw material of the porous layer, a sol containing zirconium silicate as a main component was used, the sol being named CERAMIC G-401 (manufactured by Kabushikikaisha Nippan Kenkyusho, solid content concentration: 16% by mass (LOT number: 31118), 21% by mass (LOT number: 31022), solvent: isopropyl alcohol).

(40) (3) Production Example of Bimodal Carrier (Step 1)

(41) Bimodal Carrier a

(42) (Step 1-1)

(43) 5 g of a silica carrier was impregnated with the zirconium silicate sol under conditions of 25 C. and an atmospheric pressure over 1 hour by the IW method while the silica carrier was ultrasonically vibrated. The zirconium silicate sol used was obtained by adding 1 mL of isopropanol (manufactured by Kanto Chemical Co., Inc.) to 7.81 g of CERAMIC G-401 (LOT number: 31118).

(44) (Step 1-2)

(45) After the impregnation, the silica carrier was left to stand under reduced pressure with an aspirator at 25 C. for 1 hour. Then, the silica carrier was dried at 120 C. in an air atmosphere under an atmospheric pressure overnight. After drying, the temperature of the silica carrier was increased to 400 C. at 2 C./min in an air atmosphere under an atmospheric pressure using a muffle furnace, and held at 400 C. for 2 hours to calcine the silica carrier. Then, the silica carrier was cooled to 25 C. in an air atmosphere under an atmospheric pressure to obtain bimodal carrier a. The physical property values of obtained bimodal carrier a are shown in Table 1.

(46) Bimodal Carrier b

(47) Bimodal carrier b was obtained in the same manipulation as in the production example of bimodal carrier a except that, in the production example of bimodal carrier a, a silica carrier was impregnated with a zirconium silicate sol obtained by adding 0.45 g of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Pluronic P123 (manufactured by BASF A.G., molecular weight: 5800, the number of moles of added ethylene oxy groups: 20, the number of moles of added propylene oxy groups: 70, the number of moles of added ethylene oxy groups: 20), and 1 mL of isopropanol (manufactured by Kanto Chemical Co., Inc.) to 7.81 g of CERAMIC G-401 (LOT number: 31118), and a calcining temperature was changed to 600 C. from 400 C. The physical property values of obtained bimodal carrier b are shown in Table 1.

(48) Bimodal Carrier c

(49) A zirconium silicate sol was used, which was obtained by adding 0.61 g of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Pluronic P123 (manufactured by BASF A.G., molecular weight: 5800, the number of moles of added ethylene oxy groups: 20, the number of moles of added propylene oxy groups: 70, the number of moles of added ethylene oxy groups: 20) and 2.5 mL of isopropanol (manufactured by Kanto Chemical Co., Inc.) to 10.2 g of CERAMIC G-401 (LOT number: 31022).

(50) 5 g of a silica carrier was impregnated with a half amount of the zirconium silicate sol under an atmospheric pressure at 25 C. over 1 hour while the silica carrier was ultrasonically vibrated. After the impregnation, the same manipulation as in step 1-2 of bimodal carrier a was performed except that the calcining temperature was changed to 600 C. from 400 C. in step 1-2 of bimodal carrier a.

(51) The obtained powder was further impregnated with the remaining half amount of the zirconium silicate sol under an atmospheric pressure at 25 C. over 1 hour while the powder was ultrasonically vibrated. After the impregnation, bimodal carrier c was obtained in the same manipulation as in step 1-2 of bimodal carrier a except that the calcining temperature was changed to 600 C. from 400 C. in step 1-2 of bimodal carrier a. The physical property values of obtained bimodal carrier c are shown in Table 1.

(52) TABLE-US-00001 TABLE 1 Bimodal Bimodal Bimodal carrier a carrier b carrier c Amount of ZrSiO.sub.4 supported with 25 25 43 respect to 100 parts by mass of silica carrier (parts by mass) Peak position in small pore 4 10 17 range (nm) Peak position in large pore 57 55 62 range (nm) Total pore volume (mL/g) 0.82 0.78 0.80

3. Production Example of Cobalt Supported Catalyst (Step 2)

Example 1 (Co Supported Catalyst A)

(53) 3 g of bimodal carrier a was impregnated with a cobalt nitrate aqueous solution under conditions of 25 C. and an atmospheric pressure over 1 hour by the IW method while bimodal carrier a was ultrasonically vibrated. The cobalt nitrate aqueous solution used was obtained by dissolving 1.65 g of cobalt(II) nitrate hexahydrate (manufactured by Kanto Chemical Co., Inc.) in 1.85 mL of deionized water.

(54) After the impregnation, bimodal carrier a was left to stand at 25 C. under reduced pressure with an aspirator for 1 hour. Then, bimodal carrier a was dried at 120 C. in an air atmosphere under an atmospheric pressure overnight. After drying, the temperature of bimodal carrier a was increased to 400 C. at 2 C./min in an air atmosphere under an atmospheric pressure using a muffle furnace, and held at 400 C. for 2 hours for calcining. The calcined catalyst was left to stand as it is in a reduction furnace. After air in the muffle furnace was replaced by nitrogen, the temperature of the catalyst was increased to 400 C. over 3 hours in a state where 100 1 hydrogen was aerated at 80 mL/min under an atmospheric pressure in the muffle furnace, and held at 400 C. for 10 hours for reduction.

(55) After the end of the reduction, the atmosphere was switched to nitrogen, and the catalyst was cooled to 25 C. Then, nitrogen containing 1% by volume of oxygen was aerated at 15 mL/min in the muffle furnace, to perform a surface immobilization treatment until oxygen absorption was no longer observed, thereby obtaining Co supported catalyst A. The physical property values of obtained Co supported catalyst A are shown in Table 2.

Example 2 (Co Supported Catalyst B)

(56) Co supported catalyst B was obtained in the same manipulation as in the production example of Co supported catalyst A except that 3 g of bimodal carrier b was impregnated with a cobalt nitrate aqueous solution obtained by dissolving 1.65 g of cobalt(II) nitrate hexahydrate (manufactured by Kanto Chemical Co., Inc.) in 1.72 mL of deionized water over 1 hour by the IW method while bimodal carrier b was ultrasonically vibrated. The physical property values of obtained Co supported catalyst B are shown in Table 2.

Comparative Example 1 (Co Supported Catalyst C)

(57) Co supported catalyst C was obtained in the same manipulation as in the production example of Co supported catalyst A except that 3 g of bimodal carrier c was impregnated with a cobalt nitrate aqueous solution obtained by dissolving 1.65 g of cobalt(II) nitrate hexahydrate (manufactured by Kanto Chemical Co., Inc.) in 1.72 mL of deionized water over 1 hour by the IW method while bimodal carrier c was ultrasonically vibrated. The physical property values of obtained Co supported catalyst C are shown in Table 2.

(58) In Co supported catalyst C, peaks of adsorption-desorption isotherms derived from a small pore and a large pore obtained by a nitrogen adsorption method overlapped with each other. Therefore, the pore volumes of the small pore and the large pore could not be obtained. Table 2 shows that the pore volumes are unmeasurable.

Comparative Example 2 (Co Supported Catalyst D)

(59) Co supported catalyst D was obtained in the same manipulation as in the production example of Co supported catalyst A except that 5 g of the silica carrier CARiACT Q-50 was impregnated with a cobalt nitrate aqueous solution obtained by dissolving 2.79 g of cobalt(II) nitrate hexahydrate (manufactured by Kanto Chemical Co., Inc.) in 5.27 mL of deionized water over 1 hour by the IW method while the silica carrier was ultrasonically vibrated. The physical property values of obtained Co supported catalyst D are shown in Table 2. In Table 2, Co supported catalyst D has no small pore, which shows that the peak position of a small pore range and the pore volume are undetected.

(60) TABLE-US-00002 TABLE 2 Co Co Co Co supported supported supported supported catalyst A catalyst B catalyst C catalyst D Peak position in small 6.7 11.5 35 Undetected pore range (d.sub.1) (nm) Pore volume of small 0.17 0.19 Unmea- Undetected pore (V.sub.1) (mL/g) surable Peak position in large 59.0 59.3 59.7 58.6 pore range (d.sub.2) (nm) Pore volume of 0.52 0.50 Unmea- 1.5 large pore (V.sub.2) (mL/g) surable d.sub.1/d.sub.2 (ratio) 0.11 0.19 0.59 V.sub.1/V.sub.2 (ratio) 0.33 0.38 Total pore volume 0.75 0.82 0.67 1.5 (mL/g) Total specific surface 233 297 203 170 area (m.sup.2/g) Co content (% by 8.5 8.5 8.7 9.2 mass)

4. Step of Reacting Carbon Monoxide with Hydrogen

(61) (1) Reaction Manipulation

(62) The reactor of the reaction apparatus used was a semi batch type autoclave having an inner volume of 80 mL. 20 mL of n-hexadecane (manufactured by Kanto Chemical Co., Inc.) and 0.5 g of the ground catalyst were placed in the reactor, and a gauge pressure was increased to 6.0 MPa. Gas (H.sub.2/CO (mole ratio)=2, hydrogen content=65% by volume, carbon monoxide content=32% by volume, argon content=3% by volume) was flowed at 40 mL/min (the mass (W/F) of the charged catalyst to the number of moles of hydrogen and carbon monoxide supplied per hour=5 g.Math.h/mol), and the temperature was increased to 240 C. from 25 C. over 1 hour and 20 minutes. The time when the temperature reached 240 C. was taken as reaction onset. At this time, the contents in the reactor were stirred at the rotation number of 1200 rpm. The selection catalysts, the reaction conditions, and the reaction results of Examples and Comparative Examples are shown in Table 3.

(63) TABLE-US-00003 TABLE 3 Examples Cmparative Examples 1 2 1 2 3 Reaction Catalyst Co supported Co supported Co supported Co supported Co supported conditions catalyst A catalyst B catalyst C catalyst D catalyst A Reaction Temperature ( C.) 240 240 240 240 240 Gauge pressure (MPa) 6 6 6 6 1 Reaction time (h) 17 17 17 17 17 Stirring speed (rpm) 1200 1200 1200 1200 1200 Supply molar ratio of H.sub.2/CO 2 2 2 2 2 Composition hydrogen content (% by volume) 65 65 65 65 65 of raw carbon monoxide content 32 32 32 32 32 material gas (% by volume) Argon content (% by volume) 3 3 3 3 3 Raw material gas supply flow rate (mL/min) 40 40 40 40 40 Amount of catalyst loaded (g) 0.5 0.5 0.5 0.5 0.5 Solvent type n-hexadecane n-hexadecane n-hexadecane n-hexadecane n-hexadecane Amount of solvent loaded (mL) 20 20 20 20 20 Evaluation CO conversion (mol %) 12 11 37 34 70 results ROH selectivity (c-mol %) 5 9 7 7 0 Number of Amount of generated ROH 2 23 46 39 Undetected carbon atoms having 1 to 7 carbon atoms of ROH Amount of generated ROH having 89 67 48 55 Undetected (c-mol %) 8 to 22 carbon atoms Amount of generated ROH 9 10 6 6 Undetected having 23 or more carbon atoms Olefin selectivity (c-mol %) 33 40 31 35 16 Paraffine selectivity (c-mol %) 62 51 62 57 80

(64) In Table 3, undetected shows that the amount of generated ROH having each number of carbon atoms cannot be detected.

(65) The contrast of Examples 1 and 2 with Comparative Examples 1 and 2 shows that an alcohol having 8 or more and 22 or less carbon atoms can be selectively produced in the production of an aliphatic alcohol using a syngas as a raw material according to the catalyst of the present invention.

(66) The contrast of Example 1 with Comparative Example 3 shows that an alcohol having 8 or more and 22 or less carbon atoms can be selectively produced in the production of an aliphatic alcohol using a syngas as a raw material according to the catalyst of the present invention and the specific reaction pressure.