JP2008088140A - Method for synthesizing chemical industry feedstock and fuel composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide easily available compounds each as a catalyst with no need of any complicated preparation as the catalyst, in order to retrieve in a simple process a chemical industry feedstock such as butanol or butadiene, or a fuel composition, with ethanol as a raw material. <P>SOLUTION: At least one compound selected from the group consisting of a kaolin-group clay mineral, a pyrophyllite-group clay mineral, a smectite-group clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, lithium phosphate, aluminum phosphate and magnesium phosphate is used as catalyst(s). Further, when n-butanol is to be synthesized, a titanium oxide can also be used as a catalyst, and when a fuel composition is to be synthesized, titanium oxide, magnesium oxide, calcium hydroxide or sepiolite can also be used as a catalyst, and in addition, a mixture of a calcium compound and a phosphoric acid compound can also be used as a catalyst. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for synthesizing a chemical industrial raw material, an organic compound useful as a fuel composition, or a mixture thereof from ethanol using a clay mineral or other compound as a catalyst.

  Experiments have been conducted to synthesize chemical industrial raw materials such as butanol and butadiene, and fuels such as gasoline, using various compounds as catalysts from alcohol.

  As a method for synthesizing butanol from ethanol, a method using an oxide of an alkaline earth metal as a catalyst (Non-Patent Document 1), a method using a zeolite substituted with an alkali metal (Non-Patent Document 2), a mixture of metal oxides As a method for producing butadiene from ethanol (non-patent documents 4, 5 and 6), porous acicular clays, and the like. However, it is industrially unsuitable for reasons such as difficulty in catalyst preparation and high reaction temperature.

  In addition, a method for synthesizing butanol, butadiene and a fuel composition using a calcium phosphate catalyst has already been disclosed (Patent Document 3). To increase the yield of butanol, butadiene and a fuel composition, calcium phosphate is used. There is a problem that it is difficult to prepare the catalyst because fine adjustment of the molar ratio of phosphorus and calcium in the catalyst is necessary.

“Dimerisation of ethanol to butanol over solid-base catalysts” A.S. Ndou, N. plint, N. J. Coville, Applied catalysis A: General, 251, p. 337-345 (2003) “Bimolecular Condensation of Ethanol to 1-Butanol Catalyzed by Alkali Cation Zeolites” C. Yang, Z. Meng, J. of Catalysis, 142, p. 37-44 (1993) “Kinetics of a Complex Reaction System-Preparation of n-Butanol from Ethanol in One Step, V. NAGARAJAN, Indian Journal of Technology Vol. 9, October 1971, pp. 380-386 “BUTADIENE FROM ETHYL ALCOHOL” B. B. CORSON, H. E. JONES, C. E. WELLING, J. A. HINCLEY, AND E. STAHLY, INDUSTRIAL AND ENGINEERING CHEMISTRY, Vol. 42. No.2 ONE-STEP CATALYTIC CONVERSION OF ETHANOL TO BUTADIENE IN THE FIXED BED. I. SINGLE-OXIDE CATALYSIS, S. K. BHATTACHARYYA and N. D. GANGULY, J. appl. Chem., 12, March, 1962) ONE-STEP CATALYTIC CONVERSION OF ETHANOL TO BUTADIENE IN THE FIXED BED. II. BINARY- AND TERNARY-OXIDE CATALYSIS, S. K. BHATTACHARYYA and N. D. GANGULY, J. appl. Chem., 12, March, 1962) JP-A-57-102822 JP 58-59928 A International Publication No. WO99 / 38822

  The present invention provides, as a catalyst, a compound that can be easily obtained in order to collect chemical industrial raw materials and fuel compositions such as butanol and butadiene, etc., using ethanol as a raw material, by a simple process, and does not require difficult preparation as a catalyst. Is an issue.

  Ethanol, which is a starting material for the process of the present invention, is synthesized by converting sugars currently obtained from sugarcane, beet, etc. by fermentation. In recent years, technology for synthesizing ethanol from biomass, which is agricultural and forestry waste, has been established, and it can be expected that the production amount of ethanol will increase dramatically. Moreover, since the production cost of ethanol is comparable to or less than that of crude oil, synthesis of chemical industrial raw materials, fuel compositions, etc. using ethanol as a raw material is an important issue in the future.

  The process of the present invention can use plant-derived ethanol as a raw material, and the reaction proceeds easily at normal pressure. Therefore, existing fossil / mineral resources that emit carbon dioxide and promote global warming are used as raw materials. Compared to the synthesis method, it is an important synthesis method for the global environment.

  As a result of intensive research to synthesize chemical industrial raw materials and fuel compositions from ethanol using various compounds, the present inventors can easily obtain them as reagents other than the known catalysts. It has been found that by using a possible compound as a catalyst, an organic compound useful as a chemical industrial raw material or a fuel composition or a mixture thereof can be synthesized from ethanol.

That is, the present invention
(1) Ethanol, kaolin group clay mineral, pyrophyllite group clay mineral, smectite group clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, lithium phosphate, aluminum phosphate And a method of synthesizing one or a mixture of two or more organic compounds from ethanol, characterized by contacting with at least one compound selected from the group consisting of magnesium phosphate,
(2) The method according to (1), wherein the organic compound is 1,3-butadiene,
(3) A method of synthesizing one or a mixture of two or more organic compounds from ethanol, wherein ethanol is brought into contact with a mixture of a calcium compound and a phosphate compound,
(4) The method according to (3) above, wherein the organic compound is 1,3-butadiene,
(5) Ethanol, kaolin clay mineral, pyrophyllite clay mineral, smectite clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, lithium phosphate, aluminum phosphate A method for synthesizing n-butanol from ethanol, which comprises contacting with at least one compound selected from the group consisting of magnesium phosphate and titanium oxide,
(6) A method of synthesizing n-butanol from ethanol, which comprises contacting ethanol with a mixture of a calcium compound and a phosphate compound,
(7) Ethanol, kaolin group clay mineral, pyrophyllite group clay mineral, smectite group clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, lithium phosphate, aluminum phosphate A method of synthesizing a fuel composition from ethanol, characterized by contacting with at least one compound selected from the group consisting of magnesium phosphate, titanium oxide, magnesium oxide, calcium hydroxide and sepiolite,
(8) A method for synthesizing a fuel composition from ethanol, comprising contacting ethanol with a mixture of a calcium compound and a phosphate compound;
(9) Kaolin group clay mineral, pyrophyllite group clay mineral, smectite group clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, lithium phosphate, aluminum phosphate and phosphoric acid The present invention relates to an ethanol conversion catalyst containing at least one compound selected from the group consisting of magnesium, and (10) an ethanol conversion catalyst containing a mixture of a calcium compound and a phosphate compound.

  The catalyst of the present invention is inexpensive and easily available, is stable to the reaction and regeneration treatment, and efficiently selects ethanol, n-butanol, 1,3-butadiene, etc. by selecting the reaction temperature and contact time. A fuel composition which is a chemical industrial raw material or a mixture thereof can be obtained.

(Ethanol conversion catalyst)
The compound used as the ethanol conversion catalyst of the present invention is kaolin group clay mineral, pyrophyllite group clay mineral, smectite group clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, phosphoric acid It is at least one compound selected from the group consisting of lithium, aluminum phosphate, magnesium phosphate, titanium oxide, calcium hydroxide, and sepiolite. In particular, when used as a mixture, a mixture of a calcium compound and a phosphoric acid compound can be widely used without being limited to the calcium compound and the phosphoric acid compound.

Kaolin group clay minerals are clay minerals with a basic structure of 1: 1 of tetrahedral and octahedral layers, and Lizardite [Mg ₃ Si ₂ O ₅ (OH) ₄ ], Bercherin [( Fe ²⁺ , Fe ³⁺ , Mg) _2-3 (Si, Al) ₂ O ₅ (OH) ₄ ], amethyite [Mg ₂ Al (Si, Al) O ₅ (OH) ₄ ], cronstudite [Fe ²⁺ Fe ³⁺ (SiFe ³⁺ ) O ₅ (OH) ₄ ], nepoite [Ni ₃ Si ₂ O ₅ (OH) ₄ ], keriaite [(Mn ²⁺ , Mg, Al) ₃ (Si, Al) ₂ O ₅ (OH) _4], Fureiponaito _{[(Zn, Al) 3 (} Si, Al) 2 O 5 (OH) 4], Bryn Doria Ito ^{[(Ni, Mg, Fe 2+} ) 3 (Si, Al) O ₅ (OH) ₄ ], kaolinite [Al ₂ Si ₂ O ₅ (OH) ₄ ], dickite [Al ₂ Si ₂ O ₅ (OH) ₄ ], nacrite [Al ₂ Si ₂ O ₅ (OH) ₄ ], Includes halloysite [Al ₂ Si ₂ O ₅ (OH) ₄ ], audinite [(Fe ³⁺ , Mg, Al, Fe ²⁺ ) _2-3> (Si, Al) ₂ O ₅ (OH) ₄ ] Is done.

Pyrophyllite group clay minerals are clay minerals with a basic structure of 2: 1 tetrahedral and octahedral layers. Talc [Mg ₃ Si ₄ O ₁₀ (OH) ₂ ], Willemsite [(Ni, Mg) ₃ Si ₄ O ₁₀ (OH) ₂ ], Kerolite [Mg ₃ Si ₄ O ₁₀ (OH) ₂ ], Pimelite [Ni ₃ Si ₄ O ₁₀ (OH) ₂ ], Pyrophyllite [Al ₂ Si ₄ O ₁₀ (OH) ₂ ], ferripyrophyllite [Fe ³⁺ Si ₄ O ₁₀ (OH) ₂ ] and the like are included.

Smectite group clay minerals are clay minerals in which the tetrahedral layer and the octahedral layer have a basic structure of 2: 1. Saponite [(Ca / 2, Na) _0.3 (Mg, Fe ²⁺ ) ₃ (Si, Al) ₄ O ₁₀ (OH) ₂ · 4H ₂ O], Hectorite [Na _0.3 (Mg, Li) ₃ Si ₄ O ₁₀ (F, OH) ₂ · 4H ₂ O], Sauconite [Na _0.3 Zn ₃ (Si, Al) ₄ O ₁₀ (OH) ₂・ 4H ₂ O], Steven Sight [(Ca / 2) _0.3 Mg ₃ Si ₄ O ₁₀ (OH) ₂・ 4H ₂ O], Swine Holderite [(Ca / 2, Na) _0.3 (Li, Mg) ₂ (Si, Al) ₄ O ₁₀ (OH, F) ₂・ 2H ₂ O], Montmorillonite [(Ca / 2, Na) _0.3 (Al, Mg) ₂ (Si ) ₄ O ₁₀ (OH) ₂ · nH ₂ O], beiderite [(Ca / 2, Na) _0.3 Al ₂ (Si, Al) ₄ O ₁₀ (OH) ₂ · nH ₂ O], nontronite [Na _0.3 Fe ³⁺ (Si, Al) ₄ O ₁₀ (OH) ₂・ nH ₂ O], vorcon score [Ca _0.3 (Cr ³⁺ , Mg, Fe ³⁺ ) ₃ (Si, Al) ₄ O ₁₀ (OH) ₂ · nH ₂ O] and the like are included.

Hydrotalcite is a clay mineral having a composition of Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O, and sepiolite is Si ₁₂ Mg ₈ O ₃₀ (OH) ₄ (H ₂ O) ₄ · 8H _2. It is a clay mineral having a composition of O.
Chitin is a mucopolysaccharide having 1,4-linked N-acetyl-β-D-glucosamine, and the molecular weight is not particularly limited, but is usually about 100,000 to 1,000,000.
The above compounds can be used alone or in combination of two or more.

In the case of a mixture of a calcium compound and a phosphoric acid compound, the Ca / P molar ratio is usually adjusted to 0.05 to 20. In this case, the types of the calcium compound and the phosphate compound are not particularly limited, but the calcium compound is preferably calcium oxide or calcium silicate, and the phosphate compound is preferably aluminum phosphate, magnesium phosphate or lithium phosphate.
In the case where n-butanol is synthesized, titanium oxide can also be used as a catalyst in addition to the above compounds. Moreover, when what is synthesize | combined is a fuel composition which is a mixture of an organic compound, in addition to the said compound, a titanium oxide or magnesium oxide can also be used as a catalyst.

  In the present invention, the properties of the compound used as the catalyst are not particularly limited, and the reagent powder may be used as it is, and if necessary, in any shape such as granules, spheres, pellets, and honeycombs. After molding, it can be dried and fired. Firing is performed at 100 ° C to 800 ° C, preferably 300 ° C to 700 ° C. In the case of a mixture of a calcium compound and a phosphoric acid compound, baking at 200 ° C. or higher is preferable.

(Organic compounds produced or mixtures thereof)
The “organic compound” synthesized using the ethanol conversion catalyst of the present invention includes any organic compound synthesized from ethanol. For example, paraffins, olefins, dienes, trienes, alcohols, There are organic compounds such as ethers, ketones, aldehydes, and esters. Specifically, methane, ethane, ethylene, acetaldehyde, propylene, acetone, butene, 1,3-butadiene, 1-butanol, 3-buten-1-ol, t-crotyl alcohol, c-crotyl alcohol, diethyl Examples include ether, butyraldehyde, 2-butanone, t-crotonaldehyde, c-crotonaldehyde, 2-pentanol, 2-pentanone, butyl ethyl ether, hexanol, hexanal, 2-ethylhexanol, octanol, and octanal. Each of these can be used as an industrial raw material, and a mixture of two or more of these can be used as a fuel composition. When used as a fuel composition, ethanol as a raw material may also be included.
In the present invention, when synthesizing organic compounds useful for these chemical industrial raw materials and fuel compositions and a mixture of two or more thereof using ethanol as a raw material, the particle size of the catalyst to be used is increased in order to increase their selectivity. The surface area and the reaction conditions (contact time, reaction temperature, pressure, etc.) are selected as appropriate.

(Synthesis method)
The reaction temperature suitable for bringing ethanol into contact with the catalyst to produce an organic compound or a mixture thereof can usually be selected in the range of 100 ° C to 700 ° C. Preferably 250 to 600 degreeC is desirable. When using the mixture of a calcium compound and a phosphoric acid compound as a catalyst, it is 100 to 400 degreeC normally.
The reaction mode in the reaction tower may be any of a batch system, a continuous system, a fixed bed, a moving bed, a fluidized bed, or a slurry bed, and can be carried out at normal pressure, under pressure or under reduced pressure.

The contact time between ethanol and the catalyst is usually 0.1 seconds or more and 10 seconds or less by a continuous method in consideration of industrial economy, but the reaction temperature is 0.1 seconds or less or a batch method or the like. By adjusting, economical production is possible even for 10 seconds or more.
The yield of the organic compound or a mixture thereof may be short when the contact temperature between ethanol and the catalyst is high. However, as the contact temperature between ethanol and the catalyst decreases, the contact time needs to be longer. Become. However, the lower the contact temperature, the lighter the burden of manufacturing measures.

  Although ethanol can be carried out in the liquid phase, it can be reacted efficiently by contacting with the catalyst directly in the gas phase or in the presence of an inert carrier gas such as nitrogen or helium. At this time, in order to maintain the catalytic activity, a reactive gas such as hydrogen or hydrocarbon may be entrained in the carrier gas.

In the case of synthesizing an organic compound or a mixture thereof from ethanol, carbon may be deposited on the catalyst surface over a long period of use, resulting in a decrease in ethanol conversion rate and a heterogeneous reaction. In that case, a regeneration treatment is periodically performed in which the catalyst is heated in an oxygen atmosphere. Thereby, the activity of the catalyst can be recovered. Therefore, in the case of reaction conditions with a large amount of carbon deposition on the catalyst, a plant according to the above-described method incorporating a catalyst regeneration treatment apparatus is effective.
The organic compounds and mixtures thereof thus obtained can be separated and purified using conventionally used separation and purification methods such as rectification, microporous membrane separation, extraction and adsorption methods. .

Examples of the present invention will be described below, but the scope of the present invention is not limited thereto.
Example A (single catalyst)
(catalyst)
Calcium fluoride, calcium sulfate, magnesium hydroxide, calcium hydroxide, lithium phosphate, magnesium phosphate, hydrotalcite, calcium silicate, kaolinite, talc and magnesium oxide are reagents from Wako Pure Chemical Industries, Ltd. Sepiolite is Aid Plus from Mizusawa Chemical Co., Ltd., Chitin is Chitin EX KH000003 from Funakoshi Co., Ltd., Aluminum phosphate is a reagent from Kanto Chemical Co., and Titanium oxide is ST- from Ishihara Sangyo Co., Ltd. 01 was used.

(Evaluation of catalyst characteristics)
As the reaction apparatus, a fixed bed gas flow type catalytic reaction apparatus (manufactured by Okura Riken Co., Ltd.) was used. Various catalysts were filled in the reaction tube according to the set contact time, and as a pretreatment, a heat dehydration treatment was performed at 500 ° C. for 30 minutes in a carrier gas (1% Ar / He base; flow rate 112 ml / min) atmosphere. After completion of the pretreatment, the ethanol flow rate and carrier gas flow rate were adjusted so that the ethanol concentration was 16 vol%, and the reaction was carried out at normal pressure.
The reaction temperature was 100 to 700 ° C., sampling was performed every 50 ° C., and the contact time was 0.1 to 10 seconds. When the contact time was 0.1 second, 0.2 cc, 4 cc when the contact time was 2 seconds, and 9 cc when the contact time was 10 seconds, were charged into the reaction tube.
A gas chromatograph mass spectrometer (GC-MS) is used for identification of reaction gas components, and a gas chromatograph (GC) (detector: FID) is used for measuring the ethanol conversion and synthesis gas selectivity. The amount of each component was quantified from the peak area value.

(N-butanol)
Table 1 shows the butanol yield of each catalyst at each reaction temperature.

Table 1 shows the yield of n-butanol of various catalysts at a reaction temperature of 150 ° C to 700 ° C. The contact time of Test Examples 1 to 3 was about 10 seconds, the contact time of Test Examples 4 to 5 was about 0.1 second, and the contact time of Test Example 6 and Comparative Example 1 was about 2 seconds.
The yield of n-butanol of each catalyst reached its maximum at a reaction temperature of 350 to 500 ° C.
Further, the butanol yield in the case of using magnesium hydroxide as a catalyst in Test Example 6 is an industrially advantageous value of a high butanol yield at a lower reaction temperature than in the case of using magnesium oxide as a catalyst that has already been disclosed. Met.

(1,3-butadiene)
Table 2 shows the butadiene yield of each catalyst at each reaction temperature.

Table 2 shows the yield of 1,3-butadiene at a reaction temperature of 150 ° C. to 700 ° C. for various catalysts. The contact time is about 2 seconds.
The yield of 1,3-butadiene for each catalyst reached its maximum at a reaction temperature of 450 to 550 ° C.
In addition, the yield of 1,3-butadiene when using magnesium hydroxide as a catalyst in Test Example 10 is lower than that when magnesium oxide is used as a catalyst, and the butadiene yield is high. It was an advantageous value.

(Fuel composition)
Tables 3 and 4 show the yields of the fuel composition (C4 + or higher) at various reaction temperatures for various catalysts.

Tables 3 and 4 show the yields of the fuel compositions of various catalysts at reaction temperatures of 150 ° C. to 700 ° C., and the contact time is a result of about 2 seconds.
The yield of the fuel composition of each catalyst reached its maximum value at a reaction temperature of 250 to 600 ° C.

(C2 + organic compounds)
Table 5 shows the yield of C2 + or higher organic compounds (excluding ethanol) at various reaction temperatures for various catalysts.

Table 5 shows the yield of C2 + or higher organic compounds (excluding ethanol) at various reaction temperatures of 100 ° C. to 700 ° C., and the contact time is about 2 seconds.
The yield of C2 + or higher organic compounds (excluding ethanol) of each catalyst was particularly high at a reaction temperature of 500 ° C. or higher.

Example B (mixed catalyst of calcium compound and phosphate compound)
A mixture of a calcium compound and a phosphoric acid compound was used as an ethanol conversion catalyst, and an ethanol conversion reaction was carried out according to Example A with a contact time of about 2 seconds. The numerical values in the table indicate%.

Example B-1 (when the Ca / P ratio is 1.64)
(N-butanol)
Tables 6 to 10 show butanol yields at various reaction temperatures of catalysts prepared by mixing a calcium compound and a phosphoric acid compound so that the Ca / P ratio is 1.64. About the mixed catalyst of Test Examples 28-30, after mixing a calcium compound and a phosphoric acid compound, what was baked at 600 degreeC for 2 hours was used. A calcium compound and a phosphoric acid compound used for comparison were similarly fired.

(1,3-butadiene)
Tables 11 to 15 show butadiene yields at various reaction temperatures of catalysts in which a calcium compound and a phosphoric acid compound are mixed so that the Ca / P ratio is 1.64. About the mixed catalyst of Test Examples 34 and 35, after mixing a calcium compound and a phosphoric acid compound, what was baked at 600 degreeC for 2 hours was used. A calcium compound and a phosphoric acid compound used for comparison were similarly fired.

(Fuel composition)
Tables 16 and 17 show the yield (C4 + or higher) of the fuel composition at each reaction temperature of the catalyst in which the calcium compound and the phosphoric acid compound were mixed so that the Ca / P ratio was 1.64. About the mixed catalyst used for these tests, after mixing a calcium compound and a phosphoric acid compound, what was baked at 600 degreeC for 2 hours was used. A calcium compound and a phosphoric acid compound used for comparison were similarly fired.

Example B-2 (when Ca / P ratio is varied)
(N-butanol)
Tables 18 to 20 show butanol yields at various reaction temperatures of various mixed catalysts prepared by adjusting the calcium compound and the phosphate compound at a Ca / P ratio of 0.2 to 10. About the mixed catalyst of Test Examples 39 and 40, after mixing a calcium compound and a phosphoric acid compound, what was baked at 600 degreeC for 2 hours was used. A calcium compound and a phosphoric acid compound used for comparison were similarly fired. The butanol yield at Test Example 38 at a reaction temperature of 450 ° C. is shown in FIG.

(1,3-butadiene)
Tables 21 to 23 show the butadiene yields at various reaction temperatures of various mixed catalysts prepared by adjusting the calcium compound and the phosphoric acid compound at a Ca / P ratio of 0.2 to 10. About the mixed catalyst of Test Example 43, a calcium compound and a phosphoric acid compound were mixed and then calcined at 600 ° C. for 2 hours. A calcium compound and a phosphoric acid compound used for comparison were similarly fired. For the CaSiO ₃ and AlPO ₄ mixed catalyst of Test Example 42, the test was performed on the catalyst mixed only and the catalyst calcined at 600 ° C. for 2 hours, and both obtained the same results. The calcium compound and the phosphoric acid compound used as comparisons had similar results. The butadiene yield at Test Example 42 and reaction temperature of 550 ° C. is shown in FIG.

(Fuel composition)
Tables 24 and 25 show the yield (C4 + or higher) of the fuel composition at each reaction temperature of various mixed catalysts prepared by adjusting the calcium compound and the phosphoric acid compound at a Ca / P ratio of 0.2 to 10. As for the mixed catalyst of Test Example 45, a calcium compound and a phosphoric acid compound were mixed and then calcined at 600 ° C. for 2 hours. A calcium compound and a phosphoric acid compound used for comparison were similarly fired. Regarding the mixed catalyst of Test Example 44, tests were performed on a mixture of calcium compound and phosphoric acid compound, and a mixture of the mixture and calcined at 600 ° C. for 2 hours. . The calcium compound and the phosphoric acid compound used as comparisons had similar results. The yield of the fuel composition with Test Example 45 and reaction temperature of 550 ° C. is shown in FIG.

FIG. 1 shows the reaction temperature and the yield of n-butanol in the case of using calcium fluoride, hydrotalcite, magnesium hydroxide, and magnesium oxide as a comparison among the catalysts listed in Table 1. It is a graph to show. FIG. 2 shows the reaction temperature and the yield of 1,3-butadiene when fluorinated apatite, hydrotalcite, magnesium hydroxide, and magnesium oxide as a comparison are used as catalysts among the catalysts listed in Table 2. It is a graph which shows. FIG. 3 is a graph showing the reaction temperature and the yield of the fuel composition when calcium silicate, fluorinated apatite, magnesium hydroxide, or titanium oxide is used as a catalyst among the catalysts listed in Table 3. FIG. 4 is a graph showing the reaction temperature and the yield of C2 + or higher organic compounds (excluding ethanol) when aluminum phosphate and talc listed in Table 5 are used as catalysts. FIG. 5 is a graph showing the butanol yield at a reaction temperature of 450 ° C. in Test Example 39. FIG. 6 is a graph showing the yield of butadiene at a reaction temperature of 550 ° C. in Test Example 42. FIG. 7 is a graph showing the yield of the fuel composition when the reaction temperature is 550 ° C. in Test Example 45.

Claims (10)

Ethanol, kaolin clay mineral, pyrophyllite clay mineral, smectite clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, lithium phosphate, aluminum phosphate and phosphoric acid A method of synthesizing one or a mixture of two or more organic compounds from ethanol, wherein the method comprises contacting at least one compound selected from the group consisting of magnesium. The method according to claim 1, wherein the organic compound is 1,3-butadiene. A method of synthesizing one or a mixture of two or more organic compounds from ethanol, wherein ethanol is brought into contact with a mixture of a calcium compound and a phosphate compound. The method according to claim 3, wherein the organic compound is 1,3-butadiene. Ethanol, kaolin group clay mineral, pyrophyllite group clay mineral, smectite group clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, lithium phosphate, aluminum phosphate, phosphoric acid A method for synthesizing n-butanol from ethanol, which comprises contacting with at least one compound selected from the group consisting of magnesium and titanium oxide. A method for synthesizing n-butanol from ethanol, which comprises contacting ethanol with a mixture of a calcium compound and a phosphate compound. Ethanol, kaolin group clay mineral, pyrophyllite group clay mineral, smectite group clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, lithium phosphate, aluminum phosphate, phosphoric acid A method for synthesizing a fuel composition from ethanol, comprising contacting with at least one compound selected from the group consisting of magnesium, titanium oxide, magnesium oxide, calcium hydroxide, and sepiolite. A method for synthesizing a fuel composition from ethanol, comprising contacting ethanol with a mixture of a calcium compound and a phosphate compound. Kaolin group clay mineral, pyrophyllite group clay mineral, smectite group clay mineral, hydrotalcite, calcium silicate, calcium fluoride, calcium sulfate, magnesium hydroxide, chitin, lithium phosphate, aluminum phosphate and magnesium phosphate An ethanol conversion catalyst containing at least one compound selected from the group. An ethanol conversion catalyst containing a mixture of a calcium compound and a phosphate compound.

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