ETHANOL

Abstract

The present disclosure provides ethanol comprising an inorganic component and/or an organic component. The inorganic component May contain at least one component selected from the group consisting of: silicon having a content of 10 mg/L or more and 100 mg/L or less; chromium having a content of 0.6 mg/L or less; iron having a content of 2.0 mg/L or less; sodium having a content of 150 mg/L or more and 1000 mg/L or less; and potassium having a content of 1.0 mg/L or more and 10 mg/L or less. The organic component may contain at least one component selected from the group consisting of: aliphatic hydrocarbon having a content of 0.16 mg/L or more and 10 mg/L or less; aromatic hydrocarbon having a content of 0.4 mg/L or more and 10 mg/L or less; and dialkyl ether having a content of 0.1 mg/L or more and 100 mg/L or less.

Claims

1. A method for manufacturing ethanol composition, comprising: a step of converting a carbon source into a synthetic gas comprising carbon monoxide and hydrogen; a microbial fermentation step of supplying the synthetic gas comprising carbon monoxide and hydrogen to a microbial fermentation tank to obtain an ethanol-containing liquid by microbial fermentation; a purification step of purifying the ethanol-containing liquid in which microorganisms is removed; wherein a purified ethanol composition comprises at least one inorganic component selected from the group consisting of: silicon having a content of 10 mg/L or more and 100 mg/L or less; chromium having a content of 0.6 mg/L or less; iron having a content of 2.0 mg/L or less; sodium having a content of 150 mg/L or more and 1000 mg/L or less; and potassium having a content of 1.0 mg/L or more and 10 mg/L or less, and at least one organic component selected from the group consisting of: aliphatic hydrocarbon which is at least one selected from the group consisting of n-hexane, n-heptane, n-octane, n-decane, n-dodecane, and n-tetradecane, having total content of 0.16 mg/L or more and 10 mg/L or less; aromatic hydrocarbon which is at least one selected from the group consisting of toluene, ethyl benzene, o-xylene, m-xylene and p-xylene, having total content of 0.4 mg/L or more and 10 mg/L or less; and dibutyl ether having a content of 0.1 mg/L or more and 100 mg/L or less, the concentration of ethanol in the ethanol composition is 75% by volume or more.

2. The method according to claim 1, further comprising the step of purifying the synthetic gas.

3. The method according to claim 1, wherein the carbon source is derived from waste.

4. The method according to claim 1, a heating distillation is performed in the purification step.

5. The method according to claim 1, the concentration of ethanol in the ethanol composition is 90% by volume or more.

6. The method according to claim 1, the concentration of ethanol in the ethanol composition is 95% by volume or more.

Description

EXAMPLES

[0223] Hereinafter, the present invention will be described in more details with reference to the examples, but the present invention shall not be limited to the following examples as long as the gist of the invention is not deviated.

<Ethanol Component Evaluation Method>

[0224] In the following Examples and Comparative Examples, the contents of Si, Cr, Fe, Na and K in ethanol were measured using an inductively coupled plasma mass spectrometry (ICP-MS) ELAN DRCII manufactured by Perkin-Elmer.

[0225] In addition, the content of aliphatic hydrocarbon (n-hexane, n-heptane, n-octane, n-decane, n-dodecane, and n-tetradecane), aromatic compound (toluene, ethylbenzene, m-xylene, p-xylene), and dibutyl ether in ethanol was measured using a gas chromatography apparatus (GC 2014, manufactured by SHIMADZU) GC/MS method. The measurement conditions were as follows.

[0226] Column: DB-WAX (60 m in length, 0.25 mm in inner diameter, 0.25 m in film thickness)

[0227] Oven temperature: 40 C., 1 minute.fwdarw.5 C./min.fwdarw.100 C., 10 minutes.fwdarw.10 C./min.fwdarw.>250 C., 4 minutes

[0228] Sampling time: 5 minutes

[0229] Carrier gas: He (3.0 mL/min)

<Butadiene Quantitative Method>

[0230] Quantitative evaluation of butadiene was carried out by analysis using a gas chromatography apparatus (GC-2014, manufactured by SHIMADZU). The measurement conditions were as follows.

<Analysis Conditions of GC/MS Method>

[0231] Column: Rt-Q-BOND (length 30 m, inner diameter 0.32 mm, film thickness 10 m)

[0232] Oven temperature: 60 C., 11.5 minutes.fwdarw.10 C./min.fwdarw.100 C., 14.5 minutes.fwdarw.10 C./min.fwdarw.250 C.;

[0233] Sampling time: 5 minutes;

[0234] Carrier gas: He (30 cm/s);

[0235] Split ratio: 75

<Ethyl Benzoate Determination Method>

[0236] Quantitative evaluation of ethyl benzoate was performed by analysis using a gas chromatography apparatus. The measurement conditions were as follows.

<Analysis conditions of the GC/MS method>

[0237] Column: DB-1 (length 30.0 m, inner diameter 0.254 mm, film thickness 0.25 m)

[0238] Heating condition: 30 C.-300 C. 15 C./min

[0239] Carrier gas: He 100 kPa

[0240] Split ratio: 50

<Combustion Efficiency Quantification Method>

[0241] Quantitative evaluation of combustion efficiency of ethanol was carried out by total heat generation analysis using a cone calorimeter manufactured by FTT.

Example 1

Preparation of Ethanol

[0242] Ethanol was prepared as follows.

(Raw Material Gas Generation Step)

[0243] Gas discharged after combustion of general waste in a waste incineration facility was used. The raw material gas consisted of about 30% by volume of carbon monoxide, about 30% by volume of carbon dioxide, about 30% by volume of hydrogen and about 10% by volume of nitrogen.

(Synthetic Gas Purification Step)

[0244] Using a PSA device, which is an impurity removing apparatus for the raw material gas produced as described above, carbon dioxide contained in the synthetic gas was removed so that the content will be 60 to 80% by volume of the original content (about 30% by volume) under conditions in which the gas temperature was heated to 80 C., followed by re-cooling using a double-tube-type heat exchanger using steam at 150 C. by using a double-tube-type heat exchanger using temperature increase of gas and cooling water at 25 C. to precipitate impurities and remove the precipitated impurities with a filter, thereby giving a synthetic gas.

(Microbial Fermentation Step)

[0245] The synthetic gas thus obtained was continuously supplied to a continuous fermentation apparatus (microbial fermentation tank) equipped with a main reactor, a synthetic gas supply hole, and a discharge hole, which was packed with a seed of Clostridium autoethanogenum (microorganism) and a liquid medium for culturing the microorganism (containing an appropriate amount of phosphorus compounds, nitrogen compounds, various minerals, and the like), and culture (microbial fermentation) was carried out continuously for 300 hours. Thereafter, about 8000 L of a culture solution containing ethanol was extracted from the discharge hole.

(Separation Step)

[0246] The culture solution obtained in the fermentation step was used in a solid-liquid separation filter device to obtain an ethanol-containing liquid under conditions of a culture solution introduction pressure of 200 kPa or more.

(Distillation Process)

[0247] Subsequently, the ethanol-containing liquid was introduced into a distillation apparatus equipped with a heater using steam at 170 C. After the temperature at the distillation column bottom was raised to 101 C. within 8 to 15 minutes, the ethanol-containing liquid was introduced from the middle of the distillation column, and during continuous operation, purified ethanol was obtained by continuous operation under the conditions of 15 seconds/L, at 101 C. at the bottom, 99 C. at the middle, and 91 C. at the top.

[0248] The content of Si in the obtained ethanol was 50 mg/L.

[0249] The content of chromium in the obtained ethanol was less than 0.5 mg/L.

[0250] The content of iron in the obtained ethanol was less than 0.5 mg/L.

[0251] The content of sodium in the obtained ethanol was 190 mg/L.

[0252] The content of potassium in the obtained ethanol was 2.9 mg/L.

[0253] The obtained ethanol contained n-hexane at 0.1 mg/L, n-heptane at 0.04 mg/L, n-octane at 0.02 mg/L, n-decane at 0.32 mg/L, n-dodecane at 0.1 mg/L and tetradecane at 0.03 mg/L.

[0254] The content of toluene in the obtained ethanol was 0.07 mg/L, the content of ethylbenzene was 0.8 mg/L, and the total content of m-xylene and p-xylene was 0.2 mg/L.

[0255] The content of dibutyl ether in the obtained ethanol was 20 mg/L.

(Production Method of Butadiene)

[0256] Butadiene was produced using the ethanol obtained as described above. First, the ethanol obtained was vaporized by passing it through a single tube heated to 90 C. in order to prepare a gas to be used for the reaction, and the vaporized ethanol gas was combined with nitrogen. At this time, mass flow was used to control the flow rate of ethanol gas to SV360L/hr/L, and nitrogen to SV840L/hr/L, thereby obtaining a mixed gas of 30% by volume of ethanol (gas conversion) and 70% by volume of nitrogen (gas conversion). Subsequently, a stainless steel cylindrical reaction tube having a diameter of inch (1.27 cm) and a length of 15.7 inch (40 cm) filled with 0.85 g of a butadiene synthesis catalyst mainly composed of Hf, Zn and Ce was continuously supplied with the mixed gas while maintaining the temperature of 350 C. and the pressure (pressure of the reaction bed) of 0.1 MPa, thereby obtaining a butadiene-containing gas. The butadiene-containing gas thus obtained was used for quantifying the butadiene content using a gas chromatography apparatus of GC-2014 (manufactured by SHIMADZU). The results were as shown in Tables 1 and 2.

Comparative Example 1

[0257] Butadiene was produced by the same method as in Example 1 using 99 ethanol (manufactured by Amakasu Chemical Industry Co., Ltd.) which is ethanol derived from fossil fuel, and the content of butadiene was determined in the same manner as in Example 1. The results were as shown in Tables 1 and 2. None of the concentrations of Si, Cr, Fe, Na, and K in 99 degrees ethanol derived from fossil fuels were measurable (below the detection limit). Further, none of the concentrations of toluene, ethylbenzene, m-xylene and p-xylene, n-hexane, n-heptane, n-octane, n-decane, n-dodecane, and n-tetradecane, dibutylether were measurable (below the detection limit).

Comparative Example 2

[0258] Butadiene was manufactured by the same method as in Example 1 using 99 degrees ethanol (manufactured by Amakasu Chemical Industry Co., Ltd.) derived from the saccharification and fermentation of plants, and the content of butadiene was quantified in the same manner as in Example 1. The results were as shown in Tables 1 and 2. None of the concentrations of Si, Cr, Fe, Na, and K in 99 degrees ethanol derived from the saccharification and fermentation of plants were measurable (below the detection limit). Further, none of the concentrations of toluene, ethylbenzene, m-xylene and p-xylene, n-hexane, n-heptane, n-octane, n-decane, n-dodecane, and n-tetradecane, dibutylether were measurable (below the detection limit).

TABLE-US-00001 TABLE 1 Comp. Ex. 2 Comp. Ex. 1 Derived from Ex. 1 Derived saccharification Derived from from fossil and Ethanol Raw material synthetic gas fuel fermentation Concentration Si 50 <10 <10 of inorganic Cr Less than 0.5 0.7 0.7 components Fe Less than 0.5 2.8 in ethanol Na 190 120 140 (mg/L) K 2.9 0.9 <0.5 Content of butadiene 61.2 57.2 57.5 (vol %)

TABLE-US-00002 TABLE 2 Ex. 1 Comp. Ex. 2 Derived Comp. Ex. 1 Derived from from Derived saccharification synthetic from fossil and Ethanol Raw material gas fuel fermentation Concentration n-hexane 0.1 <0.1 <0.1 of organic n-heptane 0.04 <0.01 <0.01 components n-octane 0.02 <0.01 <0.01 in ethanol n-decane 0.32 <0.01 <0.01 (mg/L) n-dodecane 0.1 <0.01 <0.01 n-tetradecane 0.03 <0.01 <0.01 Total of 0.61 <0.15 <0.15 aliphatic hydrocarbons toluene 0.07 <0.01 <0.01 ethyl benzene 0.8 <0.1 <0.1 m-xylene 0.2 <0.2 <0.2 p-xylene Total of 1.07 <0.31 <0.31 aromatic compounds Dibutyl ether 20 <0.01 <0.01 Butadiene content (vol %) 61.2 57.2 57.5

[0259] As shown in Tables 1 and 2, it has been found that ethanol produced using the gas discharged after burning general waste in a waste incineration facility has a higher conversion efficiency to butadiene than ethanol derived from conventional fossil fuels or ethanol derived from saccharification and fermentation from plants.

Example 2

Production of Ethyl Benzoate

[0260] Ethyl benzoate was produced using the same ethanol as that used in Example 1 in the following manner. First, 36.8 g of benzoic acid and 200 ml of ethanol were mixed under a stream of argon, 9 ml of concentrated sulfuric acid was added thereto, and the mixture was stirred under reflux for 5 hours. Thereafter, the mixture was allowed to cool to room temperature, unreacted ethanol was removed under reduced pressure, and ethyl benzoate synthesized with 100 ml of diethyl ether was recovered. The recovered solution was washed with distilled water, dried using magnesium sulfide, and then filtered and concentrated.

[0261] The obtained filtrate was subjected to component analysis using a gas chromatography apparatus, and the amount of ethyl benzoate synthesized was determined. The analytical conditions at this time are as follows. The analytical results are shown in Tables 3 and 4.

[0262] Column: DB-1 (Length 30.0 m, Inner Diameter 0.254 mm, Film Thickness 0.25 m)

[0263] Heating condition: 30-300 C. 15 C./min

[0264] Carrier gas: He 100 kPa

[0265] Split ratio: 50

Comparative Example 3

[0266] Ethyl benzoate was manufactured and quantified in the same manner as in Example 2 except that ethanol derived from petrochemicals used in Comparative Example 1 was used. The analytical results were as shown in Tables 3 and 4.

Comparative Example 4

[0267] Ethyl benzoate was manufactured and quantified in the same manner as in Example 2 except that ethanol derived from petrochemicals used in Comparative Example 2 was used. The analytical results were as shown in Tables 3 and 4.

TABLE-US-00003 TABLE 3 Comp. Ex. 4 Comp. Ex. 3 Derived from Ex. 2 Derived saccharification Derived from from fossil and Ethanol Raw material synthetic gas fuel fermentation Concentration Si 50 <10 <10 of inorganic Cr Less than 0.5 0.7 0.7 components Fe Less than 0.5 2.8 in ethanol Na 190 120 140 (mg/L) K 2.9 0.9 <0.5 Yield of ethyl benzoate 94.4 93.2 93.4 (vol %)

TABLE-US-00004 TABLE 4 Comp. Ex. 2 Ex. 3 Comp. Ex. 4 Derived Derived Derived from from from saccharification synthetic fossil and Ethanol Raw material gas fuel fermentation Concentration n-hexane 0.1 <0.1 <0.1 of organic n-heptane 0.04 <0.01 <0.01 components n-octane 0.02 <0.01 <0.01 in ethanol n-decane 0.32 <0.01 <0.01 (mg/L) n-dodecane 0.1 <0.01 <0.01 n-tetradecane 0.03 <0.01 <0.01 Total of aliphatic 0.61 <0.15 <0.15 hydrocarbons toluene 0.07 <0.01 <0.01 ethyl benzene 0.8 <0.1 <0.1 m-xylene 0.2 <0.2 <0.2 p-xylene Total of 1.07 <0.31 <0.31 aromatic compounds Dibutyl ether 20 <0.01 <0.01 Yield of ethyl benzoate (vol %) 94.4 93.2 93.4

[0268] As shown in Tables 3 and 4, it has been found that ethanol produced using the gas discharged after burning general waste in a waste incineration facility has higher conversion efficiency to ethyl benzoate than ethanol derived from conventional fossil fuels or ethanol derived from saccharification and fermentation from plants.

Example 3

[0269] The combustion efficiency of ethanol was quantified using the same ethanol as that used in Example 1. The fuel efficiency was quantified by adding 30 g of ethanol to a heat-resistant container which is 60 mm long60 mm wide30 mm high under non-heating conditions, subsequently igniting, and measuring the amount of oxygen reduction until complete combustion in a cone calorimeter (manufactured by FTT), and calculating the total heat generation based on the amount of oxygen reduction. The quantitative results were as shown in Tables 5 and 6.

Comparative Example 5

[0270] The combustion efficiency of ethanol was quantified in the same manner as in Example 3 except that ethanol used in Comparative Example 1 was used.

[0271] The quantitative results were as shown in Tables 5 and 6.

Comparative Example 6

[0272] The combustion efficiency of ethanol was determined in the same manner as in Example 3 except that ethanol used in Comparative Example 2 was used. The quantitative results were as shown in Tables 5 and 6.

TABLE-US-00005 TABLE 5 Comp. Ex. 6 Derived from Ex. 3 Comp. Ex. 5 saccharification Derived from Derived from and Ethanol Raw material synthetic gas fossil fuel fermentation Concentration Si 50 <10 <10 of inorganic Cr Less than 0.5 0.7 0.7 components Fe Less than 0.5 2.8 in ethanol Na 190 120 140 (mg/L) K 2.9 0.9 <0.5 combustion efficiency 7.78 7.54 7.57 (kw/kg)

TABLE-US-00006 TABLE 6 Comp. Ex. 3 Ex. 5 Comp. Ex. 6 Derived Derived Derived from from from saccharification synthetic fossil and Ethanol Raw material gas fuel fermentation Concentration n-hexane 0.1 <0.1 <0.1 of organic n-heptane 0.04 <0.01 <0.01 components n-octane 0.02 <0.01 <0.01 in ethanol n-decane 0.32 <0.01 <0.01 (mg/L) n-dodecane 0.1 <0.01 <0.01 n-tetradecane 0.03 <0.01 <0.01 Total of aliphatic 0.61 <0.15 <0.15 hydrocarbons toluene 0.07 <0.01 <0.01 ethyl benzene 0.8 <0.1 <0.1 m-xylene 0.2 <0.2 <0.2 p-xylene Total of aromatic 1.07 <0.31 <0.31 compounds Dibutyl ether 20 <0.01 <0.01 combustion efficiency (kw/kg) 7.78 7.54 7.57

[0273] As shown in Tables 5 and 6, it has been found that ethanol produced by using gas discharged after burning general waste in a waste incineration facility has higher combustion efficiency than ethanol derived from conventional fossil fuels or ethanol derived from saccharification fermentation from plants.