Ethanol

Abstract

The present invention provides a novel alcohol and a derivative thereof, which have higher industrial value than existing petrochemical raw materials and are practical. The retention time of the ethanol in gas chromatography measured by gas chromatography mass spectrometry (GC / MS) has at least one of the following peaks (A)-(D): (A) a peak of 5-25 seconds to 5-35 seconds and two peaks of 2-55-3-5 seconds, (B) a peak of 12-30 seconds to 12-40 seconds, (C) a peak of 6-36 seconds to 6-45 seconds, and (D) a peak of 15-00 seconds to 15-15 seconds.

Description

[0001] This application is a divisional application of the patent application No. 202080011240.5 with the title of "Ethanol" filed in China on January 28, 2020.

[0002] Cross Reference of Related Applications

[0003] This application claims priority based on Japanese Patent Application No. 2019-012564 filed on January 28, 2019, and Japanese Patent Application No. 2019-012568, Japanese Patent Application No. 2019-050436 filed on March 18, 2019, Japanese Patent Application No. 2019-050465, Japanese Patent Application No. 2019-050472, Japanese Patent Application No. 2019-050474, Japanese Patent Application No. 2019-050480, Japanese Patent Application No. 2019-050484, and Japanese Patent Application No. 2019-050489, Japanese Patent Application No. 2019-117720 filed on June 25, 2019, Japanese Patent Application No. 2019-117745, Japanese Patent Application No. 2019-117749, and Japanese Patent Application No. 2019-117754, and Japanese Patent Application No. 2019-126455 filed on July 5, 2019, the entire disclosures of all of which are incorporated herein by reference in their entirety. TECHNICAL FIELD

[0004] The present application relates to ethanol, and more particularly, to ethanol in which the content of specific trace components is adjusted, and particularly to novel ethanol derived from resources other than conventional petroleum resources or biomass resources, which is a resource recycling type based on a gas containing carbon monoxide and hydrogen. BACKGROUND

[0005] Petroleum chemical products are used in every corner of our lives. On the other hand, various environmental problems caused by mass production and mass consumption of products used daily are becoming a problem on a global scale. For example, polyethylene and polyvinyl chloride, which are representative of petroleum chemical industry products, are consumed and discarded in large quantities, and their waste is becoming a major cause of environmental pollution. In addition, in the case of mass production of petroleum chemical industry products, global-scale environmental problems such as fear of depletion of fossil fuel resources and increase in carbon dioxide in the atmosphere are also being discussed.

[0006] Concern about such environmental problems is increasing worldwide, and in recent years, methods for producing various organic substances using raw materials other than naphtha, which is a raw material for products of the petrochemical industry, are being explored. For example, a method for producing bioethanol using a sugar fermentation method from edible raw materials such as corn is attracting attention. However, such a sugar fermentation method using edible raw materials requires the use of limited agricultural land area for purposes other than food production, and raises issues such as a rise in food prices.

[0007] To address this point, methods using non-edible raw materials that have been discarded in the past are currently being explored. Specifically, the current situation is that although methods for producing alcohols using cellulose and the like derived from discarded materials, waste paper, which are non-edible raw materials, using a fermentation method, a method for producing alcohols from a biomass raw material gas, as described above, using a catalyst from a synthesis gas, and the like have been proposed, none have yet been put into practical use. In addition, even if these de-petrolized raw materials can be used to produce various petrochemical products, they ultimately become discarded plastics that cannot be naturally decomposed, and thus are difficult to use as an effective cure for environmental problems.

[0008] However, approximately 60 million tons of combustible waste is discarded in Japan each year. The energy thereof is approximately 200 million kilocalories, which is much greater than the energy possessed by naphtha, a raw material for plastics in Japan, and these wastes can be said to be a resource in terms of weight. If these waste resources can be converted into petrochemical products, an ultimate resource recycling society that is not dependent on petroleum resources can be realized. From this point of view, Patent Documents 1 and 2 disclose technologies for producing ethanol from a synthesis gas (a gas mainly composed of CO and H2) produced from waste, and producing ethanol from the synthesis gas using a fermentation method.

[0009] However, as pointed out in Patent Document 3, a wide variety of impurities, including substances that are toxic to microorganisms, are contained in a synthesis gas produced from waste, and thus, productivity is a significant issue in terms of producing ethanol from a synthesis gas using microbial fermentation. In addition, various components derived from impurities in a synthesis gas are contained in an alcohol obtained by microbial fermentation of a synthesis gas, and these components cannot be completely removed by purification treatment such as distillation. Therefore, development of derivatives from an alcohol obtained by microbial fermentation from a synthesis gas is also a significant technical issue.

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: Japanese Patent Application Publication No. 2016-059296

[0013] Patent Document 2: International Publication No. WO 2015 / 037710

[0014] Patent Literature 3: Japanese Patent Application Publication No. 2018-058042 SUMMARY

[0015] Technical Problem to be Solved by the Invention

[0016] According to the inventor's investigations, it is known that C2 raw material represented by ethanol in the past is a starting material for various chemicals, and as described above, alcohol manufactured using resources other than petroleum resources or biomass resources (recyclable resources) is different from chemical raw materials derived from naphtha in that it contains various trace amounts of unknown substances. However, in the past technology, the characteristics of these substances were not clear, and it was not fully investigated whether all of the substances should be removed or only specific substances should be removed. Therefore, although alcohol manufactured using recyclable resources is proposed in the patent literature, the current situation is that there is still room for technical improvement to put the alcohol into practical use.

[0017] On the other hand, according to the literature, although general fermentation, distillation methods, the most suitable composition of synthesis gas, and the like are disclosed, the details of the processes and the like are not described, and in addition, even the obtained alcohol substance is not confirmed.

[0018] Therefore, the present invention is an invention made in view of the background art, and the object thereof is to provide a new type of alcohol and its derivatives that are more industrially valuable than existing petrochemical raw materials and are practical.

[0019] Technical Means for Solving the Technical Problem

[0020] As a result of the inventor's intensive discussions to solve the problem described above, it was determined that various trace amounts of substances contained in alcohol manufactured using recyclable resources can be controlled within a specific range by a new manufacturing method, and it was found that various derivatives thereof can exhibit more excellent effects than alcohol derived from existing petrochemical sources. For example, it was found that in a process of synthesizing butadiene from ethanol, the ethanol conversion rate can be improved compared to the case where petrochemical-derived ethanol is used in the past, and alcohol having the same or higher level of practicality as petrochemical-derived alcohol can be obtained, and the present invention was completed based on this finding.

[0021] More specifically, it was found that when ethanol is manufactured from a gas substrate containing carbon monoxide and hydrogen using waste as a carbon source, the conversion rate of ethanol is improved when butadiene is synthesized from the ethanol. As a result of detailed investigation of the reason for this fact, it was found that ethanol derived from recyclable resources using a gas containing carbon monoxide and hydrogen as a substrate has a unique peak in the gas chromatogram determined by gas chromatography-mass spectrometry that is not present in ethanol derived from fossil fuels. The present invention is based on this finding.

[0022] That is, the present application includes the following gist.

[0023] [1] Ethanol having, in a gas chromatogram determined by a gas chromatography mass spectrometry (GC / MS method), a retention time of at least one peak selected from the group consisting of (A) to (D) below,

[0024] (A) a peak of 5 minutes 25 seconds to 5 minutes 35 seconds and two peaks of 2 minutes 55 seconds to 3 minutes 5 seconds,

[0025] (B) a peak of 12 minutes 30 seconds to 12 minutes 40 seconds,

[0026] (C) a peak of 6 minutes 36 seconds to 6 minutes 45 seconds, and

[0027] (D) a peak of 15 minutes 0 second to 15 minutes 15 seconds.

[0028] [2] The ethanol according to [1], wherein,

[0029] the gas chromatogram has the peak of (A) and further has a peak of 5 minutes 30 seconds to 5 minutes 35 seconds.

[0030] [3] The ethanol according to [1], wherein,

[0031] the peak of (B) is derived from n-tetradecane.

[0032] [4] The ethanol according to [3], wherein,

[0033] the concentration of n-tetradecane is 0.01 mg / L or more and 1.0 mg / L or less.

[0034] [5] The ethanol according to [1], wherein,

[0035] the peak of (C) is derived from n-decane.

[0036] [6] The ethanol according to [5], wherein,

[0037] the concentration of n-decane is 0.01 mg / L or more and 1.0 mg / L or less.

[0038] [7] The ethanol according to [1], wherein,

[0039] the peak of (D) is derived from n-hexadecane.

[0040] [8] The ethanol according to [7], wherein,

[0041] the concentration of n-hexadecane is 0.01 mg / L or more and 1.0 mg / L or less.

[0042] [9] The ethanol according to any one of [1] to [8], which is based on a gas containing carbon monoxide and hydrogen.

[0043]

[10] The ethanol according to [9], wherein,

[0044] the gas containing carbon monoxide and hydrogen is derived from waste.

[0045]

[11] The ethanol according to any one of [1] to

[10] , which is derived from microbial fermentation.

[0046]

[12] A method for producing ethanol, comprising:

[0047] a step of converting a carbon source into a synthesis gas containing carbon monoxide and hydrogen,

[0048] a microbial fermentation step of supplying the synthesis gas containing carbon monoxide and hydrogen to a microbial fermentation tank to obtain an ethanol-containing liquid by microbial fermentation,

[0049] a separation step of separating the ethanol-containing liquid into a liquid or solid component containing microorganisms and a gas component containing ethanol,

[0050] a liquefaction step of liquefying the gas component by condensing it,

[0051] a purification step of purifying ethanol from a liquid obtained by the liquefaction step,

[0052] wherein the ethanol purified has a retention time in a gas chromatogram determined by a gas chromatography mass spectrometry (GC / MS method) having at least one of peaks selected from the following (A) to (D):

[0053] (A) a peak at 5 minutes 25 seconds to 5 minutes 35 seconds and two peaks at 2 minutes 55 seconds to 3 minutes 5 seconds,

[0054] (B) a peak at 12 minutes 30 seconds to 12 minutes 40 seconds,

[0055] (C) a peak at 6 minutes 36 seconds to 6 minutes 45 seconds, and

[0056] (D) a peak at 15 minutes 0 second to 15 minutes 15 seconds.

[0057]

[13] The method according to

[12] , further comprising a step of purifying the synthesis gas.

[0058]

[14] The method according to

[12] or

[13] , wherein,

[0059] the carbon source is derived from waste.

[0060]

[15] The ethanol according to any one of [1] to

[11] for use in a chemical product, a polymer raw material, or a fuel.

[0061]

[16] A chemical product using the ethanol according to any one of [1] to

[11] as a raw material.

[0062]

[17] A fuel containing the ethanol according to any one of [1] to

[11] and / or ethyl tert-butyl ether using the ethanol according to any one of [1] to [6] as a raw material.

[0063]

[18] A polymer raw material using the ethanol according to any one of [1] to

[11] as a raw material.

[0064]

[19] The polymer raw material according to

[18] selected from the group consisting of ethylene, propylene, butadiene, ethyl acetate, isobutylene, (methyl) methyl acrylate, acrylic acid, aminocaproic acid, and diethyl carbonate.

[0065]

[20] A polymer made from the polymer raw material according to

[18] or

[19] .

[0066]

[21] A molded article made from the polymer according to

[20] .

[0067] Effects of the Invention

[0068] According to the present application, by using ethanol containing a specific trace amount of organic component, various heterogeneous effects can be obtained compared to commercially available industrial ethanol. For example, according to the present application, when butadiene is synthesized using ethanol as a raw material, the ethanol conversion rate can be improved, the reaction rate when carboxylic acid is synthesized by adding ethanol to carboxylic acid can be improved, the combustion efficiency when ethanol is used as a fuel can be improved, and the like. Furthermore, even with existing alcohols, by causing them to contain a specific organic component in a specific amount, the same effects can be expected to be obtained.

[0069] In addition, the ethanol of the present application, for example, can be used as a raw material for the production of butadiene, ethylene, propylene, isobutylene, acetaldehyde, acetic acid, ethyl acetate, (methyl) methyl acrylate, ethyl tert-butyl ether ethylene glycol, ester compositions, polyesters, acrylic acid, aminocaproic acid, diethyl carbonate, polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyisobutylene, polymethyl methacrylate (PMMA), ethylene propylene diene rubber (EPDM), polybutylene terephthalate (PBT), polyethylene furanoate (PEF), polyurethane (PU), and the like. In addition, the ethanol of the present application can be used for various uses of chemical products such as cosmetics, perfumes, fuels, antifreezes, sterilizing agents, disinfectants, cleaning agents, mold removers, lotions, shampoos, soaps, antiperspirants, face washes, solvents, paints, adhesives, diluents, food additives, and the like. Attached Figure Description

[0070] [ Figure A1 Gas chromatography of ethanol used in Example A1.

[0071] [ Figure A2 Gas chromatography of ethanol used in Comparative Example A1.

[0072] [ Figure A3 Gas chromatography of ethanol used in Comparative Example A2.

[0073] [ Figure B1 Gas chromatography of ethanol used in Examples B1, Comparative Examples B1 and B2.

[0074] [ Figure B2 [Enlarged chromatogram of Example B1]

[0075] [ Figure C Gas chromatography of ethanol used in Examples C1, Comparative Examples C1 and C2.

[0076] [ Figure D1 Gas chromatography of ethanol used in Examples D1, Comparative Examples D1 and D2.

[0077] [ Figure D2 [Enlarged chromatogram of Example D1]

[0078] Specific embodiments of the present invention

[0079] Hereinafter, an example of a preferred embodiment of the present invention will be described. However, the following embodiments are merely illustrative examples of the present invention, and the present invention is not limited to the following embodiments.

[0080] <Definition>

[0081] In this invention, "ethanol" refers to a composition of ethanol produced through synthesis or purification that contains water or unavoidable impurities (inclusion components), and does not refer to pure ethanol as a compound (ethanol represented by the chemical formula: CH3CH2OH).

[0082] In addition, in this invention, the content of each component, such as inorganic and organic components, in the alcohol raw material refers to the amount (mg) of each component relative to 1L of alcohol.

[0083] Ethanol

[0084] The ethanol involved in this invention, in a gas chromatogram determined by gas chromatography-mass spectrometry (GC / MS), has a retention time having at least one of the peaks selected from (A) to (D) below.

[0085] (A) peaks at 5 minutes 25 seconds ~ 5 minutes 35 seconds and two peaks at 2 minutes 55 seconds ~ 3 minutes 5 seconds,

[0086] (B) a peak at 12 minutes 30 seconds ~ 12 minutes 40 seconds,

[0087] (C) a peak at 6 minutes 36 seconds ~ 6 minutes 45 seconds, and

[0088] (D) a peak at 15 minutes 0 seconds ~ 15 minutes 15 seconds.

[0089] The peaks of (A) ~ (D) are obtained by analyzing ethanol by a GC / MS method under the following analysis conditions.

[0090] That is, the two peaks of (A) are obtained by analyzing ethanol by a GC / MS method under the following analysis conditions.

[0091] <Analysis conditions of GC / MS method>

[0092] Column: Capillary column (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm)

[0093] Oven temperature: 40°C, 1 minute → 5°C / minute → 100°C, 10 minutes → 10°C / minute → 250°C, 4 minutes

[0094] Injection time: 5 minutes

[0095] Carrier gas: He (3.0 mL / minute)

[0096] Further, the peaks of (B) ~ (D) are obtained by analyzing ethanol by a GC / MS method under the following analysis conditions.

[0097] <Analysis conditions of GC / MS method>

[0098] Column: DB-5MS (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm)

[0099] Oven temperature: 40°C → 10°C / minute → 300°C

[0100] Carrier gas: He (1.28 mL / minute)

[0101] Injection port temperature: 300°C

[0102] Detector temperature: 300°C

[0103] Detector: hydrogen flame ionization detector

[0104] Injection amount: 1 μL (split ratio 1:20)

[0105] In a gas chromatogram obtained by measuring ethanol having a purity of 100%, i.e., completely free of impurities, under the conditions described above by the GC / MS method, no peak having a retention time of 2 minutes 55 seconds to 3 minutes 5 seconds, a peak having a retention time of 12 minutes 30 seconds to 12 minutes 40 seconds, a peak having a retention time of 6 minutes 36 seconds to 6 minutes 45 seconds, and a peak having a retention time of 15 minutes 0 seconds to 15 minutes 15 seconds were present. Further, in a gas chromatogram obtained by measuring commercially available industrial ethanol derived from fossil fuels under the conditions described above by the GC / MS method, no peak having a retention time of 2 minutes 55 seconds to 3 minutes 5 seconds, a peak having a retention time of 12 minutes 30 seconds to 12 minutes 40 seconds, a peak having a retention time of 6 minutes 36 seconds to 6 minutes 45 seconds, and a peak having a retention time of 15 minutes 0 seconds to 15 minutes 15 seconds were present. Further, ethanol produced by fermentation using a biomass material such as cellulose also did not have a peak having a retention time of 2 minutes 55 seconds to 3 minutes 5 seconds, a peak having a retention time of 12 minutes 30 seconds to 12 minutes 40 seconds, a peak having a retention time of 6 minutes 36 seconds to 6 minutes 45 seconds, and a peak having a retention time of 15 minutes 0 seconds to 15 minutes 15 seconds. Thus, it can be considered that the peak having a retention time of 2 minutes 55 seconds to 3 minutes 5 seconds, the peak having a retention time of 12 minutes 30 seconds to 12 minutes 40 seconds, the peak having a retention time of 6 minutes 36 seconds to 6 minutes 45 seconds, and the peak having a retention time of 15 minutes 0 seconds to 15 minutes 15 seconds are unique to ethanol derived from microbial fermentation using a gas containing carbon monoxide and hydrogen as a substrate.

[0106] Although not bound by theory, it can be considered that, in the production process of ethanol derived from microbial fermentation using a gas containing carbon monoxide and hydrogen as a substrate, the synthesis gas used contains various trace components in addition to carbon monoxide and hydrogen, and that even alcohol obtained by a purification process such as distillation inevitably contains substances such as aldehydes having a higher boiling point than ethanol. It can be considered that, in the present application, the inclusion of these inevitable substances in ethanol enables the improvement of the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, the improvement of the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and the like.

[0107] The peak having a retention time of 12 minutes 30 seconds to 12 minutes 40 seconds is presumed to be derived from n-tetradecane. The content of n-tetradecane relative to the entire ethanol is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, further preferably 0.03 mg / L or more, more further preferably 0.05 mg / L or more, and in addition, is preferably 1 mg / L or less, more preferably 0.5 mg / L or less, further preferably 0.2 mg / L or less, and more further preferably 0.1 mg / L or less. By setting the content of n-tetradecane to the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material can be improved, the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid can be improved, the combustion efficiency when using ethanol as a fuel can be improved, and the like.

[0108] The peak with a retention time of 6 minutes 36 seconds to 6 minutes 45 seconds is presumed to originate from n-decane. The content of n-decane, relative to the total ethanol content, is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, further preferably 0.03 mg / L or more, even more preferably 0.05 mg / L or more, and preferably 1 mg / L or less, more preferably 0.5 mg / L or less, even more preferably 0.2 mg / L or less, and even more preferably 0.1 mg / L or less. By ensuring the n-decane content is within the aforementioned range, the ethanol conversion rate during the synthesis of butadiene from ethanol can be improved, the reaction rate during the synthesis of carboxylic acid esters from the addition of ethanol to carboxylic acids can be improved, and the combustion efficiency when using ethanol as fuel can be improved, etc.

[0109] Peaks with retention times of 15 minutes 00 seconds to 15 minutes 15 seconds are presumed to originate from n-hexadecane. The content of n-hexadecane, relative to the total ethanol content, is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, further preferably 0.03 mg / L or more, even more preferably 0.05 mg / L or more, and preferably 1 mg / L or less, more preferably 0.5 mg / L or less, even more preferably 0.2 mg / L or less, and even more preferably 0.1 mg / L or less. By setting the content of n-decane within the aforementioned range, the ethanol conversion rate during the synthesis of butadiene from ethanol can be improved, the reaction rate during the synthesis of carboxylic acid esters from the addition of ethanol to carboxylic acids can be improved, and the combustion efficiency when using ethanol as fuel can be improved, etc.

[0110] Ethanol derived from microbial fermentation using a gaseous substrate containing carbon monoxide and hydrogen preferably exhibits peaks with retention times of 2 min 55 sec to 3 min 5 sec, and also peaks with retention times of 5 min 30 sec to 5 min 35 sec. For the same reasons mentioned above, it can be assumed that even ethanol obtained through purification processes such as distillation will contain substances such as aldehydes with boiling points very close to ethanol. It can be assumed that these unavoidable substances play a role in the reaction process using ethanol as a raw material, thereby increasing the ethanol conversion rate and reaction rate.

[0111] The ethanol of the present invention is obtained by further purification of the ethanol-containing liquid extracted from the microbial fermentation tank described below, and may also contain other components besides the unavoidable substances described above. For example, it may contain trace amounts of aromatic compounds. Examples of aromatic compounds contained in ethanol include toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene; it may contain only one of them or more than two. Ethylbenzene is preferably included as an aromatic compound.

[0112] The lower limit of the content (total) of aromatic compounds contained in the ethanol can be 0.001 mg / L or more, preferably 0.01 mg / L or more, more preferably 0.1 mg / L or more, further preferably 0.4 mg / L or more, and particularly preferably 1.0 mg / L or more, relative to the entire ethanol. In addition, the upper limit of the content (total) of aromatic compounds contained in the ethanol can be 100 mg / L or less, preferably 50 mg / L or less, more preferably 1 mg / L or less, further preferably 7 mg / L or less, and particularly preferably 3.0 mg / L or less.

[0113] By setting the content of aromatic compounds to the above-mentioned range, the conversion rate of ethanol when synthesizing butadiene using ethanol as a raw material, the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, the combustion efficiency when using ethanol as a fuel, and the like can be improved.

[0114] When ethylbenzene is contained in the ethanol, the content of ethylbenzene, relative to the entire ethanol, is preferably 0.1 mg / L or more, more preferably 0.2 mg / L or more, further preferably 0.3 mg / L or more, and still further preferably 0.5 mg / L or more, and is also preferably 5 mg / L or less, more preferably 3 mg / L or less, further preferably 2 mg / L or less, and still further preferably 1 mg / L or less. By setting the content of ethylbenzene to the above-mentioned range, the conversion rate of ethanol when synthesizing butadiene using ethanol as a raw material, the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, the combustion efficiency when using ethanol as a fuel, and the like can be improved.

[0115] When toluene is contained in the ethanol, the content of toluene, relative to the entire ethanol, is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, further preferably 0.03 mg / L or more, and still further preferably 0.05 mg / L or more, and is also preferably 1 mg / L or less, more preferably 0.5 mg / L or less, further preferably 0.2 mg / L or less, and still further preferably 0.1 mg / L or less. By setting the content of toluene to the above-mentioned range, the conversion rate of ethanol when synthesizing butadiene using ethanol as a raw material, the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, the combustion efficiency when using ethanol as a fuel, and the like can be improved.

[0116] When the ethanol contains o-xylene, the content of the o-xylene, relative to the entire ethanol, is preferably 0.1 mg / L or more, more preferably 0.2 mg / L or more, further preferably 0.3 mg / L or more, still further preferably 0.5 mg / L or more, and furthermore, is preferably 5 mg / L or less, more preferably 3 mg / L or less, further preferably 2 mg / L or less, still further preferably 1 mg / L or less. By setting the content of the o-xylene within the above range, the conversion rate of the ethanol when the ethanol is used as a raw material to synthesize butadiene, the reaction rate when the carboxylic acid is synthesized by adding the ethanol to the carboxylic acid, the combustion efficiency when the ethanol is used as a fuel, and the like can be improved.

[0117] When the ethanol contains m-xylene and / or p-xylene, the content (total) of the m-xylene and / or p-xylene, relative to the entire ethanol, is preferably 0.2 mg / L or more, more preferably 0.3 mg / L or more, further preferably 0.4 mg / L or more, still further preferably 0.5 mg / L or more, and furthermore, is preferably 5 mg / L or less, more preferably 3 mg / L or less, further preferably 2 mg / L or less, still further preferably 1 mg / L or less. By setting the content of the m-xylene and / or p-xylene within the above range, the conversion rate of the ethanol when the ethanol is used as a raw material to synthesize butadiene, the reaction rate when the carboxylic acid is synthesized by adding the ethanol to the carboxylic acid, the combustion efficiency when the ethanol is used as a fuel, and the like can be improved.

[0118] Further, the ethanol according to the present application can further contain a trace amount of an aliphatic hydrocarbon. As the aliphatic hydrocarbon, n-hexane, n-heptane, n-octane, n-dodecane, n-tetradecane, and the like can be exemplified, and one kind thereof can be contained alone or two or more kinds thereof can be contained. As the aromatic compound, one or more kinds of n-hexane and n-dodecane are preferably contained.

[0119] The content (total) of the aliphatic hydrocarbon contained in the ethanol is preferably 0.001 mass ppm or more, preferably 0.005 mass ppm or more, more preferably 0.01 mass ppm or more, further preferably 0.1 mass ppm or more, and furthermore, can be 100 mass ppm or less, preferably 50 mass ppm or less, more preferably 10 mass ppm or less, further preferably 5 mass ppm or less, relative to the entire ethanol.

[0120] When the ethanol contains n-hexane, the content of the n-hexane, relative to the entire ethanol, is preferably 0.1 mass ppm or more, more preferably 0.2 mass ppm or more, further preferably 0.3 mass ppm or more, still further preferably 0.5 mass ppm or more, and furthermore, is preferably 5 mass ppm or less, more preferably 3 mass ppm or less, further preferably 2 mass ppm or less, still further preferably 1 mass ppm or less.

[0121] When n-heptane is contained in the ethanol, the content of the n-heptane, relative to the entire ethanol, is preferably 0.01 mass ppm or more, more preferably 0.02 mass ppm or more, further preferably 0.03 mass ppm or more, more further preferably 0.05 mass ppm or more, and in addition, is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, further preferably 0.2 mass ppm or less, more further preferably 0.1 mass ppm or less.

[0122] When n-octane is contained in the ethanol, the content of the n-octane, relative to the entire ethanol, is preferably 0.01 mass ppm or more, more preferably 0.02 mass ppm or more, further preferably 0.03 mass ppm or more, more further preferably 0.05 mass ppm or more, and in addition, is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, further preferably 0.2 mass ppm or less, more further preferably 0.1 mass ppm or less.

[0123] When n-dodecane is contained in the ethanol, the content of the n-dodecane, relative to the entire ethanol, is preferably 0.01 mass ppm or more, more preferably 0.02 mass ppm or more, further preferably 0.03 mass ppm or more, more further preferably 0.05 mass ppm or more, and in addition, is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, further preferably 0.2 mass ppm or less, more further preferably 0.1 mass ppm or less.

[0124] When n-tetradecane is contained in the ethanol, the content of the n-tetradecane, relative to the entire ethanol, is preferably 0.01 mass ppm or more, more preferably 0.02 mass ppm or more, further preferably 0.03 mass ppm or more, more further preferably 0.05 mass ppm or more, and in addition, is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, further preferably 0.2 mass ppm or less, more further preferably 0.1 mass ppm or less.

[0125] Further, the ethanol according to the present application can further contain a trace amount of a dialkyl ether. As the dialkyl ether, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, and diamyl ether can be given, and only one of them can be contained, or two or more of them can be contained. As the dialkyl ether, dibutyl ether is preferably contained.

[0126] The content of the dialkyl ether contained in the ethanol (total) with respect to the entire ethanol is preferably 0.001 mg / L or more, preferably 0.01 mg / L or more, more preferably 0.1 mg / L or more, further preferably 1.0 mg / L or more, and in addition, can be 100 mg / L or less, preferably 80 mg / L or less, more preferably 50 mg / L or less, further preferably 30 mg / L or less. By making the content of the dialkyl ether within the range of values described above, the ethanol conversion rate when ethanol is used as a raw material to synthesize butadiene, the reaction rate when ethanol is added to a carboxylic acid to synthesize a carboxylic acid ester, the combustion efficiency when ethanol is used as a fuel, and the like can be improved.

[0127] When dibutyl ether is contained in the ethanol, the content of the dibutyl ether with respect to the ethanol is preferably 1 mg / L or more, more preferably 2 mg / L or more, further preferably 5 mg / L or more, and more further preferably 10 mg / L or more, and in addition, is preferably 50 mg / L or less, more preferably 40 mg / L or less, further preferably 30 mg / L or less, and more further preferably 25 mg / L or less. By making the content of the dibutyl ether within the range of values described above, the ethanol conversion rate when ethanol is used as a raw material to synthesize butadiene, the reaction rate when ethanol is added to a carboxylic acid to synthesize a carboxylic acid ester, the combustion efficiency when ethanol is used as a fuel, and the like can be improved.

[0128] The ethanol of the present application contains an organic compound described above in an extremely small amount, and can contain a compound containing an element such as Si, K, Na, Fe, Cr, and the like. The compound containing these elements is sometimes an inorganic compound, and sometimes an organometallic compound. For example, when Si is contained, silica or an organosiloxane can be contained.

[0129] When Si is contained in the ethanol, the content of the Si with respect to the ethanol is preferably 10 mg / L or more, more preferably 20 mg / L or more, and further preferably 30 mg / L or more, and in addition, is preferably 100 mg / L or less, more preferably 90 mg / L or less, and further preferably 80 mg / L or less. The content of the Si refers to the amount of Si element of the Si compound. By making the content of the Si within the range of values described above, the ethanol conversion rate when ethanol is used as a raw material to synthesize butadiene, the reaction rate when ethanol is added to a carboxylic acid to synthesize a carboxylic acid ester, the combustion efficiency when ethanol is used as a fuel, and the like can be improved.

[0130] When K is contained in the ethanol, the content of K, relative to the ethanol, is preferably 1.0 mg / L or more, more preferably 1.5 mg / L or more, further preferably 2.0 mg / L or more, still further preferably 2.5 mg / L or more, and furthermore, preferably 10 mg / L or less, more preferably 7 mg / L or less, and further preferably 5 mg / L or less. The content of K refers to the amount of K element converted from K compounds. By setting the content of K within the above range, the ethanol conversion rate in the synthesis of butadiene using ethanol as a raw material, the reaction rate in the synthesis of carboxylic acid ester by adding ethanol to carboxylic acid, the combustion efficiency in the use of ethanol as a fuel, and the like can be improved.

[0131] When Na is contained in the ethanol, the content of Na, relative to the ethanol, is preferably 150 mg / L or more, more preferably 170 mg / L or more, further preferably 190 mg / L or more, and furthermore, preferably 1000 mg / L or less, more preferably 500 mg / L or less, further preferably 400 mg / L or less, and more preferably 300 mg / L or less. The content of Na refers to the amount of Na element converted from Na compounds. By setting the content of Na within the above range, the ethanol conversion rate in the synthesis of butadiene using ethanol as a raw material, the reaction rate in the synthesis of carboxylic acid ester by adding ethanol to carboxylic acid, the combustion efficiency in the use of ethanol as a fuel, and the like can be improved.

[0132] When Fe is contained in the ethanol, the content of Fe, relative to the ethanol, is preferably 2.0 mg / L or less, more preferably 1.5 mg / L or less, further preferably 1.0 mg / L or less, and more preferably 0.5 mg / L or less. The content of Fe refers to the amount of Fe element converted from Fe compounds. By setting the content of Fe within the above range, the ethanol conversion rate in the synthesis of butadiene using ethanol as a raw material, the reaction rate in the synthesis of carboxylic acid ester by adding ethanol to carboxylic acid, the combustion efficiency in the use of ethanol as a fuel, and the like can be improved.

[0133] When Cr is contained in the ethanol, the content of Cr, relative to the ethanol, is preferably 0.6 mg / L or less, and more preferably 0.5 mg / L or less. The content of Cr refers to the amount of Cr element converted from Cr compounds. By setting the content of Cr within the above range, the ethanol conversion rate in the synthesis of butadiene using ethanol as a raw material, the reaction rate in the synthesis of carboxylic acid ester by adding ethanol to carboxylic acid, the combustion efficiency in the use of ethanol as a fuel, and the like can be improved.

[0134] Although the ethanol of the present invention contains the inorganic components as described above and the desired trace amounts of organic components such as aromatic hydrocarbons and aliphatic hydrocarbons, the concentration of ethanol (pure ethanol as a compound), which is the main component of ethanol, is 75% by volume or more, preferably 80% by volume or more, more preferably 90% by volume or more, even more preferably 95% by volume or more, even more preferably 98% by volume or more, and preferably 99.99% by volume or less, even more preferably 99.9% by volume or less, even more preferably 99.9% by volume or less, even more preferably 99.5% by volume or less.

[0135] The ethanol concentration in the ethanol of this invention can be set according to the intended use. For example, if it is for cosmetics, it is preferably 90% by volume or more, and if it is for disinfectants, it is preferably 75% by volume or more. The upper limit can also be set appropriately according to the intended use. From the viewpoint of transportation costs, the higher the ethanol concentration in the product, the more preferred it is.

[0136] <Methods for producing ethanol>

[0137] As a method for producing ethanol with the characteristic gas chromatographic peaks described above, ethanol can be produced by microbial fermentation using syngas containing carbon monoxide derived from waste or exhaust gases. In such a method, the content of aromatic compounds and the purification conditions in the feed gas derived from waste or exhaust gases can be controlled, thereby controlling the amount of aromatic compounds in the final product. Hereinafter, as an example, a method for producing ethanol using syngas containing carbon monoxide derived from waste or exhaust gases through microbial fermentation will be described.

[0138] The method for producing ethanol includes the following steps: a step of converting a carbon source into a synthesis gas containing carbon monoxide and hydrogen; a microbial fermentation step of supplying the synthesis gas containing carbon monoxide and hydrogen to a microbial fermentation tank to obtain an ethanol-containing liquid through microbial fermentation; a separation step of separating the ethanol-containing liquid into a liquid or solid component containing microorganisms and a gaseous component containing ethanol; a liquefaction step of condensing the gaseous component to liquefy it; and a purification step of purifying ethanol from the liquid obtained in the liquefaction step. However, as needed, it may include a raw material gas generation step, a synthesis gas preparation step, and a wastewater treatment step. The following describes each step.

[0139] <Raw Gas Generation Process>

[0140] The raw material gas generation step is a step of generating a raw material gas by gasifying a carbon source in a gasification section. In the raw material gas generation step, a gasifier can be used. The gasifier is a furnace that burns (incomplete combustion) the carbon source, and examples thereof include a shaft furnace, a kiln, a fluidized bed furnace, a gasification reforming furnace, and the like. From the viewpoint of obtaining a high furnace bed load and excellent operation operability by partially burning the waste, the gasifier is preferably a fluidized bed furnace. By gasifying the waste in a fluidized bed furnace at a low temperature (about 450 to 600°C) and in a low-oxygen atmosphere, the waste can be decomposed into coke containing a large amount of gas (carbon monoxide, carbon dioxide, hydrogen, methane, and the like) and a carbon component. Further, since the non-combustible matter contained in the waste can be separated from the bottom of the furnace in a sanitary and low-oxidized state, valuable substances such as iron and aluminum in the non-combustible matter can be selectively recovered. Thus, such gasification of the waste can achieve efficient resource recovery.

[0141] The temperature of the gasification in the raw material gas generation step is not particularly limited, and is usually 100 to 2500°C, and preferably 200 to 2100°C.

[0142] The reaction time of the gasification in the raw material gas generation step is usually 2 seconds or more, and is preferably 5 seconds or more.

[0143] The carbon source used in the raw material gas generation step is not particularly limited, and examples thereof include coke from an iron plant, blast furnace gas, coal used in a coal-fired power plant, general waste and industrial waste introduced into an incinerator (particularly a gasifier), carbon dioxide from various industrial by-products, and various carbon-containing materials for recovery.

[0144] More specifically, the carbon source is preferably waste, and specific examples thereof include plastic waste, kitchen garbage, municipal solid waste (MSW), industrial solid waste, waste tires, biomass waste, bedding, household garbage such as paper, waste such as construction materials, and waste derived from coal, petroleum, compounds of petroleum, natural gas, shale gas, and the like. Among these, various wastes are preferable from the viewpoint of sorting cost, and unsorted municipal solid waste is more preferable.

[0145] The raw material gas obtained by gasifying the carbon source contains carbon monoxide and hydrogen as essential components, but can further contain carbon dioxide, oxygen, nitrogen. As other components, the raw material gas can further contain components such as soot, tar, nitrogen compounds, sulfur compounds, phosphorus compounds, aromatic compounds, and the like.

[0146] As for the raw material gas, it can be generated as a gas containing carbon monoxide without particular limitation, for example, 0.1% by volume or more, preferably 10% by volume or more, more preferably 20% by volume or more, by performing heat treatment (so-called: gasification) of combusting (incomplete combustion) a carbon source, i.e., by partially oxidizing the carbon source in the raw material gas generation step.

[0147] <synthesis gas purification step>

[0148] The synthesis gas purification step is a step of removing or reducing various contaminant substances, dust particles, impurities, and specific substances such as compounds in an undesirable amount from the raw material gas. When the raw material gas is derived from waste, the raw material gas generally has a tendency to contain 0.1% by volume or more to 80% by volume or less of carbon monoxide, 0.1% by volume or more to 70% by volume or less of carbon dioxide, 0.1% by volume or more to 80% by volume or less of hydrogen, and further, 1 mg / L or more of nitrogen compounds, 1 mg / L or more of sulfur compounds, 0.1 mg / L or more of phosphorus compounds, and / or 10 mg / L or more of aromatic compounds. In addition, it can contain other environmental pollutants, dust particles, impurities, and the like. Therefore, when the synthesis gas is supplied to the microbial fermentation tank, it is preferable to reduce or remove those substances or compounds in an undesirable amount for the stable cultivation of microorganisms from the raw material gas, and adjust the content of each component contained in the raw material gas to a range appropriate for the stable cultivation of microorganisms.

[0149] In particular, in the synthesis gas purification step, the carbon dioxide gas in the synthesis gas is adsorbed to the regenerative adsorbent material (zeolite) using a pressure swing adsorption device filled with the regenerative adsorbent material, and the carbon dioxide gas concentration in the synthesis gas is reduced. Further, the synthesis gas can be treated with other known treatment steps to remove impurities and adjust the gas composition. As the other treatment steps, for example, the synthesis gas can be treated with one or two or more of a gas cooler (water separation device), a low-temperature separation device (cryogenic type), a cyclone separator, a bag filter and the like fine particle (soot) separation device, a scrubber (water-soluble impurity separation device), a desulfurization device (sulfide separation device), a membrane separation type separation device, a deoxidation device, a pressure swing adsorption type separation device (PSA), a temperature swing adsorption type separation device (TSA), a pressure and temperature swing adsorption type separation device (PTSA), a separation device using activated carbon, a deoxidation catalyst, specifically a separation device using a copper catalyst or a palladium catalyst, and the like.

[0150] The synthesis gas used in the method for producing ethanol of the present application contains at least carbon monoxide as an essential component, and can further contain hydrogen, carbon dioxide, and nitrogen.

[0151] As for the synthesis gas used in the present application, a raw material gas is produced by gasifying a carbon source (raw material gas production step), and then, the raw material gas is subjected to adjustment of the concentration of each component of carbon monoxide, carbon dioxide, hydrogen and nitrogen, and the gas is obtained by a step of reducing or removing the above-mentioned substances and compounds, and this gas can be used as the synthesis gas.

[0152] The carbon monoxide concentration in the synthesis gas is usually 20 vol% or more and 80 vol% or less, preferably 25 vol% or more and 50 vol% or less, and more preferably 35 vol% or more and 45 vol% or less, relative to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas.

[0153] The hydrogen concentration in the synthesis gas is usually 10 vol% or more and 80 vol% or less, preferably 30 vol% or more and 55 vol% or less, and more preferably 40 vol% or more and 50 vol% or less, relative to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas.

[0154] The carbon dioxide concentration in the synthesis gas is usually 0.1 vol% or more and 40 vol% or less, preferably 0.3 vol% or more and 30 vol% or less, and more preferably 0.5 vol% or more and 10 vol% or less, and particularly preferably 1 vol% or more and 6 vol% or less, relative to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas.

[0155] The nitrogen concentration in the synthesis gas is usually 40 vol% or less, preferably 1 vol% or more and 20 vol% or less, and more preferably 5 vol% or more and 15 vol% or less, relative to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas.

[0156] The concentrations of carbon monoxide, carbon dioxide, hydrogen and nitrogen can be controlled within the specified ranges by changing the elemental composition of the carbon source, which is a hydrocarbon (carbon and hydrogen) or nitrogen, in the raw material gas production step, or by appropriately changing the combustion temperature, the oxygen concentration of the gas supplied during combustion, or the like. For example, to change the carbon monoxide or hydrogen concentration, there is a method of changing the carbon source to one in which the ratio of a hydrocarbon (carbon and hydrogen) such as waste plastic is high, or the like, and to reduce the nitrogen concentration, there is a method of supplying a gas having a high oxygen concentration in the raw material gas production step, or the like.

[0157] The synthetic gas used in the present application is not particularly limited except for the components described above, and can contain sulfur compounds, phosphorus compounds, nitrogen compounds, and the like. The content of each of these compounds is preferably 0.05 mg / L or more, more preferably 0.1 mg / L or more, further preferably 0.5 mg / L or more, and, on the other hand, is preferably 2000 mg / L or less, more preferably 1000 mg / L or less, further preferably 80 mg / L or less, further more preferably 60 mg / L or less, and particularly preferably 40 mg / L or less. By having the content of sulfur compounds, phosphorus compounds, nitrogen compounds, and the like be 0.05 mg / L or more, it is possible to appropriately cultivate microorganisms, and, by having the content be 2000 mg / L or less, it is possible to prevent the culture medium from being contaminated with various nutrients that are not consumed by microorganisms.

[0158] As the sulfur compounds, sulfur dioxide, CS2, COS, and H2S can be generally mentioned, of which H2S and sulfur dioxide are preferred from the viewpoint that they are easily consumed as nutrients by microorganisms. Therefore, it is more preferred that H2S and sulfur dioxide be contained in the synthetic gas in a total amount within the range described above. As the phosphorus compounds, phosphoric acid is preferred from the viewpoint that it is easily consumed as a nutrient by microorganisms. Therefore, it is more preferred that phosphoric acid be contained in the synthetic gas within the range described above.

[0159] As the nitrogen compounds, nitrogen monoxide, nitrogen dioxide, acrylonitrile, acetonitrile, and HCN can be mentioned, of which HCN is preferred from the viewpoint that it is easily consumed as a nutrient by microorganisms. Therefore, it is more preferred that HCN be contained in the synthetic gas within the range described above.

[0160] In addition, the synthetic gas can contain 0.01 mg / L or more and 90 mg / L or less of aromatic compounds, and is preferably 0.03 mg / L or more, more preferably 0.05 mg / L or more, and further preferably 0.1 mg / L or more, and, on the other hand, is preferably 70 mg / L or less, more preferably 50 mg / L or less, and further preferably 30 mg / L or less. By having the content be 0.01 mg / L or more, it is possible to appropriately cultivate microorganisms, and, by having the content be 90 mg / L or less, it is possible to prevent the culture medium from being contaminated with various nutrients that are not consumed by microorganisms.

[0161] <Microorganism fermentation step>

[0162] The microorganism fermentation step is a step of producing ethanol by microorganism fermentation of the synthesis gas in a microorganism fermentation tank. The microorganism fermentation tank is preferably a continuous fermentation device. In general, the microorganism fermentation tank can use a microorganism fermentation tank having an arbitrary shape, and examples of the microorganism fermentation tank include a stirring type, a gas lift type, a bubble column type, a circulation type, an open rod type, and a photobiological type. In the present application, a known circulation reactor having a main tank portion and a reflux portion can be suitably used as the microorganism fermentation tank. At this time, it is preferable to further include a circulation step of circulating the liquid medium between the main tank portion and the reflux portion.

[0163] As for the synthesis gas supplied to the microorganism fermentation tank, as long as the component conditions of the synthesis gas are satisfied, the gas obtained by the raw material gas production step can be directly used as the synthesis gas, or another specified gas can be added to the gas from which impurities and the like have been removed or eliminated from the raw material gas, and then used as the synthesis gas. As the other specified gas, for example, at least one compound selected from the group consisting of sulfur compounds such as sulfur dioxide, phosphorus compounds, and nitrogen compounds can be added as the synthesis gas.

[0164] The synthesis gas and the microorganism culture solution can be continuously supplied to the microorganism fermentation tank, but the synthesis gas and the microorganism culture solution do not need to be supplied at the same time, and the synthesis gas can be supplied to the microorganism fermentation tank to which the microorganism culture solution has been previously supplied. It is known that certain anaerobic microorganisms can produce ethanol and the like from substrate gas such as synthesis gas by fermentation, and such gas-utilizing microorganisms are cultured in a liquid medium. For example, the liquid medium and the gas-utilizing bacteria can be supplied and stored first, and the liquid medium can be stirred in this state while the synthesis gas is supplied into the microorganism fermentation tank. Thus, the gas-utilizing bacteria can be cultured in the liquid medium, and ethanol can be produced from the synthesis gas by the fermentation of the gas-utilizing bacteria.

[0165] The temperature of the medium and the like (culture temperature) in the microorganism fermentation tank can be an arbitrary temperature, but can be preferably around 30 to 45°C, more preferably around 33 to 42°C, and further preferably around 36.5 to 37.5°C. In addition, the culture time is preferably 12 hours or more, more preferably 7 days or more, particularly preferably 30 days or more, and most preferably 60 days or more, and the upper limit is not particularly limited, but is preferably 720 days or less, and more preferably 365 days or less, from the viewpoint of periodic maintenance of the equipment and the like. Note that the culture time refers to the time from when the inoculum is added to the culture tank to when the entire amount of the culture solution in the culture tank is discharged.

[0166] The microorganism (s) contained in the microbial culture solution is not particularly limited as long as it is a microorganism that can produce ethanol by microbial fermentation of a synthesis gas in which carbon monoxide is the main raw material. For example, the microorganism (s) is a microorganism that produces ethanol from a synthesis gas by the fermentation action of a gas-utilizing bacterium, and particularly preferably a microorganism having an acetyl-CoA metabolic pathway. Among the gas-utilizing bacteria, Clostridium is more preferable, and particularly preferably Clostridium autoethanogenum, but is not limited thereto. Further examples are described below.

[0167] The gas-utilizing bacteria include both eubacteria and archaea. As the eubacteria, for example, Clostridium bacteria, Moorella bacteria, Acetobacterium bacteria, Carboxydocella bacteria, Rhodopseudomonas bacteria, Eubacterium bacteria, Butyribacterium bacteria, Oligotropha bacteria, Bradyrhizobium bacteria, Ralsotonia bacteria as aerobic hydrogen-oxidizing bacteria, and the like can be given.

[0168] On the other hand, as archaea, for example, there can be mentioned Methanobacterium bacteria, Methanobrevibacter bacteria, Methanocalculus, Methanococcus bacteria, Methanosarcina bacteria, Methanosphaera bacteria, Methanothermobacter bacteria, Methanothrix bacteria, Methanoculleus bacteria, Methanofollis bacteria, Methanogenium bacteria, Methanospirillium bacteria, Methanosaeta bacteria, Thermococcus bacteria, Thermofilum bacteria, Archaeoglobus bacteria, and the like. Among these, as archaea, Methanosarcina bacteria, Methanococcus bacteria, Methanothermobacter bacteria, Methanothrix bacteria, Thermococcus bacteria, Thermofilum bacteria, and Archaeoglobus bacteria are preferred.

[0169] Further, from the viewpoint of excellent resource utilization of carbon monoxide and carbon dioxide, as archaea, Methanosarcina bacteria, Methanothermobacter bacteria, or Methanococcus bacteria are preferred, and particularly, Methanosarcina bacteria or Methanococcus bacteria are preferred. Note that, as specific examples of Methanosarcina bacteria, for example, there can be mentioned Methanosarcina barkeri, Methanosarcina mazei, Methanosarcina acetivorans, and the like.

[0170] As the bacteria having high ethanol production ability, the following can be mentioned: Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Clostridium carboxidivorans, Moorella thermoacetica, Acetobacterium woodii, and the like. Among these, Clostridium autoethanogenum is particularly preferred.

[0171] The medium used for culturing the microorganism(s) is not particularly limited as long as it has an appropriate composition according to the bacteria, and is a liquid containing water as a main component, and a nutrient component (e.g., vitamins, phosphoric acid, etc.) dissolved or dispersed in the water. The components of such a medium are prepared so that the gas resource-utilizing bacteria can grow and multiply well. For example, when Clostridium is used as the microorganism, the medium can be referred to “0097” to “0099” of U.S. Patent Application Publication No. 2017 / 260552, and the like.

[0172] The ethanol-containing liquid obtained by the microbial fermentation step can be obtained in the form of a suspension containing microorganisms, their corpses, proteins derived from microorganisms, and the like. The protein concentration in the suspension varies depending on the type of microorganism, but is generally 30 to 1000 mg / L. Note that the protein concentration in the ethanol-containing liquid can be measured by the Kjeldahl method.

[0173] <Separation Step>

[0174] Next, the ethanol-containing liquid obtained by the microbial fermentation step is subjected to a separation step. In the present application, the ethanol-containing liquid is heated to a temperature of room temperature to 500°C under a pressure of 0.01 to 1000 kPa (absolute pressure), and separated into a liquid or solid component containing microorganisms and a gaseous component containing ethanol. In the conventional method, the ethanol-containing liquid obtained by the microbial fermentation step is distilled to separate and purify the desired ethanol, but since the ethanol-containing liquid contains microorganisms, proteins derived from microorganisms, and the like, if the ethanol-containing liquid is directly distilled as it is, foaming occurs in the distillation apparatus, which hinders continuous operation. In addition, as a method for purifying a foaming liquid, a membrane evaporator is known, but the concentration efficiency of the membrane evaporator is low, and is not suitable for the purification of a liquid containing a solid component. In the present application, before the ethanol-containing liquid obtained by the microbial fermentation step is subjected to a distillation operation or the like to separate and purify the desired ethanol, the ethanol-containing liquid is first heated and separated into a liquid or solid component containing microorganisms and a gaseous component containing ethanol, and the desired ethanol is separated and purified only from the separated gaseous component containing ethanol. By carrying out the separation step, foaming does not occur in the distillation apparatus during the distillation operation for separating and purifying ethanol, and thus the distillation operation can be continuously performed. In addition, since the ethanol concentration in the gaseous component containing ethanol is higher than the ethanol concentration in the ethanol-containing liquid, the separation and purification of ethanol can be more efficiently performed in the purification step described later.

[0175] In the present application, from the viewpoint of efficiently separating into a liquid or solid component containing microorganisms, cadavers thereof, proteins derived from microorganisms, and the like, and a gaseous component containing ethanol, it is preferable that the heating of the ethanol-containing liquid be carried out under a pressure of 10 to 200 kPa, more preferably under a pressure of 50 to 150 kPa, further preferably under normal pressure, preferably at a temperature of 50 to 200°C, more preferably at a temperature of 80°C to 180°C, further preferably at a temperature of 100 to 150°C.

[0176] The heating time in the separation step is not particularly limited as long as it is a time during which the gaseous component can be obtained, and is usually 5 seconds to 2 hours, preferably 5 seconds to 1 hour, and more preferably 5 seconds to 30 minutes, from the viewpoint of efficiency or economy.

[0177] Regarding the separation process, any device that can efficiently separate ethanol-containing liquids into liquid or solid components (microorganisms, their remains, proteins derived from microorganisms, etc.) and gaseous components (ethanol) using thermal energy is acceptable without particular restrictions. For example, rotary dryers, fluidized bed dryers, vacuum dryers, and conduction-heated dryers can be used. In particular, from the viewpoint of efficiency in separating liquid or solid components and gaseous components from ethanol-containing liquids with low solid component concentrations, conduction-heated dryers are preferred. Examples of conduction-heated dryers include drum dryers and disc dryers.

[0178] <Liquefaction Process>

[0179] The liquefaction process is a process of liquefying the gaseous components containing ethanol obtained in the separation process by condensing them. The apparatus used in the liquefaction process is not particularly limited, but a heat exchanger is preferred, and a condenser is particularly preferred. Examples of condensers include water-cooled, air-cooled, and evaporative types, with water-cooled condensers being preferred. The condenser can be a single-stage condenser or can contain multiple stages.

[0180] The liquefied product obtained through the liquefaction process preferably does not contain the components found in ethanol, such as microorganisms, their remains, or proteins derived from microorganisms. However, in this invention, the presence of proteins in the liquefied product is not excluded. When proteins are present in the liquefied product, their concentration is preferably 40 mg / L or less, more preferably 20 mg / L or less, and even more preferably 15 mg / L or less.

[0181] The heat of condensation of the gaseous components obtained through the condenser can be reused as a heat source in the purification process described later. By reusing the heat of condensation, ethanol can be produced efficiently and economically.

[0182] <Purification Process>

[0183] Next, ethanol is purified from the liquefied product obtained in the liquefaction process. If the ethanol-containing liquid obtained in the microbial fermentation process has already had its microbial and other components removed, it can be supplied to the purification process without undergoing the separation process described above. The purification process separates the ethanol-containing liquid obtained in the liquefaction process into a distillate with an increased concentration of ethanol as the target substance and a bottoms liquid with a decreased concentration of ethanol as the target substance. Examples of apparatus used in the purification process include, for instance, a distillation apparatus, a permeabilization membrane treatment apparatus, a zeolite dehydration membrane treatment apparatus, a low-boiling-point apparatus for removing substances with a lower boiling point than ethanol, a high-boiling-point apparatus for removing substances with a higher boiling point than ethanol, and an ion exchange membrane treatment apparatus. These apparatuses can be used individually or in combination of two or more. As a unit operation, heating distillation or membrane separation can be suitably used.

[0184] In the heating distillation, using a distillation apparatus, the desired ethanol of high purity can be obtained in the form of distillate. The temperature in the distillation apparatus during the distillation of ethanol is not particularly limited, and is preferably 100°C or lower, more preferably around 70 to 95°C. By setting the temperature in the distillation apparatus in the range, the separation of ethanol and other components, i.e., the distillation of ethanol, can be more reliably performed.

[0185] In particular, the ethanol-containing liquid obtained in the liquefaction step is introduced into a distillation apparatus equipped with a heater using steam of 100°C or higher, the temperature at the bottom of the distillation column is raised to 90°C or higher within 30 minutes, and then the ethanol-containing liquid is introduced from the middle of the distillation column, and by performing the distillation step in such a manner that the temperature difference between the bottom, the middle, and the top of the column is within ±15°C, ethanol of high purity can be obtained. The distillation temperature difference is preferably ±13°C, more preferably ±11°C. If the distillation temperature difference is as described above, the separation from other components, i.e., the distillation of ethanol, can be more reliably performed.

[0186] It is considered that the ethanol-containing liquid contains tetradecane or decane having a higher boiling point than ethanol. In the present application, by adjusting the distillation conditions, for example, by setting the temperature at the uppermost part of the distillation column to a temperature 5 to 10°C higher than usual, aromatic compounds can also be distilled off, and the aromatic compounds contained in the ethanol in the distillate can be adjusted. As a result, the content of the aromatic compounds in the final ethanol can be adjusted.

[0187] The pressure in the distillation apparatus during the distillation of ethanol can be atmospheric pressure, but is preferably less than atmospheric pressure, more preferably around 60 to 95 kPa (absolute pressure). By setting the pressure in the distillation apparatus in the range, the separation efficiency of ethanol can be improved, and the yield of ethanol can be further improved. The yield of ethanol (the concentration of ethanol contained in the distillate after distillation) is preferably 90% by volume or more, more preferably 95% by volume or more.

[0188] In the membrane separation, a publicly known separation membrane can be appropriately used, and for example, a zeolite membrane can be appropriately used.

[0189] The concentration of ethanol contained in the distillate separated in the purification step is preferably 20% to 99.99% by volume, more preferably 60% to 99.9% by volume.

[0190] On the other hand, the concentration of ethanol contained in the column bottom discharge liquid is preferably 0.001% to 10% by volume, more preferably 0.01% to 5% by volume.

[0191] The bottom discharge liquid separated in the purification step is substantially free of nitrogen compounds. Note that "substantially free of" in the present application means that the concentration of nitrogen compounds in the bottom discharge liquid obtained in the purification step is such that the water treatment step is not required, and does not mean that the concentration of nitrogen compounds is 0 mg / L. In the separation step, the ethanol-containing liquid is separated into a liquid or solid component containing microorganisms and a gaseous component containing ethanol, as described above, and not the ethanol-containing liquid obtained from the microorganism fermentation step is purified of the desired ethanol. At this time, since the nitrogen compounds remain on the side of the liquid or solid component containing microorganisms, the gaseous component containing ethanol is almost free of nitrogen compounds. Therefore, it can be said that when the ethanol is purified from the liquefied product obtained by liquefying the gaseous component, the bottom discharge liquid obtained is substantially free of nitrogen compounds. If the bottom discharge liquid contains nitrogen compounds, the concentration of nitrogen compounds is 0.1 to 200 mg / L, preferably 0.1 to 100 mg / L, and more preferably 0.1 to 50 mg / L.

[0192] In addition, for the same reason as described above, the bottom discharge liquid separated in the purification step is substantially free of phosphorus compounds. Note that "substantially free of" means that the concentration of phosphorus compounds in the bottom discharge liquid obtained in the purification step is such that the water treatment step is not required, and does not mean that the concentration of phosphorus compounds is 0 mg / L. If the bottom discharge liquid contains phosphorus compounds, the concentration of phosphorus compounds is 0.1 to 100 mg / L, preferably 0.1 to 50 mg / L, and more preferably 0.1 to 25 mg / L. Thus, according to the method of the present application, it can be said that the bottom discharge liquid discharged in the purification step of ethanol is substantially free of nitrogen compounds, phosphorus compounds, and also almost free of other organic matter, and thus the water treatment step necessary in the past can be simplified.

[0193] <Water treatment step>

[0194] The bottom discharge liquid separated in the purification step can also be supplied to the water treatment step. In the water treatment step, organic matter such as nitrogen compounds and phosphorus compounds can be further removed from the bottom discharge liquid. In this step, the organic matter can be removed by anaerobic treatment or aerobic treatment of the bottom discharge liquid. The removed organic matter can also be used as fuel (heat source) in the purification step.

[0195] The treatment temperature in the water treatment step is usually 0 to 90°C, preferably 20 to 40°C, and more preferably 30 to 40°C.

[0196] The bottom discharge liquid obtained by the separation step is less burdensome in terms of water treatment and the like, since the liquid or solid component containing microorganisms and the like is removed, compared to the bottom discharge liquid obtained by directly supplying the bottom discharge liquid from the microorganism fermentation step to the purification step.

[0197] The concentration of nitrogen compounds in the treated liquid obtained by treating the bottom effluent in the liquid treatment step is preferably 0.1 to 30 mg / L, more preferably 0.1 to 20 mg / L, further preferably 0.1 to 10 mg / L, and particularly preferably contains no nitrogen compounds. In addition, the concentration of phosphorus compounds in the treated liquid is preferably 0.1 to 10 mg / L, more preferably 0.1 to 5 mg / L, further preferably 0.1 to 1 mg / L, and particularly preferably contains no phosphorus compounds in the bottom effluent.

[0198] <Use of ethanol>

[0199] The ethanol of the present application can be used as a raw material for the production of various organic compounds. For example, the ethanol of the present application can be used as a raw material for the production of butadiene, ethylene, propylene, isobutylene, acetaldehyde, acetic acid, ethyl acetate, methyl (meth)acrylate, ethyl tert-butyl ether glycol, ester composition, polyester, acrylic acid, aminocaproic acid, diethyl carbonate, polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyisobutylene, polymethyl methacrylate (PMMA), ethylene propylene diene rubber (EPDM), polybutylene terephthalate (PBT), polyethylene terephthalate (PEF), polyurethane (PU), and the like. As one example, a method for synthesizing butadiene using the ethanol of the present application as a raw material, and a method for producing polyethylene and polyester will be described below, and of course, can be used for other chemical products or polymer raw materials.

[0200] <Method for synthesizing butadiene>

[0201] Butadiene is mainly produced by purifying C4 fraction produced as a by-product when ethylene is synthesized from petroleum (i.e., naphtha cracking), and is a raw material for synthetic rubber. However, in recent years, instead of chemical industry raw materials obtained from petroleum, there is an urgent need for a technology for converting ethanol not derived from fossil fuels (ethanol derived from microbial fermentation) into 1,3-butadiene. As such a method for synthesizing butadiene using ethanol derived from microbial fermentation as a raw material, a method using MgO as a catalyst, a method using a mixture of AI2O3 and ZnO, a catalyst having a magnesium silicate structure, and the like are known. In addition to the above, vanadium, manganese, iron, cobalt, nickel, copper, zinc, gallium, niobium, silver, indium, cerium, and the like are also used as catalysts.

[0202] By allowing the ethanol of the present application to contact and heat with the catalyst described above, an ethanol conversion reaction occurs, and 1,3-butadiene can be obtained. By synthesizing butadiene using the ethanol of the present application as a raw material, a final resource recycling society independent of petroleum resources can be realized.

[0203] As the heating temperature for the conversion reaction, the temperature in the reaction system is, for example, 300 to 450°C, preferably around 350 to 400°C. If the temperature in the reaction system is lower than the range, the catalyst activity cannot be sufficiently obtained, and there is a tendency that the reaction rate decreases and the manufacturing efficiency decreases. On the other hand, if the temperature in the reaction system is higher than the range, there is a possibility that the catalyst easily deteriorates.

[0204] The reaction can be performed by a conventional method such as batch, semi-batch, continuous, and the like. When batch or semi-batch is adopted, the conversion rate of ethanol can be improved, but even if continuous is adopted, the ethanol according to the present application can be converted at a higher efficiency than the prior art. The reason is not clear, but it can be considered that, as for the ethanol according to the present application which is derived from a cyclic resource including a gas of carbon monoxide and hydrogen, there is a unique peak in the gas chromatogram determined by gas chromatography mass spectrometry, which is not observed in ethanol derived from fossil fuels.

[0205] As the method of contacting the raw material with the catalyst, for example, a suspension bed type, a flow bed type, a fixed bed type, and the like can be given. In addition, it can be either of a gas phase method or a liquid phase method. From the viewpoint that the recovery and regeneration treatment of the catalyst are more convenient, a fixed bed type gas phase continuous flow reaction apparatus in which the catalyst is packed into a reaction tube to form a catalyst layer and the raw material is circulated in the form of a gas to react in the gas phase is preferably used. When the reaction is performed in the gas phase, the ethanol according to the present application can be gasified and supplied to the reactor without dilution, or can be supplied to the reactor with appropriate dilution with an inert gas such as nitrogen, helium, argon, carbonic acid gas, and the like.

[0206] After the conversion reaction of ethanol is completed, the reaction product (1,3-butadiene) can be separated and purified by, for example, a separation means such as filtration, concentration, distillation, extraction, or a combination thereof.

[0207] <Polyethylene>

[0208] The ethanol according to the present application can be suitably used as a raw material for polyethylene, which is used for various purposes as a general-purpose plastic. The conventional polyethylene is manufactured by synthesizing ethylene from petroleum, and then polymerizing the ethylene monomer. By using the ethanol according to the present application to manufacture polyethylene, a final resource circulation society which is independent of petroleum resources can be realized.

[0209] First, the ethanol of the present application is used as a raw material to synthesize ethylene as a raw material for polyethylene. The method for producing ethylene is not particularly limited and can be obtained by a conventionally known method. As an example, ethylene can be obtained by a dehydration reaction of ethanol. When ethylene is obtained by a dehydration reaction of ethanol, a catalyst is generally used. The catalyst is not particularly limited and a conventionally known catalyst can be used. It is advantageous in terms of the process that a fixed bed flow-through reaction in which the catalyst and the product are easily separated, for example, is preferred, and γ-alumina or the like is preferred.

[0210] Since the dehydration reaction is an endothermic reaction, it is generally performed under heating. The heating temperature is not particularly limited, but if the reaction is to be performed at a commercially available reaction rate, it is preferably 100°C or higher, more preferably 250°C or higher, and further preferably 300°C or higher. The upper limit is not particularly limited, but from the viewpoint of energy consumption and equipment, it is preferably 500°C or lower, and more preferably 400°C or lower.

[0211] The reaction pressure is not particularly limited, but in order to easily perform the subsequent gas-liquid separation, a pressure of 1 atm or higher is preferred. A fixed bed flow-through reaction in which the catalyst is easily separated industrially is preferred, but a liquid phase suspension bed, a fluidized bed, or the like can also be used.

[0212] In the dehydration reaction of ethanol, the amount of water contained in the ethanol supplied as a raw material affects the yield of the reaction. In general, in the dehydration reaction, in consideration of the removal efficiency of water, it is preferred that there is no water. However, in the dehydration reaction of ethanol using a solid catalyst, if there is no water, the amount of other olefins, particularly butene, tends to increase. The lower limit of the allowable water content is 0.1% by mass or more, and it is preferably 0.5% by mass or more. The upper limit is not particularly limited, but from the viewpoint of material consumption and heat consumption, it is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.

[0213] By performing the dehydration reaction of ethanol as described above, a mixture of ethylene, water, and a small amount of unreacted ethanol can be obtained. Since ethylene is a gas under the conditions of normal temperature and about 5 MPa or less, water and ethanol can be removed by performing a gas-liquid separation on the mixture to obtain ethylene. This method can be performed by a conventionally known method. Next, the ethylene obtained by the gas-liquid separation is further distilled. At this time, the distillation method, the operation temperature, the residence time, and the like are not particularly limited except that the operation pressure is 1 atm or higher.

[0214] In the case of ethanol derived from a cyclic resource containing a gaseous matrix of carbon monoxide and hydrogen, as described in this invention, a unique peak, not observed in ethanol derived from fossil fuels, is present in the gas chromatogram as determined by gas chromatography-mass spectrometry. Therefore, it can be assumed that ethylene obtained from ethanol contains trace amounts of impurities. Depending on the intended use of ethylene, these trace impurities may cause problems and can therefore be removed through purification. The purification method is not particularly limited and can be carried out using conventionally known methods. As a suitable purification operation, adsorption purification can be cited, for example. The adsorbent used is not particularly limited and can be conventionally known adsorbents. For example, as a method for purifying impurities in ethylene, caustic water treatment can be used in combination. When performing caustic water treatment, it is preferable to perform it before adsorption purification. In this case, water removal treatment is required after caustic treatment and before adsorption purification.

[0215] The polymerization method for monomers containing ethylene is not particularly limited and can be carried out using conventionally known methods. The polymerization temperature and pressure can be appropriately adjusted according to the polymerization method and apparatus. There are no particular limitations on the polymerization apparatus; conventionally known apparatus can be used. An example of a polymerization method for monomers containing ethylene will be described below.

[0216] The polymerization method for polyolefins, particularly ethylene polymers or copolymers of ethylene and α-olefins, can be suitably selected based on the type of polyethylene as the target material, such as the density and branching of high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). For example, as the polymerization catalyst, multi-site catalysts such as Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts are preferred, and the polymerization can be carried out in a multi-stage manner, with one or more stages, through any of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0217] The single-site catalyst refers to a catalyst capable of forming uniform active species, typically prepared by contacting a metallocene transition metal compound or a non-metallocene transition metal compound with an activating catalyst promoter. Compared to multi-site catalysts, single-site catalysts are preferred because their uniform active site structure allows for the polymerization of high-molecular-weight polymers with highly uniform structures. Metallocene catalysts are particularly preferred as single-site catalysts. A metallocene catalyst comprises: a transition metal compound of Group IV of the periodic table containing ligands with a cyclopentadiene skeleton, a catalyst promoter, an organometallic compound added as needed, and various catalyst components of a support.

[0218] In the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadiene skeleton, the cyclopentadiene skeleton refers to a cyclopentadienyl group, a substituted cyclopentadienyl group, and the like. As the substituted cyclopentadienyl group, a cyclopentadienyl group having a substituent of a hydrocarbon group having 1 to 30 carbon atoms or the like. As the transition metal, zirconium, titanium, hafnium, and the like can be mentioned, and zirconium and hafnium are particularly preferable. The transition metal compound generally has two ligands having a cyclopentadiene skeleton, and it is preferable that the respective ligands having a cyclopentadiene skeleton are bonded to each other via a cross-linking group. The transition metal compound can be used as a catalyst component in the form of one or a mixture of two or more.

[0219] The catalytic aid refers to a substance that can make the transition metal compound effective as a polymerization catalyst, or make the ionically charged balance in the state of activation of the catalyst. As the catalytic aid, an aluminoxane soluble in benzene or an organic aluminum oxide compound insoluble in benzene, an ion-exchangeable layered silicate, a boron compound, an ionic compound containing a cation with or without an active hydrogen group and a non-coordinating anion, a lanthanum salt such as lanthanum oxide, tin oxide, a phenoxy compound containing fluorine, and the like can be mentioned.

[0220] The transition metal compound can be used in the form of being supported by a carrier of an inorganic or organic compound. As the carrier, a porous oxide of an inorganic or organic compound is preferable, and specifically, an ion-exchangeable layered silicate such as montmorillonite, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or the like, or a mixture thereof can be mentioned.

[0221] Further, as the organic metal compound used as needed, an organic aluminum compound, an organic magnesium compound, an organic plumbous compound, and the like can be mentioned. Among them, the use of an organic aluminum is preferable.

[0222] In addition, as the polyolefin, a polymer of ethylene or a copolymer of ethylene and an α-olefin can be used alone, or two or more thereof can be used in mixture.

[0223] <Acetaldehyde>

[0224] As an industrial raw material, acetaldehyde is an important chemical. Acetaldehyde, for example, can be used as a raw material for acetic acid or ethyl acetate.

[0225] Acetaldehyde can be produced by oxidizing ethanol by a publicly known method. For example, acetaldehyde can be produced by oxidizing ethanol with chlorine. Chlorine is generally reacted with ethanol in a gaseous state. Chlorine can be supplied at a concentration of about 100% or can be diluted with an inert gas (for example, nitrogen, helium, neon, argon, etc.) and then supplied. The degree of dilution at this time can be, for example, 50% by weight or less, and preferably 25% by weight or less, taking into account the reaction efficiency. In the case of ethanol and chlorine, for example, it is preferable to react at a supply amount of 25 to 100 seem with respect to 100 g of an ethanol aqueous solution.

[0226] The oxidation of ethanol by chlorine is preferably performed using chlorine gas, hydrogen chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, sulfurous chloride, hypochlorite compounds, and the like, which are chlorine-containing compounds. In the case of this oxidation, for example, it can be achieved by a photo reaction, a thermal reaction, a catalyst reaction, and the like. Among these, it is preferable to oxidize ethanol by photochlorination or thermal chlorination based on chlorine gas, and more preferable to oxidize ethanol by photochlorination based on chlorine gas. As the photo reaction, a method in which light of various wavelengths such as ultraviolet rays, visible rays, and the like is irradiated can be cited, and it is preferable to perform the reaction by irradiating light from a light source having a wavelength of about 300 to 500 nm. The light source is not particularly limited, and a fluorescent lamp, a mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, an excimer lamp, an LED lamp, and the like can be used. The reaction temperature is more appropriate at about 0 to 80°C, and is preferably about 0 to 50°C. The reaction time is more appropriate at about 1 to 5 hours.

[0227] In addition, as another example, ethanol can be oxidized in the presence of oxygen molecules and a catalyst in a gaseous phase to produce acetaldehyde. As such a catalyst, for example, a base metal oxide in which gold fine particles are dispersed or fixed can be used. As the base metal oxide, La2O3, MoO3, Bi2O3, SrO, Y2O3, MgO, BaO, WO3, CuO, and a composite oxide containing one or more of these can be cited.

[0228] As for the oxidation reaction of ethanol, the reaction is carried out by bringing a gas containing ethanol and oxygen molecules into contact with the catalyst, for example, at 100 to 280°C. The oxygen molecules used in the reaction can be supplied in the form of oxygen gas, or air can be used. In addition, the raw gas used as the gas can contain a dilution gas (carrier gas) as needed. At this time, the device used in the reaction can be a general device used when a gas phase reaction is generally carried out. For example, the reaction is carried out by filling the catalyst into a reaction tube, and heating the reaction tube to a prescribed temperature, in this state, feeding a gas containing ethanol and oxygen gas or air into the reaction tube, bringing these raw gases and the catalyst into contact, and recovering the reaction gas. As for the reaction pressure, it is carried out at normal pressure, and if necessary, it can be pressurized to about 0.5 to 5 Pa (gauge pressure). As the dilution gas, for example, a so-called inert gas such as nitrogen, argon, helium, carbon dioxide, etc. can be used. As for the amount of dilution gas used, it is appropriately determined in accordance with the composition, flow rate, reaction heat, etc. of the raw gas, but generally, it is preferably 1 to 100 volume times relative to ethanol.

[0229] The ratio of ethanol and oxygen molecules (oxygen gas) supplied to the reaction tube is not particularly limited, but it is 0.5 to 100% by volume, preferably 1 to 10% by volume, and more preferably 2 to 5% by volume, by oxygen gas or air relative to ethanol. The amount of catalyst used is also not particularly limited, but generally, it is about 0.1 to 1.0 g in the case where the inner diameter of the reaction tube is 6 to 10 mm. From a practical point of view, it is preferable to use an amount within a range of 10,000 to 40,000 hr -1 · ml · g cat -1 from the viewpoint of the relationship with the gas flow rate.

[0230] In addition, acetaldehyde can be produced by dehydrogenating ethanol in the presence of a catalyst. As such a catalyst, for example, a solid catalyst containing copper as an active species can be used. As for the copper as an active species, it is in a form having activity to convert ethanol into acetaldehyde, and it can be in any one of a metallic copper (monomer), a copper compound (oxide, hydroxide, copper salt (copper sulfate, copper phosphate, copper nitrate, copper carbonate, etc. inorganic acid salt; copper salt of carboxylic acid, etc. organic acid salt, etc.), etc.). The solid catalyst can contain at least one selected from such copper monomer and copper compound. The copper as an active species is preferably in the form of metallic copper. In addition, the copper can be used directly in the form of metallic copper or a copper compound, or it can be used in the form of being supported on a carrier. Note that the copper as an active species can be used in combination with a catalytic aid, etc. as long as it functions as a main catalyst of the solid catalyst. In addition, the solid catalyst can be in a form in which both the copper and the catalytic aid are supported on a carrier.

[0231] As for the dehydrogenation reaction, it is only necessary to contact ethanol with a solid catalyst, and it can be a liquid phase reaction, but generally, a gas phase reaction in which gaseous ethanol is contacted with a solid catalyst is more often used. From the viewpoint of the equilibrium relationship between ethanol and acetaldehyde, catalyst life, and the like, it can be about 150 to 350°C, preferably 170 to 300°C, and further preferably 200 to 280°C. Note that the higher the reaction temperature, the more the equilibrium shifts to the acetaldehyde side, and thus the conversion rate can be increased. The reaction can be performed under pressurized conditions, but from the viewpoint of convenience, it can also be performed under normal pressure. In addition, from the viewpoint of being favorable for the ethanol conversion rate, it can also be performed under reduced pressure.

[0232] <acetic acid>

[0233] Acetic acid is an important chemical as an industrial raw material. Acetic acid, for example, can be used as a raw material for vinyl acetate monomer, acetic anhydride, acetate ester, and the like.

[0234] Acetic acid can be produced by oxidation of acetaldehyde by a method known in the art. For example, acetaldehyde can be subjected to air oxidation in the presence of a catalyst to produce acetic acid. As the catalyst, manganese acetate or cobalt acetate can be mentioned.

[0235] <ethyl tert-butyl ether>

[0236] Ethyl tert-butyl ether (ETBE) is an important chemical as an industrial raw material. ETBE, for example, can be used as a substitute fuel for gasoline, particularly a high-octane fuel.

[0237] ETBE can be synthesized from ethanol and isobutene by a method known in the art. For example, it can be produced by reacting ethanol and isobutene in the presence of a reaction catalyst. The molar ratio of isobutene to the raw material ethanol is preferably 0.1 to 10 moles, more preferably 0.5 to 2 moles.

[0238] As the reaction catalyst, a cation exchange resin is preferably used, and a strongly acidic cation exchange resin is more preferably used. As such a strongly acidic cation exchange resin, a porous type (MR form) styrene-based resin into which a strongly acidic group such as a sulfonic acid group (-SO3H) is introduced as an ion exchange group is preferable. The particle diameter of the strongly acidic cation exchange resin is preferably 0.5 to 1.0 mm. The amount of the reaction catalyst used is preferably 1 to 90 g, more preferably 1 to 90 g, and further preferably 4 to 9 g, per 1 mole of ethanol.

[0239] Further, the method of using the reaction catalyst is not particularly limited, and the reaction catalyst can be used in a fixed bed, a fluidized bed, or a suspended bed. Further, the reaction of isobutylene and ethanol is not particularly limited, and is preferably performed in a pressurized gas-liquid mixed phase reaction in which ethanol is in a liquid phase. In this case, the yield of ETBE is further improved.

[0240] <ester>

[0241] By reacting ethanol with various carboxylic acids, a wide variety of esters can be synthesized. For example, ethyl benzoate can be obtained by reacting ethanol with benzoic acid, and diethylene glycol, which is a raw material for polyesters, can be obtained from ethanol via ethylene. By using the ethanol of the present application to produce polyethylene, a final resource recycling society that is independent of petroleum resources can be realized.

[0242] Polyesters include diol units and dicarboxylic acid units, and are obtained by condensation polymerization using ethylene glycol as the diol unit and terephthalic acid, isophthalic acid, or the like as the dicarboxylic acid unit. Ethylene glycol can be obtained from the ethanol of the present application, for example, by a method in which ethanol is converted to ethylene glycol via ethylene oxide by a method known in the art.

[0243] As the dicarboxylic acid, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and derivatives thereof can be used without particular limitation. As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, and the like can be given, and as the derivative of the aromatic dicarboxylic acid, lower alkyl esters of the aromatic dicarboxylic acid can be given, specifically, methyl esters, ethyl esters, propyl esters, and butyl esters, and the like. Among these, terephthalic acid is preferred, and as the derivative of the aromatic dicarboxylic acid, dimethyl terephthalate is preferred. Further, as the aliphatic dicarboxylic acid, specifically, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexane dicarboxylic acid, and the like, which are chain or alicyclic dicarboxylic acids having 2 to 40 carbon atoms in general, can be given. Further, as the derivative of the aliphatic dicarboxylic acid, lower alkyl esters of the aliphatic dicarboxylic acid such as methyl esters, ethyl esters, propyl esters, and butyl esters, or cyclic anhydrides of the aliphatic dicarboxylic acid such as succinic anhydride can be given. Among these, adipic acid, succinic acid, dimer acid, or a mixture thereof is preferred, and particularly, a substance in which succinic acid is the main component is preferred. As the derivative of the aliphatic dicarboxylic acid, methyl esters of adipic acid and succinic acid, or a mixture thereof is more preferred.

[0244] The polyester can be obtained by a method known in the art in which the diol unit and the dicarboxylic acid unit are condensed. Specifically, the polyester can be produced by a general melt polymerization method, or a known solution heating dehydration condensation method using an organic solvent, in which the esterification and / or transesterification of the dicarboxylic acid component and the diol component is performed, and then the condensation polymerization is performed under reduced pressure.

[0245] The polycondensation reaction is preferably performed in the presence of a polymerization catalyst, and examples of the polymerization catalyst include titanium compounds, zirconium compounds, germanium compounds, and the like.

[0246] The reaction temperature of the esterification reaction and / or the transesterification reaction of the dicarboxylic acid component and the diol component is usually in the range of 150 to 260°C, and the reaction atmosphere is usually an inert gas atmosphere of nitrogen, argon, or the like.

[0247] In the polycondensation reaction step, a chain extender (coupling agent) can be added to the reaction system. In the case of the chain extender, it is added to the reaction system in a uniform molten state without a solvent after the completion of the polycondensation, and reacts with the polyester obtained by the polycondensation.

[0248] In the case of the obtained polyester, solid state polymerization can be performed as needed in order to further increase the degree of polymerization after solidification or to remove oligomers such as cyclic trimers.

[0249] In the polyester production step, various additives can be added within a range that does not impair the properties thereof, and examples of the additives include plasticizers, ultraviolet stabilizers, coloration inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, friction reducing agents, release agents, antioxidants, ion exchangers, coloring pigments, and the like.

[0250] The ethanol of the present application is not limited to the above-described polymer, and can be used as a raw material for various other polymers. Since the molded product of the obtained polymer is a carbon neutral material, a final resource recycling society that is independent of petroleum resources can be realized.

[0251] <Articles containing ethanol>

[0252] The ethanol of the present application can be used not only as a raw material for the above-described polymer, but also as various articles. As the articles, for example, chemical products such as cosmetics, perfumes, fuels, deicing fluids, bactericides, disinfectants, detergents, mold removers, lotions, shampoos, soaps, antiperspirants, face washes, solvents, paints, adhesives, diluents, food additives, and the like can be mentioned. By being used for these uses, it can exert an appropriate effect according to the use.

[0253] <Fuels>

[0254] The ethanol of the present application can also be used as a raw material for fuels (for example, jet fuel, lamp oil, light oil, gasoline), and the like. Since the ethanol has a high bactericidal ability, they can also function as bactericides that prevent the proliferation of bacteria and the like in the fuel system such as the engine and the piping.

[0255] In the Japan Automobile Research, Inc. standards (2006), the concentration of ethanol in fuel ethanol is set to 99.5% by volume or more. In other countries (e.g., India), the concentration of ethanol in fuel ethanol is also regulated to be 99.5% by volume or more. Therefore, ethanol having a purity of 99.5 to 99.9% by volume can be preferably used for ethanol-dedicated vehicles. In addition, since fuel ethanol can be used for purposes other than ethanol-dedicated vehicles, the versatility of ethanol having a purity of 99.5 to 99.9% by volume is particularly high.

[0256] In addition, the ethanol of the present application can be mixed with gasoline and used as ethanol-gasoline blend fuel. By using ethanol-gasoline blend fuel, environmental load can be reduced. The purity of ethanol used in ethanol-gasoline blend fuel is 92.0% by volume or more, preferably 95.0% by volume or more, and further preferably 99.5% by volume or more.

[0257] The content of ethanol in ethanol-gasoline blend fuel is preferably 1% by volume or more and 15% by volume or less, more preferably 2% by volume or more and 12% by volume or less, and further preferably 3% by volume or more and 10% by volume or less. If the content of ethanol is 1% by volume or more, the advantage of increasing the octane number by blending ethanol can be obtained, and by setting the content to 15% by volume or less, a significant change in evaporation characteristics due to azeotropic phenomenon with other gasoline base materials can be prevented, and further, the normal operability of gasoline vehicles can be ensured.

[0258] In addition, the water content in ethanol-gasoline blend fuel is preferably 0.01% by mass or more and 0.9% by mass or less, and more preferably 0.01% by mass or more and 0.7% by mass or less. The lower limit of the water content depends on the saturated water content of the gasoline base material and the water content in ethanol, but is substantially around 0.01% by mass. If the upper limit is 0.9% by mass or less, phase separation can be prevented, and even if phase separation occurs, the gasoline engine can be normally operated by the gasoline layer. Note that the water content can be measured by "Crude Petroleum and Petroleum Products - Water Test Method" described in JIS K2275, and for example, Karl Fischer coulometric titration can be used.

[0259] As the gasoline base material, a commonly used gasoline base material can be arbitrarily used without particular limitation. As the gasoline base material, for example, light naphtha obtained from atmospheric distillation of crude oil, desulfurized light naphtha in which the light naphtha is preferably desulfurized, catalytically reformed gasoline obtained by catalytically reforming heavy naphtha after desulfurization, and benzene-removed catalytically reformed gasoline obtained by removing benzene from the catalytically reformed gasoline, benzene-removed light catalytically reformed gasoline, benzene-removed heavy catalytically reformed gasoline, and a mixture thereof, cracked gasoline obtained by catalytic cracking and hydrocracking, light cracked gasoline, heavy cracked gasoline, and a mixture thereof, isomerized gasoline obtained by isomerizing light naphtha, and the like can be mentioned.

[0260] Further, ETBE using ethanol of the present application as a raw material can be mixed with gasoline and used as ETBE blended gasoline. Environmental load can be reduced by using ETBE blended gasoline. The content of ETBE in ETBE blended gasoline is preferably 1% by volume or more and 15% by volume or less, more preferably 2% by volume or more and 12% by volume or less, and further preferably 3% by volume or more and 10% or less. If the content of ETBE is 1% by volume or more, the advantage of improving the octane number by blending ETBE can be obtained, and by setting the content to 15% by volume or less, a significant change in evaporation characteristics due to azeotropic phenomenon with other gasoline base materials can be prevented, and the normal operability of a gasoline vehicle can be ensured. Examples

[0261] Hereinafter, the present application will be further explained in detail by examples, but the present application is not limited to the following examples as long as the gist of the present application is not exceeded.

[0262] [Example A]

[0263] <Ethanol component evaluation method>

[0264] In the following examples and comparative examples, ethanol component evaluation was performed by analysis using an olfactory gas chromatograph mass spectrometer (JMS-Q1050GC Ultra Quad GC / MS manufactured by JEOL Ltd.). The measurement conditions were as follows.

[0265] <Analysis conditions of GC / MS method>

[0266] Column: DB-WAX (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm)

[0267] Oven temperature: 40°C, 1 minute→5°C / minute→100°C, 10 minutes→10°C / minute→250°C, 4 minutes

[0268] Injection time: 5 minutes

[0269] Carrier gas: He (3.0 mL / minute)

[0270] <Butadiene quantitative method>

[0271] Quantitative evaluation of butadiene was performed by analysis using a gas chromatograph device (GC-2014, manufactured by Shimadzu Corporation). The measurement conditions were as follows:

[0272] <Analysis conditions of GC / MS method>

[0273] Column: Rt-Q-BOND (length 30 m, inner diameter 0.32 mm, film thickness 10 μm)

[0274] Oven temperature: 60°C, 11.5 min→ 10°C / min→ 100°C, 14.5 min→ 10°C / min→ 250°C

[0275] Injection time: 5 min

[0276] Carrier gas: He (30 cm / s)

[0277] Split ratio: 75

[0278] <Quantitative method of ethyl benzoate>

[0279] Quantitative evaluation of ethyl benzoate was performed by analysis using a gas chromatograph. The measurement conditions were as follows:

[0280] <Analysis conditions of GC / MS method>

[0281] Column: DB-1 (length 30.0 m, inner diameter 0.254 mm, film thickness 0.25 m)

[0282] Temperature rising conditions: 30°C - 300°C 15°C / min

[0283] Carrier gas: He 100 kPa

[0284] Split ratio: 50

[0285] <Quantitative method of combustion efficiency>

[0286] Quantitative evaluation of the combustion efficiency of ethanol was performed by total heat of combustion analysis using a cone calorimeter manufactured by FTT Corporation.

[0287] [Example Al]

[0288] <Preparation of ethanol>

[0289] Ethanol was manufactured as described below.

[0290] (Feed gas generation step)

[0291] A gas discharged after combustion of general waste by a waste incineration facility was used. The composition of the feed gas was: carbon monoxide about 30 vol%, carbon dioxide about 30 vol%, hydrogen about 30 vol%, and nitrogen about 10 vol%.

[0292] (Synthetic gas purification step)

[0293] Using the PSA apparatus manufactured above as a device for removing impurities from the raw material gas, the carbon dioxide contained in the synthesis gas is removed to 60-80% by volume (approximately 30% by volume) under the condition of heating the gas temperature to 80°C. The gas is then heated by a double-tube heat exchanger using steam at 150°C and then cooled by a double-tube heat exchanger using cooling water at 25°C, causing impurities to precipitate. The precipitated impurities are then removed by a filter, thereby producing the synthesis gas.

[0294] (Microbial fermentation process)

[0295] Synthetic gas was continuously supplied to a continuous fermentation apparatus (microbial fermentation tank) equipped with a main reactor, a syngas supply port, and a discharge port, and filled with inoculum of Clostridium autoethanogenum (a microorganism) and a liquid culture medium (containing appropriate amounts of phosphorus compounds, nitrogen compounds, and various minerals) for syngas fermentation, and the fermentation was carried out continuously for 300 hours. Then, approximately 8000 L of culture medium containing ethanol was discharged from the discharge port.

[0296] (Separation process)

[0297] The culture medium obtained in the fermentation process was used to obtain an ethanol-containing liquid under a culture medium inlet pressure of 200 kPa or higher using a solid-liquid separation filter device.

[0298] (Distillation process)

[0299] Next, the ethanol-containing liquid is introduced into a distillation apparatus equipped with a heater using steam at 170°C. The temperature at the bottom of the distillation column is raised to 101°C within 8-15 minutes. Then, the ethanol-containing liquid is introduced from the middle of the distillation column. During continuous operation, the bottom of the column is set to 101°C, the middle of the column to 99°C, and the top of the column to 91°C. The operation is carried out continuously at a rate of 15 seconds per L to obtain purified ethanol.

[0300] (Ethanol composition evaluation)

[0301] The gas chromatographic analysis results of ethanol obtained as described above are as follows: Figure A1 As shown.

[0302] (Butadiene manufacturing method)

[0303] Using the obtained ethanol, butadiene was produced. First, in order to supply the obtained ethanol as a gas for the reaction, the ethanol was vaporized by passing through a single pipe heated to 90°C, and the vaporized ethanol gas and nitrogen were mixed. At this time, by adjusting the flow rate of the ethanol gas to SV 360 L / hr / L and the flow rate of the nitrogen to SV 840 L / hr / L with mass flow controllers, a mixed gas of ethanol 30 vol% (as a gas) and nitrogen 70 vol% (as a gas) was obtained. Next, by keeping a cylindrical reaction pipe of 1 / 2 inch (1.27 cm) in diameter and 15.7 inches (40 cm) in length, which was filled with 0.85 g of a butadiene synthesis catalyst mainly composed of Hf, Zn, and Ce, at a temperature of 350°C and a pressure (pressure of the reaction bed) of 0.1 MPa, and continuously supplying the mixed gas thereto, a butadiene-containing gas was obtained. The content of butadiene in the obtained butadiene-containing gas was quantified using a gas chromatograph device (GC-2014, manufactured by SHIMADZU CORPORATION). The results are shown in Table Al.

[0304] [Comparative Example Al]

[0305] Using 99-degree ethanol (manufactured by Ganjyo Chemical Industry Co., Ltd.) derived from fossil fuel ethanol, butadiene was produced by the same method as in Example Al, and the content of butadiene was quantified in the same manner as in Example Al. The results are shown in Table Al. Note that the evaluation of the components of the ethanol used was performed in the same manner as in Example Al. The results of the gas chromatograph analysis are shown in Table A2. Figure A2

[0306] [Comparative Example A2]

[0307] Using 99-degree ethanol (manufactured by Ganjyo Chemical Industry Co., Ltd.) derived from plant saccharification fermentation, butadiene was produced by the same method as in Example Al, and the content of butadiene was quantified in the same manner as in Example Al. The results are shown in Table Al. Note that the evaluation of the components of the ethanol used was performed in the same manner as in Example Al. The results of the gas chromatograph analysis are shown in Table A2. Figure A3

[0308] [Table Al]

[0309] Butadiene content

[0310]

[0311] As shown in Table Al, the ethanol produced using the gas discharged after the combustion of general waste in a waste incineration facility had a higher conversion efficiency of butadiene than the ethanol derived from fossil fuel or the ethanol derived from plant saccharification fermentation in the past.

[0312] ​​[Example A2]

[0313] (Manufacture of ethyl benzoate)

[0314] Ethyl benzoate was manufactured using the same ethanol as that used in Example Al. First, benzoic acid 36.8 g and ethanol 200 ml were mixed under a stream of argon, and concentrated sulfuric acid 9 ml was added while refluxing and stirring for 5 hours. Then, it was cooled to room temperature, and unreacted ethanol was removed under reduced pressure, and the synthesized ethyl benzoate was recovered with diethyl ether 100 ml. The recovered liquid was washed with distilled water, dried using magnesium sulfate, and then filtered and concentrated.

[0315] The obtained filtrate was subjected to component analysis using a gas chromatograph device, and the amount of synthesized ethyl benzoate was quantified. The analysis conditions at this time are shown below. The analysis results are shown in Table A2.

[0316] Column: DB-1 (length 30.0 m, inner diameter 0.254 mm, film thickness 0.25 m)

[0317] Temperature rising conditions: 30-300°C 15°C / min

[0318] Carrier gas: He 100 kPa

[0319] Split ratio: 50

[0320] [Comparative Example A3]

[0321] Ethyl benzoate was manufactured in the same manner as in Example A2, except that the petrochemically-derived ethanol used in Comparative Example Al was used, and quantification was performed. The analysis results are shown in Table A2.

[0322] [Comparative Example A4]

[0323] Ethyl benzoate was manufactured in the same manner as in Example A2, except that the petrochemically-derived ethanol used in Comparative Example A2 was used, and quantification was performed. The analysis results are shown in Table A2.

[0324] [Table A2]

[0325] Ethyl benzoate content

[0326]

[0327] As shown in Table A2, the conversion efficiency of ethyl benzoate was higher using the ethanol manufactured using the gas discharged after combustion of general waste in a waste incineration facility, compared to the conventional ethyl alcohol derived from fossil fuels or the ethyl alcohol derived from sugar fermentation of plants.

[0328] [Example A3]

[0329] The combustion efficiency of ethanol was quantified using the same ethanol as used in Example Al. The fuel efficiency was quantified by the following method: after igniting a heat-resistant container of 60 mm in length x 60 mm in width x 30 mm in height to which 30 g of ethanol was added under no heating conditions, the amount of oxygen reduction in a cone calorimeter (manufactured by FTT Corporation) until complete combustion was measured, the total heat generation was calculated based on the amount of oxygen reduction, and further the fuel efficiency was quantified. The quantification results are shown in Table A3.

[0330] [Comparative Example A5]

[0331] The combustion efficiency of ethanol was quantified in the same manner as in Example A3 except that the ethanol used in Comparative Example Al was used. The quantification results are shown in Table A3.

[0332] [Comparative Example A6]

[0333] The combustion efficiency of ethanol was quantified in the same manner as in Example A3 except that the ethanol used in Comparative Example A2 was used. The quantification results are shown in Table A3.

[0334] [Table A3]

[0335] Combustion efficiency

[0336]

[0337] [Example B]

[0338] <Ethanol component evaluation method>

[0339] In the following examples and comparative examples, the component evaluation of ethanol was performed by measurement using a gas chromatograph device (GC-2014, manufactured by SHIMADZU Corporation) GC / MS method. The measurement conditions were as follows.

[0340] <Analysis conditions of GC / MS method>

[0341] Column: DB-5MS (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm)

[0342] Oven temperature: 40°C→10°C / min→300°C

[0343] Carrier gas: He (1.28 mL / min)

[0344] Injection port temperature: 300°C

[0345] Detector temperature: 300°C

[0346] Detector: hydrogen flame ionization detector

[0347] Injection amount: 1 μL (split ratio 1:20)

[0348] <Quantitative Methods for Butadiene>

[0349] The quantitative evaluation of butadiene was carried out in the same manner as in Example A.

[0350] <Quantitative Methods for Ethyl Benzoate>

[0351] The quantitative evaluation of ethyl benzoate was performed in the same manner as in Example A.

[0352] <Quantitative Methods for Combustion Efficiency>

[0353] The quantitative evaluation of the combustion efficiency of ethanol was carried out in the same manner as in Example A.

[0354] [Example B1]

[0355] Preparation of Ethanol

[0356] Ethanol was prepared in the same manner as in Example A.

[0357] (Ethanol composition evaluation)

[0358] The gas chromatographic analysis results of ethanol obtained as described above are as follows: Figure B1 and Figure B2 (Enlarged image shown). The peak with a retention time of 12 minutes 30 seconds to 12 minutes 40 seconds is consistent with the retention time of the n-tetradecane (C14) standard, confirming that it originated from n-tetradecane. Furthermore, the n-tetradecane content in the obtained ethanol was 0.03 mg / L.

[0359] (Butadiene manufacturing method)

[0360] Butadiene was produced using the ethanol obtained as described above, in the same manner as in Example A. The butadiene content of the resulting butadiene-containing gas was quantified using a GC-2014 gas chromatograph (manufactured by SHIMADZU Co., Ltd.). The results are shown in Table B1.

[0361] [Comparative Example B1]

[0362] Butadiene was produced using 99% ethanol (manufactured by Amazake Chemical Industry Co., Ltd.), which is derived from fossil fuel ethanol, by the same method as in Example B1, and the butadiene content was quantified in the same manner as in Example B1. The results are shown in Table B1. It should be noted that the component evaluation of the ethanol used was performed in the same manner as in Example B1. Gas chromatography analysis results are as follows: Figure B1 As shown. In the enlarged chromatogram of the gas chromatogram (not shown), no peaks with retention times of 12 min 30 sec to 12 min 40 sec derived from n-tetradecane were detected.

[0363] [Comparative Example B2]

[0364] Using 99-degree ethanol (manufactured by Gankosha Chemical Industry Co., Ltd.) derived from plant saccharification fermentation, butadiene was produced by the same method as in Example B1, and the content of butadiene was quantified in the same manner as in Example B1. The results are shown in Table B1. Note that the composition evaluation of the ethanol used was performed in the same manner as in Example B1. Gas chromatography analysis results Figure B1 As shown. In the expanded chart of the gas chromatogram (not shown), no peak was detected at a retention time of 12 minutes 30 seconds to 12 minutes 40 seconds derived from n-tetradecane.

[0365] [Table B1]

[0366] Butadiene content

[0367]

[0368] As shown in Table B1, the conversion efficiency of butadiene was higher using ethanol produced using gas discharged after burning general waste in a waste incineration facility, compared to the conventional ethanol derived from fossil fuels or ethanol derived from plant saccharification fermentation.

[0369] [Example B2]

[0370] (Ethyl benzoate production)

[0371] Ethyl benzoate was produced in the same manner as in Example A using the same ethanol as that used in Example Al, and then component analysis was performed using a gas chromatography device, and the amount of ethyl benzoate produced was quantified. The analysis results are shown in Table B2.

[0372] [Comparative Example B3]

[0373] Ethyl benzoate was produced in the same manner as in Example B2 except that the ethanol derived from petrochemistry used in Comparative Example B1 was used, and quantification was performed. The analysis results are shown in Table B2.

[0374] [Comparative Example B4]

[0375] Ethyl benzoate was produced in the same manner as in Example B2 except that the ethanol derived from petrochemistry used in Comparative Example B2 was used, and quantification was performed. The analysis results are shown in Table B2.

[0376] [Table B2]

[0377] Ethyl benzoate content

[0378]

[0379] As shown in Table B2, the conversion efficiency of ethyl benzoate was higher using the ethanol produced from the gas discharged after combustion of general waste in a waste incineration facility, compared to the conventional ethanol derived from fossil fuels or the ethanol derived from saccharification fermentation of plants.

[0380] [Example B3]

[0381] The combustion efficiency of ethanol was quantified using the same ethanol as that used in Example B l. The fuel efficiency was quantified by the following method: 30 g of ethanol was added to a heat-resistant container of 60 mm in length x 60 mm in width x 30 mm in height under no heating condition, and then ignited, and the oxygen reduction amount until complete combustion in a cone calorimeter (manufactured by FTT Corporation) was measured, and the total heat generation amount was calculated based on the oxygen reduction amount, and further the fuel efficiency was quantified. The quantification results are shown in Table B3.

[0382] [Comparative Example B5]

[0383] The combustion efficiency of ethanol was quantified in the same manner as in Example B3, except that the ethanol used in Comparative Example B l was used. The quantification results are shown in Table B3.

[0384] [Comparative Example B6]

[0385] The combustion efficiency of ethanol was quantified in the same manner as in Example B3, except that the ethanol used in Comparative Example B2 was used. The quantification results are shown in Table B3.

[0386] [Table B3]

[0387] Combustion efficiency

[0388]

[0389] [Example C]

[0390] [Method for evaluating ethanol component]

[0391] The method for evaluating the ethanol component was performed in the same manner as in Example A described above.

[0392] [Method for quantifying butadiene]

[0393] The quantitative evaluation of butadiene was performed in the same manner as in Example A.

[0394] [Method for quantifying ethyl benzoate]

[0395] The quantitative evaluation of ethyl benzoate was performed in the same manner as in Example A.

[0396] [Method for quantifying combustion efficiency]

[0397] The quantitative evaluation of the combustion efficiency of ethanol was performed in the same manner as in Example A.

[0398] [Example C1]

[0399] [Preparation of ethanol]

[0400] Ethanol was prepared in the same manner as in Example A.

[0401] (Evaluation of ethanol component)

[0402] The gas chromatography analysis results of the obtained ethanol are shown in Table C1. Figure C From the fact that the peaks with a retention time of 6 minutes 36 seconds to 6 minutes 45 seconds coincided with the retention time of a standard sample of n-decane (C10), it was confirmed that they originated from n-decane. In addition, the content of n-decane in the obtained ethanol was 0.32 mg / L.

[0403] [Method for producing butadiene]

[0404] Butadiene was produced in the same manner as in Example A using the ethanol obtained as described above. The content of butadiene in the obtained butadiene-containing gas was quantified using a gas chromatography device of GC-2014 (manufactured by SHIMADZU CORPORATION). The results are shown in Table C1.

[0405] [Comparative Example C1]

[0406] Butadiene was produced by the same method as in Example C1 using 99-degree ethanol (manufactured by Ganjyo Chemical Industry Co., Ltd.) that was derived from fossil fuel ethanol, and the content of butadiene was quantified in the same manner as in Example C1. The results are shown in Table C1. Note that the evaluation of the component of the ethanol used was performed in the same manner as in Example C1. The gas chromatography analysis results are shown in Table C1. Figure C In the gas chromatography, no peaks with a retention time of 6 minutes 36 seconds to 6 minutes 45 seconds that originated from n-decane were detected.

[0407] [Comparative Example C2]

[0408] Butadiene was produced by the same method as in Example C1 using 99-degree ethanol (manufactured by Ganjyo Chemical Industry Co., Ltd.) that was derived from sugar fermentation of plants, and the content of butadiene was quantified in the same manner as in Example C1. The results are shown in Table C1. Note that the evaluation of the component of the ethanol used was performed in the same manner as in Example C1. The gas chromatography analysis results are shown in Table C1. Figure C In the gas chromatography, no peaks with a retention time of 6 minutes 36 seconds to 6 minutes 45 seconds that originated from n-decane were detected.

[0409] [Table C1]

[0410] Butadiene content

[0411]

[0412] As shown in Table C1, the conversion efficiency of butadiene was higher using the ethanol produced from the gas discharged after combustion of general waste by a waste incineration facility, compared to the conventional ethanol derived from fossil fuels or the ethanol derived from saccharification fermentation of plants.

[0413] [Example C2]

[0414] (Ethyl benzoate production)

[0415] Ethyl benzoate was produced in the same manner as Example A using the same ethanol as that used in Example C1, and the amount of ethyl benzoate synthesized was quantified using a gas chromatograph device. The results of the analysis are shown in Table C2.

[0416] [Comparative Example C3]

[0417] Ethyl benzoate was produced in the same manner as Example C2 except that the petrochemical-derived ethanol used in Comparative Example C1 was used, and quantified. The results of the analysis are shown in Table C2.

[0418] [Comparative Example C4]

[0419] Ethyl benzoate was produced in the same manner as Example C2 except that the petrochemical-derived ethanol used in Comparative Example C2 was used, and quantified. The results of the analysis are shown in Table C2.

[0420] [Table C2]

[0421] Ethyl benzoate content

[0422]

[0423] As shown in Table C2, the conversion efficiency of ethyl benzoate was higher using the ethanol produced from the gas discharged after combustion of general waste by a waste incineration facility, compared to the conventional ethanol derived from fossil fuels or the ethanol derived from saccharification fermentation of plants.

[0424] [Example C3]

[0425] The combustion efficiency of ethanol was quantified using the same ethanol as used in Example Cl. The fuel efficiency was quantified by the following method: after adding 30 g of ethanol to a heat-resistant container of 60 mm in length x 60 mm in width x 30 mm in height under no heating conditions, ignition was performed, the oxygen reduction amount until complete combustion in a cone calorimeter (manufactured by FTT Corporation) was measured, the total heat generation amount was calculated based on the oxygen reduction amount, and further the fuel efficiency was quantified. The quantification results are shown in Table C3.

[0426] [Comparative Example C5]

[0427] The combustion efficiency of ethanol was quantified in the same manner as in Example C3, except that the ethanol used in Comparative Example Cl was used. The quantification results are shown in Table C3.

[0428] [Comparative Example C6]

[0429] The combustion efficiency of ethanol was quantified in the same manner as in Example C3, except that the ethanol used in Comparative Example C2 was used. The quantification results are shown in Table C3.

[0430] [Table C3]

[0431] Combustion efficiency

[0432]

[0433] [Example D]

[0434] <Ethanol component evaluation method>

[0435] The component evaluation of ethanol was performed in the same manner as in Example A described above.

[0436] [Butadiene quantification method]

[0437] The quantitative evaluation of butadiene was performed in the same manner as in Example A described above.

[0438] [Ethyl benzoate quantification method]

[0439] The quantitative evaluation of ethyl benzoate was performed in the same manner as in Example A described above.

[0440] [Combustion efficiency quantification method]

[0441] The quantitative evaluation of the combustion efficiency of ethanol was performed in the same manner as in Example A described above.

[0442] [Example Dl]

[0443] [Preparation of ethanol]

[0444] Ethanol was prepared in the same manner as in Example A.

[0445] (Evaluation of ethanol component)

[0446] The gas chromatography analysis result of the obtained ethanol is shown in FIG. 2A and FIG. 2B (expanded chart) as described above. From the peak having a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds coinciding with the retention time of the standard sample of n-hexadecane (C16), it was confirmed that it originated from n-hexadecane. In addition, the content of n-hexadecane in the obtained ethanol was 0.05 mg / L. Figure D1 and Figure D2 (expanded chart) as described above. From the peak having a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds coinciding with the retention time of the standard sample of n-hexadecane (C16), it was confirmed that it originated from n-hexadecane. In addition, the content of n-hexadecane in the obtained ethanol was 0.05 mg / L.

[0447] (Method for producing butadiene)

[0448] Butadiene was produced in the same manner as in Example B using the ethanol obtained as described above. The content of butadiene was quantified for the obtained butadiene-containing gas using a gas chromatography device of GC-2014 (manufactured by SHIMADZU CORPORATION). The results are shown in Table D1.

[0449] [Comparative Example D1]

[0450] Butadiene was produced by the same method as in Example D1 using 99-degree ethanol (manufactured by Ganryo Kagaku Sangyo Co., Ltd.) as a fossil fuel-derived ethanol, and the content of butadiene was quantified in the same manner as in Example D1. The results are shown in Table D1. Note that the evaluation of the component of the ethanol used was performed in the same manner as in Example D1. The gas chromatography analysis result is shown in FIG. 2A and FIG. 2B (expanded chart). In the expanded chart of the gas chromatography (not shown), no peak having a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds originating from n-hexadecane was detected. Figure D1

[0451] [Comparative Example D2]

[0452] Butadiene was produced by the same method as in Example D1 using 99-degree ethanol (manufactured by Ganryo Kagaku Sangyo Co., Ltd.) as a fossil fuel-derived ethanol, and the content of butadiene was quantified in the same manner as in Example D1. The results are shown in Table D1. Note that the evaluation of the component of the ethanol used was performed in the same manner as in Example D1. The gas chromatography analysis result is shown in FIG. 2A and FIG. 2B (expanded chart). In the expanded chart of the gas chromatography (not shown), no peak having a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds originating from n-hexadecane was detected. Figure D1

[0453] [Table D1]

[0454] Butadiene content

[0455]

[0456] ​​As shown in Table D1, the conversion efficiency of butadiene was higher using the ethanol produced from the gas discharged after combustion of general waste by a waste incineration facility, compared to the conventional ethanol derived from fossil fuels or the ethanol derived from saccharification fermentation of plants.

[0457] [Example D2]

[0458] (Production of ethyl benzoate)

[0459] Ethyl benzoate was produced in the same manner as in Example B using the same ethanol as that used in Example D1, and the amount of ethyl benzoate synthesized was quantified using a gas chromatograph device.

[0460] [Comparative Example D3]

[0461] Ethyl benzoate was produced in the same manner as in Example D2 except that the petrochemical-derived ethanol used in Comparative Example D1 was used, and quantified. The results of the analysis are shown in Table D2.

[0462] [Comparative Example D4]

[0463] Ethyl benzoate was produced in the same manner as in Example D2 except that the petrochemical-derived ethanol used in Comparative Example D2 was used, and quantified. The results of the analysis are shown in Table D2.

[0464] [Table D2]

[0465] Ethyl benzoate content

[0466]

[0467] As shown in Table D2, the conversion efficiency of ethyl benzoate was higher using the ethanol produced from the gas discharged after combustion of general waste by a waste incineration facility, compared to the conventional ethanol derived from fossil fuels or the ethanol derived from saccharification fermentation of plants.

[0468] [Example D3]

[0469] The combustion efficiency of ethanol was quantified using the same ethanol as that used in Example D1. The fuel efficiency was quantified by the following method: 30 g of ethanol was added to a heat-resistant container having a length of 60 mm x a width of 60 mm x a height of 30 mm under no heating condition, and then ignited, and the amount of oxygen reduction until complete combustion in a cone calorimeter (manufactured by FTT Corporation) was measured, and the total heat generation amount was calculated based on the amount of oxygen reduction, and further the fuel efficiency was quantified. The results of the quantification are shown in Table D3.

[0470] [Comparative Example D5]

[0471] The combustion efficiency of ethanol was quantified in the same manner as in Example D3, except that ethanol used in Comparative Example Dl was used. The quantification results are shown in Table D3.

[0472] [Comparative Example D6]

[0473] The combustion efficiency of ethanol was quantified in the same manner as in Example D3, except that ethanol used in Comparative Example D2 was used. The quantification results are shown in Table D3.

[0474] [Table D3] Combustion efficiency

[0475] Combustion efficiency

[0476]

[0477] As shown in Tables A3 to D3, the ethanol produced using the gas discharged after combustion of general waste in a waste incineration facility has a higher combustion efficiency than the conventional ethanol derived from fossil fuels or the ethanol derived from saccharification fermentation of plants.

Claims

1. An ethanol, in a gas chromatogram determined by gas chromatography-mass analysis (GC / MS), having a retention time having at least one of the peaks selected from (A) to (D) below, (A) The peak from 5 minutes 25 seconds to 5 minutes 35 seconds and the two peaks from 2 minutes 55 seconds to 3 minutes 5 seconds. (B) Peak from 12 minutes 30 seconds to 12 minutes 40 seconds, (C) The peak from 6 minutes 36 seconds to 6 minutes 45 seconds, and (D) Peak from 15 minutes 00 seconds to 15 minutes 15 seconds.

2. The ethanol according to claim 1, wherein, In the gas chromatograph, the retention time has the peak of (A), and further has a peak of 5 minutes 30 seconds to 5 minutes 35 seconds.

3. The ethanol according to claim 1, wherein, The peak in (B) originates from n-tetradecane.

4. The ethanol according to claim 3, wherein, The concentration of n-tetradecane is above 0.01 mg / L and below 1.0 mg / L.

5. The ethanol according to claim 1, wherein, The peak in (C) originates from n-decane.

6. The ethanol according to claim 5, wherein, The concentration of n-decane is above 0.01 mg / L and below 1.0 mg / L.

7. The ethanol of claim 1, wherein, The peak of (D) originates from n-hexadecane.

8. The ethanol according to claim 7, wherein, The concentration of n-hexadecane is above 0.01 mg / L and below 1.0 mg / L.

9. The ethanol according to any one of claims 1 to 8, wherein the ethanol is based on a gas containing carbon monoxide and hydrogen.

10. The ethanol according to claim 9, wherein, The gas containing carbon monoxide and hydrogen is derived from waste.

11. The ethanol according to any one of claims 1 to 10, wherein it is derived from microbial fermentation.

12. A method for producing ethanol, comprising: The process of converting a carbon source into a synthesis gas containing carbon monoxide and hydrogen. The synthesis gas containing carbon monoxide and hydrogen is supplied to a microbial fermentation tank, and a microbial fermentation process is carried out to obtain an ethanol-containing liquid. The separation process of separating the ethanol-containing liquid into liquid or solid components containing microorganisms and gaseous components containing ethanol. The liquefaction process that condenses and liquefies the gas components The purification process for purifying ethanol from the liquid obtained through the liquefaction process. in, The purified ethanol, in a gas chromatogram determined by gas chromatography-mass spectrometry (GC / MS), has a retention time with at least one of the peaks selected from (A) to (D) below: (A) The peak from 5 minutes 25 seconds to 5 minutes 35 seconds and the two peaks from 2 minutes 55 seconds to 3 minutes 5 seconds. (B) Peak from 12 minutes 30 seconds to 12 minutes 40 seconds, (C) The peak from 6 minutes 36 seconds to 6 minutes 45 seconds, and (D) Peak from 15 minutes 00 seconds to 15 minutes 15 seconds.

13. The method of claim 12, further comprising the step of purifying the synthesis gas.

14. The method according to claim 12 or 13, wherein, The carbon source is derived from waste.

15. The ethanol according to any one of claims 1 to 11, used in chemical products, polymer raw materials, or fuels.

16. A chemical product made from ethanol as described in any one of claims 1 to 11.

17. A fuel comprising ethanol according to any one of claims 1 to 11 and / or ethyl tert-butyl ether derived from ethanol according to any one of claims 1 to 6.

18. A polymer raw material, wherein the ethanol according to any one of claims 1 to 11 is used as the raw material.

19. The polymer raw material according to claim 18, wherein the raw material is selected from ethylene, propylene, butadiene, ethyl acetate, isobutylene, methyl methacrylate, acrylic acid, aminocaproic acid, and diethyl carbonate.

20. A polymer made from the polymer raw material of claim 18 or 19.

21. A molded article made of the polymer of claim 20.

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