ethanol

Abstract

To provide an ethanol having a peculiar peak in a gas chromatograph measured by gas chromatography-mass spectrometry, the peak being not observed for an ethanol derived from fossil fuel.SOLUTION: The ethanol according to the present invention has a peak of retention time of 15 minutes 00 seconds to 15 minutes 15 seconds in a gas chromatograph measured by gas chromatography-mass spectrometry (GC / MS method).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to ethanol, more specifically, to ethanol with adjusted contents of specific minor components. Furthermore, the present invention relates to a novel resource-recycling ethanol that uses gas containing carbon monoxide and hydrogen as a substrate, not derived from conventional petroleum resources or biomass resources. [Background technology]

[0002] Petrochemical products are used in many aspects of our lives. However, because they are familiar products, their mass production and mass consumption have caused various environmental problems, which has become a major global issue. For example, polyethylene and polyvinyl chloride, which are representative petrochemical products, are consumed in large quantities and thrown away, and these waste products are a major cause of environmental pollution. In addition, concerns about the depletion of fossil fuel resources and the increase in carbon dioxide in the atmosphere are also being discussed as global environmental problems in the mass production of petrochemical products.

[0003] Due to the growing global awareness of such environmental issues, in recent years, methods for producing various organic substances from raw materials other than naphtha, which is the raw material for petrochemical industrial products, have been considered. For example, a method for producing bioethanol from edible raw materials such as corn by sugar fermentation has attracted attention. However, such sugar fermentation methods using edible raw materials have been pointed out as causing problems such as a rise in food prices because limited agricultural land is used for production other than food.

[0004] In order to solve this problem, the use of non-edible raw materials that have been discarded in the past has also been considered. Specifically, methods have been proposed in which non-edible raw materials such as cellulose derived from waste wood or waste paper are used to produce alcohols by fermentation, and methods have been proposed in which the above-mentioned biomass raw materials are gasified and alcohols are produced from the synthetic gas using a catalyst, but these methods have not yet been put to practical use. Furthermore, even if various petrochemical products can be produced from these non-petroleum raw materials, they will ultimately become waste plastics that do not decompose naturally, so they are not effective as a fundamental solution to environmental problems.

[0005] Incidentally, currently, approximately 60 million tons of combustible waste is disposed of in Japan per year. The amount of energy is equivalent to approximately 200 trillion kilocalories, which is far more than the amount of energy contained in naphtha, the raw material for plastics used in Japan, and this waste can be said to be a valuable resource. If these waste resources could be converted into petrochemical products, it would be possible to realize an ultimate resource-circulating society that is not dependent on petroleum resources. From this perspective, Patent Documents 1 and 2, etc. disclose a technology for producing synthetic gas (gas mainly composed of CO and H2) from waste and producing ethanol from the synthetic gas by fermentation.

[0006] However, as pointed out in Patent Document 3, synthetic gas produced from waste contains a wide variety of impurities that have not been elucidated, some of which are toxic to microorganisms, and therefore the productivity of producing alcohol from synthetic gas by microbial fermentation has been a major issue. In addition, alcohol obtained by microbial fermentation of synthetic gas also contains various components resulting from impurities in the synthetic gas, and these components cannot be completely removed even by purification treatment such as distillation. Therefore, the development of derivatives from alcohol obtained by microbial fermentation of synthetic gas has been a major technical issue. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2016-059296 A [Patent Document 2] International Publication No. 2015-037710 [Patent Document 3] JP 2018-058042 A Summary of the Invention [Problem to be solved by the invention]

[0008] According to the study by the present inventors, for example, conventional C2 raw materials such as ethanol are known to be starting materials for various chemical products, but as described above, it has been found that alcohol produced from resources (recyclable resources) that are not based on petroleum resources or biomass resources contains various trace amounts of unknown substances, unlike chemical raw materials derived from naphtha. However, in the conventional technology, the properties of the substances are unknown, and there has been no sufficient consideration in the past as to whether all substances should be removed or only specific substances should be removed. Therefore, even if the above patent documents propose alcohol produced from recyclable resources, there is still room for technical improvement before the alcohol can be put to practical use.

[0009] On the other hand, although the above-mentioned documents disclose general fermentation and distillation methods and the optimal composition of synthetic gas, they do not describe the details of the processes, nor do they specify the alcoholic substance obtained.

[0010] The present invention has been made in view of the above background art, and an object of the present invention is to provide a novel alcohol and its derivatives which are more industrially valuable and practical than existing petrochemical raw materials. [Means for solving the problem]

[0011] As a result of intensive research to solve the above problems, the inventors have identified a wide variety of trace substances contained in alcohol produced from recycled resources, and further found that it is possible to control the content within a specific range by a new production method, and further found that various derivatives thereof exhibit superior effects compared to existing petroleum-derived alcohol. For example, in the process of synthesizing butadiene from ethanol, it was found that the ethanol conversion rate is improved compared to the case where conventional petroleum-derived ethanol is used, and alcohol of a practical level equal to or higher than that of petroleum-derived alcohol can be obtained, and thus the present invention was completed.

[0012] More specifically, it was found that when ethanol is produced 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, and the reason for this was investigated in detail, and it was found that ethanol derived from a circulatory resource using a gas substrate containing carbon monoxide and hydrogen has a unique peak in a gas chromatograph measured by gas chromatography mass spectrometry that is not seen in ethanol derived from fossil fuels. The present invention is based on this finding.

[0013] That is, the present invention includes the following. [1] In a gas chromatograph measured by gas chromatography / mass spectrometry (GC / MS), Peak with retention time between 15 minutes 00 seconds and 15 minutes 15 seconds , ethanol. [2] The ethanol according to [1], wherein the peak having a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds is derived from n-tetradecane. [3] Ethanol according to [1] or [2], in which the concentration of n-hexadecane is 0.01 mg / L or more and 1.0 mg / L or less. [4] The ethanol according to any one of [1] to [3], wherein a gas containing carbon monoxide and hydrogen is used as a substrate. [5] Ethanol according to any one of [1] to [4], which is derived from microbial fermentation. [6] The ethanol described in [4], wherein the gas containing carbon monoxide and hydrogen is derived from waste. [7] A process for converting a carbon source into a synthesis gas comprising carbon monoxide and hydrogen; a microbial fermentation step of supplying the synthesis gas containing carbon monoxide and hydrogen to a microbial fermenter and obtaining an ethanol-containing liquid by microbial fermentation; a separation step of separating the ethanol-containing liquid into a liquid or solid component containing microorganisms and a gas component containing ethanol; a liquefaction step of condensing and liquefying the gas components; a purification step of purifying ethanol from the liquid obtained in the liquefaction step; Including, The purified ethanol is In a gas chromatograph measured by gas chromatography / mass spectrometry (GC / MS), Peak with retention time between 15 minutes 00 seconds and 15 minutes 15 seconds The method for producing ethanol comprising the steps of: [8] The method according to [7], further comprising the step of purifying the synthesis gas. [9] The method according to [7] or [8], wherein the carbon source is derived from waste.

[10] Ethanol according to any one of [1] to [6], which is for use in chemical products.

[11] Ethanol according to any one of [1] to [6], which is for use as fuel.

[12] Ethanol according to any one of [1] to [6] for use as a polymer raw material.

[13] A chemical product made from ethanol according to any one of [1] to [6].

[14] A fuel comprising ethanol according to any one of [1] to [6] and / or ethyl t-butyl ether derived from the ethanol according to any one of [1] to [6].

[15] A polymer raw material obtained by using ethanol as a raw material according to any one of [1] to [6].

[16] The polymer raw material according to

[15] , selected from the group consisting of ethylene, propylene, butadiene, ethyl acetate, isobutene, methyl (meth)acrylate, acrylic acid, aminohexanoic acid, and diethyl carbonate.

[17] A polymer made from the polymer raw material described in

[15] or

[16] .

[18] A molded article made of the polymer according to

[17] . Effect of the Invention

[0014] According to the present invention, by making ethanol contain a specific trace amount of organic components, various different effects can be obtained compared to commercially available industrial ethanol. For example, according to the present invention, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, to improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and to improve the combustion efficiency when using ethanol as fuel. In addition, it is expected that the same effects can be obtained even with existing alcohols by adding specific amounts of specific organic components.

[0015] The ethanol according to the present invention can be used as a raw material for the production of, for example, butadiene, ethylene, propylene, isobutene, acetaldehyde, acetic acid, ethyl acetate, methyl (meth)acrylate, ethyl-t-butyl ether ethylene glycol, ester compositions, polyesters, acrylic acid, aminohexanoic 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), etc. The ethanol according to the present invention can be used for various applications of chemical products such as cosmetics, perfumes, fuels, antifreeze, bactericides, disinfectants, cleaning agents, mold removers, detergents, hair washes, soaps, antiperspirants, face wash sheets, solvents, paints, adhesives, diluents, and food additives. [Brief description of the drawings]

[0016] [Figure 1] These are the gas chromatograms of the ethanol used in Example 1, Comparative Example 1, and Comparative Example 2. [Diagram 2] This is an enlarged view of the chromatogram of Example 1.

Mode for Carrying Out the Invention

[0017] Hereinafter, an example of a preferred mode for carrying out the present invention will be described. However, the following embodiments are illustrative for explaining the present invention, and the present invention is not limited to the following embodiments at all.

[0018] <Definition> In the present invention, "ethanol" does not mean pure ethanol as a compound (ethanol represented by the chemical formula: CH3CH2OH), but means a composition containing impurities (impurity components) inevitably contained in ethanol produced through synthesis or purification.

[0019] <Ethanol> The ethanol according to the present invention, in the gas chromatograph measured under the following conditions by gas chromatography-mass spectrometry (GC / MS method), a peak with a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds and having, ethanol. <Analysis Conditions of GC / MS Method> Column: DB-5MS (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Oven temperature: 40°C → 10°C / min → 300°C Carrier gas: He (1.28 mL / min) Inlet temperature: 300°C Detector temperature: 300°C Detector: Flame ionization detector Injection volume: 1 μL (split ratio 1:20)

[0020] Ethanol with a purity of 100%, i.e., containing absolutely no impurities, has a peak with a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds in a gas chromatograph measured under the above conditions by the GC / MS method. In addition, commercially available industrial ethanol derived from fossil fuels also has a peak with a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds in a gas chromatograph measured under the above conditions by the GC / MS method. Furthermore, ethanol produced by fermentation using biomass raw materials such as cellulose also has a peak with a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds. Thus, the peak with a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds is considered to be unique to ethanol derived from microbial fermentation using gas containing carbon monoxide and hydrogen as a substrate.

[0021] It is presumed that the peak with a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds is derived from n-hexadecane. The content of n-hexadecane is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, even more preferably 0.03 mg / L or more, even more preferably 0.05 mg / L or more, and also 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, relative to the total ethanol. By having the content of n-decane in the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and improve the combustion efficiency when using ethanol as a fuel.

[0022] Without being bound by theory, it is believed that the synthesis gas used in the production process of ethanol derived from microbial fermentation using a gas containing carbon monoxide and hydrogen as a substrate contains various trace components other than carbon monoxide and hydrogen, and that even alcohol obtained through a purification process such as distillation inevitably contains substances such as aldehyde compounds that have a boiling point higher than that of ethanol. In the present invention, it is believed that the inclusion of these unavoidable substances in ethanol can improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, and can improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid.

[0023] The ethanol of the present invention is obtained by extracting the ethanol-containing liquid obtained from the microbial fermenter and further purifying it as described below, and may contain the following other components in addition to the unavoidable substances described above. For example, it may further contain trace amounts of aromatic compounds.

[0024] Examples of aromatic compounds contained in ethanol include toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene, and only one of these may be contained, or two or more of these may be contained. As the aromatic compound, ethylbenzene is preferably contained.

[0025] The content (total) of aromatic compounds contained in ethanol is preferably 0.4 mg / L or more, more preferably 0.5 mg / L or more, even more preferably 1.0 mg / L or more, and preferably 7 mg / L or less, more preferably 5 mg / L or less, and even more preferably 3 mg / L or less, based on the total amount of ethanol. The content of aromatic compounds within the above ranges can improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and improve the combustion efficiency when using ethanol as a fuel.

[0026] When ethylbenzene is contained in ethanol, the content of ethylbenzene is preferably 0.1 mg / L or more, more preferably 0.2 mg / L or more, even more preferably 0.3 mg / L or more, even more preferably 0.5 mg / L or more, and preferably 5 mg / L or less, more preferably 3 mg / L or less, even more preferably 2 mg / L or less, and even more preferably 1 mg / L or less, based on the total ethanol. By having the content of ethylbenzene in the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, to improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and to improve the combustion efficiency when using ethanol as a fuel.

[0027] When toluene is contained in ethanol, the content of toluene is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, even more 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, based on the total ethanol. By having the toluene content within the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and improve the combustion efficiency when using ethanol as a fuel.

[0028] When o-xylene is contained in ethanol, the content of o-xylene is preferably 0.1 mg / L or more, more preferably 0.2 mg / L or more, even more preferably 0.3 mg / L or more, even more preferably 0.5 mg / L or more, and preferably 5 mg / L or less, more preferably 3 mg / L or less, even more preferably 2 mg / L or less, and even more preferably 1 mg / L or less, based on the total ethanol. By having the content of o-xylene in the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, to improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and to improve the combustion efficiency when using ethanol as a fuel.

[0029] When m-xylene and / or p-xylene are contained in ethanol, the content (total) of m-xylene and / or p-xylene is preferably 0.2 mg / L or more, more preferably 0.3 mg / L or more, even more preferably 0.4 mg / L or more, even more preferably 0.5 mg / L or more, and also preferably 5 mg / L or less, more preferably 3 mg / L or less, even more preferably 2 mg / L or less, and even more preferably 1 mg / L or less, based on the total ethanol. By having the content of m-xylene and / or p-xylene in the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and improve the combustion efficiency when using ethanol as a fuel.

[0030] The ethanol according to the present invention may further contain a small amount of dialkyl ether. Examples of dialkyl ether include dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, and dipentyl ether, and may contain only one of these, or may contain two or more of these. The dialkyl ether preferably contains dibutyl ether.

[0031] The content (total) of dialkyl ether contained in ethanol is preferably 0.001 mg / L or more, preferably 0.01 mg / L or more, more preferably 0.1 mg / L or more, even more preferably 1.0 mg / L or more, and is 100 mg / L or less, preferably 80 mg / L or less, more preferably 50 mg / L or less, and even more preferably 30 mg / L or less, based on the total amount of ethanol. The dialkyl ether content within the above range can improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and improve the combustion efficiency when using ethanol as a fuel.

[0032] When dibutyl ether is contained in ethanol, the content of dibutyl ether is preferably 1 mg / L or more, more preferably 2 mg / L or more, even more preferably 5 mg / L or more, even more preferably 10 mg / L or more, and preferably 50 mg / L or less, more preferably 40 mg / L or less, even more preferably 30 mg / L or less, and even more preferably 25 mg / L or less, relative to ethanol. By having the content of dibutyl ether in the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, to improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and to improve the combustion efficiency when using ethanol as a fuel.

[0033] The ethanol of the present invention contains a very small amount of the organic compounds as described above, but may also contain compounds containing elements such as Si, K, Na, Fe, and Cr. Compounds containing these elements may be inorganic compounds or organometallic compounds. For example, when they contain Si, they may contain silica or organosiloxane.

[0034] When ethanol contains Si, the content of Si is preferably 10 mg / L or more, more preferably 20 mg / L or more, even more preferably 30 mg / L or more, and preferably 100 mg / L or less, more preferably 90 mg / L or less, and even more preferably 80 mg / L or less, relative to ethanol. The content of Si is the amount of Si compound converted into elemental Si. By having the content of Si in the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and improve the combustion efficiency when using ethanol as a fuel.

[0035] When K is contained in ethanol, the content of K is preferably 1.0 mg / L or more, more preferably 1.5 mg / L or more, even more preferably 2.0 mg / L or more, even more preferably 2.5 mg / L or more, and preferably 10 mg / L or less, more preferably 7 mg / L or less, and even more preferably 5 mg / L or less, relative to ethanol. The K content is the amount of K compound converted into K element. By having the K content in the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and improve the combustion efficiency when using ethanol as a fuel.

[0036] When Na is contained in ethanol, the Na content is preferably 150 mg / L or more, more preferably 170 mg / L or more, even more preferably 190 mg / L or more, and also preferably 1000 mg / L or less, more preferably 500 mg / L or less, even more preferably 400 mg / L or less, and more preferably 300 mg / L or less, relative to ethanol. The Na content is the Na element equivalent amount of Na compounds. By having the Na content in the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and improve the combustion efficiency when using ethanol as a fuel.

[0037] When ethanol contains Fe, the Fe content is preferably 2.0 mg / L or less, more preferably 1.5 mg / L or less, even more preferably 1.0 mg / L or less, and even more preferably 0.5 mg / L or less, relative to ethanol. The Fe content is the Fe element equivalent amount of the Fe compound. When the Fe content is within the above numerical range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, to improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and to improve the combustion efficiency when using ethanol as a fuel.

[0038] When ethanol contains Cr, the Cr content is preferably 0.6 mg / L or less, more preferably 0.5 mg / L or less, relative to ethanol. The Cr content is the amount of Cr compounds converted into Cr elements. When the Cr content is in the above-mentioned range, it is possible to improve the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material, to improve the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid, and to improve the combustion efficiency when using ethanol as a fuel.

[0039] The ethanol of the present invention contains the inorganic components described above, and, if desired, trace amounts of organic components such as aromatic hydrocarbons and aliphatic hydrocarbons, but the concentration of ethanol, which is the main component in the ethanol (pure ethanol as a compound), is 75 vol% or more, preferably 80 vol% or more, more preferably 90 vol% or more, even more preferably 95 vol% or more, still more preferably 98 vol% or more, and is preferably 99.999 vol% or less, more preferably 99.99 vol% or less, even more preferably 99.9 vol% or less, and still more preferably 99.5 vol% or less.

[0040] The ethanol concentration in the ethanol of the present invention may be set according to the intended use, for example, 90% by volume or more is preferably used for cosmetics, and 75% by volume or more is preferably used for disinfectants, and the upper limit can also be conveniently set according to the use. In terms of transportation costs, etc., the higher the ethanol concentration, the more preferable the product.

[0041] <How ethanol is produced> As a method for producing ethanol having a unique gas chromatographic peak as described above, for example, ethanol can be produced by microbial fermentation of a synthetic gas containing carbon monoxide derived from waste or exhaust gas. In such a method, the content of aromatic compounds and the like in the raw gas derived from waste or exhaust gas and the purification conditions can be controlled to control the amount of aromatic compounds and the like contained in the final product. Hereinafter, as an example, a method for producing ethanol by microbial fermentation of a synthetic gas containing carbon monoxide derived from waste or exhaust gas will be described.

[0042] The method for producing ethanol includes the steps 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 fermenter to obtain an ethanol-containing liquid by microbial fermentation, a separation step of separating the ethanol-containing liquid into a liquid or solid component containing microorganisms and a gas component containing ethanol, a liquefaction step of condensing and liquefying the gas component, and a purification step of purifying ethanol from the liquid obtained in the liquefaction step, but may also include a raw material gas generation step, a synthesis gas preparation step, a wastewater treatment step, etc., as necessary. Each step will be described below.

[0043] <Raw material gas generation process> The raw gas generation process is a process of generating raw gas by gasifying a carbon source in a gasification section. A gasification furnace may be used in the raw gas generation process. The gasification furnace is a furnace that burns (incompletely combusts) a carbon source, and examples of such furnaces include shaft furnaces, kiln furnaces, fluidized bed furnaces, and gasification reforming furnaces. The gasification furnace is preferably a fluidized bed furnace type, since it can achieve high hearth load and excellent operability by partially burning waste. By gasifying the waste in a fluidized bed furnace at low temperature (about 450 to 600 ° C) and in a low-oxygen atmosphere, the waste is decomposed into gas (carbon monoxide, carbon dioxide, hydrogen, methane, etc.) and char containing a large amount of carbon. Furthermore, since the non-combustible materials contained in the waste are separated from the bottom of the furnace in a hygienic and low-oxidization state, it is possible to selectively recover valuable materials such as iron and aluminum from the non-combustible materials. Therefore, such gasification of waste allows efficient resource recycling.

[0044] The gasification temperature in the raw material gas production step is not particularly limited, but is usually 100 to 2500°C, and preferably 200 to 2100°C.

[0045] The reaction time for gasification in the raw material gas generation step is usually 2 seconds or more, and preferably 5 seconds or more.

[0046] The carbon source used in the raw material gas production process is not particularly limited, and various carbon-containing materials can be suitably used for the purpose of recycling, such as coke ovens in steelworks, blast furnaces (blast furnace gas), coal used in converters and coal-fired power plants, general waste and industrial waste introduced into incinerators (particularly gasifiers), and carbon dioxide by-produced by various industries.

[0047] More specifically, the carbon source is preferably waste material, and specific examples thereof include plastic waste, food waste, municipal solid waste (MSW), industrial solid waste, discarded tires, biomass waste, household waste such as bedding and paper, waste materials such as building materials, coal, petroleum, petroleum-derived compounds, natural gas, shale gas, and the like. Among these, various types of waste are preferable, and from the viewpoint of sorting costs, unsorted municipal solid waste is more preferable.

[0048] The feed gas obtained by gasifying the carbon source contains carbon monoxide and hydrogen as essential components, but may further contain carbon dioxide, oxygen, and nitrogen. As other components, the feed gas may further contain components such as soot, tar, nitrogen compounds, sulfur compounds, phosphorus compounds, and aromatic compounds.

[0049] In the above-mentioned raw material gas production step, the raw material gas may be produced by carrying out a heat treatment (commonly known as gasification) to combust (incompletely combust) a carbon source, i.e., by partially oxidizing the carbon source, as a gas containing carbon monoxide in an amount of, although not particularly limited, 0.1 vol % or more, preferably 10 vol % or more, and more preferably 20 vol % or more.

[0050] <Synthetic gas refining process> The synthesis gas purification process is a process for removing or reducing specific substances such as various pollutants, dust particles, impurities, and undesirable amounts of compounds from the raw gas. When the raw gas is derived from waste, the raw gas usually contains carbon monoxide at 0.1% to 80% by volume, carbon dioxide at 0.1% to 70% by volume, and hydrogen at 0.1% to 80% by volume, and further tends to contain nitrogen compounds at 1 mg / L or more, sulfur compounds at 1 mg / L or more, phosphorus compounds at 0.1 mg / L or more, and / or aromatic compounds at 10 mg / L or more. In addition, other environmental pollutants, dust particles, impurities, and other substances may be contained. Therefore, when supplying synthesis gas to a microbial fermenter, it is preferable to reduce or remove substances and compounds that are undesirable for stable cultivation of microorganisms from the raw gas, and to make the content of each component contained in the raw gas within a range suitable for stable cultivation of microorganisms.

[0051] In particular, in the synthesis gas purification process, a pressure swing adsorption apparatus filled with the above-mentioned regenerated adsorbent is used to adsorb carbon dioxide gas in the synthesis gas onto the regenerated adsorbent (zeolite), thereby reducing the carbon dioxide gas concentration in the synthesis gas. Furthermore, the synthesis gas may be subjected to other conventionally known treatment processes to remove impurities and adjust the gas composition. As other treatment processes, for example, one or more of a gas chiller (moisture separator), a low-temperature separation type (cryogenic type) separator, a particulate (soot) separator such as a cyclone or a bag filter, a scrubber (water-soluble impurity separator), a desulfurization device (sulfide separator), a membrane separation type separator, a deoxygenation device, a pressure swing adsorption type separator (PSA), a temperature swing adsorption type separator (TSA), a pressure temperature swing adsorption type separator (PTSA), a separator using activated carbon, and a deoxygenation catalyst, specifically, a separator using a copper catalyst or a palladium catalyst, etc. may be used for treatment.

[0052] The synthesis gas used in the ethanol production method of the present invention contains at least carbon monoxide as an essential component, and may further contain hydrogen, carbon dioxide, and nitrogen.

[0053] The synthesis gas used in the present invention may be a gas obtained by generating a raw material gas by gasifying a carbon source (raw material gas generation process), and then adjusting the concentrations of each component of carbon monoxide, carbon dioxide, hydrogen and nitrogen from the raw material gas, as well as reducing or removing the above-mentioned substances and compounds, and the gas obtained may be used as the synthesis gas.

[0054] 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, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in the synthesis gas.

[0055] 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, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in the synthesis gas.

[0056] 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, more preferably 0.5 vol.% or more and 10 vol.% or less, and particularly preferably 1 vol.% or more and 6 vol.% or less, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in the synthesis gas.

[0057] 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, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen, and nitrogen in the synthesis gas.

[0058] The concentrations of carbon monoxide, carbon dioxide, hydrogen, and nitrogen can be set within a predetermined range by changing the elemental composition of the hydrocarbons (carbon and hydrogen) and nitrogen in the carbon source in the raw gas generation process, or by appropriately changing the combustion conditions such as the combustion temperature and the oxygen concentration of the gas supplied during combustion. For example, if you want to change the carbon monoxide or hydrogen concentration, you can change the carbon source to one with a higher ratio of hydrocarbons (carbon and hydrogen), such as waste plastics, and if you want to lower the nitrogen concentration, you can supply a gas with a high oxygen concentration in the raw gas generation process.

[0059] The synthetic gas used in the present invention may contain, in addition to the above-mentioned components, sulfur compounds, phosphorus compounds, nitrogen compounds, etc., without any particular limitation. The content of each of these compounds is preferably 0.05 mg / L or more, more preferably 0.1 mg / L or more, even more preferably 0.5 mg / L or more, and is preferably 2000 mg / L or less, more preferably 1000 mg / L or less, even more preferably 80 mg / L or less, even more preferably 60 mg / L or less, and particularly preferably 40 mg / L or less. By setting the content of sulfur compounds, phosphorus compounds, nitrogen compounds, etc. to the lower limit value or more, there is an advantage that microorganisms can be suitably cultured, and by setting the content to the upper limit value or less, there is an advantage that the medium is not contaminated by various nutrient sources not consumed by the microorganisms.

[0060] Examples of sulfur compounds include sulfur dioxide, CS2, COS, and H2S, and among them, H2S and sulfur dioxide are preferred because they are easily consumed as a nutrient source for microorganisms. Therefore, it is more preferable that the sum of H2S and sulfur dioxide is contained in the synthesis gas within the above range. As the phosphorus compound, phosphoric acid is preferred because it is easily consumed as a nutrient source for microorganisms, and therefore it is more preferred that the synthesis gas contains phosphoric acid in the above range. Examples of the nitrogen compound include nitric oxide, nitrogen dioxide, acrylonitrile, acetonitrile, HCN, etc., and HCN is preferred because it is easily consumed as a nutrient source for microorganisms. Therefore, it is more preferable that HCN is contained in the synthesis gas in the above range.

[0061] The synthetic gas may contain aromatic compounds in an amount of 0.01 mg / L or more and 90 mg / L or less, preferably 0.03 mg / L or more, more preferably 0.05 mg / L or more, and even more preferably 0.1 mg / L or more, and preferably 70 mg / L or less, more preferably 50 mg / L or less, and even more preferably 30 mg / L or less. By making the content equal to or more than the lower limit, microorganisms tend to be cultured favorably, and by making the content equal to or less than the upper limit, the medium tends to be less likely to be contaminated by various nutrient sources not consumed by the microorganisms.

[0062] <Microbial fermentation process> The microbial fermentation step is a step of producing ethanol by microbial fermentation of the synthesis gas in a microbial fermenter. The microbial fermenter is preferably a continuous fermentation apparatus. In general, any shape of microbial fermenter can be used, including stirring type, airlift type, bubble column type, loop type, open bond type, and photobio type. In the present invention, the microbial fermenter can be suitably a known loop reactor having a main tank section and a reflux section. In this case, it is preferable to further include a circulation step of circulating the liquid medium between the main tank section and the reflux section.

[0063] As long as the synthesis gas to be supplied to the microbial fermenter satisfies the above-mentioned compositional conditions of the synthesis gas, the gas obtained through the raw material gas generation process may be used as the synthesis gas as it is, or another specified gas may be added to the gas obtained by reducing or removing impurities from the raw material gas, and then the synthesis gas may be used. As the other specified gas, at least one compound selected from the group consisting of sulfur compounds such as sulfur dioxide, phosphorus compounds, and nitrogen compounds may be added to prepare the synthesis gas.

[0064] The microbial fermenter may be continuously supplied with synthesis gas and a microbial culture solution, but it is not necessary to supply the synthesis gas and the microbial culture solution simultaneously, and the synthesis gas may be supplied to a microbial fermenter to which a microbial culture solution has been previously supplied. It is known that certain anaerobic microorganisms produce ethanol and the like from substrate gases such as synthesis gas by fermentation, and this type of gas-utilizing microorganism is cultured in a liquid medium. For example, a liquid medium and gas-utilizing bacteria may be supplied and accommodated, and synthesis gas may be supplied into the microbial fermenter while stirring the liquid medium in this state. This allows the gas-utilizing bacteria to be cultured in the liquid medium, and ethanol to be produced from the synthesis gas by the fermentation action of the bacteria.

[0065] In the microbial fermenter, the temperature of the medium etc. (culture temperature) may be any temperature, but is preferably about 30 to 45° C., more preferably about 33 to 42° C., and even more preferably about 36.5 to 37.5° C. The culture time is preferably 12 hours or more in continuous culture, more preferably 7 days or more, particularly preferably 30 days or more, and most preferably 60 days or more. Although there is no particular upper limit, from the viewpoint of regular maintenance of the equipment, it is preferably 720 days or less, and more preferably 365 days or less. The culture time means the time from adding the seed bacteria to the culture tank to discharging the entire amount of the culture liquid in the culture tank.

[0066] The microorganism (species) contained in the microbial culture solution is not particularly limited as long as it can produce ethanol by microbial fermentation of synthetic gas using carbon monoxide as the main raw material. For example, the microorganism (species) is preferably one that produces ethanol from synthetic gas by the fermentation action of gas-utilizing bacteria, and is particularly preferably a microorganism having a metabolic pathway of acetyl-CoA. Among gas-utilizing bacteria, the genus Clostridium is more preferable, and Clostridium autoethanogenum is particularly preferable, but is not limited thereto. Further examples are given below.

[0067] Gas-utilizing bacteria include both eubacteria and archaea. Examples of eubacteria include bacteria of the genus Clostridium, Moorella, Acetobacterium, Carboxydocella, Rhodopseudomonas, Eubacterium, Butyribacterium, Oligotropha, Bradyrhizobium, and aerobic hydrogen-oxidizing bacteria such as Larsotonia.

[0068] On the other hand, examples of archaea include bacteria of the genus Methanobacterium, bacteria of the genus Methanobrevibacter, bacteria of the genus Methanocalculus, bacteria of the genus Methanococcus, bacteria of the genus Methanosarcina, bacteria of the genus Methanosphaera, bacteria of the genus Methanothermobacter, Metha Examples include bacteria of the genus Nothrix, bacteria of the genus Methanoculleus, bacteria of the genus Methanofollis, bacteria of the genus Methanogenium, bacteria of the genus Methanospirillium, bacteria of the genus Methanosaeta, bacteria of the genus Thermococcus, bacteria of the genus Thermofilum, bacteria of the genus Arcaheoglobus, and the like. Among these, as archaea, bacteria of the genus Methanosarcina, bacteria of the genus Methanococcus, bacteria of the genus Methanothermobacter, bacteria of the genus Methanothrix, bacteria of the genus Thermococcus, bacteria of the genus Thermofilum, and bacteria of the genus Archaeoglobus are preferred.

[0069] Furthermore, because of their excellent carbon monoxide and carbon dioxide assimilation ability, archaea are preferably Methanosarcina bacteria, Methanothermobactor bacteria, or Methanococcus bacteria, and more preferably Methanosarcina bacteria or Methanococcus bacteria. Specific examples of Methanosarcina bacteria include Methanosarcina barkeri, Methanosarcina mazei, and Methanosarcina acetivorans.

[0070] Among the above-mentioned gas-utilizing bacteria, bacteria with high ethanol production ability are selected and used. For example, gas-utilizing bacteria with high ethanol production ability include Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Clostridium carboxidivorans, Moorella thermoacetica, Acetobacterium woodii, etc., among which Clostridium autoethanogenum is particularly preferred.

[0071] The medium used to culture the above-mentioned microorganisms (species) is not particularly limited as long as it has an appropriate composition according to the bacteria, but is a liquid containing water as the main component and nutrients (e.g., vitamins, phosphoric acid, etc.) dissolved or dispersed in the water. The composition of such a medium is prepared so that gas-utilizing bacteria can grow well. For example, when the genus Clostridium is used as the microorganism, the medium can be prepared by referring to U.S. Patent Application Publication No. 2017 / 260552, paragraphs "0097" to "0099", etc.

[0072] The ethanol-containing liquid obtained by the microbial fermentation process can be obtained as a suspension containing microorganisms and their carcasses, proteins derived from the microorganisms, etc. The protein concentration in the suspension varies depending on the type of microorganism, but is usually 30 to 1000 mg / L. The protein concentration in the ethanol-containing liquid can be measured by the Kjeldahl method.

[0073] <Separation process> The ethanol-containing liquid obtained by the microbial fermentation process is then subjected to a separation process. In the present invention, the ethanol-containing liquid is heated to room temperature to 500° C. under conditions of 0.01 to 1000 kPa (absolute pressure) to separate into a liquid or solid component containing microorganisms and a gas component containing ethanol. In the conventional method, the ethanol-containing liquid obtained by the microbial fermentation process is distilled to separate and purify the desired ethanol. However, since the ethanol-containing liquid contains microorganisms and proteins derived from microorganisms, if the ethanol-containing liquid is distilled as it is, foaming may occur in the distillation apparatus, hindering continuous operation. In addition, it is known to use a membrane evaporator as a method for purifying a foamable liquid, but the membrane evaporator has low concentration efficiency and is not suitable for purifying a liquid containing solid components. In the present invention, before separating and purifying the desired ethanol from the ethanol-containing liquid obtained by the microbial fermentation process by a distillation operation or the like, the ethanol-containing liquid is heated to separate into a liquid or solid component containing microorganisms and a gas component containing ethanol, and the desired ethanol is separated and purified only from the separated gas 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, so that the distillation operation can be carried out continuously. Also, since the ethanol concentration in the gaseous component containing ethanol becomes higher than the ethanol concentration in the ethanol-containing liquid, the separation and purification of ethanol can be efficiently carried out in the purification step described later.

[0074] In the present invention, from the viewpoint of efficiently separating the ethanol-containing liquid into a liquid or solid component containing microorganisms, their carcasses, proteins derived from microorganisms, etc., and a gaseous component containing ethanol, the ethanol-containing liquid is heated preferably under conditions of 10 to 200 kPa, more preferably under conditions of 50 to 150 kPa, and even more preferably at normal pressure, at a temperature of preferably 50 to 200°C, more preferably at a temperature of 80°C to 180°C, and even more preferably at a temperature of 100 to 150°C.

[0075] The heating time in the separation step is not particularly limited as long as it is a time that allows the production of gaseous components, but from the standpoint of efficiency or economy, it is usually 5 seconds to 2 hours, preferably 5 seconds to 1 hour, and more preferably 5 seconds to 30 minutes.

[0076] In the above-mentioned separation step, any device can be used without particular limitation as long as it can efficiently separate the ethanol-containing liquid into liquid or solid components (microorganisms or their carcasses, proteins derived from microorganisms, etc.) and gas components (ethanol) by thermal energy, and for example, drying devices such as rotary dryers, fluidized bed dryers, vacuum dryers, and conductive heating dryers can be used, but it is preferable to use a conductive heating dryer from the viewpoint of efficiency in separating an ethanol-containing liquid with a low solid component concentration into liquid or solid components and gas components. Examples of conductive heating dryers include drum dryers and disk dryers.

[0077] <Liquefaction process> The liquefaction step is a step of liquefying the gaseous components containing ethanol obtained in the separation step by condensation. The device used in the liquefaction step is not particularly limited, but it is preferable to use a heat exchanger, particularly a condenser. Examples of the condenser include a water-cooled type, an air-cooled type, and an evaporative type, and among these, a water-cooled type is preferable. The condenser may be a single-stage condenser or a multi-stage condenser.

[0078] It is preferable that the liquefied product obtained by the liquefaction step does not contain components contained in the ethanol-containing liquid, such as microorganisms, their remains, and proteins derived from microorganisms, but the present invention does not exclude the inclusion of proteins in the liquefied product. Even if the liquefied product contains proteins, the concentration of the proteins is preferably 40 mg / L or less, more preferably 20 mg / L or less, and even more preferably 15 mg / L or less.

[0079] The heat of condensation of the gas components obtained by the condenser may be reused as a heat source in the purification step described below. By reusing the heat of condensation, ethanol can be produced efficiently and economically.

[0080] <Purification process> Next, ethanol is purified from the liquefied product obtained in the liquefaction step. When components such as microorganisms have already been removed from the ethanol-containing liquid obtained in the microbial fermentation step, the ethanol-containing liquid can be supplied to the purification step without going through the above-mentioned separation step. The purification step is a step of separating the ethanol-containing liquid obtained in the liquefaction step into a distillate having an increased concentration of the target ethanol and a bottoms liquid having a decreased concentration of the target ethanol. Examples of the apparatus used in the purification step include a distillation apparatus, a treatment apparatus including a pervaporation membrane, a treatment apparatus including a zeolite dehydration membrane, a treatment apparatus for removing low-boiling substances having a boiling point lower than that of ethanol, a treatment apparatus for removing high-boiling substances having a boiling point higher than that of ethanol, and a treatment apparatus including an ion exchange membrane. These apparatuses may be used alone or in combination of two or more. Heat distillation or membrane separation may be suitably used as a unit operation.

[0081] In the heat distillation, a distillation apparatus is used to obtain the desired ethanol as a distillate with high purity. The temperature in the distillation apparatus during the distillation of ethanol is not particularly limited, but is preferably 100° C. or less, and more preferably about 70 to 95° C. By setting the temperature in the distillation apparatus within the above range, separation of ethanol from other components, i.e., distillation of ethanol, can be performed more reliably.

[0082] In particular, the ethanol-containing liquid obtained in the liquefaction step is introduced into a distillation apparatus equipped with a heater using steam at 100° C. or higher, and the temperature of the bottom of the distillation column is raised to 90° C. or higher within 30 minutes. The ethanol-containing liquid is then introduced from the middle of the distillation column, and the distillation step is performed with the temperature difference between the bottom, middle, and top of the column being within ±15° C., thereby obtaining high-purity ethanol. The distillation temperature difference is preferably ±13° C., and more preferably ±11° C. With the distillation temperature difference, separation from other components, i.e., distillation of ethanol, can be performed more reliably.

[0083] The ethanol-containing liquid is considered to contain hexadecane, which has a boiling point higher than that of ethanol. In the present invention, by adjusting the above distillation conditions, for example, by increasing the temperature at the top of the distillation column by 5 to 10° C. higher than usual, aromatic compounds are also distilled, and the aromatic compounds in the ethanol contained in the distillate can be adjusted. As a result, the content of aromatic compounds in the final ethanol can be adjusted.

[0084] The pressure inside the distillation apparatus during the distillation of ethanol may be normal pressure, but is preferably less than atmospheric pressure, more preferably about 60 to 95 kPa (absolute pressure). By setting the pressure inside the distillation apparatus within the above range, it is possible to improve the efficiency of ethanol separation, and thus the ethanol yield. The ethanol yield (the concentration of ethanol contained in the distillate after distillation) is preferably 90% by volume or more, more preferably 95% by volume or more.

[0085] In the membrane separation, a known separation membrane can be appropriately used, and for example, a zeolite membrane can be suitably used.

[0086] The concentration of ethanol contained in the distillate separated in the purification step is preferably 20% by volume to 99.99% by volume, and more preferably 60% by volume to 99.9% by volume. On the other hand, the concentration of ethanol contained in the bottoms is preferably 0.001% by volume to 10% by volume, and more preferably 0.01% by volume to 5% by volume.

[0087] The bottoms separated in the purification step are substantially free of nitrogen compounds. In the present invention, "substantially free" does not mean that the concentration of nitrogen compounds is 0 mg / L, but means that the bottoms obtained in the purification step have a nitrogen compound concentration at a level that does not require a wastewater treatment step. In the separation step, the ethanol-containing liquid obtained in the microbial fermentation step is not purified to obtain the desired ethanol, but the ethanol-containing liquid is separated into a liquid or solid component containing a microorganism and a gaseous component containing ethanol as described above. At that time, the nitrogen compounds remain on the liquid or solid component side containing a microorganism, so that the gaseous component containing ethanol contains almost no nitrogen compounds. Therefore, it is considered that the bottoms obtained when ethanol is purified from a liquefied product obtained by liquefying a gaseous component does not substantially contain nitrogen compounds. Even if the bottoms contain nitrogen compounds, the concentration of the 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.

[0088] For the same reason as above, the bottoms separated in the purification step are substantially free of phosphorus compounds. Note that "substantially free" does not mean that the concentration of phosphorus compounds is 0 mg / L, but means that the bottoms obtained in the purification step have a phosphorus compound concentration of such a level that a wastewater treatment step is not required. Even if the bottoms contain 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 invention, the bottoms discharged in the ethanol purification step are substantially free of nitrogen compounds and phosphorus compounds, and are considered to contain almost no other organic matter, so that the wastewater treatment step that has been required in the past can be simplified.

[0089] <Wastewater treatment process> The bottoms separated in the refining step may be supplied to a wastewater treatment step. In the wastewater treatment step, organic matter such as nitrogen compounds and phosphorus compounds can be further removed from the bottoms. In this step, the bottoms may be subjected to anaerobic or aerobic treatment to remove the organic matter. The removed organic matter may be used as fuel (heat source) in the refining step.

[0090] The treatment temperature in the wastewater treatment step is usually 0 to 90°C, preferably 20 to 40°C, and more preferably 30 to 40°C.

[0091] The bottoms obtained through the separation process have had liquid and solid components, including microorganisms, removed, and therefore require less wastewater treatment and other processes than the bottoms obtained by directly supplying the bottoms from the microbial fermentation process to the purification process.

[0092] In the wastewater treatment process, the nitrogen compound concentration in the treatment liquid obtained by treating the bottoms is preferably 0.1 to 30 mg / L, more preferably 0.1 to 20 mg / L, and even more preferably 0.1 to 10 mg / L, and it is particularly preferable that no nitrogen compounds are contained in the treatment liquid. The phosphorus compound concentration in the treatment liquid is preferably 0.1 to 10 mg / L, more preferably 0.1 to 5 mg / L, and even more preferably 0.1 to 1 mg / L, and it is particularly preferable that no phosphorus compounds are contained in the bottoms.

[0093] <Uses of ethanol> The ethanol according to the present invention can be used as a raw material for producing various organic compounds. For example, the ethanol according to the present invention can be used as a raw material for producing butadiene, ethylene, propylene, isobutene, acetaldehyde, acetic acid, ethyl acetate, methyl (meth)acrylate, ethyl-t-butyl ether ethylene glycol, ester compositions, polyesters, acrylic acid, aminohexanoic 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), etc. Below, a method for synthesizing butadiene using the ethanol according to the present invention as a raw material and a method for producing polyethylene and polyester are described as examples, but it goes without saying that the ethanol according to the present invention can also be used as a raw material for other chemical products and polymers.

[0094] <Method of synthesizing butadiene> Butadiene is produced by refining the C4 fraction, which is a by-product of synthesizing ethylene from petroleum (i.e., naphtha cracking), and is the raw material for synthetic rubber. However, in recent years, there has been a strong demand for a technology to convert ethanol (ethanol derived from microbial fermentation) that is not derived from fossil fuels into 1,3-butadiene instead of chemical industrial raw materials obtained from petroleum. As a method for synthesizing butadiene using such ethanol derived from microbial fermentation as a raw material, a method using MgO as a catalyst, a method using a mixture of Al2O3 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.

[0095] By contacting the ethanol of the present invention with the above-mentioned catalyst and heating it, an ethanol conversion reaction occurs, and 1,3-butadiene can be synthesized. By synthesizing butadiene using the ethanol of the present invention as a raw material, it is possible to realize an ultimate resource recycling society that does not depend on petroleum resources.

[0096] The heating temperature for promoting the conversion reaction is, for example, about 300 to 450°C, preferably about 350 to 400°C, in the reaction system. If the temperature in the reaction system is below the above range, the catalytic activity is not sufficient, and the reaction rate tends to decrease, resulting in a decrease in production efficiency. On the other hand, if the temperature in the reaction system is above the above range, the catalyst may be easily deteriorated.

[0097] The reaction can be carried out by a conventional method such as a batch method, a semi-batch method, or a continuous method. When a batch method or a semi-batch method is adopted, the conversion rate of ethanol can be increased, but when the ethanol according to the present invention is used, ethanol can be converted more efficiently than before, even when a continuous method is adopted. The reason for this is not clear, but it is thought to be due to the fact that the ethanol derived from a circulatory resource such as that of the present invention, which uses a gas containing carbon monoxide and hydrogen as a substrate, has a unique peak in a gas chromatograph measured by gas chromatography mass spectrometry, which is not seen in ethanol derived from fossil fuels.

[0098] Examples of the method for contacting the raw material with the catalyst include a suspension bed method, a fluidized bed method, and a fixed bed method. Either a gas phase method or a liquid phase method may be used. In terms of easy recovery and regeneration of the catalyst, it is preferable to use a fixed bed type gas phase continuous flow reactor in which the catalyst is packed in a reaction tube to form a catalyst layer, and the raw material is passed through as a gas to react in the gas phase. When the reaction is carried out in the gas phase, the ethanol of the present invention may be gasified and supplied to the reactor without dilution, or may be appropriately diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide gas and then supplied to the reactor.

[0099] After the ethanol conversion reaction is completed, the reaction product (1,3-butadiene) can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, or a combination of these.

[0100] <Polyethylene> The ethanol according to the present invention can be suitably used as a raw material for polyethylene, which is widely used as a general-purpose plastic. Conventional polyethylene is produced by synthesizing ethylene from petroleum and polymerizing the ethylene monomer. By producing polyethylene using the ethanol according to the present invention, it is possible to realize an ultimate resource-recycling society that is not dependent on petroleum resources.

[0101] First, ethylene, which is a raw material for polyethylene, is synthesized using the ethanol according to the present invention as a raw material. The method for producing ethylene is not particularly limited, and it can be obtained by a conventionally known method. As an example, ethylene can be obtained by a dehydration reaction of ethanol. A catalyst is usually used when obtaining ethylene by a dehydration reaction of ethanol, and this catalyst is not particularly limited, and a conventionally known catalyst can be used. A fixed bed flow reaction, which allows easy separation of the catalyst and the product, is advantageous in terms of the process, and for example, γ-alumina or the like is preferable.

[0102] Since the dehydration reaction is an endothermic reaction, it is usually carried out under heating conditions. As long as the reaction proceeds at a commercially useful reaction rate, the heating temperature is not limited, but is preferably 100°C or higher, more preferably 250°C or higher, and even more preferably 300°C or higher. There is no particular upper limit, but from the viewpoint of energy balance and equipment, it is preferably 500°C or lower, more preferably 400°C or lower.

[0103] The reaction pressure is not particularly limited, but is preferably equal to or higher than atmospheric pressure in order to facilitate the subsequent gas-liquid separation. From an industrial perspective, a fixed bed flow reaction is preferred because it is easy to separate the catalyst, but a liquid phase suspension bed, a fluidized bed, etc. may also be used.

[0104] In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in the ethanol supplied as a raw material. In general, when performing a dehydration reaction, it is preferable to have no water in consideration of the efficiency of removing water. However, in the case of the dehydration reaction of ethanol using a solid catalyst, the amount of other olefins, particularly butene, produced tends to increase if water is not present. The lower limit of the allowable water content is 0.1% by mass or more, preferably 0.5% by mass or more. The upper limit is not particularly limited, but from the viewpoint of material balance and heat balance, it is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0105] By carrying out the dehydration reaction of ethanol as described above, a mixture of ethylene, water and a small amount of unreacted ethanol is obtained. Since ethylene is in a gaseous state at room temperature below about 5 MPa, water and ethanol can be removed from the mixture by gas-liquid separation to obtain ethylene. This method may be performed by a known method. The ethylene obtained by gas-liquid separation is then further distilled. There are no particular restrictions on the distillation method, operation temperature, residence time, etc., except that the operation pressure at this time is normal pressure or higher.

[0106] In the ethanol derived from a circulatory resource using a gas containing carbon monoxide and hydrogen as a substrate as in the present invention, a unique peak is present in the gas chromatograph measured by gas chromatography mass spectrometry, which is not observed in the ethanol derived from a fossil fuel. Therefore, it is considered that the ethylene obtained from the ethanol contains a very small amount of impurities. Depending on the use of the ethylene, these very small amounts of impurities may be problematic, so they may be removed by purification. The purification method is not particularly limited, and may be performed by a conventionally known method. For example, an adsorption purification method may be mentioned as a suitable purification operation. The adsorbent used is not particularly limited, and a conventionally known adsorbent may be used. For example, a caustic water treatment may be used in combination as a purification method for impurities in ethylene. When caustic water treatment is performed, it is preferable to perform it before adsorption purification. In that case, it is necessary to perform a moisture removal treatment after the caustic treatment and before the adsorption purification.

[0107] The polymerization method of the monomer containing ethylene is not particularly limited, and can be carried out by a conventionally known method. The polymerization temperature and polymerization pressure are preferably adjusted appropriately depending on the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of the polymerization method of the monomer containing ethylene will be described below.

[0108] The polymerization method for polyolefins, particularly ethylene polymers and copolymers of ethylene and α-olefins, can be appropriately selected depending on the type of polyethylene to be produced, for example, differences in density and branching, such as high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), etc. For example, it is preferable to use a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as the polymerization catalyst, and carry out the polymerization in one stage or in two or more stages by any of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ionic polymerization.

[0109] The single-site catalyst is a catalyst capable of forming a uniform active species, and is usually prepared by contacting a metallocene transition metal compound or a nonmetallocene transition metal compound with an activating cocatalyst. Compared with a multi-site catalyst, a single-site catalyst is preferred because it has a uniform active site structure and can polymerize a polymer with a high molecular weight and a highly uniform structure. As the single-site catalyst, it is particularly preferred to use a metallocene catalyst. The metallocene catalyst is a catalyst containing each catalyst component of a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, and if necessary, an organometallic compound and a carrier.

[0110] In the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, etc. The substituted cyclopentadienyl group has a substituent such as a hydrocarbon group having 1 to 30 carbon atoms. The transition metal includes zirconium, titanium, hafnium, etc., and zirconium and hafnium are particularly preferred. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and it is preferred that the ligands having each cyclopentadienyl skeleton are bonded to each other by a bridging group. The above transition metal compounds can be used as a catalyst component, either alone or in a mixture of two or more kinds.

[0111] The cocatalyst refers to a catalyst that can effectively use the above-mentioned transition metal compound as a polymerization catalyst or balance the ionic charge in a catalytically activated state. Examples of the cocatalyst include benzene-soluble aluminoxanes of organoaluminum oxy compounds and benzene-insoluble organoaluminum oxy compounds, ion-exchangeable layered silicates, boron compounds, ionic compounds consisting of cations containing or not containing active hydrogen groups and non-coordinating anions, lanthanoid salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing fluoro groups.

[0112] The above-mentioned transition metal compounds may be used by being supported on an inorganic or organic carrier, preferably an inorganic or organic porous oxide, such as montmorillonite or other ion-exchangeable layered silicates, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or mixtures thereof.

[0113] Further, the organometallic compound which is used if necessary is exemplified by organoaluminum compounds, organomagnesium compounds, organozinc compounds, etc. Of these, organoaluminum compounds are preferably used.

[0114] As the polyolefin, a polymer of ethylene or a copolymer of ethylene and an α-olefin may be used alone or in combination of two or more kinds.

[0115] <Acetaldehyde> Acetaldehyde is an important industrial chemical, useful as a raw material for, for example, acetic acid and ethyl acetate.

[0116] Acetaldehyde can be produced by oxidizing ethanol using a conventional method. For example, acetaldehyde can be produced by oxidizing ethanol with chlorine. Chlorine is usually reacted with ethanol in a gaseous state. Chlorine may be supplied at a concentration of approximately 100%, or may be diluted with an inert gas (e.g., nitrogen, helium, neon, argon, etc.). In this case, the degree of dilution is 50% by weight or less, preferably 25% by weight or less, taking into consideration the reaction efficiency. Ethanol and chlorine are preferably reacted at a supply rate of 25 to 100 sccm per 100 g of an aqueous ethanol solution.

[0117] The oxidation of ethanol with chlorine is preferably carried out using a chlorine-containing compound such as chlorine gas, hydrogen chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, thionyl chloride, or a hypochlorous acid compound. This oxidation can be realized, for example, by a photoreaction, a thermal reaction, or a catalytic reaction. Among these, oxidation by photochlorination or thermal chlorination of ethanol with chlorine gas is preferred, and oxidation by photochlorination with chlorine gas is more preferred. As the photoreaction, a method of irradiating light of various wavelengths such as ultraviolet light and visible light can be mentioned, and among these, it is preferred to cause 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, or the like can be used. The reaction temperature is preferably about 0 to 80°C, and preferably about 0 to 50°C. The reaction time is preferably about 1 to 5 hours.

[0118] As another example, ethanol can be oxidized in the gas phase in the presence of oxygen molecules and a catalyst to produce acetaldehyde. As such a catalyst, for example, a base metal oxide with gold particles dispersed and fixed therein can be used. Examples of base metal oxides include La2O3, MoO3, Bi2O3, SrO, Y2O3, MgO, BaO, WO3, CuO, and composite oxides containing one or more of these.

[0119] The oxidation reaction of ethanol is carried out by contacting a gas containing ethanol and oxygen molecules with the catalyst at, for example, 100 to 280°C. The oxygen molecules used in the reaction may be supplied as oxygen gas, or air may be used. The raw material gas may contain a dilution gas (carrier gas) as necessary. The apparatus used in the reaction may be a general apparatus usually used for performing a gas phase reaction. For example, the catalyst is filled in a reaction tube, and the reaction tube is heated to a predetermined temperature, and a gas containing ethanol and oxygen gas or air is sent into the reaction tube, and the raw material gas is brought into contact with the catalyst, and the reaction gas is recovered. The reaction pressure may be normal pressure, and may be pressurized to about 0.5 to 5 Pa (atmosphere) if necessary. As the dilution gas, for example, a so-called inert gas such as nitrogen, argon, helium, or carbon dioxide is used. The amount of the dilution gas used may be appropriately determined taking into consideration the composition, flow rate, and reaction heat of the raw material gas, but it is usually preferable that the dilution gas is 1 to 100 times the volume of ethanol.

[0120] The ratio of ethanol and oxygen molecules (oxygen gas) supplied to the reaction tube is not particularly limited, but is usually 0.5 to 100% by volume of oxygen gas or oxygen gas in the air relative to ethanol, preferably 1 to 10% by volume, and more preferably 2 to 5% by volume. The amount of catalyst used is also not particularly limited, but if the inner diameter of the reaction tube is 6 to 10 mm, it is generally about 0.1 to 1.0 g. In practice, in relation to the gas flow rate, the space velocity (SV) is 10,000 to 40,000 h -1 ml g cat -1It is preferable to use an amount within the range of about 100 to 200 mg / kg.

[0121] Furthermore, acetaldehyde can also 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. The copper as an active species may be in any form that has the activity of converting ethanol to acetaldehyde, and may be in any form of metallic copper (simple substance) or a copper compound (oxide, hydroxide, copper salt (inorganic acid salt such as copper sulfate, copper phosphate, copper nitrate, copper carbonate, etc.; organic acid salt such as copper salt of carboxylic acid, etc.), etc.). The solid catalyst may contain at least one selected from such simple copper and copper compounds. The copper as an active species is preferably in the form of metallic copper. Copper may be used as it is in the form of metallic copper or a copper compound, or may be used in the form supported on a carrier. Note that the copper as an active species may act as the main catalyst of the solid catalyst, and may be used in combination with a co-catalyst, etc. Furthermore, the solid catalyst may be in a form in which both the copper and the co-catalyst are supported on a carrier.

[0122] The above dehydrogenation reaction may be a liquid phase reaction as long as ethanol is brought into contact with a solid catalyst, but is usually a gas phase reaction in which gaseous ethanol is brought into contact with a solid catalyst in the gas phase. In view of the equilibrium relationship between ethanol and acetaldehyde, catalyst life, etc., the reaction temperature may be about 150 to 350°C, preferably 170 to 300°C, and more preferably about 200 to 280°C. The higher the reaction temperature, the more the equilibrium shifts to the acetaldehyde side, and the higher the conversion rate can be. The reaction may be carried out under pressure, but may be carried out under normal pressure for convenience. It may also be carried out under reduced pressure because it is advantageous for the ethanol conversion rate.

[0123] <Acetic acid> Acetic acid is an important industrial chemical, useful as a raw material for, for example, vinyl acetate monomer, acetic anhydride, and acetate esters.

[0124] Acetic acid can be produced by oxidation of acetaldehyde by a conventional method. For example, acetic acid can be produced by air oxidation of acetaldehyde in the presence of a catalyst. Examples of the catalyst include manganese acetate and cobalt acetate.

[0125] <Ethyl t-butyl ether> Ethyl tert-butyl ether (ETBE) is an important chemical used as an industrial raw material. ETBE is useful, for example, as a gasoline substitute, especially as a premium fuel.

[0126] ETBE can be synthesized from ethanol and isobutene by a conventionally known method. 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.

[0127] As the reaction catalyst, it is preferable to use a cation exchange resin, and it is more preferable to use a strongly acidic cation exchange resin. As such a strongly acidic cation exchange resin, a porous type (MR type) styrene-based resin in which a strong acid group such as a sulfonic acid group (-SO3H) is introduced as an ion exchange group is preferable. The particle size 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 even more preferably 4 to 9 g, per 1 mole of ethanol.

[0128] The method of using the reaction catalyst is not particularly limited, and it can be used in the reaction in the form of a fixed bed, a fluidized bed, or a suspension bed. The manner in which isobutene and ethanol are reacted is not particularly limited, but it is preferable to carry out the reaction in a pressurized gas-liquid mixed phase reaction method in which ethanol can be kept in a liquid phase. In this case, the yield of ETBE obtained is further improved.

[0129] <Ester> A wide variety of esters can be synthesized by reacting ethanol with various carboxylic acids. For example, ethyl benzoate can be obtained from ethanol and benzoic acid, and diethylene glycol, a raw material for polyester, can be obtained from ethanol via ethylene. By producing polyethylene using the ethanol of the present invention, it is possible to realize an ultimate resource-recycling society that is not dependent on petroleum resources.

[0130] The polyester is composed of diol units and dicarboxylic acid units, and is obtained by a polycondensation reaction using ethylene glycol as the diol units and terephthalic acid, isophthalic acid, or the like as the dicarboxylic acid units. Ethylene glycol is obtained from the ethanol of the present invention as a raw material, and can be obtained, for example, by a method of producing ethylene glycol from ethanol via ethylene oxide using a conventionally known method.

[0131] As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and examples of derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, and butyl esters. Among these, terephthalic acid is preferred, and examples of derivatives of aromatic dicarboxylic acids include dimethyl terephthalate. Examples of aliphatic dicarboxylic acids include chain or alicyclic dicarboxylic acids having a carbon number of 2 to 40, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. Examples of derivatives of aliphatic dicarboxylic acids include lower alkyl esters such as methyl esters, ethyl esters, propyl esters, and butyl esters of the above aliphatic dicarboxylic acids, and cyclic acid anhydrides of the above aliphatic dicarboxylic acids, such as succinic anhydride. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferred, and those mainly composed of succinic acid are particularly preferred. As the derivatives of aliphatic dicarboxylic acids, methyl esters of adipic acid and succinic acid or a mixture thereof are more preferred.

[0132] The polyester can be obtained by a conventionally known method of polycondensing the above-mentioned diol unit and dicarboxylic acid unit. Specifically, the polyester can be produced by a general melt polymerization method in which an esterification reaction and / or an ester exchange reaction between the above-mentioned dicarboxylic acid component and the diol component is carried out, followed by a polycondensation reaction under reduced pressure, or a known solution heating dehydration condensation method using an organic solvent.

[0133] The polycondensation reaction is preferably carried out in the presence of a polymerization catalyst, and examples of the polymerization catalyst include titanium compounds, zirconium compounds, and germanium compounds.

[0134] The reaction temperature for the esterification reaction and / or transesterification reaction between 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 such as nitrogen or argon.

[0135] In the polycondensation reaction step, a chain extender (coupling agent) may be added to the reaction system. The chain extender is added to the reaction system in a homogeneous molten state without a solvent after the polycondensation is completed, and is reacted with the polyester obtained by the polycondensation.

[0136] After solidification, the resulting polyester may be subjected to solid-phase polymerization as necessary to further increase the degree of polymerization or to remove oligomers such as cyclic trimers.

[0137] In the production process of polyester, various additives may be added within the range that does not impair the properties of the polyester. For example, a plasticizer, an ultraviolet stabilizer, a color inhibitor, a matting agent, a deodorant, a flame retardant, a weather resistance agent, an antistatic agent, a friction reducing agent, a release agent, an antioxidant, an ion exchange agent, a color pigment, etc. may be added.

[0138] The ethanol according to the present invention can be used as a raw material for various other polymers, including but not limited to the above-mentioned polymers, and the molded products of the obtained polymers are carbon-neutral materials, making it possible to realize an ultimate resource-circulating society that is not dependent on petroleum resources.

[0139] <Products containing ethanol> The ethanol according to the present invention can be used not only as a polymer raw material as described above, but also in various products. Examples of such products include chemical products such as cosmetics, perfumes, fuels, antifreeze, bactericides, disinfectants, cleaning agents, mold removers, detergents, hair washes, soaps, antiperspirants, face wash sheets, solvents, paints, adhesives, diluents, and food additives. By using it for these purposes, it can exert an appropriate effect according to the purpose.

[0140] <Fuel> The ethanol according to the present invention can also be used as a raw material for fuels (e.g., jet fuel, kerosene, diesel, gasoline), etc. Since ethanol has high bactericidal properties, it can also function as a bactericide to prevent the proliferation of bacteria in fuel systems such as engines and piping.

[0141] The Japan Automotive Engineers Association standard (2006) specifies that the concentration of ethanol in fuel ethanol must be 99.5% by volume or more. Other countries (e.g., India) also specify that the concentration of ethanol in fuel ethanol must be 99.5% by volume or more. Therefore, ethanol with a purity of 99.5 to 99.9% by volume can be suitably used in ethanol-only vehicles. Furthermore, since fuel ethanol can be used for purposes other than ethanol-only vehicles, ethanol with a purity of 99.5 to 99.9% by volume has particularly high versatility.

[0142] The ethanol according to the present invention can also be mixed with gasoline to produce ethanol-mixed gasoline. By using ethanol-mixed gasoline, the environmental impact can be reduced. The purity of the ethanol used in ethanol-mixed gasoline is 92.0% by volume or more, preferably 95.0% by volume or more, and more preferably 99.5% by volume or more.

[0143] The ethanol content in ethanol-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 even more preferably 3% by volume or more and 10% by volume or less. If the ethanol content is 1% by volume or more, the advantage of improving the octane number by blending ethanol can be obtained, and if it is 15% by volume or less, the evaporation characteristics do not change significantly due to the azeotropic phenomenon with other gasoline base materials, and the appropriate drivability of gasoline automobiles can be ensured.

[0144] The water content in the ethanol-mixed gasoline is preferably 0.01% by mass or more and 0.9% by mass or less, 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 the ethanol, but is substantially about 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 layer allows the gasoline engine to operate properly. The water content can be measured according to "Crude oil and petroleum products - Water content test method" described in JIS K 2275, and for example, Karl Fischer coulometric titration method can be used.

[0145] As the gasoline base stock, any gasoline base stock that is normally used can be used, and is not particularly limited. For example, the gasoline base stock may be light naphtha obtained by distilling crude oil at atmospheric pressure, preferably desulfurized light naphtha obtained by desulfurizing it, catalytic reformed gasoline obtained by catalytic reforming after desulfurizing heavy naphtha, and benzene-free catalytic reformed gasoline obtained by debenzene treatment, benzene-free light catalytic reformed gasoline, benzene-free heavy catalytic reformed gasoline, and mixtures thereof, cracked gasoline obtained by catalytic cracking or hydrocracking, light cracked gasoline, heavy cracked gasoline, and mixtures thereof, isomerized gasoline obtained by isomerizing light naphtha, etc.

[0146] Furthermore, the ETBE made from ethanol according to the present invention can be mixed with gasoline to produce ETBE-blended gasoline. Using ETBE-blended gasoline can reduce the environmental impact. The ETBE content of 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 even more preferably 3% by volume or more and 10% by volume or less. If the ETBE content is 1% by volume or more, the advantage of improving the octane number by blending ETBE can be obtained, and if it is 15% by volume or less, the evaporation characteristics do not change significantly due to the azeotropic phenomenon with other gasoline base materials, and the appropriate drivability of gasoline-powered automobiles can be ensured. EXAMPLES

[0147] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

[0148] <Ethanol Component Evaluation Method> In the following examples and comparative examples, the component evaluation of ethanol was measured using a gas chromatography device (GC-2014, manufactured by SHIMADZU Corporation) by the GC / MS method. The measurement conditions were as follows. <Analysis Conditions of GC / MS Method> Column: DB-5MS (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Oven temperature: 40°C → 10°C / min → 300°C Carrier gas: He (1.28 mL / min) Inlet temperature: 300°C Detector temperature: 300°C Detector: Flame ionization detector Injection volume: 1 μL (split ratio 1:20)

[0149] <Butadiene Quantification Method> The quantitative evaluation of butadiene was performed by analysis using a gas chromatography device (GC-2014, manufactured by SHIMADZU Corporation). The measurement conditions were as follows. <Analysis Conditions of GC / MS Method> Column: Rt-Q-BOND (length 30 m, inner diameter 0.32 mm, film thickness 10 μm) Oven temperature: 60°C, 11.5 minutes → 10°C / min → 100°C, 14.5 minutes → 10°C / min → 250°C Sampling time: 5 minutes Carrier gas: He (30 cm / s) Split ratio: 75

[0150] <Ethyl Benzoate Quantification Method> The quantitative evaluation of ethyl benzoate was performed by analysis using a gas chromatography device. The measurement conditions were as follows. <Analysis Conditions of GC / MS Method> Column: DB-1 (length 30.0 m, inner diameter 0.254 mm, film thickness 0.25 m) Temperature rise conditions: 30℃-300℃ 15℃ / min Carrier gas: He 100kPa Split ratio: 50

[0151] <Combustion efficiency quantification method> The quantitative evaluation of the combustion efficiency of ethanol was carried out by total calorific value analysis using a cone calorimeter manufactured by FTT.

[0152] [Example 1] <Preparation of ethanol> Ethanol was produced as follows. (Raw material gas generation process) The gas discharged after incineration of general waste in a waste incineration facility was used. The raw gas consisted of approximately 30% by volume of carbon monoxide, approximately 30% by volume of carbon dioxide, approximately 30% by volume of hydrogen, and approximately 10% by volume of nitrogen.

[0153] (Synthetic gas refining process) The raw material gas produced as described above was heated to 80°C using a PSA apparatus, which is an impurity removal device, and the carbon dioxide contained in the synthesis gas was removed so that the carbon dioxide content was 60 to 80% by volume of the original content (approximately 30% by volume).The gas was then heated in a double-pipe heat exchanger using steam at 150°C and re-cooled using a double-pipe heat exchanger using cooling water at 25°C to precipitate impurities, which were then removed using a filter, thereby producing a synthesis gas.

[0154] (Microbial fermentation process) The synthesis gas obtained as described above was continuously supplied to a continuous fermentation apparatus (microbial fermentation tank) equipped with a main reactor, synthesis gas supply port, and discharge port, and filled with a seed culture of Clostridium autoethanogenum (a microorganism) and a liquid medium for bacterial culture (containing appropriate amounts of phosphorus compounds, nitrogen compounds, various minerals, etc.), and the culture (microbial fermentation) was carried out continuously for 300 hours. After that, about 8000 L of the culture liquid containing ethanol was extracted from the discharge port.

[0155] (separation process) The culture liquid obtained in the above fermentation step was subjected to a solid-liquid separation filter device under conditions of a culture liquid introduction pressure of 200 kPa or more to obtain an ethanol-containing liquid.

[0156] (Distillation process) The ethanol-containing liquid was then introduced into a distillation apparatus equipped with a heater using steam at 170° C. After the temperature of the bottom of the distillation column was raised to 101° C. within 8 to 15 minutes, the ethanol-containing liquid was introduced from the middle of the distillation column, and during continuous operation, the column was continuously operated at 101° C. at the bottom, 99° C. at the middle, and 91° C. at the top at 15 sec / L to obtain purified ethanol.

[0157] (Ethanol component evaluation) The results of gas chromatographic analysis of the ethanol obtained as described above are shown in Figure 1 and Figure 2 (enlarged view). The peak with a retention time of 15 minutes 00 seconds to 15 minutes 15 seconds was confirmed to be derived from n-hexadecane, since the retention time matched that of a standard sample of n-hexadecane (C16). The content of n-hexadecane in the obtained ethanol was 0.05 mg / L.

[0158] (Butadiene manufacturing method) Butadiene was produced using the ethanol obtained as described above. First, the obtained ethanol was vaporized through a single tube heated to 90°C to prepare a gas to be used in the reaction, and the vaporized ethanol gas was merged with nitrogen. The flow rate of the ethanol gas was controlled by mass flow so that the SV of the ethanol gas was 360 L / hr / L and the SV of the nitrogen was 840 L / hr / L, thereby producing a mixed gas of 30% by volume (gas equivalent) of ethanol and 70% by volume (gas equivalent). Next, a butadiene-containing gas was obtained by continuously supplying the mixed gas to a cylindrical reaction tube made of stainless steel with a diameter of 1 / 2 inch (1.27 cm) and a length of 15.7 inches (40 cm) and filled with 0.85 g of a butadiene synthesis catalyst mainly composed of Hf, Zn, and Ce, while maintaining the temperature at 350°C and the pressure (pressure of the reaction bed) at 0.1 MPa. The butadiene content of the obtained butadiene-containing gas was quantified using a gas chromatography apparatus GC-2014 (manufactured by Shimadzu Corporation). The results are shown in Table 1.

[0159] [Comparative Example 1] Butadiene was produced in the same manner as in Example 1 using 99% ethanol (manufactured by Amakasu Chemical Industry Co., Ltd.), which is fossil fuel-derived ethanol, and the butadiene content was quantified in the same manner as in Example 1. The results are shown in Table 1. The components of the ethanol used were evaluated in the same manner as in Example 1. The results of the gas chromatographic analysis are shown in Figure 1. In an enlarged view of the gas chromatograph (not shown), no peaks derived from n-hexadecane with retention times of 15 minutes 00 seconds to 15 minutes 15 seconds were detected.

[0160] [Comparative Example 2] Butadiene was produced in the same manner as in Example 1 using 99% ethanol (manufactured by Amakasu Chemical Industry Co., Ltd.) derived from the saccharification and fermentation of plants, and the butadiene content was quantified in the same manner as in Example 1. The results were as shown in Table 1. The components of the ethanol used were evaluated in the same manner as in Example 1. The results of the gas chromatographic analysis were as shown in Figure 1. In an enlarged view of the gas chromatograph (not shown), no peaks derived from n-hexadecane with retention times of 15 minutes 00 seconds to 15 minutes 15 seconds were detected.

[0161] [Table 1]

[0162] As shown in Table 1, ethanol produced from the gas emitted after incinerating general waste in a waste incineration facility has a higher conversion efficiency to butadiene than ethanol derived from conventional fossil fuels or ethanol derived from saccharification and fermentation of plants.

[0163] [Example 2] (Production of Ethyl Benzoate) Ethyl benzoate was produced as follows using the same ethanol as used in Example 1. First, 36.8 g of benzoic acid and 200 ml of ethanol were mixed under an argon stream, and 9 ml of concentrated sulfuric acid was added and stirred for 5 hours under reflux. After that, it was allowed to cool to room temperature, and unreacted ethanol was removed under reduced pressure, and ethyl benzoate synthesized with 100 ml of diethyl ether was recovered. The recovered liquid was washed with distilled water, dried using magnesium sulfide, and then filtered and concentrated. The obtained filtrate was subjected to component analysis using a gas chromatograph to quantitatively determine the amount of ethyl benzoate synthesized. The analysis conditions are shown below. The analysis results are shown in Table 2. Column: DB-1 (length 30.0 m, inner diameter 0.254 mm, film thickness 0.25 m) Temperature rise conditions: 30-300℃ 15℃ / min Carrier gas: He 100kPa Split ratio: 50

[0164] [Comparative Example 3] Ethyl benzoate was produced and quantified in the same manner as in Example 2, except that the petrochemically derived ethanol used in Comparative Example 1 was used. The analytical results are shown in Table 2.

[0165] [Comparative Example 4] Ethyl benzoate was produced and quantified in the same manner as in Example 2, except that the petrochemically derived ethanol used in Comparative Example 2 was used. The analytical results are shown in Table 2.

[0166] [Table 2]

[0167] As shown in Table 2, ethanol produced from the gas emitted after incinerating general waste in a waste incineration facility was found to have a higher conversion efficiency to ethyl benzoate than ethanol derived from conventional fossil fuels or ethanol derived from saccharification and fermentation of plants.

[0168] [Example 3] The combustion efficiency of ethanol was quantified using the same ethanol as used in Example 1. The fuel efficiency was quantified by adding 30 g of ethanol to a heat-resistant container measuring 60 mm long x 60 mm wide x 30 mm high under non-heated conditions, igniting it, measuring the amount of oxygen lost until the ethanol was completely burned in a cone calorimeter (manufactured by FTT), and calculating the total calorific value based on the amount of oxygen lost. The quantitative results are shown in Table 3.

[0169] [Comparative Example 5] The combustion efficiency of ethanol was quantified in the same manner as in Example 3, except that the ethanol used in Comparative Example 1 was used. The quantitative results are shown in Table 3.

[0170] [Comparative Example 6] The combustion efficiency of ethanol was quantified in the same manner as in Example 3, except that the ethanol used in Comparative Example 2 was used. The quantitative results are shown in Table 3.

[0171] [Table 3]

[0172] As shown in Table 3, ethanol produced from the gas emitted after burning general waste in waste incineration facilities has higher combustion efficiency than ethanol derived from conventional fossil fuels or ethanol derived from saccharification and fermentation of plants.

Claims

1. A waste-derived ethanol composition obtained by a method comprising: a step of generating a raw material gas containing carbon monoxide and hydrogen by gasifying waste as a carbon source; a step of purifying the raw material gas using a pressure swing adsorption separation device to obtain a synthesis gas containing carbon monoxide and hydrogen; a microbial fermentation step of supplying the synthesis gas to a fermenter containing Clostridium bacteria as microorganisms and obtaining an ethanol-containing liquid by microbial fermentation; a separation step of separating the ethanol-containing liquid into microorganisms and / or microbial-derived proteins and ethanol; and a purification step of purifying the ethanol composition, wherein In a gas chromatograph measured under the following conditions using gas chromatography-mass spectrometry (GC / MS), The retention time peaks between 15 minutes 00 seconds and 15 minutes 15 seconds. A waste-derived ethanol composition having the following characteristics. <Analysis conditions for GC / MS method> Column: DB-5MS (length 30m, inner diameter 0.25mm, film thickness 0.25μm) Oven temperature: 40°C → 10°C / minute → 300°C Carrier gas: He (1.28 mL / min) Inlet temperature: 300℃ Detector temperature: 300°C Detector: Flame ionization detector Injection volume: 1 μL (split ratio 1:20)

2. A waste-derived ethanol composition obtained by a method comprising: a step of generating a raw material gas containing carbon monoxide and hydrogen by gasifying waste as a carbon source; a step of purifying the raw material gas using a pressure swing adsorption separation device to obtain a synthesis gas containing carbon monoxide and hydrogen; a microbial fermentation step of supplying the synthesis gas to a fermenter containing Clostridium bacteria as microorganisms and obtaining an ethanol-containing liquid by microbial fermentation; and a purification step of purifying the ethanol-containing liquid after removing the microorganisms, wherein In a gas chromatograph measured under the following conditions using gas chromatography-mass spectrometry (GC / MS), The retention time peaks between 15 minutes 00 seconds and 15 minutes 15 seconds. A waste-derived ethanol composition having the following characteristics. <Analysis conditions for GC / MS method> Column: DB-5MS (length 30m, inner diameter 0.25mm, film thickness 0.25μm) Oven temperature: 40°C → 10°C / minute → 300°C Carrier gas: He (1.28 mL / min) Inlet temperature: 300℃ Detector temperature: 300°C Detector: Flame ionization detector Injection volume: 1 μL (split ratio 1:20)

3. The waste-derived ethanol composition according to claim 1 or 2, wherein the retention time peak between 15 minutes 00 seconds and 15 minutes 15 seconds is derived from n-hexadecane.

4. The waste-derived ethanol composition according to claim 3, wherein the concentration of n-hexadecane is 0.01 mg / L or more and 1.0 mg / L or less.

5. A step of generating a raw material gas containing carbon monoxide and hydrogen by gasifying waste as a carbon source, The process involves purifying the aforementioned raw material gas using a pressure swing adsorption separation device to obtain synthesis gas containing carbon monoxide and hydrogen. The synthesis gas is supplied to a fermenter containing Clostridium bacteria as microorganisms, and a microbial fermentation step is taken to obtain an ethanol-containing liquid by microbial fermentation. A separation step of separating the ethanol-containing solution into microorganisms and / or proteins derived from microorganisms and ethanol, A purification process for purifying the ethanol composition and Includes, The purified ethanol composition is In a gas chromatograph measured under the following conditions using gas chromatography-mass spectrometry (GC / MS), The retention time peaks between 15 minutes 00 seconds and 15 minutes 15 seconds. A method for producing a waste-derived ethanol composition having the following characteristics. <Analysis conditions for GC / MS method> Column: DB-5MS (length 30m, inner diameter 0.25mm, film thickness 0.25μm) Oven temperature: 40°C → 10°C / minute → 300°C Carrier gas: He (1.28 mL / min) Inlet temperature: 300℃ Detector temperature: 300°C Detector: Flame ionization detector Injection volume: 1 μL (split ratio 1:20)

6. A step of generating a raw material gas containing carbon monoxide and hydrogen by gasifying waste as a carbon source, The process involves purifying the aforementioned raw material gas using a pressure swing adsorption separation device to obtain synthesis gas containing carbon monoxide and hydrogen. The synthesis gas is supplied to a fermenter containing Clostridium bacteria as microorganisms, and a microbial fermentation step is taken to obtain an ethanol-containing liquid by microbial fermentation. A purification step is performed to purify the ethanol-containing solution after removing the microorganisms. Includes, The purified ethanol composition is In a gas chromatograph measured under the following conditions using gas chromatography-mass spectrometry (GC / MS), The retention time peaks between 15 minutes 00 seconds and 15 minutes 15 seconds. A method for producing a waste-derived ethanol composition having the following characteristics. <Analysis conditions for GC / MS method> Column: DB-5MS (length 30m, inner diameter 0.25mm, film thickness 0.25μm) Oven temperature: 40°C → 10°C / minute → 300°C Carrier gas: He (1.28 mL / min) Inlet temperature: 300℃ Detector temperature: 300°C Detector: Flame ionization detector Injection volume: 1 μL (split ratio 1:20)

7. A method for producing a waste-derived ethanol composition according to claim 5 or 6, wherein the retention time peak between 15 minutes 00 seconds and 15 minutes 15 seconds is derived from n-hexadecane.

8. The method for producing a waste-derived ethanol composition according to claim 7, wherein the concentration of n-hexadecane is 0.01 mg / L or more and 1.0 mg / L or less.

9. The waste-derived ethanol composition according to claim 1 or 2, for use in chemical products.

10. A waste-derived ethanol composition according to claim 1 or 2, for use as fuel.

11. The waste-derived ethanol composition according to claim 1 or 2, for use as a polymer raw material.

12. A chemical product made from the waste-derived ethanol composition described in Claim 1 or 2.

13. A fuel comprising the waste-derived ethanol composition according to claim 1 or 2 and / or ethyl-t-butyl ether made from the waste-derived ethanol composition according to claim 1 or 2.

14. Ethanol-blended gasoline comprising the waste-derived ethanol composition according to claim 1 or 2 and gasoline.

15. The ethanol-mixed gasoline according to claim 14, wherein the amount of water in the ethanol-mixed gasoline is 0.01% by mass or more and 0.9% by mass or less.

16. A polymer raw material made from the waste-derived ethanol composition according to claim 1 or 2.

17. The polymer raw material according to claim 16, selected from the group consisting of ethylene, propylene, butadiene, ethyl acetate, isobutene, methyl (meth)acrylate, acrylic acid, aminohexanoic acid, and diethyl carbonate.

18. A polymer made from the polymer raw material described in claim 16 or 17.

19. A molded article made of the polymer according to claim 18.

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