JP2021004192A - ethanol - Google Patents

Abstract

To provide ethanol containing a specific organic component.SOLUTION: Ethanol of the invention contains dialkyl ether of 0.1 mg/L or more and 100 mg/L or less.SELECTED DRAWING: None

Description

The present invention relates to ethanol, and more particularly to ethanol in which the content of a specific trace component is adjusted. Furthermore, the present invention relates to a novel resource-recycling ethanol using a gas containing carbon monoxide and hydrogen as a substrate, which is not derived from conventional petroleum resources or biomass resources.

Petrochemical products are used in many parts of our lives. On the other hand, since it is a familiar product, it is a big problem on a global scale that it causes various environmental problems due to mass production and mass consumption. For example, polyethylene and polyvinyl chloride, which are representative of petrochemical industrial products, are consumed in large quantities and thrown away, and these wastes are a major cause of environmental pollution. In addition, concerns about the depletion of fossil fuel resources and the global environmental problem of increased carbon dioxide in the atmosphere are being discussed in the mass production of petrochemical industrial products.

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 a raw material for petrochemical industrial products, have been studied. For example, a method of producing bioethanol from an edible raw material such as corn by a sugar fermentation method has attracted attention. However, it has been pointed out that the sugar fermentation method using such edible raw materials causes problems such as soaring food prices because the limited agricultural land area is used for production other than food.

In order to solve this problem, it is also considered to use non-edible raw materials that have been conventionally discarded. Specifically, a method of producing alcohols by a fermentation method using waste materials or cellulose derived from waste paper as non-edible raw materials, or a method of gasifying the above-mentioned biomass raw materials and using a catalyst from synthetic gas to alcohol. Although methods for producing the same kind have been proposed, they have not yet been put into practical use. Moreover, even if various petrochemical products can be produced from these demineralized raw materials, they will eventually become waste plastics that do not decompose naturally, so it can be said that they are not effective as a drastic solution to environmental problems. ..

By the way, the amount of combustible waste currently disposed of in Japan amounts to about 60 million tons / year. The amount of energy is equivalent to about 200 trillion kcal, which greatly exceeds the amount of energy possessed by naphtha for plastic raw materials in Japan, and it can be said that these garbage are also heavy resources. If these waste resources can be converted into petrochemical products, it will be possible to realize the ultimate resource recycling society that does not depend on petroleum resources. From the above viewpoint, Patent Documents 1 and 2 and the like disclose a technique for producing a synthetic gas (a gas containing CO and H ₂ as a main component) from waste and producing ethanol from the synthetic gas by a fermentation method. There is.

However, as pointed out in Patent Document 3, the syngas produced from waste contains a wide variety of impurities that have not been elucidated, and some of them are toxic to microorganisms. Therefore, the productivity of alcohol produced from synthetic gas by microbial fermentation has been a big issue. In addition, alcohol obtained by microbial fermentation of synthetic gas also contains various components caused by impurities in the synthetic gas, and these components cannot be completely removed by purification treatment such as distillation. Therefore, the development of derivative products from alcohols obtained by microbial fermentation of synthetic gas has been a major technical issue.

Japanese Unexamined Patent Publication No. 2016-059296 International Publication 2015-037710 Japanese Unexamined Patent Publication No. 2018-058042

According to the studies by the present inventors, for example, the conventional C2 raw material represented by ethanol is known as a starting material for various chemical products, but as described above, it does not depend on petroleum resources or biomass resources. It was found that alcohol produced from resources (recycling resources) contains various trace amounts of unknown substances, unlike chemical raw materials derived from naphtha. However, in the prior art, the properties of substances are also unknown, and in the past, sufficient studies have not been made as to whether all substances should be removed or only specific substances should be removed. Therefore, even if alcohol produced from a recycling-oriented resource is proposed in the above patent document, there is still room for technological improvement in order to put the alcohol into practical use.

On the other hand, according to the above document, although a general fermentation / distillation method and an optimum composition of a synthetic gas are disclosed, details of the process and the like are not described, and even the obtained alcohol substance is specified. Not even done.

Therefore, the present invention has been made in view of such background technology, and an object of the present invention is to provide a practical novel alcohol having industrial value more than existing petrochemical raw materials and a derivative product thereof.

As a result of diligent studies to solve the above problems, the present inventors have identified a wide variety of trace substances contained in alcohol produced from recycling-oriented resources, and further determined the content by a novel production method. It has become possible to control to a specific range, and in addition, it has been found that the various derivatives exert superior effects as compared with existing petrochemical-derived alcohols. For example, in the step of synthesizing butadiene from ethanol, the ethanol conversion rate is improved as compared with the case of using conventional ethanol derived from petrification, and an alcohol at a practical level equal to or higher than that of alcohol derived from petrification can be obtained. The heading led to the present invention.

More specifically, when ethanol was produced from a gas substrate containing carbon monoxide and hydrogen whose carbon source was waste, the fact that butadiene was synthesized from the ethanol improved the conversion rate of ethanol was found, and the reason for this was found. Upon closer examination, it was found that ethanol derived from a circulating resource whose substrate is a gas containing carbon monoxide and hydrogen contains a trace amount of organic components. The present invention is based on such findings.

That is, the present invention includes the following gist.
[1] Ethanol having a dialkyl ether content of 0.1 mg / L or more and 100 mg / L or less.
[2] The ethanol according to [1], which uses a gas containing carbon monoxide and hydrogen as a substrate.
[3] The ethanol according to [1] or [2], which is derived from microbial fermentation.
[4] The ethanol according to any one of [1] to [3], wherein the dialkyl ether contains at least one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, and dipentyl ether. ..
[5] The ethanol according to [2], wherein the gas containing carbon monoxide and hydrogen is derived from waste.
[6] A step of converting a carbon source into a synthetic gas containing carbon monoxide and hydrogen, and
A microbial fermentation step in which the synthetic gas containing carbon monoxide and hydrogen is supplied to a microbial fermentation tank 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,
A purification step of purifying ethanol from the liquid material obtained in the liquefaction step, and
Including
A method for producing ethanol, wherein the content of dialkyl ether in the purified ethanol is 0.1 mg / L or more and 100 mg / L or less.
[7] The method according to [6], further comprising a step of purifying the synthetic gas.
[8] The method according to [6] or [7], wherein the carbon source is derived from waste.
[9] The ethanol according to any one of [1] to [5], which is used for chemical products.
[10] The ethanol according to any one of [1] to [5], which is used as a fuel.
[11] Ethanol according to any one of [1] to [5] for polymer raw materials.
[12] A chemical product using ethanol as a raw material according to any one of [1] to [5].
[13] A fuel containing the ethanol according to any one of [1] to [5] and / or the ethyl-t-butyl ether made from the ethanol according to any one of [1] to [5].
[14] The polymer raw material using ethanol as a raw material according to any one of [1] to [5].
[15] The polymer raw material according to [14], which is selected from the group consisting of ethylene, propylene, butadiene, ethyl acetate, isobutylene, methyl (meth) acrylate, acrylic acid, aminohexanoic acid, and diethyl carbonate.
[16] A polymer made from the polymer raw material according to [14] or [15].
[17] A molded product made of the polymer according to [16].

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

The ethanol according to the present invention includes, for example, butadiene, ethylene, propylene, isobutene, acetaldehyde, acetic acid, ethyl acetate, methyl (meth) acrylate, ethyl-t-butyl ether ethylene glycol, ester composition, polyester, acrylic acid, amino. Hexanoic acid, diethyl carbonate, polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyisobutylene, polymethylmethacrylate (PMMA), ethylene propylene diene rubber (EPDM), polybutylene terephthalate (PBT), polyethylene furanoate. (PEF), polyurethane (PU) and the like can be used as a raw material for production. The ethanol according to the present invention includes cosmetics, perfumes, fuels, antifreezes, bactericides, disinfectants, cleaning agents, mold removers, detergents, hair wash agents, soaps, antiperspirants, face wash sheets, solvents, paints, adhesives, etc. It can be used for various uses of chemical products such as diluents and food additives.

Hereinafter, an example of a preferred embodiment of the present invention will be described. However, the following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments.

<Definition>
In the present invention, "ethanol" does not mean pure ethanol as a compound (chemical formula: ethanol represented by CH ₃ CH ₂ OH), but is inevitably contained in ethanol produced through synthesis or purification. It shall mean a composition containing impurities (contaminants).

<Ethanol>
The content (total) of dialkyl ether in ethanol according to the present invention is 0.1 mg / L or more and 100 mg / L or less. Examples of dialkyl ethers include dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, and dipentyl ether. Only one of these may be included, or two or more thereof may be included. The dialkyl ether preferably contains dibutyl ether.

The content (total) of dialkyl ether contained in ethanol is preferably 1.0 mg / L or more, more preferably 2.0 mg / L or more, still more preferably 5.0 mg / L, based on the total ethanol. Above, even more preferably 10.0 mg / L or more, preferably 80 mg / L or less, more preferably 60 mg / L or less, still more preferably 50 mg / L or less, still more preferably 30 mg / L or less. Is. When the content of dialkyl ether is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material can be improved, or the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid can be improved. It can be improved or the combustion efficiency when ethanol is used as a fuel can be improved.

When dibutyl ether is contained in ethanol, the content of dibutyl ether is preferably 1.0 mg / L or more, more preferably 2.0 mg / L or more, still more preferably 5.0 mg / L or more with respect to ethanol. L or more, still more preferably 10.0 mg / L or more, preferably 80 mg / L or less, more preferably 60 mg / L or less, still more preferably 50 mg / L or less, still more preferably 30 mg / L. It is as follows. When the content of dibutyl ether is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material can be improved, or the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid can be improved. It can be improved or the combustion efficiency when ethanol is used as a fuel can be improved.

The ethanol according to the present invention is preferably ethanol using a gas containing carbon monoxide and hydrogen as a substrate, or ethanol derived from microbial fermentation. This is because it is convenient in the manufacturing process to contain the aromatic compound at the above concentration in these ethanols. Here, ethanol having 100% purity, that is, containing no impurities, does not contain dialkyl ether at the above concentration. In addition, although commercially available industrial ethanol derived from fossil fuels and ethanol produced by a fermentation method using a biomass raw material such as cellulose do not contain aromatic compounds at the above concentrations, they should have the above concentrations. May be added with an aromatic compound.

Although not bound by theory, ethanol derived from microbial fermentation using a gas containing carbon monoxide and hydrogen as a substrate uses various synthetic gases other than carbon monoxide and hydrogen in the manufacturing process. It is thought that it contains trace components of. Therefore, it is difficult to remove all impurities even if the alcohol is obtained through a purification process such as distillation, and it is considered that the alcohol inevitably contains an organic substance. In the present invention, by containing these unavoidable substances in ethanol, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or ethanol is added to carboxylic acid to synthesize a carboxylic acid ester. It is considered that the reaction rate can be improved and the combustion efficiency when ethanol is used as a fuel can be improved.

The ethanol of the present invention is obtained by extracting an ethanol-containing liquid obtained from a microbial fermenter and further purifying it as described later, but it contains other components in addition to the above-mentioned unavoidable substances. May be good. For example, a trace amount of aromatic compound may be contained. Examples of the aromatic compound include toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene, and only one of these may be contained, or two or more of them may be contained. The aromatic compound preferably contains ethylbenzene.

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, and further preferably 0. It is 7 mg / L or more, more preferably 1.0 mg / L or more, preferably 10 mg / L or less, more preferably 7 mg / L or less, still more preferably 5 mg / L or less. Even more preferably, it is 3 mg / L or less. When the content of the aromatic compound is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or the reaction rate when ethanol is added to carboxylic acid to synthesize carboxylic acid ester. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

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, still more preferably 0.3 mg, based on the total ethanol. / L or more, still more preferably 0.5 mg / L or more, preferably 5 mg / L or less, more preferably 3 mg / L or less, still more preferably 2 mg / L or less. Even more preferably, it is 1 mg / L or less. When the content of ethylbenzene is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, and the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid is improved. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

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, still more preferably 0.03 mg, based on the total ethanol. / L or more, still more preferably 0.05 mg / L or more, preferably 1 mg / L or less, more preferably 0.5 mg / L or less, still more preferably 0.2 mg / L. It is less than or equal to, and even more preferably 0.1 mg / L or less. When the toluene content is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, and the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid is improved. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

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, still more preferably 0.2 mg / L or more, based on the total ethanol. Is 0.3 mg / L or more, more preferably 0.5 mg / L or more, preferably 5 mg / L or less, more preferably 3 mg / L or less, still more preferably 2 mg / L. It is less than or equal to, and even more preferably 1 mg / L or less. When the content of o-xylene is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or the reaction rate when ethanol is added to carboxylic acid to synthesize carboxylic acid ester. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When m-xylene and / or p-xylene is contained in ethanol, the content (sum) of m-xylene and / or p-xylene is preferably 0.2 mg / L or more with respect to the total ethanol. , More preferably 0.3 mg / L or more, still more preferably 0.4 mg / L or more, even more preferably 0.5 mg / L or more, and preferably 5 mg / L or less. It is preferably 3 mg / L or less, more preferably 2 mg / L or less, and even more preferably 1 mg / L or less. When the content of m-xylene and / or p-xylene is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or ethanol is added to carboxylic acid to form a carboxylic acid ester. It is possible to improve the reaction rate at the time of synthesis and improve the combustion efficiency when ethanol is used as a fuel.

Further, the ethanol according to the present invention may further contain a trace amount of an aliphatic hydrocarbon. Examples of the aliphatic hydrocarbon include n-hexane, n-heptane, n-octane, n-decane, n-dodecane, n-tetradecane, hexadecane and the like, and only one of these may be contained. Two or more types may be included. The aliphatic hydrocarbon preferably contains one or more of n-hexane, n-decane, and n-dodecane.

The content (total) of aliphatic hydrocarbons contained in ethanol is preferably 0.16 mg / L or more, preferably 0.2 mg / L or more, and more preferably 0.3 mg / L or more with respect to the total ethanol. It is L or more, more preferably 0.5 mg / L or more, and 10 mg / L or less, preferably 7 mg / L or less, more preferably 5 mg / L or less, still more preferably 3 mg / L or less. When the content of the aliphatic hydrocarbon is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or the reaction when ethanol is added to carboxylic acid to synthesize carboxylic acid ester. It is possible to improve the rate and improve the combustion efficiency when ethanol is used as a fuel.

When n-hexane is contained in ethanol, the content of n-hexane is preferably 0.1 mg / L or more, more preferably 0.2 mg / L or more, and further preferably 0.2 mg / L or more, based on the total ethanol. Is 0.3 mg / L or more, more preferably 0.5 mg / L or more, preferably 5 mg / L or less, more preferably 3 mg / L or less, still more preferably 2 mg / L. It is less than or equal to, and even more preferably 1 mg / L or less. When the content of n-hexane is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or the reaction rate when ethanol is added to carboxylic acid to synthesize carboxylic acid ester. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When n-heptane is contained in ethanol, the content of n-heptane is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, still more preferably 0.02 mg / L or more, based on the total ethanol. Is 0.03 mg / L or more, more preferably 0.05 mg / L or more, preferably 1 mg / L or less, more preferably 0.5 mg / L or less, still more preferably 0. It is .2 mg / L or less, and even more preferably 0.1 mg / L or less. When the content of n-heptane is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or the reaction rate when ethanol is added to carboxylic acid to synthesize carboxylic acid ester. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When n-octane is contained in ethanol, the content of n-octane is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, still more preferably 0.02 mg / L or more, based on the total ethanol. Is 0.03 mg / L or more, more preferably 0.05 mg / L or more, preferably 1 mg / L or less, more preferably 0.5 mg / L or less, still more preferably 0. It is .2 mg / L or less, and even more preferably 0.1 mg / L or less. When the content of n-octane is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or the reaction rate when ethanol is added to carboxylic acid to synthesize carboxylic acid ester. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When n-decane is contained in ethanol, the content of n-decane is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, still more preferably 0.02 mg / L or more, based on the total ethanol. Is 0.03 mg / L or more, more preferably 0.05 mg / L or more, and preferably 1 mg / L or less, more preferably 0.5 mg / L or less, still more preferably 0. It is .2 mg / L or less, and even more preferably 0.1 mg / L or less. When the content of n-decane is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or the reaction rate when ethanol is added to carboxylic acid to synthesize carboxylic acid ester. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When n-dodecane is contained in ethanol, the content of n-dodecane is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, still more preferably 0.02 mg / L or more, based on the total ethanol. Is 0.03 mg / L or more, more preferably 0.05 mg / L or more, preferably 1 mg / L or less, more preferably 0.5 mg / L or less, still more preferably 0. It is .2 mg / L or less, and even more preferably 0.1 mg / L or less. When the content of n-dodecane is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or the reaction rate when ethanol is added to carboxylic acid to synthesize carboxylic acid ester. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When n-tetradecane is contained in ethanol, the content of n-tetradecane is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, still more preferably 0.02 mg / L or more, based on the total ethanol. Is 0.03 mg / L or more, more preferably 0.05 mg / L or more, preferably 1 mg / L or less, more preferably 0.5 mg / L or less, still more preferably 0. It is .2 mg / L or less, and even more preferably 0.1 mg / L or less. When the content of n-tetradecane is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, or the reaction rate when ethanol is added to carboxylic acid to synthesize carboxylic acid ester. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When hexadecane is contained in ethanol, the content of hexadecane is preferably 0.01 mg / L or more, more preferably 0.02 mg / L or more, still more preferably 0.03 mg, based on the total ethanol. / L or more, still more preferably 0.05 mg / L or more, preferably 1 mg / L or less, more preferably 0.5 mg / L or less, still more preferably 0.2 mg / L. It is less than or equal to, and even more preferably 0.1 mg / L or less. When the content of hexadecane is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, and the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid is improved. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

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

When Si is contained in ethanol, the content of Si is preferably 10 mg / L or more, more preferably 20 mg / L or more, still more preferably 30 mg / L or more, and more preferably 30 mg / L or more with respect to ethanol. , It is preferably 100 mg / L or less, more preferably 90 mg / L or less, and further preferably 80 mg / L or less. The Si content is the Si element equivalent amount of the Si compound. When the Si content is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, and the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid is improved. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

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, still more preferably 2.0 mg / L or more with respect to ethanol. It is L or more, more preferably 2.5 mg / L or more, preferably 10 mg / L or less, more preferably 7 mg / L or less, still more preferably 5 mg / L or less. The K content is the K element equivalent amount of the K compound. When the K content is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, and the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid is improved. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When Na is contained in ethanol, the content of Na is preferably 150 mg / L or more, more preferably 170 mg / L or more, still more preferably 190 mg / L or more, and more preferably 190 mg / L or more, with respect to ethanol. It is preferably 1000 mg / L or less, more preferably 500 mg / L or less, further preferably 400 mg / L or less, and even more preferably 300 mg / L or less. The Na content is the Na element equivalent amount of the Na compound. When the Na content is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, and the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid is improved. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When Fe is contained in ethanol, the Fe content is preferably 2.0 mg / L or less, more preferably 1.5 mg / L or less, still more preferably 1.0 mg / L with respect to ethanol. It is less than or equal to, and even more preferably 0.5 mg / L or less. The Fe content is an Fe element equivalent amount of the Fe compound. When the Fe content is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, and the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid is improved. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

When Cr is contained in ethanol, the content of Cr is preferably 0.6 mg / L or less, more preferably 0.5 mg / L or less, based on ethanol. The Cr content is the Cr element equivalent amount of the Cr compound. When the Cr content is within the above numerical range, the ethanol conversion rate when synthesizing butadiene using ethanol as a raw material is improved, and the reaction rate when synthesizing a carboxylic acid ester by adding ethanol to a carboxylic acid is improved. It is possible to improve the combustion efficiency when ethanol is used as a fuel.

The ethanol of the present invention contains the above-mentioned inorganic components and, if desired, a trace amount of organic components such as aromatic hydrocarbons and aliphatic hydrocarbons, and is the main component of ethanol (as a compound). The concentration of (pure ethanol) is 75% by volume or more, preferably 80% by volume or more, more preferably 90% by volume or more, still more preferably 95% by volume or more, still more preferably 98% by volume, based on the total ethanol. % Or more, preferably 99.99% by volume or less, more preferably 99.99% by volume or less, still more preferably 99.9% by volume or less, still more preferably 99.5% by volume or less.

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 for cosmetics and 75% by volume or more for disinfectant ethanol. It is preferably used, and the upper limit can also be conveniently set according to the application. The higher the concentration of ethanol as a product, the more preferable it is from the viewpoint of transportation cost and the like.

<Ethanol manufacturing method>
As a method for producing ethanol having a peculiar gas chromatograph 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 and purification conditions of the aromatic compound and the like in the raw material gas derived from the waste and exhaust gas may be controlled, and the amount of the aromatic compound and the like contained in the final product may be controlled. 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.

The method for producing ethanol is a step of converting a carbon source into a synthetic gas containing carbon monoxide and hydrogen, and a microorganism that supplies the synthetic gas containing carbon monoxide and hydrogen to a microbial fermenter to obtain an ethanol-containing liquid by microbial fermentation. It was obtained in a fermentation step, 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 liquefaction step. A purification step of purifying ethanol from a liquid material is included as a step, but a raw material gas generation step, a synthetic gas preparation step, a wastewater treatment step, and the like may be included, if necessary. Hereinafter, each step will be described.

<Raw material gas generation process>
The raw material gas generation step is a step of generating a raw material gas by gasifying the carbon source in the gasification section. A gasification furnace may be used in the raw material gas generation step. The gasification furnace is a furnace that burns (incompletely burns) a carbon source, and examples thereof include a shaft furnace, a kiln furnace, a fluidized bed furnace, and a gasification reforming furnace. The gasification furnace is preferably a fluidized bed type because partial combustion of waste enables a high hearth load and excellent operation operability. By gasifying the waste in a fluidized bed furnace with a low temperature (about 450 to 600 ° C) and a low oxygen atmosphere, it is decomposed into char containing a large amount of gas (carbon monoxide, carbon dioxide, hydrogen, methane, etc.) and carbon. To do. Furthermore, since the incombustibles contained in the waste are separated from the bottom of the furnace in a hygienic and low-oxidation state, it is possible to selectively recover valuable resources such as iron and aluminum in the incombustibles. Therefore, gasification of such waste enables efficient resource recycling.

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

The reaction time for gasification in the raw material gas generation step is usually 2 seconds or longer, preferably 5 seconds or longer.

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

More specifically, the carbon source is preferably waste, specifically plastic waste, garbage, municipal solid waste (MSW), industrial solid waste, waste tires, biomass waste, futons. Household waste such as paper and paper, waste such as building materials, coal, petroleum, petroleum-derived compounds, natural gas, shale gas, etc. are mentioned, and among them, various wastes are preferable, and they are not sorted from the viewpoint of sorting cost. Urban solid waste is more preferred.

The raw material 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 raw material gas may further contain components such as soot, tar, nitrogen compounds, sulfur compounds, phosphorus compounds, and aromatic compounds.

The raw material gas is produced from carbon monoxide by performing a heat treatment (commonly known as gasification) for burning (incomplete combustion) the carbon source in the above raw material gas generation step, that is, by partially oxidizing the carbon source. Although there is no limitation, it may be produced as a gas containing 0.1% by volume or more, preferably 10% by volume or more, and more preferably 20% by volume or more.

<Syngas purification process>
The syngas purification step is a step of removing or reducing specific substances such as various pollutants, dust particles, impurities, and unfavorable amounts of compounds from the raw material gas. When the raw material gas is derived from waste, the raw material gas usually contains carbon monoxide of 0.1% by volume or more and 80% by volume or less, carbon dioxide of 0.1% by volume or more and 70% by volume or less, and hydrogen of 0. .1% by volume or more and 80% by volume or less, 1 mg / L or more of nitrogen compound, 1 mg / L or more of sulfur compound, 0.1 mg / L or more of phosphorus compound, and / or 10 mg / L or more of aromatic compound It tends to include. It may also contain other substances such as environmental pollutants, soot and dust particles, and impurities. Therefore, when supplying the synthetic gas to the microbial fermenter, the content of each component contained in the raw material gas is reduced or removed from the raw material gas, such as substances unfavorable for stable culture of microorganisms and unfavorable amounts of compounds. Is preferably in a range suitable for stable culture of microorganisms.

In particular, in the synthetic gas purification step, the carbon dioxide gas in the synthetic gas is adsorbed on the regenerated adsorbent (zeolite) by using the pressure swing adsorber filled with the regenerated adsorbent, and the carbon dioxide gas concentration in the synthetic gas. To reduce. Further, the synthetic gas may be subjected to other conventionally known treatment steps to remove impurities and adjust the gas composition. Other treatment steps include, for example, a gas chiller (moisture separation device), a low temperature separation method (deep cooling method) separation device, a cyclone, a fine particle (success) separation device such as a bag filter, and a scrubber (water-soluble impurity separation device). , Scrubber (sulfide separation device), membrane separation type separation device, oxygen scavenger, pressure swing adsorption type separation device (PSA), temperature swing adsorption type separation device (TSA), pressure temperature swing adsorption method separation Treatment can be performed using one or more of an apparatus (PTSA), a separation apparatus using activated carbon, an oxygen scavenger catalyst, specifically, a separation apparatus using a copper catalyst or a palladium catalyst.

The syngas used in the method for producing ethanol of the present invention contains at least carbon monoxide as an essential component, and may further contain hydrogen, carbon dioxide, and nitrogen.

The synthetic gas used in the present invention produces a raw material gas by gasifying the carbon source (raw material gas generation step), and then adjusts the concentration of each component of carbon monoxide, carbon dioxide, hydrogen and nitrogen from the raw material gas. At the same time, the gas obtained through the steps of reducing or removing the above-mentioned substances and compounds may be used as the synthetic gas.

The carbon monoxide concentration in the synthetic gas is usually 20% by volume or more and 80% by volume or less, preferably 25% by volume or more and 50% by volume, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthetic gas. By volume or less, more preferably 35% by volume or more and 45% by volume or less.

The hydrogen concentration in the synthetic gas is usually 10% by volume or more and 80% by volume or less, preferably 30% by volume or more and 55% by volume, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthetic gas. It is more preferably 40% by volume or more and 50% by volume or less.

The carbon dioxide concentration in the synthetic gas is usually 0.1% by volume or more and 40% by volume or less, preferably 0.3% by volume or more, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthetic gas. It is 30% by volume or less, more preferably 0.5% by volume or more and 10% by volume or less, and particularly preferably 1% by volume or more and 6% by volume or less.

The concentration of nitrogen in the synthetic gas is usually 40% by volume or less, preferably 1% by volume or more and 20% by volume or less, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthetic gas. More preferably, it is 5% by volume or more and 15% by volume or less.

The concentrations of carbon monoxide, carbon dioxide, hydrogen and nitrogen can be determined by changing the elemental composition of hydrocarbons (carbon and hydrogen) and nitrogen as carbon sources in the raw material gas generation process, as well as the combustion temperature and oxygen concentration of the supply gas during combustion. By appropriately changing the combustion conditions such as, the predetermined range can be obtained. For example, if you want to change the carbon monoxide or hydrogen concentration, change to a carbon source with a high ratio of hydrocarbons (carbon and hydrogen) such as waste plastic, and if you want to reduce the nitrogen concentration, change the oxygen concentration in the raw material gas generation process. There is a method of supplying high gas.

The synthetic gas used in the present invention is not particularly limited, but may contain a sulfur compound, a phosphorus compound, a nitrogen compound and the like in addition to the above-mentioned components. The content of each of these compounds is preferably 0.05 mg / L or more, more preferably 0.1 mg / L or more, still more preferably 0.5 mg / L or more, and preferably 2000 mg / L or less. It is more preferably 1000 mg / L or less, still 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 compound, phosphorus compound, nitrogen compound, 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, the microorganism does not consume. It has the advantage that the medium is not contaminated by various nutrient sources.

Examples of the sulfur compound usually include sulfur dioxide, CS ₂ , COS, and H ₂ S, and among them, H ₂ S and sulfur dioxide are preferable because they are easily consumed as nutrient sources for microorganisms. Therefore, it is more preferable that the sum of H _{2 S} and sulfur dioxide are included in the above range in the synthesis gas.
As the phosphorus compound, it is preferable that phosphoric acid is easily consumed as a nutrient source for microorganisms. Therefore, it is more preferable that phosphoric acid is contained in the synthetic gas in the above range.
Examples of the nitrogen compound include nitric oxide, nitrogen dioxide, acrylonitrile, acetonitrile, HCN and the like, and HCN is preferable because it is easily consumed as a nutrient source for microorganisms. Therefore, it is more preferable that HCN is contained in the above range in the synthetic gas.

Further, the synthetic gas may contain an aromatic compound 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, still more preferably 0.1 mg / L. It is L or more and preferably 70 mg / L or less, more preferably 50 mg / L or less, still more preferably 30 mg / L or less. When the content is set to the lower limit or higher, the microorganisms tend to be suitably cultured, and when the content is set to the upper limit or lower, the medium is less likely to be contaminated by various nutrient sources not consumed by the microorganisms. It is in.

<Microbial fermentation process>
The microbial fermentation step is a step of producing ethanol by microbially fermenting the above-mentioned syngas in a microbial fermenter. The microbial fermentation tank is preferably a continuous fermentation apparatus. In general, a microbial fermenter having an arbitrary shape can be used, and examples thereof include a stirring type, an air lift type, a bubble tower type, a loop type, an open bond type, and a photobio type. However, a known loop reactor having a main tank portion and a reflux portion can be preferably used. In this case, it is preferable to further include a circulation step of circulating the liquid medium between the main tank portion and the reflux portion.

As the synthetic gas supplied to the microbial fermenter, the gas obtained through the raw material gas generation step may be used as it is as the synthetic gas as long as the above-mentioned component conditions of the synthetic gas are satisfied, and impurities and the like are reduced from the raw material gas. Alternatively, another predetermined gas may be added to the removed gas, and then the synthetic gas may be used. As another predetermined gas, at least one compound selected from the group consisting of, for example, a sulfur compound such as sulfur dioxide, a phosphorus compound, and a nitrogen compound may be added to obtain a synthetic gas.

The synthetic gas and the microbial culture solution may be continuously supplied to the microbial fermenter, but it is not necessary to supply the synthetic gas and the microbial culture solution at the same time, and the microbial fermenter to which the microbial culture solution has been supplied in advance is used. Syngas may be supplied. It is known that certain anaerobic microorganisms produce ethanol and the like from substrate gases such as syngas by fermentation, and these gas-utilizing microorganisms are cultivated in a liquid medium. For example, a liquid medium and gas-utilizing bacteria may be supplied and contained, and the synthetic gas may be supplied into the microbial fermentation tank while stirring the liquid medium in this state. As a result, gas-utilizing bacteria can be cultivated in a liquid medium, and ethanol can be produced from the synthetic gas by the fermentation action thereof.

In the microbial fermentation tank, the temperature of the medium or the like (culture temperature) may be any temperature, but is preferably about 30 to 45 ° C, more preferably about 33 to 42 ° C, still more preferably 36.5 to 37. It can be about 5.5 ° C. The culturing time is preferably 12 hours or more in continuous culturing, more preferably 7 days or more, particularly preferably 30 days or more, most preferably 60 days or more, and although the upper limit is not particularly set, equipment maintenance, etc. From the viewpoint, it is preferably 720 days or less, more preferably 365 days or less. In addition, the culture time means the time from the addition of the inoculum to the culture tank until the total amount of the culture solution in the culture tank is discharged.

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

Gas assimilating bacteria include both eubacteria and archaea. Examples of eubacteria include Clostridium bacteria, Moorella bacteria, Acetobacterium bacteria, Carboxydocella bacteria, Rhodopseudomonas bacteria, and eubacterium. Examples thereof include (Eubacterium) bacteria, Butyribacterium (Butyribacterium) bacteria, Oligotropha (Oligotropha) bacteria, Bradyrrhizobium (Bradyrhizobium) bacteria, and Ralsotonia (Ralsotonia) bacteria which are aerobic hydrogen oxidizing bacteria.

On the other hand, as paleobacteria, for example, Methanosaeta, Methanosabrevibacter, Methanosacalculus, Methanococcus, Methanosarcina, Methanosphaera, Methanothermobacter, Methanothrix, Methanoculleus, Methanofollis, Methanogenium Examples include bacteria, Methanosaeta spp., Methanosaeta spp., Thermococcus spp., Thermofilum spp., Arcaheoglobus spp. Among these, as archaea, Methanosarcina spp., Methanococcus spp., Methanothermobacter spp., Methanothrix spp., Thermococcus spp., Thermofilum spp., And Archaeoglobus spp. Are preferred.

Further, since the archaea are excellent in assimilation of carbon monoxide and carbon dioxide, the archaea are preferably Methanosarcina, Methanothermobactor, or Methanococcus, and particularly preferably Methanosarcina or Methanococcus. Specific examples of Methanosarcina genus bacteria include Methanosarcina barkeri, Methanosarcina mazei, and Methanosarcina acetivorans.

From the above gas-utilizing bacteria, a bacterium having a high ability to produce target ethanol is selected and used. For example, as gas-utilizing bacteria with high ethanol-producing ability, Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Clostridium carboxidivorans, for example, Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Clostridium carboxidivorans. , Moorella thermoacetica, Acetobacterium woodii and the like, and among these, Clostridium autoethanogenum is particularly preferable.

The medium used for culturing the above-mentioned microorganisms (species) is not particularly limited as long as it has an appropriate composition according to the bacteria, but is not particularly limited, but is mainly water and nutrients dissolved or dispersed in this water (for example, vitamins, etc.). It is a liquid containing (phosphoric acid, etc.). 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 a microorganism, reference can be made to US Patent Application Publication No. 2017/260552, "0907" to "00099" and the like.

The ethanol-containing liquid obtained by the microbial fermentation step can be obtained as a suspension containing microorganisms, their carcasses, proteins derived from microorganisms, and the like. 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.

<Separation process>
The ethanol-containing liquid obtained by the microbial fermentation step is then subjected to a separation step. In the present invention, the ethanol-containing liquid is heated to room temperature to 500 ° C. under the condition of 0.01 to 1000 kPa (absolute pressure) to separate a liquid or solid component containing microorganisms and a gas component containing ethanol. .. In the conventional method, the ethanol-containing liquid obtained in the microbial fermentation step is distilled to separate and purify the desired ethanol. However, since the ethanol-containing liquid contains a microorganism or a protein derived from the microorganism, it contains ethanol. If the liquid is distilled as it is, foaming may occur in the distillation apparatus and continuous operation may be hindered. Further, it is known that a membrane evaporator is used as a method for purifying an effervescent liquid, but the membrane evaporator has low concentration efficiency and is not suitable for purifying a liquid containing a solid component. In the present invention, before separating and purifying the desired ethanol from the ethanol-containing liquid obtained by the microbial fermentation step by a distillation operation or the like, the ethanol-containing liquid is heated to form a liquid or solid component containing microorganisms and a gas containing ethanol. It is separated into components, and the desired ethanol is separated and purified from only the separated gaseous components containing ethanol. By carrying out the separation step, in the distillation operation at the time of separation and purification of ethanol, foaming does not occur in the distillation apparatus, so that the distillation operation can be continuously performed. Further, since the concentration of ethanol contained in the gas component containing ethanol is higher than the concentration of ethanol in the ethanol-containing liquid, ethanol can be efficiently separated and purified in the purification step described later.

In the present invention, from the viewpoint of efficiently separating a liquid or solid component containing a microorganism, a carcass thereof, a protein derived from the microorganism, etc., and a gas component containing ethanol, it is more preferable under the condition of 10 to 200 kPa. Is heating the ethanol-containing solution under conditions of 50 to 150 kPa, more preferably under normal pressure, preferably at a temperature of 50 to 200 ° C, more preferably at a temperature of 80 ° C to 180 ° C, still more preferably at a temperature of 100 to 150 ° C. I do.

The heating time in the separation step is not particularly limited as long as the gas component can be obtained, but from the viewpoint of efficiency or economy, it is usually 5 seconds to 2 hours, preferably 5 seconds to 1 hour, and more. It is preferably 5 seconds to 30 minutes.

The above-mentioned separation step is not particularly limited as long as it is an apparatus capable of efficiently separating an ethanol-containing liquid into a liquid or solid component (microorganisms and their carcasses, proteins derived from microorganisms, etc.) and a gas component (ethanol) by heat energy. It can be used, and for example, a dryer such as a rotary dryer, a fluidized layer dryer, a vacuum dryer, or a conduction heating dryer can be used, but a liquid or liquid from an ethanol-containing liquid having a particularly low solid component concentration can be used. From the viewpoint of efficiency in separating the solid component and the gas component, it is preferable to use a conduction heating type dryer. Examples of the conduction heating type dryer include a drum type dryer and a disc type dryer.

<Liquidation process>
The liquefaction step is a step of liquefying the gas component containing ethanol obtained in the above separation step by condensation. The apparatus used in the liquefaction step is not particularly limited, but it is preferable to use a heat exchanger, particularly a condenser (condenser). Examples of the condenser include a water-cooled type, an air-cooled type, an evaporation type, and the like, and the water-cooled type is preferable among them. The condenser may have one stage or a plurality of stages.

It can be said that it is preferable that the liquefied product obtained by the liquefaction step does not contain the components contained in the ethanol-containing liquid such as microorganisms, their carcasses, and proteins derived from microorganisms. It does not exclude the inclusion of protein in it. Even when the protein is contained in the liquefied product, its concentration is preferably 40 mg / L or less, more preferably 20 mg / L or less, still more preferably 15 mg / L or less.

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

<Refining process>
Next, ethanol is purified from the liquefied product obtained in the liquefaction step. The ethanol-containing liquid obtained in the microbial fermentation step can be supplied to the purification step without going through the above-mentioned separation step when components such as microorganisms have already been removed. 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 target ethanol and a canned liquid having a reduced concentration of target ethanol. The equipment used in the purification process is, for example, a distillation apparatus, a treatment apparatus containing a permeation vaporization membrane, a treatment apparatus containing a zeolite dehydration membrane, a treatment apparatus for removing a low boiling point substance having a boiling point lower than that of ethanol, and a high boiling point having a boiling point higher than that of ethanol. Examples thereof include a processing device for removing substances, a processing device containing an ion exchange membrane, and the like. These devices may be used alone or in combination of two or more. As the unit operation, heat distillation or membrane separation may be preferably used.

In thermal distillation, a distillation apparatus can be used to obtain the desired ethanol as a distillate with high purity. The temperature inside the distiller during the distillation of ethanol is not particularly limited, but is preferably 100 ° C. or lower, and more preferably about 70 to 95 ° C. By setting the temperature in the distiller within the above range, separation of ethanol and other components, that is, distillation of ethanol can be performed more reliably.

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 at the bottom of the distillation column is raised to 90 ° C. or higher within 30 minutes. High-purity ethanol can be obtained by introducing the above ethanol-containing liquid from the central part of the distillation column and performing the distillation step within ± 15 ° C. in the temperature difference between the bottom part, the central part of the column, and the crown. .. The distillation temperature difference is preferably ± 13 ° C, more preferably ± 11 ° C. With the above distillation temperature difference, separation from other components, that is, distillation of ethanol can be performed more reliably.

It is considered that the ethanol-containing liquid contains dialkyl ether having a boiling point higher than that of ethanol (for example, dibutyl ether, dipentyl ether, etc.). In the present invention, by adjusting the above distillation conditions, for example, by raising the temperature of the uppermost part of the distillation column to 10 ° C. or more higher than usual, the aromatic compound is also distilled and contained in the distillate. Aromatic compounds in ethanol can be adjusted. As a result, the content of aromatic compounds in the final ethanol can be adjusted.

The pressure in the distillation apparatus during 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 in the distillation apparatus within the above range, the separation efficiency of ethanol can be improved, and thus the yield of ethanol can be improved. The yield of ethanol (concentration of ethanol contained in the distillate after distillation) is preferably 90% by volume or more, more preferably 95% by volume or more.

In the membrane separation, a known separation membrane can be appropriately used, and for example, a zeolite membrane can be preferably used.

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

The canned liquor separated during the purification process is substantially free of nitrogen compounds. In the present invention, "substantially free" does not mean that the concentration of the nitrogen compound is 0 mg / L, and the canned liquid obtained in the purification step does not require a wastewater treatment step. It means that it is the nitrogen compound concentration of. In the separation step, instead of purifying the desired ethanol from the ethanol-containing liquid obtained in the microbial fermentation step, the ethanol-containing liquid is divided into a liquid or solid component containing microorganisms and a gas component containing ethanol as described above. Separate into. At that time, since the nitrogen compound remains on the liquid or solid component side containing microorganisms, the nitrogen compound is hardly contained in the gas component containing ethanol. Therefore, it is considered that the canned out liquid obtained when ethanol is purified from the liquefied liquefied gas component does not substantially contain the nitrogen compound. Even when the canned liquid is contained in the nitrogen compound, the concentration of the nitrogen compound is 0.1 to 200 mg / L, preferably 0.1 to 100 mg / L, and more preferably 0.1 to 50 mg / L. is there.

Further, for the same reason as described above, the canned out liquid separated in the purification step does not substantially contain a phosphorus compound. In addition, "substantially free" does not mean that the concentration of the phosphorus compound is 0 mg / L, and the phosphorus compound obtained in the purification step does not require the wastewater treatment step. It means that it is a concentration. Even when the canned liquid is contained in the phosphorus compound, the concentration of the phosphorus compound is 0.1 to 100 mg / L, preferably 0.1 to 50 mg / L, and more preferably 0.1 to 25 mg / L. is there. As described above, according to the method of the present invention, the canned effluent discharged in the ethanol purification step contains substantially no nitrogen compound or phosphorus compound, and hardly contains other organic substances. Therefore, it is possible to simplify the wastewater treatment process that has been conventionally required.

<Wastewater treatment process>
The canned liquid separated in the purification step may be supplied to the wastewater treatment step. In the wastewater treatment step, organic substances such as nitrogen compounds and phosphorus compounds can be further removed from the canned liquid. In this step, organic substances may be removed by anaerobic or aerobic treatment of the canned liquid. The removed organic matter may be used as a fuel (heat source) in the refining process.

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.

Since the liquid or solid component containing microorganisms is removed from the canned liquid obtained through the separation step, wastewater treatment and the like are performed more than the canned liquid obtained by being directly supplied from the microbial fermentation step to the purification step. Load is reduced.

In the wastewater treatment step, the concentration of the nitrogen compound in the treatment liquid obtained by treating the canned liquid is preferably 0.1 to 30 mg / L, more preferably 0.1 to 20 mg / L, and further preferably 0.1. It is particularly preferably 10 mg / L and does not contain a nitrogen compound. The concentration of the phosphorus compound in the treatment liquid is preferably 0.1 to 10 mg / L, more preferably 0.1 to 5 mg / L, still more preferably 0.1 to 1 mg / L, and is contained in the canned liquid. It is particularly preferable that no phosphorus compound is contained.

<Use of ethanol>
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 includes butadiene, ethylene, propylene, isobutene, acetaldehyde, acetic acid, ethyl acetate, methyl (meth) acrylate, ethyl-t-butyl ether ethylene glycol, ester composition, polyester, acrylic acid, aminohexanoic acid. , Diethyl carbonate, polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyisobutylene, polymethylmethacrylate (PMMA), ethylene propylene diene rubber (EPDM), polybutylene terephthalate (PBT), polyethylene furanoate (PEF) ), Polypropylene (PU) and the like can be used as a raw material for production. Hereinafter, the method for synthesizing butadiene using ethanol as a raw material and the method for producing polyethylene and polyester of the present invention will be described as an example, but it goes without saying that they can also be used for other chemical products and polymer raw materials.

<Butadiene synthesis method>
Butadiene is mainly produced by purifying the C4 fraction produced as a by-product during the synthesis (that is, naphtha cracking) of ethylene from petroleum, and is a raw material for synthetic rubber. However, in recent years, there has been an urgent need for a technique for converting ethanol that is not derived from fossil fuels (ethanol derived from microbial fermentation) into 1,3-butadiene instead of the chemical industry raw material obtained from petroleum. Known methods for synthesizing butadiene using ethanol derived from microbial fermentation as a raw material include a method using MgO as a catalyst, a method using a mixture of Al ₂ O ₃ and Zn O, a catalyst having a magnesium silicate structure, and the like. ing. As the catalyst, vanadium, manganese, iron, cobalt, nickel, copper, zinc, gallium, niobium, silver, indium, cerium and the like are used in addition to the above.

By bringing the ethanol of the present invention into contact 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.

The heating temperature for advancing the conversion reaction is such that the temperature in the reaction system is, for example, 300 to 450 ° C, preferably 350 to 400 ° C. If the temperature in the reaction system is lower than the above range, the catalytic activity cannot be sufficiently obtained, the reaction rate tends to decrease, and the production efficiency tends to decrease. On the other hand, if the temperature in the reaction system exceeds the above range, the catalyst may easily deteriorate.

The reaction can be carried out by a conventional method such as a batch type, a semi-batch type or a continuous type. When the batch type or the semi-batch type is adopted, the conversion rate of ethanol can be increased, but in the case of the ethanol according to the present invention, even if the continuous type is adopted, ethanol is converted more efficiently than before. can do. Although the reason for this is not clear, ethanol derived from a circulating resource using a gas containing carbon monoxide and hydrogen as a substrate, as in the present invention, is derived from fossil fuel in the gas chromatograph measured by gas chromatography-mass spectrometry. It is considered that this is due to the presence of a peculiar peak not found in ethanol.

Examples of the method of bringing the raw material into contact with the catalyst include a suspension bed method, a fluidized bed method, a fixed bed method and the like. Further, either the gas phase method or the liquid phase method may be used. A fixed-bed gas phase continuous flow reactor in which the catalyst is filled in a reaction tube to form a catalyst layer, and the raw material is circulated as a gas to react in the gas phase because the catalyst can be easily recovered and regenerated. It is preferable to use it. 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 being diluted, or appropriately diluted with an inert gas such as nitrogen, helium, argon or carbon dioxide to the reactor. May be supplied.

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

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

First, ethylene, which is a raw material for polyethylene, is synthesized using 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 ethylene is obtained by a dehydration reaction of ethanol, but the catalyst is not particularly limited, and a conventionally known catalyst can be used. Advantageous in the process is a fixed bed flow reaction in which the catalyst and the product can be easily separated, and for example, γ-alumina is preferable.

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 a temperature of 100 ° C. or higher, more preferably 250 ° C. or higher, still more preferably 300 ° C. or higher is suitable. The upper limit is not particularly limited, but is preferably 500 ° C. or lower, more preferably 400 ° C. or lower, from the viewpoint of energy balance and equipment.

The reaction pressure is also not particularly limited, but a pressure higher than normal pressure is preferable in order to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which the catalyst can be easily separated is preferable, but a liquid phase suspension bed, a fluidized bed, or the like may also be used.

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. Generally, when a dehydration reaction is carried out, it is preferable that there is 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, especially butene, tends to increase in the absence of water. The lower limit of the allowable water content is 0.1% by mass or more, preferably 0.5% by mass or more. Although the upper limit is not particularly limited, it is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less from the viewpoint of mass balance and heat balance.

By performing the ethanol dehydration reaction as described above, a mixed portion of ethylene, water and a small amount of unreacted ethanol can be obtained. However, since ethylene is a gas at about 5 MPa or less at room temperature, gas and liquid are obtained from these mixed portions. Ethylene can be obtained by removing water and ethanol by separation. This method may be performed by a known method. Subsequently, ethylene obtained by gas-liquid separation is further distilled, and the distillation method, operating temperature, residence time, and the like are not particularly limited except that the operating pressure at this time is normal pressure or higher.

Ethanol derived from a circulating resource using a gas containing carbon monoxide and hydrogen as a substrate, as in the present invention, is unique in gas chromatographs measured by gas chromatograph mass spectrometry, which is not found in ethanol derived from fossil fuels. There is a peak of. Therefore, it is considered that ethylene obtained from ethanol contains a very small amount of impurities. Depending on the use of ethylene, these trace amounts of impurities may cause a problem, and may be removed by purification. The purification method is not particularly limited, and can be performed by a conventionally known method. As a suitable purification operation, for example, an adsorption purification method can be mentioned. The adsorbent used is not particularly limited, and conventionally known adsorbents can be used. For example, caustic water treatment may be used in combination as a method for purifying impurities in ethylene. When caustic water treatment is performed, it is desirable to perform it before adsorption purification. In that case, it is necessary to perform a water removal treatment after the caustic treatment and before the adsorption purification.

The method for polymerizing the monomer containing ethylene is not particularly limited, and a conventionally known method can be used. The polymerization temperature and the polymerization pressure may be appropriately adjusted according to the polymerization method and the polymerization apparatus. The polymerization apparatus is not particularly limited, and conventionally known apparatus can be used. Hereinafter, an example of a method for polymerizing a monomer containing ethylene will be described.

The method for polymerizing a polyolefin, particularly an ethylene polymer or a copolymer of ethylene and α-olefin, is a method of polymerizing a target type of polyethylene, for example, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE). ), And linear low-density polyethylene (LLDPE) or the like, which can be appropriately selected depending on the difference in density and branching. For example, a multisite catalyst such as a Ziegler-Natta catalyst or a single site catalyst such as a metallocene catalyst is used as a polymerization catalyst by any of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization. It is preferable to carry out in one stage or in two or more stages.

The above-mentioned single-site catalyst is a catalyst capable of forming a uniform active species, and is usually prepared by contacting a metallocene-based transition metal compound or a non-metallocene-based transition metal compound with an activation co-catalyst. .. Compared with the multisite catalyst, the single-site catalyst is preferable because it has a uniform active site structure and can polymerize a polymer having a high molecular weight and a high uniformity structure. As the single-site catalyst, it is particularly preferable to use a metallocene-based catalyst. The metallocene-based catalyst is a catalyst containing a transition metal compound of Group IV of the Periodic Table, which contains a ligand having a cyclopentadienyl skeleton, a cocatalyst, an organometallic compound if necessary, and each catalyst component of the carrier. is there.

In a 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 or the like. The substituted cyclopentadienyl group has a substituent such as a hydrocarbon group having 1 to 30 carbon atoms. Examples of the transition metal include zirconium, titanium, and hafnium, and zirconium and hafnium are particularly preferable. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and the ligands having each cyclopentadienyl skeleton are preferably bonded to each other by a cross-linking group. The above-mentioned transition metal compound can have one or a mixture of two or more as a catalyst component.

The co-catalyst is one that can effectively use the above-mentioned transition metal compound as a polymerization catalyst, or can equalize the ionic charge in a catalytically activated state. As co-catalysts, benzene-soluble organoxane of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, ion-exchange layered silicates, boron compounds, cations containing or not containing active hydrogen groups and non-coordinating anions are used. Examples thereof include ionic compounds, lanthanoid salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing a fluoro group.

The above-mentioned transition metal compound may be used by supporting it on a carrier of an inorganic or organic compound. As the carrier, a porous oxide of an inorganic or organic compound is preferable, and specifically, an ion-exchangeable layered silicate such as montmorillonite, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O. ₃ , CaO, ZnO, BaO, ThO _2, etc. or a mixture thereof can be mentioned.

Further, examples of the organometallic compound used as necessary include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Of these, organoaluminum is preferably used.

Further, as the polyolefin, a polymer of ethylene or a copolymer of ethylene and α-olefin may be used alone, or two or more kinds may be mixed and used.

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

Acetaldehyde can be produced by oxidizing ethanol by a conventionally known method. For example, ethanol can be oxidized with chlorine to produce acetaldehyde. Chlorine usually reacts with ethanol in the gaseous state. Chlorine may be supplied at a concentration of approximately 100%, or may be diluted with an inert gas (for example, nitrogen, helium, neon, argon, etc.) and supplied. In this case, the degree of dilution is 50% by weight or less, preferably 25% by weight or less in consideration of the reaction efficiency. It is preferable that ethanol and chlorine are reacted with, for example, 100 g of an aqueous ethanol solution in a supply amount of 25 to 100 sccm.

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, and hypochlorous acid compound. This oxidation can be realized, for example, by a photoreaction, a thermal reaction, a catalytic reaction, or the like. Among these, oxidation by photochlorination and thermal chlorination of ethanol by chlorine gas is preferable, and oxidation by photochlorination by chlorine gas is more preferable. Examples of the photoreaction include a method of irradiating light having various wavelengths such as ultraviolet rays and visible light. Among these, it is preferable to irradiate light from a light source having a wavelength of about 300 to 500 nm to cause the reaction. .. The light source is not particularly limited, and fluorescent lamps, mercury lamps, halogen lamps, xenon lamps, metal halide lamps, excima lamps, LED lamps and the like can be used. The reaction temperature is preferably about 0 to 80 ° C, preferably about 0 to 50 ° C. The reaction time is preferably about 1 to 5 hours.

In addition, 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 in which gold fine particles are dispersed and fixed can be used. Examples of the base metal oxide include La ₂ O ₃ , MoO ₃ , Bi ₂ O ₃ , SrO, Y ₂ O ₃ , MgO, BaO, WO ₃ , CuO and a composite oxide containing one or more of them.

The oxidation reaction of ethanol is carried out by bringing a gas containing ethanol and oxygen molecules into contact with the catalyst, for example, at 100 to 280 ° C. The oxygen molecules used in the reaction may be supplied as oxygen gas or air may be used. Further, the raw material gas, which is the gas, may contain a diluting gas (carrier gas), if necessary. The device used for the reaction at this time may be a general device usually used for performing a gas phase reaction. For example, the catalyst is filled in the reaction tube, and in a state where the reaction tube is heated to a predetermined temperature, a gas containing ethanol and oxygen gas or air is sent into the reaction tube, and these raw material gases and the catalyst are brought into contact with each other to bring the reaction gas into contact with the catalyst. It is done by collecting. The reaction pressure may be normal pressure, and may be pressurized to about 0.5 to 5 Pa (atmospheric pressure) if necessary. As the diluting gas, for example, a so-called inert gas such as nitrogen, argon, helium, or carbon dioxide is used. The amount of the diluting gas used may be appropriately determined in consideration of the composition of the raw material gas, the flow rate, the heat of reaction, etc., but it is usually preferably 1 to 100 times the volume of ethanol.

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 with respect to ethanol. It is preferably 1 to 10% by volume, more preferably 2 to 5% by volume. The amount of the catalyst used is not particularly limited, but if the inner diameter of the reaction tube is 6 to 10 mm, it may be generally about 0.1 to 1.0 g. Practically, it is preferable to use an amount having a space velocity (SV) in the range of about 10,000 to 40,000 hr ^-1 · ml · g _cat ^-1 in relation to the gas flow rate.

In addition, 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. Copper as an active species may be in a form having an activity of converting ethanol into acetaldehyde, and may be metallic copper (single substance), copper compound (oxide, hydroxide, copper salt (copper sulfate, copper phosphate, copper nitrate). , Inorganic acid salts such as copper carbonate; organic acid salts such as copper salts of carboxylic acids), etc.) may be in any form. The solid catalyst may contain at least one selected from such simple substances and copper compounds. Copper as the active species is preferably in the form of metallic copper. Further, copper may be used as it is in the form of metallic copper or a copper compound, or may be used in the form of being supported on a carrier. 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 or the like. Further, the solid catalyst may be in a form in which both copper and a co-catalyst are supported on a carrier.

The dehydrogenation reaction may be a liquid phase reaction as long as ethanol can be brought into contact with the solid catalyst, but it is usually a gas phase reaction in which gaseous ethanol and the solid catalyst are brought into contact with each other in a gas phase. From the viewpoint of the equilibrium relationship between ethanol and acetaldehyde, the catalyst life, etc., the temperature may be 150 to 350 ° C., preferably 170 to 300 ° C., and more preferably 200 to 280 ° C. As the reaction temperature is higher, the equilibrium shifts to the acetaldehyde side, so that the conversion rate can be improved. The reaction may be carried out under pressure, but may be carried out under normal pressure from the viewpoint of convenience. It can also be carried out under reduced pressure because it is advantageous for the ethanol conversion rate.

<Acetic acid>
Acetic acid is an important chemical as an industrial raw material. Acetic acid is useful as a raw material for, for example, vinyl acetate monomer, acetic anhydride, acetic acid ester and the like.

Acetic acid can be produced by oxidizing acetaldehyde by a conventionally known 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.

<Ethyl-t-butyl ether>
Ethyl-t-butyl ether (ETBE) is an important chemical as an industrial raw material. ETBE is useful, for example, as an alternative fuel to gasoline, especially as a high-octane fuel.

ETBE can be synthesized from ethanol and isobutylene by a conventionally known method. For example, it can be produced by reacting ethanol and isobutylene in the presence of a reaction catalyst. The molar ratio of isobutylene to ethanol as a raw material is preferably 0.1 to 10 mol, more preferably 0.5 to 2 mol.

It is preferable to use a cation exchange resin as the reaction catalyst, and it is more preferable to use a strongly acidic cation exchange resin. Such strongly acidic cation exchange resin, a styrene resin of a sulfonic acid group as an ion exchange group (-SO 3 _H) porous type strong acid group is introduced, such as (MR type) is preferred. 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 with respect to 1 mol of ethanol.

The method of using the reaction catalyst is not particularly limited, and the reaction catalyst can be used in the reaction in a fixed bed, a fluidized bed, or a suspension bed. The form of reacting isobutylene with ethanol is not particularly limited, but it is preferable to use a pressurized gas-liquid mixed phase reaction method in which ethanol can maintain a liquid phase. In this case, the yield of the obtained ETBE is further improved.

<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, which is 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 does not depend on petroleum resources.

Polyester is composed of a diol unit and a dicarboxylic acid unit, and is obtained by a polycondensation reaction using ethylene glycol as a diol unit and terephthalic acid, isophthalic acid or the like as a dicarboxylic acid unit. Ethylene glycol is made from the ethanol of the present invention. For example, ethylene glycol can be obtained from ethanol by a method of producing ethylene glycol via ethylene oxide by a conventionally known method.

As the dicarboxylic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and derivatives thereof can be used without limitation. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the derivative of the aromatic dicarboxylic acid include lower alkyl esters of the aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl. Esters and the like can be mentioned. Among these, terephthalic acid is preferable, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid. Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid having 2 or more and 40 or less carbon atoms. Examples thereof include chain or alicyclic dicarboxylic acids. Further, as a derivative of the aliphatic dicarboxylic acid, a lower alkyl ester such as a methyl ester, an ethyl ester, a propyl ester and a butyl ester of the aliphatic dicarboxylic acid, or a cyclic acid anhydride of the aliphatic dicarboxylic acid such as succinic anhydride is used. Can be mentioned. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and succinic acid as a main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, a methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable.

The polyester can be obtained by a conventionally known method of polycondensing the above-mentioned diol unit and dicarboxylic acid unit. Specifically, a general method of melt polymerization such as performing an esterification reaction and / or a transesterification reaction between the above dicarboxylic acid component and a diol component and then performing a polycondensation reaction under reduced pressure, or an organic solvent. It can be produced by a known solution heating dehydration condensation method using.

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.

The reaction temperature of 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 under an inert gas atmosphere such as nitrogen or argon. ..

In the polycondensation reaction step, a chain extender (coupling agent) may be added to the reaction system. After the completion of polycondensation, the chain extender is added to the reaction system in a uniform molten state without a solvent, and is reacted with the polyester obtained by polycondensation.

After solidification, the obtained polyester may be subjected to solid phase polymerization, if necessary, in order to further increase the degree of polymerization and remove oligomers such as cyclic trimers.

In the polyester manufacturing process, various additives may be added as long as their properties are not impaired, for example, plasticizers, ultraviolet stabilizers, anticoloring agents, matting agents, deodorants, flame retardants, etc. A weather resistant agent, an antistatic agent, a friction reducing agent, a mold release agent, an antioxidant, an ion exchanger, a coloring pigment and the like can be added.

Ethanol according to the present invention can be used as a raw material for various other polymers, not limited to the above-mentioned polymers, and since the obtained polymer molded product is a carbon-neutral material, it is the ultimate independent of petroleum resources. It will be possible to realize a resource recycling society.

<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. Products include, for example, cosmetics, perfumes, fuels, antifreezes, disinfectants, disinfectants, cleaning agents, mold removers, detergents, hair wash agents, soaps, antiperspirants, face wash sheets, solvents, paints, adhesives, diluents. , Chemical products such as food additives. By using it for these purposes, it is possible to exert an appropriate effect according to the application.

<Fuel>
Ethanol according to the present invention can also be used as a raw material such as fuel (for example, jet fuel, kerosene, light oil, gasoline). Since ethanol has a high bactericidal ability, it can also function as a bactericidal agent for preventing the growth of bacteria and the like in a fuel system such as an engine or piping.

According to the standards of the Society of Automotive Engineers of Japan (2006), the concentration of ethanol in fuel ethanol is 99.5% by volume or more. In other countries (for example, India), the concentration of ethanol in fuel ethanol is specified to be 99.5% by volume or more. Therefore, ethanol having a purity of 99.5 to 99.9% by volume can be suitably used for an ethanol-only vehicle. Further, since fuel ethanol can be used for applications other than ethanol-only vehicles, ethanol having a purity of 99.5 to 99.9% by volume is particularly versatile.

Further, the ethanol according to the invention can be mixed with gasoline and used as ethanol-mixed gasoline. By using ethanol-mixed gasoline, the environmental load can be reduced. The purity of ethanol used in the 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.

The content of ethanol in the ethanol-mixed gasoline is preferably 1% by volume or more and 15% by volume or less, more preferably 2% by volume or more and 12% by volume or less, and further preferably 3% by volume or more and 10% by volume or less. .. If the content of ethanol 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 will be significantly changed due to the azeotropic phenomenon with other gasoline base materials. It is possible to ensure proper drivability of gasoline-powered vehicles.

The water content in the ethanol-mixed gasoline is preferably 0.01% by mass or more and 0.9% by mass or less, and more preferably 0.01% by mass or more and 0.7% by mass or less. The lower limit of the water content depends on the saturated water content of the gasoline base material and the water content in ethanol, but is substantially 0.01% by mass. If the upper limit is 0.9% by mass or less, phase separation can be prevented, and even in the case of phase separation, the gasoline layer enables proper operation of the gasoline engine. The water content can be measured by the "crude oil and petroleum products-moisture test method" described in JIS K 2275, and for example, the Karl Fischer titration method can be used.

As the gasoline base material, a commonly used gasoline base material can be arbitrarily used and is not particularly limited. Examples of the gasoline base material include light naphtha obtained by atmospheric distillation of crude oil, preferably desulfurized light naphtha obtained by desulfurizing it, catalytically modified gasoline obtained by catalytically reforming heavy naphtha after desulfurization. Debenzene-treated debenzene contact-modified gasoline, debenzene light contact-modified gasoline, debenzene heavy-contact modified gasoline, and their mixture, decomposed gasoline obtained by catalytic decomposition or hydrocracking method. , Lightly decomposed gasoline, heavyly decomposed gasoline, and a mixture thereof, isomerized gasoline obtained by isomerizing light naphtha, and the like.

Further, the ethanol-based ETBE according to the invention can be mixed with gasoline and used as ETBE mixed gasoline. By using ETBE mixed gasoline, the environmental load can be reduced. The ETBE content of the ETBE mixed gasoline is preferably 1% by volume or more and 15% by volume or less, more preferably 2% by volume or more and 12% by volume or less, and further preferably 3% by volume or more and 10% or less. When the content of ETBE is 1% by volume or more, the advantage of improving the octane number by blending ETBE can be obtained, and when it is 15% by volume or less, the evaporation characteristics are significantly changed due to the azeotropic phenomenon with other gasoline base materials. It is possible to ensure proper drivability of gasoline-powered vehicles.

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.

<Ethanol component evaluation method>
In the following Examples and Comparative Examples, the content of dibutyl ether in ethanol was measured using a gas chromatography device (GC-2014, manufactured by SHIMADZU) GC / MS method. The measurement conditions were as follows.
Column: DB-WAX (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm)
Oven temperature: 40 ° C, 1 minute → 5 ° C / min → 100 ° C, 10 minutes → 10 ° C / min → 250 ° C, 4 minutes Sampling time: 5 minutes Carrier gas: He (3.0 mL / min)

<Butadiene quantification method>
Quantitative evaluation of butadiene was performed by analysis using a gas chromatography device (GC-2014, manufactured by SHIMADZU). The measurement conditions were as follows.
<Analytical conditions for 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

<Ethyl benzoate quantification method>
Quantitative evaluation of ethyl benzoate was performed by analysis using a gas chromatography device. The measurement conditions were as follows.
<Analytical conditions for GC / MS method>
Column: DB-1 (length 30.0 m, inner diameter 0.254 mm, film thickness 0.25 m)
Heating conditions: 30 ° C-300 ° C 15 ° C / min
Carrier gas: He 100 kPa
Split ratio: 50

<Combustion efficiency quantification method>
A quantitative evaluation of the combustion efficiency of ethanol was performed by total calorific value analysis using a cone calorie meter manufactured by FTT.

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

(Syngas purification process)
The original content of carbon dioxide contained in the synthetic gas under the condition that the gas temperature of the raw material gas produced above was heated to 80 ° C. using a PSA device which is an impurity removing device. After removing the gas to 60 to 80% by volume (about 30% by volume), the temperature of the gas was raised and cooling water at 25 ° C. was used in a double-tube heat exchanger using steam at 150 ° C. A synthetic gas was produced by recooling using a double-tube heat exchanger to precipitate impurities and removing the precipitated impurities with a filter.

(Microbial fermentation process)
Inoculum of Clostridium autoethanogenum (microorganism) equipped with a main reactor, synthetic gas supply hole, and discharge hole, and a liquid medium for culturing the bacteria (including appropriate amounts of phosphorus compound, nitrogen compound, various minerals, etc.) The synthetic gas obtained as described above was continuously supplied to the filled continuous fermentation apparatus (microbial fermentation tank), and culturing (microbial fermentation) was continuously carried out for 300 hours. Then, about 8000 L of the culture solution containing ethanol was extracted from the discharge hole.

(Separation process)
An ethanol-containing solution was obtained from the culture solution obtained in the above fermentation step using a solid-liquid separation filter device under the condition that the culture solution introduction pressure was 200 kPa or more.

(Distillation process)
Subsequently, the ethanol-containing liquid was introduced into a distillation apparatus equipped with a heater using steam at 170 ° C. After raising the temperature of the bottom of the distillation column to 101 ° C. within 8 to 15 minutes, the ethanol-containing liquid was introduced from the center of the distillation column, and during continuous operation, the bottom of the column was 101 ° C. and the center of the column was 99 ° C. The crown was continuously operated at 91 ° C. under the condition of 15 seconds / L to obtain purified ethanol. The content of dibutyl ether in the obtained ethanol was 20 mg / L.

(Butadiene production method)
Butadiene was produced using the ethanol obtained as described above. First, in order to use the obtained ethanol as a gas to be used for the reaction, ethanol was passed through a single tube heated to 90 ° C. and vaporized, and the vaporized ethanol gas was merged with nitrogen. By controlling the flow rate of ethanol gas at this time to SV360L / hr / L and nitrogen to SV840L / hr / L by mass flow, 30% by volume of ethanol (gas conversion) and 70% by volume of nitrogen (gas conversion) can be obtained. It was a mixed gas. Subsequently, a stainless steel cylinder having a diameter of 1/2 inch (1.27 cm) and a length of 15.7 inches (40 cm) filled with 0.85 g of a butadiene synthesis catalyst containing Hf, Zn and Ce as main components. Butadiene-containing gas was obtained by continuously supplying the mixed gas while maintaining the temperature of 350 ° C. and the pressure (pressure of the reaction bed) of 0.1 MPa. The butadiene content of the obtained butadiene-containing gas was quantified using a gas chromatography device of GC-2014 (manufactured by SHIMADZU). The results were as shown in Table 1.

[Comparative Example 1]
Butadiene was produced by the same method as in Example 1 using 99 degree ethanol (manufactured by Amakasu Chemical Industry Co., Ltd.), which is a fossil fuel-derived ethanol, and the butadiene content was quantified in the same manner as in Example 1. The results were as shown in Table 1. The amount of dibutyl ether in 99-degree ethanol, which is fossil fuel-derived ethanol, was below the detection limit.

[Comparative Example 2]
Butadiene was produced by the same method as in Example 1 using 99-degree ethanol (manufactured by Amakasu Chemical Industry Co., Ltd.) derived from 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 amount of dibutyl ether in 99-degree ethanol, which is fossil fuel-derived ethanol, was below the detection limit.

As shown in Table 1, ethanol produced using the gas emitted after burning general waste in a waste incineration facility is compared with ethanol derived from conventional fossil fuels and ethanol derived from saccharification fermentation from plants. , It was found that the conversion efficiency to butadiene is high.

[Example 2]
(Manufacturing of ethyl benzoate)
Ethyl benzoate was produced as follows using the same ethanol as that used in Example 1. First, 36.8 g of benzoic acid and 200 ml of ethanol were mixed under an argon stream, 9 ml of concentrated sulfuric acid was added, and the mixture was stirred for 5 hours while refluxing. Then, the mixture was allowed to cool to room temperature, unreacted ethanol was removed under reduced pressure, and ethyl benzoate synthesized with 100 ml of diethyl ether was recovered. The recovered liquid was washed with distilled water, dried with magnesium sulfide, and then filtered and concentrated.
The obtained filtrate was subjected to component analysis using a gas chromatography device, and the amount of ethyl benzoate synthesized was quantified. The analysis conditions at that time are shown below. The analysis results are as 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 ° C 15 ° C / min
Carrier gas: He 100 kPa
Split ratio: 50

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

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

As shown in Table 2, ethanol produced using the gas emitted after burning general waste in a waste incineration facility is compared with ethanol derived from conventional fossil fuels and ethanol derived from saccharification fermentation from plants. , It was found that the conversion efficiency to ethyl benzoate was high.

[Example 3]
The combustion efficiency of ethanol was quantified using the same ethanol as that used in Example 1. The fuel efficiency is such that under unheated conditions, 30 g of ethanol is added to a heat-resistant container with a length of 60 mm, a width of 60 mm, and a height of 30 mm, and then ignition is performed until the fuel is completely burned in a cone calorie meter (manufactured by FTT). The amount of oxygen reduction was measured and quantified by calculating the total calorific value based on the amount of oxygen reduction. The quantitative results are as shown in Table 3.

[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 as shown in Table 3.

[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 as shown in Table 3.

As shown in Table 3, ethanol produced using the gas emitted after burning general waste in a waste incineration facility is compared with ethanol derived from conventional fossil fuels and ethanol derived from saccharification fermentation from plants. , It turned out that the combustion efficiency is high.

Claims (17)

Ethanol having a dialkyl ether content of 0.1 mg / L or more and 100 mg / L or less. The ethanol according to claim 1, wherein a gas containing carbon monoxide and hydrogen is used as a substrate. The ethanol according to claim 1 or 2, which is derived from microbial fermentation. The ethanol according to any one of claims 1 to 3, wherein the dialkyl ether comprises at least one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, and dipentyl ether. The ethanol according to claim 2, wherein the gas containing carbon monoxide and hydrogen is derived from waste. The process of converting a carbon source into a synthetic gas containing carbon monoxide and hydrogen,
A microbial fermentation step in which the synthetic gas containing carbon monoxide and hydrogen is supplied to a microbial fermentation tank 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,
A purification step of purifying ethanol from the liquid material obtained in the liquefaction step, and
Including
A method for producing ethanol, wherein the content of dialkyl ether in the purified ethanol is 0.1 mg / L or more and 100 mg / L or less. The method according to claim 6, further comprising a step of purifying the synthetic gas. The method according to claim 6 or 7, wherein the carbon source is derived from waste. The ethanol according to any one of claims 1 to 5, which is for a chemical product. The ethanol according to any one of claims 1 to 5, which is used as a fuel. The ethanol according to any one of claims 1 to 5, which is used as a polymer raw material. A chemical product using ethanol as a raw material according to any one of claims 1 to 5. A fuel comprising ethanol according to any one of claims 1 to 5 and / or ethyl-t-butyl ether from the ethanol according to any one of claims 1 to 5. A polymer raw material using ethanol as a raw material according to any one of claims 1 to 5. The polymer raw material according to claim 14, which is selected from the group consisting of ethylene, propylene, butadiene, ethyl acetate, isobutene, methyl (meth) acrylate, acrylic acid, aminohexanoic acid, and diethyl carbonate. A polymer made from the polymer raw material according to claim 14 or 15. A molded product made of the polymer according to claim 16.