KR20180066564A - Method of biomass decoposition using solvothermolysis of 2 phase reaction system - Google Patents

Abstract

The present invention provides a method for decomposing a biomass, which comprises the steps of: (a) preparing a mixture including a polar solvent including water, a non-polar solvent, and a biomass; (b) preparing a biomass decomposition product by performing a solvent pyrolysis reaction on the mixture under subcritical or supercritical conditions; (c) separating a lower layer including a polar solvent dissolution component and a polar solvent in the biomass decomposition product and an upper layer including a non-polar solvent dissolution component and a non-polar solvent in the biomass decomposition product by lowering temperature after the solvent pyrolysis reaction; (d) separating the upper layer from the separated upper layer and lower layer; and (e) separating the non-polar solvent dissolution component from the non-polar solvent in the separated upper layer.

Description

TECHNICAL FIELD The present invention relates to a biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biomass solution,

TECHNICAL FIELD The present invention relates to a biomass decomposition method, and more particularly, to a biomass decomposition method using a solvent pyrolysis reaction of a two-phase reaction system.

As fossil fuels have recently become depleted, the need for alternative energy continues to increase. As a result, biomass capable of conversion to energy, particularly woody biomass, has emerged as an important resource. Woody biomass, which accounts for most of the global biomass, is a useful resource. The woody biomass is expected to replace petroleum because it can produce useful materials such as bioethanol and chemical derivatives through saccharification and fermentation, while reducing carbon dioxide emissions. According to the World Biofuels Outlook (2007), biofuels promotion policies were adopted in 40 out of the 50 countries surveyed, and 27 countries introduced legislation on biofuel adoption. Trees are a good resource for producing bio-oils. Because the tree is not a food resource, it can be used to produce biomass in many countries.

The biggest barrier to continued use of biomass is lignocellulose. The lignocellulose is difficult to convert to a valuable liquid fuel because cellulose and lignin are natural polymers with very strong bonds (Bioresource Technology 100 (2009) 6496-6504). In particular, lignin is an aromatic structure, which has the potential to replace petrochemical-based aromatic chemical raw materials. However, since it has a complicated chemical structure, it is difficult to efficiently decompose and separate by conventional methods.

Recently, direct thermochemical processes have attracted interest because they have simple and low energy consumption compared with indirect methods. Direct thermochemical methods are characterized by rapid pyrolysis, high pressure liquefaction and liquefaction in supercritical fluids (Energy & Fuels 2006, 20, 848-889 // Characterization of Bio-oils Produced from Fast Pyrolysis of Corn Stalks in an Auger Reactor ). Biomass liquefaction processes using supercritical and subcritical solvents have been reported to have advantages such as increased reaction efficiency due to diffusivity of solvent and increased yield of deoxygenation reaction due to self-hydrogen donation. Particularly, water or alcohol is mainly used as a solvent. These substances are relatively inexpensive, have low toxicity, and change into nonpolar state under supercritical conditions and have an additional effect of increasing affinity with organic matter.

Water and alcohol at room temperature and normal pressure are strongly polar solvents, but at higher temperatures and pressures than a certain level, the polarity is lowered and the affinity with organic matter increases. In the solvent pyrolysis reaction using these solvents, it is possible to carry out the effective decomposition reaction by using these characteristics. However, as the polarity increases again in the cooling process after completion of the reaction, precipitation of the reaction product occurs and a side reaction such as re- There is a problem that the yield is lowered.

It is an object of the present invention to solve the above problems and to provide a biomass decomposition method capable of increasing the yield of organic compounds as decomposition products in the biomass decomposition reaction, compared with the conventional solvent pyrolysis technique.

Another object of the present invention is to provide a biomass decomposing method which can reduce the energy of a distillation process for separating a final product and a solvent by using a nonpolar organic solvent having a lower boiling point than water.

According to an aspect of the present invention, there is provided a method of preparing a mixture comprising: (a) preparing a mixture comprising a polar solvent comprising water, a nonpolar solvent and biomass; (b) subjecting the mixture to solvent pyrolysis under subcritical or supercritical conditions to produce a biomass degradation product; (c) lowering the temperature after the solvent pyrolysis reaction to separate the biomass decomposition products into a lower layer containing a polar solvent dissolution component and a polar solvent, and a lower layer comprising a nonpolar solvent dissolution component and a nonpolar solvent in the biomass decomposition product ; (d) separating the upper layer from the upper and lower layers separated from each other; And (e) separating the non-polar solvent dissolution component from the non-polar solvent in the separated upper layer.

Wherein the polar solvent further comprises an alcohol, wherein the alcohol is a substituted or unsubstituted straight-chain C1 to C10 alcohol or a substituted or unsubstituted C3 to C10 branched alcohol, C6 linear alkyl group or a C3 to C6 branched alkyl group.

The alcohol may be at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, n-pentanol and n-hexanol.

The biomass may be at least one selected from the group consisting of cellulose, lignocellulose, hemicellulose, and lignin.

The nonpolar solvent may also be a substituted or unsubstituted C5 to C14 linear alkyl, a substituted or unsubstituted C5 to C14 branched alkyl, a substituted or unsubstituted C5 to C14 cycloalkyl, a substituted or unsubstituted C7 to C14 cycloalkyl, C14 alkylaryl, substituted or unsubstituted C7-C14 arylalkyl, or substituted or unsubstituted C10-C18 cycloalkylaryl,

The group corresponding to the substitution may be a straight chain alkyl group of C1 to C6, a branched alkyl group of C3 to C6, or a cycloalkyl group of C6 to C10.

The non-polar solvent may be selected from the group consisting of n-pentane, iso- pentane, neopentane, cyclopentane, n-hexane, isohexane, n-heptane, cyclohexane, cycloheptane, n-decane, n-dodecane, benzene, toluene, xylene, tetralin, decalin, chloroform and dichloromethane.

The solvent pyrolysis reaction may be carried out at a temperature of 200 to 500 ° C and a pressure of 4 to 40 MPa.

The non-polar solvent-soluble component of the biomass decomposition product may be at least one selected from the group consisting of guaiacol, alkyl diacol, eugenol, vanillin, syringol and alkyl syringol have.

The non-polar solvent soluble fraction of the biomass decomposition product may be at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural and derivatives thereof.

Also, step (e) can separate the nonpolar solvent soluble component from the nonpolar solvent by distillation.

In addition, the nonpolar solvent can be uniformly mixed with the polar solvent under subcritical or supercritical conditions, and can be separated from the polar solvent under normal temperature and normal pressure conditions.

According to another aspect of the present invention, there is provided an organic compound which is a non-polar solvent dissolution component produced by the decomposition method of the biomass.

In the present invention, a nonpolar organic solvent which has sufficient solubility to organic components and is not mixed with water is introduced at room temperature and normal pressure to prevent precipitation during the cooling process after the thermal decomposition reaction of the solvent. As a result, the water and the nonpolar solvent can be efficiently decomposed in the reaction condition, and in the cooling process, the decomposition products can be separated into two phases and the decomposition products can be immediately extracted into the nonpolar layer, Respectively.

The present invention can increase the yield of organic compounds obtained by solvent pyrolysis of biomass over conventional solvent pyrolysis techniques. At the same time, by using an organic solvent having a lower boiling point than water, energy for a distillation process for separating a final product and a solvent can be reduced.

These drawings are for the purpose of describing an exemplary embodiment of the present invention, and therefore the technical idea of the present invention should not be construed as being limited to the accompanying drawings.
1 is a gas chromatogram of the product prepared by the decomposition reaction of the biomass of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.

However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of related arts will be omitted if it is determined that the gist of the present invention may be blurred .

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

Furthermore, terms including an ordinal number such as the first, second, etc. to be used below can be used to describe various elements, but the constituent elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component

Also, when an element is referred to as being "formed" or "laminated" on another element, it may be directly attached or laminated to the front surface or one surface of the other element, It will be appreciated that other components may be present in the < / RTI >

Hereinafter, the supercritical reaction extraction method of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Hereinafter, a method for decomposing biomass of the present invention will be described.

The method of decomposing a biomass of the present invention comprises the steps of: (a) preparing a mixture comprising a polar solvent, water, a non-polar solvent and biomass comprising water; (b) subjecting the mixture to solvent pyrolysis under subcritical or supercritical conditions to produce a biomass degradation product; (c) lowering the temperature after the solvent pyrolysis reaction to separate the biomass decomposition products into a lower layer containing a polar solvent dissolution component and a polar solvent, and a lower layer comprising a nonpolar solvent dissolution component and a nonpolar solvent in the biomass decomposition product ; (d) separating the upper layer from the upper and lower layers separated from each other; And (e) separating the nonpolar solvent soluble component from the nonpolar solvent in the separated upper layer.

Step (a): Biomass  Manufacture of an inclusion mixture

A mixture comprising a polar solvent comprising water, a non-polar solvent and biomass is prepared.

The polar solvent may include water, and may further include a polar solvent.

Substituted or unsubstituted straight chain alcohols of C1 to C10 or substituted or unsubstituted C3 to C10 branched alcohols may be used as the alcohols, and the groups corresponding to the substituents may be straight chain alkyl groups of C1 to C6 or C3 to C6 Lt; / RTI >

As the alcohol, methanol, ethanol, propanol, isopropanol, n-butanol, n-pentanol and n-hexanol may be used alone or in combination of two or more. Methanol or ethanol may be preferably used.

As the biomass, cellulose, lignocellulose, hemicellulose or lignin may be used alone or in combination of two or more kinds, preferably lignin.

Substituted or unsubstituted C5-C14 straight-chain alkyl, substituted or unsubstituted C5-C14 branched alkyl, substituted or unsubstituted C5-C14 cycloalkyl, substituted or unsubstituted C7- C14 alkylaryl, substituted or unsubstituted C7-C14 arylalkyl, or substituted or unsubstituted C10-C18 cycloalkylaryl, wherein the group corresponding to the substitution is a straight-chain alkyl group having from 1 to 6 carbon atoms, A branched alkyl group of C3 to C6, or a C6 to C10 cycloalkyl group.

As the non-polar solvent, it is possible to use n-pentane, iso- pentane, neopentane, cyclopentane, n-hexane, isohexane, n-heptane, cyclohexane, cycloheptane, n-heptane, n-decane, n-dodecane, benzene, toluene, xylene, tetralin, decalin, chloroform and dichloromethane can be used singly or in combination of two or more and preferably n-heptane or toluene.

Step (b): Biomass  Decomposition product preparation

The mixture is subjected to a solvent thermal decomposition reaction under subcritical or supercritical conditions to produce a biomass decomposition product.

In addition, the temperature of the solvent pyrolysis reaction may be set to 200 to 500 ° C. If the temperature is less than 200, the reaction rate of the solvent pyrolysis is too low, and if it is more than 500, the product will undergo over-decomposition reaction, which is not preferable.

In the solvent pyrolysis reaction, the pressure may be 4 to 40 MPa. If the pressure is less than 4 MPa, the reaction solvent is not sufficiently liquefied to lower the reaction efficiency. If the pressure is more than 40 MPa, the cost of the reaction equipment and the risk of leakage are increased.

Step (c): In the lower layer and the upper layer Layer separation

A lower layer containing a polar solvent dissolution component and a polar solvent in the biomass decomposition product by lowering the temperature to room temperature and normal pressure after the thermal decomposition reaction of the solvent and a lower layer comprising a nonpolar solvent dissolution component and a nonpolar solvent in the biomass decomposition product, .

Wherein the non-polar solvent soluble fraction of the biomass degradation product may be guaiacol, alkyl diacol, eugenol, vanillin, syringol and alkyl syringol.

Wherein the non-polar solvent soluble fraction of the biomass degradation product may be furfural, 5-hydroxymethylfurfural and derivatives thereof.

Step (d)

The upper layer is separated from the upper and lower layers separated from each other. The lower layer may be opened by opening the drain valve at the lower portion of the reactor.

Step (e): Nonpolar solvent  Separation of dissolved components

The non-polar solvent dissolution component can be separated from the non-polar solvent in the separated upper layer.

Wherein the nonpolar solvent dissolving component can be separated from the nonpolar solvent by distillation as a separation method.

It is preferable to use a nonpolar solvent which can be uniformly mixed with a polar solvent under subcritical or supercritical conditions and can be separated from a polar solvent under normal temperature and normal pressure conditions.

According to another aspect of the present invention, there is provided an organic compound which is a non-polar solvent dissolution component produced by the decomposition method of the biomass.

[Example]

Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.

Example  One

0.5 g of lignin, 2.5 g of water and 2.5 g of n-heptane were added to the high-pressure reactor to prepare a mixture, and a single phase was formed at a temperature of 350 ° C. to perform thermal decomposition of the solvent for 60 minutes. Where the reaction pressure was determined by the amount of solvent. After the pyrolysis of the solvent, the reactor was cooled to room temperature, the internal pressure was removed, and the pressure was lowered to an upper layer containing heptane and a lower layer containing water. The lower layer was separated to obtain an upper layer in which an organic compound such as hypohalcohol was dissolved, and the separated upper layer was distilled to obtain an organic compound.

Example  2

An organic compound was obtained in the same manner as in Example 1 except that toluene was used in place of n-heptane.

Example  3

An organic compound was obtained in the same manner as in Example 1, except that toluene was used instead of n-heptane and the reaction temperature was changed to 300 ° C instead of 350 ° C.

Example  4

The procedure of Example 1 was repeated except for using toluene instead of n-heptane and using 1.25 g of water and 1.25 g of water instead of 2.5 g of water and changing the reaction temperature to 300 ° C instead of 350 ° C. ≪ / RTI >

Example  5

The procedure of Example 1 was repeated except for using toluene instead of n-heptane and using 1.25 g of water and 1.25 g of methanol instead of 2.5 g of water and changing the reaction temperature to 300 ° C instead of 350 ° C. ≪ / RTI >

Comparative Example  One

An organic compound was obtained in the same manner as in Example 1 except that n-heptane was not used and 5 g of water was used instead of 2.5 g of water.

Comparative Example  2

An organic compound was obtained in the same manner as in Example 1 except that n-heptane was not used and 2.5 g of water and 2.5 g of methanol were used instead of 2.5 g of water and the reaction temperature was changed to 300 ° C instead of 350 ° C.

Temperature (℃) Time (min) menstruum Biomass decomposition product (yield,%) Water (wt) Polar solvent (wt) Nonpolar solvent (wt) Methanol ethanol n-heptane toluene Monomer Diacol Example 1 350 60 2.5 0 0 2.5 0 6.4 1.1 Example 2 350 60 2.5 0 0 0 2.5 6.7 2.3 Example 3 300 60 2.5 0 0 0 2.5 5.6 3.3 Example 4 300 60 1.25 0 1.25 0 2.5 3.0 1.3 Example 5 300 60 1.25 1.25 0 0 2.5 3.9 1.6 Comparative Example 1 350 60 5 0 0 0 0 0.1 0.1 Comparative Example 2 300 60 2.5 2.5 0 0 0 2.3 0.2

[Test Example]

Monomers and Hyacol Yield analysis

Referring to Table 1, the yield analysis of monomers including hypoacrole was carried out by gas chromatography. Referring to FIG. 1 and Table 1, in Comparative Example 1 in which only water is used as a solvent and in Example 1 in which water and heptane are used together, and in Example 2 in which water and toluene are used in combination, The yield of the reaction mixture was remarkably increased. When the yield of hyacinth, a representative component, was compared, it was confirmed that the yield was increased by 10 to 20 times.

Comparison of Comparative Example 2 using water and methanol as a solvent and Example 5 using water, methanol and toluene showed that the yield of the other components was not greatly changed, but the yield of hyperalcohol was increased 8 times. In the case of Example 4 in which ethanol was used instead of methanol, a selective increase in the yield of hyacolec can be confirmed.

Comparing the results of Examples 2 and 3, it can be confirmed that when the reaction temperature is lowered from 350 ° C to 300 ° C, the yield of the total monomers is lowered, but the yield of the hyperalcohol is increased and the selectivity is increased.

As described above, the biomass is introduced into a two-phase reaction system at room temperature composed of water, an arbitrary alcohol and an optional nonpolar solvent, followed by solvent pyrolysis under supercritical conditions and then returned to a room temperature state. It is a technology that can suppress the side reaction by separating the organic matter component immediately after the reaction.

Therefore, the pyrolysis technique of the present invention is a technology for pyrolysis of biomass in water or other organic solvent at high temperature and high pressure, and has a high reaction efficiency and low oxygen content of the reaction product as compared with the existing pyrolysis technology have. In addition, most of the biomass can be used directly without removing moisture, reducing the energy and cost of the pretreatment process.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (12)

(a) preparing a mixture comprising a polar solvent comprising water, a nonpolar solvent and biomass;
(b) subjecting the mixture to solvent pyrolysis under subcritical or supercritical conditions to produce a biomass degradation product;
(c) lowering the temperature after the solvent pyrolysis reaction to separate the biomass decomposition products into a lower layer containing a polar solvent dissolution component and a polar solvent, and a lower layer comprising a nonpolar solvent dissolution component and a nonpolar solvent in the biomass decomposition product ;
(d) separating the upper layer from the upper and lower layers separated from each other; And
(e) separating the nonpolar solvent soluble component from the nonpolar solvent in the separated upper layer;
A method of decomposing biomass, comprising: The method according to claim 1,
Wherein the polar solvent further comprises an alcohol,
Wherein the alcohol is a substituted or unsubstituted straight-chain C1 to C10 alcohol or a substituted or unsubstituted C3 to C10 branched alcohol,
Wherein the group corresponding to the substitution is a C1 to C6 linear alkyl group or a C3 to C6 branched alkyl group. 3. The method of claim 2,
Wherein the alcohol is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, n-pentanol and n-hexanol. The method according to claim 1,
Wherein the biomass is at least one selected from the group consisting of cellulose, lignocellulose, hemicellulose, and lignin. The method according to claim 1,
Wherein said nonpolar solvent is selected from the group consisting of substituted or unsubstituted C5 to C14 linear alkyls, substituted or unsubstituted C5 to C14 branched alkyls, substituted or unsubstituted C5 to C14 cycloalkyls, substituted or unsubstituted C7 to C14 Substituted or unsubstituted C7 to C14 arylalkyl, or substituted or unsubstituted C10 to C18 cycloalkylaryl,
Wherein the group corresponding to the substitution is a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, or a C6 to C10 cycloalkyl group. 6. The method of claim 5,
Wherein the nonpolar solvent is selected from the group consisting of n-pentane, iso-pentane, neopentane, cyclopentane, n-hexane, isohexane, n-heptane, cyclohexane, cycloheptane, Wherein the biomass is at least one selected from the group consisting of undecane, n-dodecane, benzene, toluene, xylene, tetralin, decalin, chloroform and dichloromethane. The method according to claim 1,
Wherein the solvent pyrolysis reaction is carried out at a temperature of 200 ° C to 500 ° C and a pressure of 4 to 40 MPa. The method according to claim 1,
Characterized in that the non-polar solvent soluble component of the biomass degradation product is at least one member selected from the group consisting of guaiacol, alkyl diacol, eugenol, vanillin, syringol and alkyl syringe. Of the biomass. The method according to claim 1,
Wherein the non-polar solvent soluble fraction of the biomass degradation product is at least one selected from the group consisting of furfural, 5-hydroxymethylfurfural and derivatives thereof. The method according to claim 1,
Wherein step (e) separates the non-polar solvent soluble component from the non-polar solvent by distillation. The method according to claim 1,
Wherein the nonpolar solvent is uniformly mixed with the polar solvent under subcritical or supercritical conditions and is separated from the polar solvent under normal temperature and normal pressure conditions. An organic compound which is a non-polar solvent dissolution component produced by the decomposition method of biomass according to claim 1.

Images