JP2014139283A - Production method of liquefied biomass and production system of liquefied biomass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of liquefied biomass, with which the liquefied biomass is produced from cellulose-based biomass at a low cost and with excellent efficiency.SOLUTION: A production system 100 of liquefied biomass comprises: a production plant 10 of liquefied biomass to produce the liquefied biomass from a cellulose-based biomass raw material; and a production plant 20 of biodiesel fuel to produce the biodiesel fuel from waste edible oil. Waste glycerin, which is a by-product of the biodiesel fuel and produced in the production plant 20 of biodiesel fuel, is supplied to the production plant 10 of liquefied biomass. In a mixing and impregnating treatment part 12, the cellulose-based biomass raw material and the waste glycerin are mixed with each other, and the cellulose-based biomass raw material is impregnated in the waste glycerin so that a substance impregnated in the waste glycerin is obtained. The impregnation substance is heat treated in a microwave heat treatment part 13 in the presence of an acid catalyst so that cellulose in the cellulose-based biomass raw material is liquefied.

Description

  The present invention relates to a method for producing a biomass liquefaction using cellulosic biomass as a raw material and a biomass liquefaction production system.

  With the background of global warming, energy problems, and the expectation for the multifaceted functions of forests, the effective use of biomass resources has attracted attention. Promising biomass resources from the perspective of reducing carbon dioxide, securing food resources, and conserving forest resources include herbaceous biomass (soft biomass, such as corn core, leaves, stems, rice straw, bacas, and palm shells). ), Woody biomass (hard biomass) such as thinned wood, construction waste, and forest land residue is drawing attention. Currently, processes for processing cellulose-based biomass containing these celluloses as raw materials and using them as liquid biomass fuels are being developed.

  In patent document 1, after adding the cellulosic biomass raw material obtained by pre-processing cellulosic biomass to organic solvents, such as ethylene glycol, and making a cellulosic biomass dispersion solution, the biomass heat-processed in presence of a solid catalyst A method for producing a liquefied fuel has been proposed.

JP 2011-89000 A

  The organic solvent such as ethylene glycol mixed with the cellulosic biomass material in Patent Document 1 is derived from petroleum, and thus contributes to an increase in the production cost of the biomass liquefied fuel, and to the fossil fuel by using renewable energy. There was still room for improvement in terms of reducing dependence on

  An object of this invention is to provide the manufacturing method of the biomass liquefaction which can manufacture a biomass liquefaction efficiently from a cellulosic biomass at low cost.

In order to solve the above problems, the method for producing a biomass liquefaction according to the present invention includes the following steps A and B;
A) A step of mixing a cellulose-based biomass raw material obtained by crushing cellulosic biomass and glycerin, impregnating the cellulose-based biomass raw material with the glycerin, and obtaining an impregnated product of glycerin,
B) A process of obtaining a biomass liquefaction by heat-treating the impregnated product in the presence of an acid catalyst and liquefying cellulose in the cellulose-based biomass raw material,
It has.

  In the method for producing a biomass liquefaction according to the present invention, the impregnation in the step A may be performed under reduced pressure.

  In the method for producing a biomass liquefaction according to the present invention, the acid catalyst may be a liquid, and may be added at a stage of mixing the cellulosic biomass raw material and the glycerin to obtain a mixture.

  In the method for producing a biomass liquefaction according to the present invention, the acid catalyst may be sulfuric acid.

  In the method for producing a biomass liquefaction according to the present invention, the heat treatment in the step B may be performed by microwave irradiation.

In the method for producing a biomass liquefaction according to the present invention, the step A is
A1) Crushing cellulosic biomass to obtain the cellulosic biomass raw material,
A2) A step of immersing the cellulosic biomass raw material in an organic solvent to extract an essential oil component contained in the cellulosic biomass raw material,
A3) A step of mixing the cellulosic biomass raw material and glycerin to obtain a mixture,
May be included.

  In the method for producing a biomass liquefaction according to the present invention, the organic solvent in the step A2 may be an organic solvent miscible with glycerin. In this case, the organic solvent may be an aliphatic monohydric alcohol having 1 to 10 carbon atoms or a monohydric alcohol having 1 to 5 carbon atoms.

  In the method for producing a biomass liquefaction according to the present invention, the cellulosic biomass may be woody biomass.

  In the method for producing a biomass liquefaction according to the present invention, the woody biomass may be derived from coniferous trees or hardwoods.

  In the method for producing a biomass liquefaction according to the present invention, the woody biomass may be derived from conifers.

  In the method for producing a biomass liquefaction according to the present invention, the woody biomass may contain bark.

  In the method for producing a biomass liquefaction according to the present invention, the glycerin in the step A may be obtained by purifying crude glycerin containing an alkali metal or an alkaline earth metal and water. in this case. The crude glycerin may further contain a fatty acid, a salt of fatty acid, or a fatty acid ester, and may also be a by-product of biodiesel fuel produced by transesterification of fats and oils.

  In the method for producing a biomass liquefaction according to the present invention, the biomass liquefaction may be used as a biomass liquefied fuel, a chemical raw material, a resin raw material, a caking additive, or a soil modifier.

  A biomass liquefaction production system according to the present invention includes a biodiesel fuel production plant that produces biodiesel fuel from biomass and a biomass liquefaction production plant that produces biomass liquefaction from cellulosic biomass raw materials. System. In this biomass liquefaction production system, the biodiesel fuel production plant supplies waste glycerin obtained as a by-product of biodiesel fuel to the biomass liquefaction production plant, and the biomass liquefaction production plant comprises the cellulose The biomass raw material and the waste glycerin are mixed, and after the cellulose-based biomass raw material is impregnated with the waste glycerin to obtain an impregnated waste glycerin, the impregnated product is heat-treated in the presence of an acid catalyst, It is characterized by liquefying cellulose in a cellulosic biomass raw material.

In the biomass liquefaction production system of the present invention, the biomass liquefaction production plant includes the following ac:
a) a treatment unit for subjecting the waste glycerin to a distillation treatment to reduce inorganic salts contained in the waste glycerin;
b) a processing unit for treating the waste glycerin with an ion exchange resin in order to reduce inorganic salts contained in the waste glycerin;
c) A processing unit for treating the waste glycerin with an organic acid in order to reduce the fatty acid or fatty acid ester contained in the waste glycerin;
You may have at least one of these.

  According to the present invention, by using glycerin as a solubilizer for cellulosic biomass, it can be used as a biomass liquefied fuel, a biomass-derived chemical raw material, a resin raw material, a caking additive, a soil modifier, etc. Possible biomass liquefaction can be efficiently produced at low cost. This can replace coal and oil. In particular, when waste glycerin, which is a by-product of biodiesel fuel, is used as glycerin, it is possible to reduce disposal costs and production costs and to effectively use carbon resources.

It is drawing which shows schematic structure of the biomass liquefaction manufacturing system which concerns on one embodiment of this invention. It is a graph which shows the measurement result of the time-dependent weight change of the glycerol impregnation amount to the cedar by the difference in impregnation conditions.

The manufacturing method of the biomass liquefaction of this Embodiment is the following process A and B;
A) A step of mixing a cellulosic biomass raw material obtained by crushing cellulosic biomass with glycerin, impregnating the cellulosic biomass raw material with glycerin, and obtaining an impregnated product of glycerin,
B) The step of obtaining a biomass liquefaction by heat-treating the impregnation obtained in step A in the presence of an acid catalyst and liquefying cellulose in the cellulosic biomass raw material,
Is provided.

[Step A]
In Step A, a cellulose-based biomass raw material obtained by crushing cellulose-based biomass and glycerin are mixed, and the cellulose-based biomass raw material is impregnated with glycerin to obtain an impregnated product of glycerin. This step A is
A1) Crushing cellulosic biomass to obtain a cellulosic biomass raw material,
A2) A step of immersing the cellulosic biomass material in an organic solvent to extract an essential oil component contained in the cellulosic biomass material,
A3) A step of mixing a cellulosic biomass raw material and glycerin to obtain a mixture,
A4) A step of impregnating the cellulose-based biomass raw material in the mixture obtained in step A3 with glycerin to obtain an impregnated product of glycerin,
Can be included.

<Woody biomass>
Cellulosic biomass used in step A1 is biomass containing cellulose, for example, herbaceous biomass (soft biomass) such as corn core / leaf / stem, rice straw, bacas, palm shell, thinned wood, construction waste, Examples include woody biomass (hard biomass) such as forest land residue. As woody biomass, for example, those derived from coniferous trees, those derived from broadleaf trees can be used. The woody biomass may include, for example, tree trunks, branches, bark, roots, leaves, fruits, seed coats, flowers, and the like.

<Crushing process>
Cellulose biomass can be crushed by, for example, a commercially available wood grinder. The particle size of the cellulosic biomass raw material obtained by crushing increases the impregnation efficiency of glycerin in step A and facilitates liquefaction in step B. For example, the thinnest thickness of the crushed pieces is 50 mm or less, preferably 0 It is preferable to be within a range of 3 to 6 mm. In addition, before performing a grinding | pulverization process, you may perform pre-processing, such as washing | cleaning and drying, with respect to cellulosic biomass. Here, when the drying pretreatment is performed, in order to facilitate the impregnation of glycerin, the amount of water contained in the cellulosic biomass is preferably not less than 5% by weight, and the water contained in the cellulosic biomass. It is particularly desirable that the amount of be about 40% by weight. From such a viewpoint, in order to adjust the moisture in the cellulosic biomass raw material, for example, immersion in water or continuous pouring of water can be performed as necessary.

<Extraction processing of essential oil components>
The extraction process of the essential oil component in step A2 is an optional step, and is preferably performed when the essential oil component is included in the cellulosic biomass raw material. For example, woody biomass derived from conifers contains more essential oil components such as terpenes than woody biomass derived from hardwoods, so it may be difficult to impregnate glycerin into cellulosic biomass materials after crushing . Therefore, it is preferable to implement this process A2 at the stage of the cellulosic biomass raw material after crushing with respect to the coniferous woody biomass.

  As the organic solvent in step A2, an organic solvent miscible with glycerin is preferably used. For example, an aliphatic monohydric alcohol having 1 to 10 carbon atoms or a ketone having 1 to 5 carbon atoms is preferably used. More preferably, it is a monohydric alcohol or ketone having 1 to 5 carbon atoms. Specifically, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, pentanol, acetone, methyl ethyl ketone, or the like is preferably used as the organic solvent.

  The method of extracting the essential oil component in step A2 is not particularly limited as long as the essential oil component can be extracted, but the cellulosic biomass raw material is immersed in an organic solvent and heated to a temperature in the range of 20 to 120 ° C., for example. It is preferable to do. In this case, the immersion time in the organic solvent is preferably in the range of 5 to 60 minutes.

<Glycerin>
As glycerin for solubilizing the cellulosic biomass material in step A3, industrial glycerin can be used. However, in order to effectively use waste and reduce the production cost of biomass liquefaction, for example, fats and oils It is more preferable to use crude glycerin such as waste glycerin, which is a by-product when producing biodiesel fuel by transesterification of the product, and waste glycerin, which is a by-product when producing soap and higher fatty acids.

  Waste glycerin, a by-product of biodiesel fuel, contains impurities such as inorganic salts such as sodium chloride, sodium sulfate, potassium chloride, sodium sulfate, fatty acids, fatty acid salts, fatty acid esters, and water. Impurities reduce the conversion efficiency to biomass liquefaction. The effect | action which solubilizes a cellulosic biomass raw material can be improved by performing the process which reduces the impurity in waste glycerin. For example, when waste glycerin contains inorganic salts such as sodium chloride, liquefaction is inhibited in the process of heat treatment using sulfuric acid as an acid catalyst, and the liquefied product is gelled to produce liquefied fuel. Conversion does not proceed efficiently, and the liquefaction rate decreases. Therefore, when waste glycerin is used, it is preferable to perform pretreatment in order to reduce the amount of inorganic salts contained in the waste glycerin, the amount of fatty acids, and fatty acid esters. As a pretreatment for reducing the amount of inorganic salts contained in the waste glycerin, the waste glycerin can be treated by, for example, distillation treatment, ion exchange resin treatment or the like. Further, as a pretreatment for reducing the amount of fatty acid or fatty acid ester contained in the waste glycerin, it is effective to treat the waste glycerin with, for example, an organic acid.

<Distillation treatment>
When performing the treatment by distillation, for example, simple distillation such as flash distillation can be performed, and multistage distillation can also be performed. In that case, any known means can be used such as atmospheric pressure or reduced pressure, or using an azeotropic material. By such treatment, fatty acids, fatty acid esters, fatty acid salts and the like can be removed in addition to metal salts.

<Ion exchange treatment>
When processing with an ion exchange resin, the metal content contained in waste glycerin can be removed using, for example, a cation exchange resin.

<Organic acid treatment>
As the organic acid used for the organic acid treatment, for example, organic acids having 1 to 4 carbon atoms such as formic acid, acetic acid, propionic acid, butanoic acid, maleic acid and fumaric acid are particularly preferable. The pH of the organic acid used for the organic acid treatment is preferably in the range of 1 to 4, for example, in order to efficiently extract inorganic salts into the aqueous phase.

  When waste glycerin is treated with an organic acid, for example, the waste glycerin and the organic acid may be sufficiently mixed and then allowed to stand, and the separated glycerin layer may be collected. The mixing ratio (weight ratio) of waste glycerin and organic acid in this organic acid treatment is preferably in the range of 1: 1 to 40: 1, for example, in order to sufficiently increase the removal efficiency of fatty acids and fatty acid esters. : More preferably, it is in the range of 1 to 20: 1. Moreover, it is preferable to reduce to 1 weight part or less of content of the inorganic salt contained in glycerol after an organic acid process with respect to 100 weight part of glycerol after an organic acid process. Organic acids are considered to remove them by binding to fatty acids and fatty acid esters contained in waste glycerin. The organic acid also has an action of removing them by binding to metal ions in the metal salt.

  When glycerin used for solubilizing the cellulosic biomass in this embodiment and ethylene glycol, which is a known solubilizer, are compared, ethylene glycol liquefies hemicellulose and lignin first, but glycerin is cellulose and It is considered that the mechanism of action is different in that hemicellulose is liquefied predominantly.

<Mixing process>
The mixing of the cellulosic biomass raw material and glycerin in step A3 can be performed at room temperature, for example. As will be described later, when a liquid acid catalyst is used as the acid catalyst, it can be added in this mixing step.

<Impregnation treatment>
Impregnation of glycerol into the cellulosic biomass raw material in step A4 can be performed under normal pressure conditions, pressurized conditions, or reduced pressure conditions. From the viewpoint of shortening the impregnation time, it is preferable to carry out under reduced pressure. The decompression condition is preferably in the range of 0.001 to 0.1 MPa, more preferably in the range of 0.005 to 0.03 MPa, for example, in order to allow impregnation of glycerin in a short time. . In the case of normal pressure conditions, the impregnation time is preferably in the range of 24 hours to 240 hours, for example, in order to increase the liquefaction efficiency by the heat treatment in Step B. For example, in the case of a reduced pressure condition in the range of 0.005 to 0.03 MPa, the impregnation time is preferably in the range of, for example, 5 minutes to 120 minutes in order to increase the liquefaction efficiency by the heat treatment in Step B. As an end point of the glycerol impregnation treatment to the cellulosic biomass raw material, the weight increase rate after the impregnation treatment based on the weight of the cellulosic biomass raw material before the impregnation treatment is, for example, 200% or more, preferably 400% or more. Time points can be used as a guide. When the weight increase rate after the impregnation treatment is less than 200%, solubilization of cellulose by glycerin becomes insufficient, and the liquefaction rate tends to decrease.

[Step B]
In Step B, the biomass liquefaction product can be obtained by heat-treating the impregnation product in the presence of an acid catalyst to liquefy the cellulose in the cellulosic biomass raw material.

<Acid catalyst>
Examples of the acid catalyst include Bronsted, such as sulfuric acid, hydrochloric acid, nitric acid, persulfuric acid, perchloric acid, formic acid, acetic acid, phthalic acid, maleic acid, fumaric acid, succinic acid, malic acid, citric acid, and paratoluenesulfonic acid. Liquid acid catalysts such as acids, Lewis acids such as theolite, silica alumina, and alumina, activated carbons having acidic groups such as sulfone groups, solid acid catalysts such as graphite and coke, and the like can be used.

  The acid catalyst may be present in the impregnated product during the heat treatment in Step B, but it is preferably added at the stage of mixing the cellulosic biomass raw material and glycerin in Step A3 to obtain a mixture. From such a viewpoint, it is preferable to use a liquid acid catalyst such as sulfuric acid as the acid catalyst.

  The addition amount of the acid catalyst is preferably in the range of 0.5 to 15 parts by weight, for example, in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the cellulose-based biomass raw material from the viewpoint of increasing the efficiency of liquefaction. The content is more preferably in the range, and most preferably in the range of 3 to 5 parts by weight.

<Heat treatment>
In the process B, the method of heat-treating the impregnated material is not particularly limited, and for example, heating by microwave irradiation, heating by electricity such as a heating coil or a heater, indirect heating by induction heating or infrared rays, direct or by combustion of fuel or It can be performed by indirect heating, heating by the above or a heat medium, or the like. Among these, heating by microwave irradiation capable of uniform and rapid heat treatment is more preferable. For example, the frequency of the microwave may be 2.45 GHz, and the output may be in the range of 0.3 KW to 1000 KW. In addition to commercially available microwave heating devices (for example, manufactured by Milestone General Co., trade name ETHOS), microwave irradiation is performed on the industrial level by microwave oscillators such as semiconductor oscillators, vacuum tube oscillators, traveling wave tubes, magnetrons. Or a klystron or a gyrotron.

  From the viewpoint of increasing the efficiency of liquefaction, the temperature at which the impregnated material is heat-treated can be set within a range of 100 to 300 ° C., for example.

<Biomass liquefaction>
The biomass liquefied product obtained as described above is obtained by liquefying cellulose, hemicellulose, and lignin in cellulosic biomass raw materials in glycerin. For example, biomass liquefied fuel, biomass-derived chemical raw materials, resin raw materials, caking It can be preferably used as a material, a soil modifier, or the like.

<Biomass liquefied fuel>
Biomass liquefaction is as it is, for example, boiler fuel, heating fuel, fuel for power generation, fuel for firing during cement production, fuel in ceramic industry, fuel for iron making, fuel for mining industry, fuel for chemical industry, fuel for oil refining, agriculture It can be used as industrial fuel such as industrial fuel, auxiliary fuel during waste combustion treatment, and fuel for hot water supply. Further, the biomass liquefied fuel can be used as a petroleum alternative fuel with higher combustion efficiency by refining and reforming.

<Chemical raw materials, resin raw materials>
By liquefying biomass, each component such as cellulose, hemicellulose, and lignin can be easily taken out. Therefore, the biomass liquefaction is further subjected to chemical reactions usually used such as decomposition, hydrogenation, esterification, transesterification, polymerization, and separation operations such as distillation, extraction, recrystallization, etc. Can be processed into resin products. Thus, biomass liquefaction can be utilized as a chemical raw material or a resin raw material.

<Soil modifier>
The liquefied biomass obtained by liquefying biomass can be used as a soil modifier having a low toxicity and a low environmental impact, which is entirely made of natural products. Thereby, the soil with small water retention can be improved. In addition, the soil can be improved by easily solidifying the soil that has low cohesiveness and is easily scattered by wind and rain.

<Binder>
The liquefied biomass obtained by liquefying the biomass can be used as a caking material composed entirely of biomass. Thereby, coal, wood, or the like, or solid matter or solid fuel such as a pulverized product or dry-distilled product thereof can be caking.

[Biomass liquefaction manufacturing system]
Next, a biomass liquefaction manufacturing system according to an embodiment of the present invention will be described with reference to FIG. In FIG. 1, schematic structure of the biomass liquefaction manufacturing system 100 is shown. The biomass liquefaction production system 100 includes a biomass liquefaction production plant 10 that produces biomass liquefaction from cellulosic biomass, and a biodiesel fuel production plant 20 that produces biodiesel fuel from waste cooking oil.

  The biomass liquefaction manufacturing plant 10 manufactures liquefaction from cellulosic biomass such as thinned wood other than wood products such as timber produced from forest resources. The biomass liquefaction manufacturing plant 10 mixes a pulverization processing unit 11 that crushes cellulose-based biomass to obtain a cellulose-based biomass material, a cellulose-based biomass material, and glycerin, impregnates the cellulose-based biomass material with glycerin, and glycerin. The mixing / impregnation processing unit 12 for obtaining the impregnated product and the microwave heating processing unit 13 for heat-treating the impregnated product with microwaves in the presence of an acid catalyst to liquefy the cellulosic biomass material. The pulverization processing unit 11 performs the process A1. The mixing / impregnation processing unit 12 performs the processes of the above steps A3 and A4. The mixing / impregnation processing unit 12 may be divided into a mixing unit and an impregnation unit. In the microwave heating process part 13, the process B is performed.

  Moreover, the biomass liquefaction manufacturing plant 10 may be equipped with the essential oil extraction process part 14 which immerses a cellulose biomass raw material in an organic solvent and extracts an essential oil component as arbitrary structures. The essential oil extraction processing unit 14 performs the process A2. Furthermore, as an arbitrary configuration, a moisture impregnation processing unit (not shown) for adjusting the moisture content of the cellulosic biomass raw material may be provided.

  Furthermore, the biomass liquefaction manufacturing plant 10 is provided with a simple distillation apparatus, ion exchange apparatus, organic acid addition apparatus, tanks for these, etc. for pre-processing waste glycerin as an arbitrary configuration. be able to. For example, as shown in FIG. 1, the biomass liquefaction manufacturing plant 10 is an organic acid treatment unit 15 </ b> A that performs organic acid treatment on waste glycerin as a treatment unit for performing pretreatment, and distillation on waste glycerin. A distillation processing unit 15B that performs processing, an ion exchange processing unit 15C that performs ion exchange processing on waste glycerin, and the like can be included. In the organic acid treatment unit 15A, the distillation treatment unit 15B, and the ion exchange treatment unit 15C, an organic acid treatment, a distillation treatment, and an ion exchange treatment can be performed as pretreatment for the waste glycerin, respectively.

  In FIG. 1, the essential oil extraction processing unit 14, the organic acid processing unit 15 </ b> A, the distillation processing unit 15 </ b> B, the ion exchange processing unit 15 </ b> C, and the path through these are shown by broken lines.

  The biodiesel fuel production plant 20 includes a pretreatment unit 21 that performs pretreatment such as deoxidation and dehydration on waste cooking oil as biomass, and an esterification treatment that performs an esterification reaction between the waste cooking oil after pretreatment and methanol. And a separation processing unit 23 for separating the fatty acid methyl ester obtained by the esterification reaction and the waste glycerin. In the biodiesel fuel production plant 20, triglyceride in waste cooking oil is deoxidized and dehydrated in the pretreatment unit 21, and then esterified with methanol in the presence of a catalyst such as potassium hydroxide or sodium hydroxide to biodiesel fuel. The fatty acid methyl ester which is the main component of (BDF (registered trademark)) is produced. Biodiesel fuel and waste glycerin are separated by the specific gravity difference in the separation processing unit 23.

  In the biomass liquefaction production system 100 of the present embodiment, waste glycerin obtained as a by-product of biodiesel fuel in the biodiesel fuel production plant 20 is supplied to the biomass liquefaction production plant 10 for effective use. That is, the biomass liquefaction manufacturing plant 10 mixes the cellulosic biomass raw material and waste glycerin in the mixing / impregnation processing unit 12, and impregnates the cellulosic biomass raw material with waste glycerin to obtain an impregnation product of waste glycerin. This impregnated material is heat-treated in the presence of an acid catalyst in the microwave heat treatment unit 13 to liquefy the cellulosic biomass material.

  As described above, in the biomass liquefaction production system 100 according to the present embodiment, waste produced as a by-product in the biodiesel fuel production plant 20 by linking the biomass liquefaction production plant 10 and the biodiesel fuel production plant 20. Glycerin can be used for solubilization of the cellulosic biomass material in the biomass liquefaction manufacturing plant 10. Therefore, it is possible to effectively use waste glycerin and reduce the disposal cost and the manufacturing cost.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following examples, various measurements and evaluations are as follows unless otherwise specified.

[Measurement of liquefaction rate]
The measurement of the liquefaction rate of the cellulosic biomass raw material was carried out using the reaction product after the liquefaction reaction as filter paper No. Suction-filter using 5A, collect the filtrate as a biomass liquefaction, dry the filtrate as a residue, weigh it, and subtract the ratio of the residue (wt%) to the charged amount (dry) from 100. Calculated as a percentage (%).
Liquefaction rate (%) = 100−residue (dry) / charged amount (dry) × 100

[Measurement of viscosity]
The viscosity was measured at 20 ° C. based on the JIS-K-2283 crude oil and petroleum product-kinematic viscosity test method and viscosity index calculation method.

Hereinafter, the cellulosic biomass raw materials, glycerin and their abbreviations used in the examples of the present invention are as follows.
(A) Cellulose biomass raw material beech (1): beech (hardwood) fine powdered sawdust (particle size; less than 0.425 mm)
Beech (2): Beech sawdust (particle size; 0.425 mm to 1 mm)
Cherry (1): Cherry (hardwood) sawdust (particle size; 0.425 mm to 1 mm)
Cedar (1): fine powder of cedar (coniferous) oga powder (particle size; less than 0.425 mm), as a result of component analysis by the Van Soest method, cellulose: 41.3 wt%, hemicellulose: 14.7 wt%, lignin: 32. 3 wt%, essential oil components such as terpenes; 2.2 wt%, ash content: 0.3 wt%.
Cedar (2): Cedar chips (particle size: 2cm-3cm, length: 3cm-5cm)
Bark (1): Cedar bark (particle size: 0.425 mm to 1 mm), as a result of component analysis by VanSoest method, cellulose: 27.8 wt%, hemicellulose; 13.5 wt%, lignin: 13.5 wt%, terpenes It was 21.4 wt%, ash content; 2.2 wt%.

(B) Glycerol Glycerin (1): Wako Pure Chemical Industries, Ltd., reagent glycerin (purity: 99 wt%, organic impurities; 0 wt%, moisture: 789 ppm, viscosity: 1,499 mPa · s, appearance: colorless and transparent liquid, pH; 6)
Glycerin (2): Waste glycerin (purity; produced as a by-product when a biodiesel fuel containing fatty acid methyl ester as a main component is produced by adding methanol and potassium hydroxide to an oil and fat containing waste edible oil to cause a transesterification reaction. 40-50 wt%, organic impurities; 30-40 wt% as fatty acid esters, moisture; 0.84 wt%, viscosity; 530 mPa · s, black liquid, pH; 11)

[Example 1]
After mixing 10 g of beech (1) with 90 g of glycerin (1), 0.6 g of 50 wt% sulfuric acid was added and mixed. This mixture was allowed to stand at room temperature for 3 days in the atmosphere to obtain a glycerin impregnated product 1.

  The obtained glycerin impregnated product 1 was heated at 200 ° C. for 20 minutes (maximum temperature reached: 204 ° C.) using a microwave heating apparatus (product name: ETHOS, manufactured by Milestone General Co.), and the biomass liquefied product 1 was obtained. Obtained. The liquefaction rate at this time was 95.1%. The results are shown in Table 1.

[Example 2]
After mixing 10 g of beech (2) with 90 g of glycerin (1), 0.6 g of 50 wt% sulfuric acid was added and mixed. The mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator and held at room temperature for 30 minutes to obtain a glycerin impregnated product 2.

  In the same manner as in Example 1, the obtained glycerin impregnated product 2 was heated at 200 ° C. for 20 minutes by microwave irradiation (maximum reached temperature; 204 ° C.) to obtain a biomass liquefaction product 2. The liquefaction rate at this time was 88.6%. The results are shown in Table 1.

[Example 3]
After 10 g of cherry (1) was mixed with 90 g of glycerin (1), 0.6 g of 50 wt% sulfuric acid was added and mixed. This mixture was allowed to stand at room temperature for 24 hours in the atmosphere to obtain a glycerin impregnated product 3.

  In the same manner as in Example 1, the obtained glycerin impregnated product 3 was heated at 200 ° C. for 20 minutes by microwave irradiation (maximum reached temperature; 204 ° C.) to obtain a biomass liquefaction product 3. The liquefaction rate at this time was 76.1%. The results are shown in Table 1.

[Example 4]
After mixing 10 g of cedar (1) with 90 g of glycerin (1), 0.6 g of 50 wt% sulfuric acid was added and mixed. The mixture was allowed to stand at room temperature for 3 days in the atmosphere to obtain a glycerin impregnated product 4.

  In the same manner as in Example 1, the obtained glycerin impregnated product 4 was heated at 200 ° C. for 20 minutes by microwave irradiation (maximum reached temperature; 204 ° C.) to obtain a biomass liquefaction product 4. The liquefaction rate at this time was 65.9%. The results are shown in Table 1.

  The results of Examples 1 to 4 are summarized in Table 1.

[Example 5]
After mixing 10 g of cedar (2) with 90 g of glycerin (1), 0.6 g of 50 wt% sulfuric acid was added and mixed. The mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator and held at room temperature for 30 minutes to obtain glycerin impregnated product 5.

  In the same manner as in Example 1, the obtained glycerin impregnated product 5 was heated at 200 ° C. for 20 minutes by microwave irradiation (maximum reached temperature; 201 ° C.) to obtain a biomass liquefaction product 5. The liquefaction rate at this time was 84.6%. Moreover, the residue which remained on the filter paper was wash | cleaned with methanol by the synthesis | combination of biomass liquefaction 5, and the methanol melt | dissolution component was removed. After the residue was dried, the liquefaction rate was calculated to be 87.1%. The results are shown in Table 2.

[Example 6]
After 10 g of cedar (2) was mixed with 90 g of glycerin (1), 0.6 g of 50 wt% sulfuric acid was added and mixed. This mixture was allowed to stand at room temperature for 6 days in the atmosphere to obtain a glycerin impregnated product 6.

The obtained glycerin impregnated product 6 was subjected to a heat treatment by microwave irradiation in the same manner as in Example 1 to obtain a biomass liquefied product 6. The liquefaction rate at this time was 69.2%.
Moreover, the residue which remained on the filter paper was wash | cleaned with methanol by the synthesis | combination of the biomass liquefaction 6, and the methanol melt | dissolution component was removed. After this residue was dried, the liquefaction rate was calculated to be 70.4%. The results are shown in Table 2.

[Example 7]
Cedar (2) was immersed in methanol, boiled at 70 ° C. for 30 minutes, and then filtered to obtain cedar (2) ′. When the methanol solvent after the immersion treatment was analyzed by gas chromatography, peaks derived from essential oil components (essential oil components such as terpenes) were confirmed.

  A glycerin-impregnated product 7 was obtained in the same manner as in Example 5 except that cedar (2) 'was used instead of the cedar (2) in Example 5, and further a biomass liquefaction product 7 was obtained. The liquefaction rate at this time was 83.6%. The results are shown in Table 2.

[Example 8]
Cedar (2) was immersed in methanol, boiled at 70 ° C. for 30 minutes, and filtered to obtain cedar (2) ′. Then, glycerin impregnated product 8 was obtained in the same manner as in Example 6, and biomass was further obtained. Liquid product 8 was obtained. The liquefaction rate at this time was 82.9%. The results are shown in Table 2.

[Example 9]
Cedar (1) was immersed in methanol, boiled at 70 ° C. for 30 minutes, and filtered to obtain cedar (1) ′. Then, glycerin impregnated product 9 was obtained in the same manner as in Example 4, and biomass was further obtained. A liquefied product 9 was obtained. The liquefaction rate at this time was 68.9%. Moreover, the residue which remained on the filter paper was wash | cleaned with methanol by the synthesis | combination of the biomass liquefaction 9, and the methanol melt | dissolution component was removed. After the residue was dried, the liquefaction rate was calculated to be 89.4%.
The results are shown in Table 2.

[Example 10]
Cedar (1) is immersed in methanol, boiled at 70 ° C. for 30 minutes, filtered to obtain cedar (1) ′, 10 g of cedar (1) ′ is dispersed in 90 g of glycerin (1) After that, 0.6 g of 50 wt% sulfuric acid was added and mixed. The mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator and held at room temperature for 30 minutes to obtain a glycerin impregnated product 10.

  The obtained glycerin impregnated product 10 was subjected to heat treatment by microwave irradiation in the same manner as in Example 1 to obtain a biomass liquefaction product 10. The liquefaction rate at this time was 68.9%. Moreover, by synthesizing the biomass liquefaction 10, the residue 10 remaining on the filter paper was washed with methanol to remove methanol-soluble components. After the residue was dried, the liquefaction rate was calculated to be 97.6%. The results are shown in Table 2.

[Example 11]
After mixing 10 g of bark (1) with 90 g of glycerin (1), 0.6 g of 50 wt% sulfuric acid was added and mixed. The mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator and held at room temperature for 30 minutes to obtain glycerin impregnated product 11.

  The obtained glycerin impregnated material 11 was heated at 200 ° C. by microwave irradiation for 15 minutes to obtain a biomass liquefied material 11. The liquefaction rate at this time was 8.0%. The results are shown in Table 2.

[Example 12]
The bark (1) was immersed in methanol, boiled at 70 ° C. for 30 minutes, and then filtered to obtain bark (1) ′. After 10 g of bark (1) ′ was dispersed in 90 g of glycerin (1), 0.6 g of 50 wt% sulfuric acid was added and mixed. The mixture was depressurized to 0.0095 MPa to 0.015 MPa using a vacuum desiccator and held at room temperature for 30 minutes to obtain glycerin impregnated product 12.

  The obtained glycerin impregnated material 12 was subjected to heat treatment by microwave irradiation in the same manner as in Example 11 to obtain a biomass liquefied material 12. The liquefaction rate at this time was 44.3%. The results are shown in Table 2.

  The results of Examples 5 to 12 are summarized in Table 2.

  From Example 10, when the undissolved part was washed with methanol, the liquefaction rate was improved, and it was possible to dissolve almost. This is considered that a part of the undissolved part contains components such as polymerized lignin, which are dissolved in methanol. Moreover, in the process of liquefaction of biomass raw material, in the chip-shaped cedar (2), the glycerin impregnation condition tends to affect the effect, and in the fine cedar (1), pulverization promotes resinization. For this reason, it has been found that washing the residue after liquefaction with an organic solvent tends to affect the effect.

<Verification of glycerin impregnation amount>
10 g of cedar (2) was mixed with 90 g of glycerin (1), and the change in weight of cedar (2) over time due to different impregnation conditions was measured. The measurement results are shown in FIG. The vertical axis in FIG. 2 indicates the weight ratio of the cedar (2) before impregnation to the weight of 1.0, and the horizontal axis indicates “classification of impregnation time”. In addition, “vacuum” in FIG. 2 is a measured value of a sample impregnated under a reduced pressure of 0.0095 MPa to 0.015 MPa, and “left” is a measured value of a sample impregnated by being left in the atmosphere. is there. The contents of the impregnation time category are as shown in Table 3. According to this verification, it is considered that the 30-minute vacuum impregnation of glycerin has an effect comparable to the 6-day standing impregnation.

(Example 13)
Arbitrary residue 13 'obtained by the synthesis of the biomass liquefaction of each example was collected, and the methanol solvent after the immersion treatment in methanol was analyzed by gas chromatography. As a result, it was derived from essential oil components (terpenes). The peak to be confirmed was confirmed.

  5 g of the residue 13 'was collected and mixed with 45 g of glycerin (1), and 0.3 g of 50 wt% sulfuric acid was added and mixed. The mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, and held at room temperature for 30 minutes to obtain a glycerin impregnated product 13.

  The obtained glycerin impregnated product 13 was heated at 200 ° C. for 15 minutes by microwave irradiation to obtain a biomass liquefaction product 13. At this time, the liquefaction rate with respect to the residue 13 'was 92.6%. According to Example 13, it was found that the residue that was insufficiently liquefied could be liquefied by extraction with essential oil and glycerol impregnation under reduced pressure.

[Example 14]
A biomass liquefaction 14 was obtained in the same manner as in Example 6 except that heating with a mantle heater was used instead of the heating treatment with microwave irradiation in Example 6. The liquefaction rate at this time was 73.3%. The results are shown in Table 4.

[Example 15]
After mixing 20 g of cedar (2) with 80 g of glycerin (1), 2.4 g of 25 wt% sulfuric acid was added and mixed. This mixture was allowed to stand at room temperature for 20 days in the atmosphere to obtain a glycerin impregnated product 15.

  The obtained glycerin impregnated product 15 was heated at 200 ° C. for 20 minutes by microwave irradiation (maximum temperature reached: 205 ° C.) to obtain a biomass liquefied product 15. The liquefaction rate at this time was 56.4%. The results are shown in Table 4.

(Reference Example 1)
A heat treatment was performed in the same manner as in Example 15 except that a normal heat treatment with a mantle heater was used instead of the heat treatment by microwave irradiation in Example 15, but the biomass liquefaction component was fixed. The results are shown in Table 4.

  The results of Examples 14 and 15 and Reference Example 1 are shown in Table 4. In addition, “raw material concentration [wt%]” in Table 4 indicates a ratio (wt%) of the biomass raw material to the total amount of the biomass raw material and the glycerin used.

[Example 16]
A biomass liquefaction 16 was obtained in the same manner as in Example 6 except that heating at 200 ° C. for 10 minutes by microwave irradiation was used instead of heating at 200 ° C. for 20 minutes by microwave irradiation in Example 6. The liquefaction rate at this time was 46.5%. The results are shown in Table 5.

[Example 17]
A biomass liquefaction 17 was obtained in the same manner as in Example 6 except that heating at 210 ° C. for 10 minutes by microwave irradiation was used instead of heating at 200 ° C. for 20 minutes by microwave irradiation in Example 6. The liquefaction rate at this time was 81.4%. The results are shown in Table 5.

[Example 18]
A biomass liquefaction 18 was obtained in the same manner as in Example 6 except that heating at 220 ° C. for 10 minutes by microwave irradiation was used instead of heating at 200 ° C. for 20 minutes by microwave irradiation in Example 6. The liquefaction rate at this time was 95.0%. The results are shown in Table 5.

  The results of Examples 16 to 18 are summarized and shown in Table 5.

(Reference Example 2)
After mixing 7 g of concentrated sulfuric acid with 100 ml of glycerin (2), the mixture was allowed to stand for 3 days in a separatory funnel. After the lower layer separated into two layers was separated, a solid containing potassium sulfate was filtered to obtain a filtrate having a pH of about 2. 27 g of the obtained filtrate was mixed with 3 g of cedar (2) and allowed to stand at room temperature for 7 days in the atmosphere, and then heated at 200 ° C. for 15 minutes by microwave irradiation, but the cedar (2) was almost liquefied. I didn't.

(Reference Example 3)
After mixing 100 ml of glycerin (2) and 100 ml of distilled water, 6.7 g of concentrated sulfuric acid was mixed, and then allowed to stand overnight in a separatory funnel. After the lower layer separated into two layers was separated, a solid containing potassium sulfate was filtered to obtain a filtrate having a pH of about 3 to 4. 27 g of the obtained filtrate was mixed with 3 g of cedar (2) and allowed to stand at room temperature for 7 days in the atmosphere, and then heated at 200 ° C. for 15 minutes by microwave irradiation, but the cedar (2) was almost liquefied. I didn't.

(Reference Example 4)
After mixing 70.3 g of glycerin (2), 20.1 g of methanol, and 6.5 g of concentrated sulfuric acid, the mixture was allowed to stand for 48 hours. After separating the glycerin layer separated into three layers (upper layer; fatty acid ester, middle layer to lower layer; glycerin layer, lower layer; precipitation of potassium sulfate), solids containing potassium sulfate were filtered. 27 g of the obtained filtrate was mixed with 3 g of cedar (2) and allowed to stand at room temperature for 7 days in the atmosphere, and then heated at 200 ° C. for 15 minutes by microwave irradiation, but the cedar (2) was almost liquefied. I didn't.

[Example 19]
After mixing 40 ml of acetic acid with 200 ml of glycerin (2), the mixture was allowed to stand overnight in a separatory funnel. The lower layer (glycerin layer) separated into two layers was collected. The collected 80 to 100 ml glycerin layer is mixed with 50 wt% sulfuric acid to make it acidic, and 3 g of cedar (2) is mixed with 27 g of the solution from which the solids containing potassium sulfate have been removed, and the atmosphere is kept at room temperature for 4 days. After standing, biomass liquefaction 19 was obtained by heating at 200 ° C. for 15 minutes by microwave irradiation. The liquefaction rate at this time was about 10 to 20%.

[Example 20]
A biomass liquefaction 20 was obtained in the same manner as in Example 19 except that heating at 210 ° C. for 15 minutes by microwave irradiation was used instead of heating at 200 ° C. for 15 minutes by microwave irradiation in Example 19. The liquefaction rate at this time was about 70 to 80%.

[Example 21]
Instead of being left at room temperature for 4 days in the atmosphere in Example 19, the pressure was reduced to 0.0095 MPa to 0.015 MPa and kept at room temperature for 30 minutes, and instead of heating at 200 ° C. for 15 minutes by microwave irradiation, A biomass liquefaction 21 was obtained in the same manner as in Example 19 except that heating was performed at 210 ° C. for 15 minutes by microwave irradiation. The liquefaction rate at this time was 80 to 90%. In addition, the boiling of the solvent was confirmed in the said pressure reduction. This is thought to be due to the boiling of low-boiling substances produced by mixing water or acetic acid in the solvent.

[Example 22]
After mixing 11.0 g of acetic acid with 151.1 g of glycerin (2) [weight ratio of glycerin (2) and acetic acid; 14: 1], the mixture was allowed to stand for 2 hours in a separatory funnel. The lower layer (glycerin layer) separated into two layers was collected. 9.8 g of 50 wt% sulfuric acid was mixed with the collected 69.4 g of glycerin layer (pH; 8), and then allowed to stand for 3 hours. The solid matter containing precipitated potassium sulfate was filtered off to obtain 62.0 g of glycerin (4) (pH; 4).

  After 3 g of cedar (2) was mixed with 27 g of glycerin (4), 0.18 g of 50 wt% sulfuric acid was added and mixed. This mixture was allowed to stand at room temperature overnight in the atmosphere, and then biomass liquefaction 22 was obtained by heating at 210 ° C. for 15 minutes by microwave irradiation. The liquefaction rate at this time was 48.0%. The results are shown in Table 6.

[Example 23]
In the same manner as in Example 22, glycerin (4) was prepared. A biomass liquefied product 23 was obtained in the same manner as in Example 22 except that 0.21 g of 50 wt% sulfuric acid was added instead of adding 0.18 g of 50 wt% sulfuric acid in Example 22. The liquefaction rate at this time was 84.7%. The results are shown in Table 6.

[Example 24]
In the same manner as in Example 22, glycerin (4) was prepared. A biomass liquefaction 24 was obtained in the same manner as in Example 22 except that 0.24 g of 50 wt% sulfuric acid was added instead of adding 0.18 g of 50 wt% sulfuric acid in Example 22. The liquefaction rate at this time was 70.3%. The results are shown in Table 6.

[Example 25]
In the same manner as in Example 22, glycerin (4) was prepared. A biomass liquefaction 25 was obtained in the same manner as in Example 22 except that 0.38 g of 50 wt% sulfuric acid was added instead of adding 0.18 g of 50 wt% sulfuric acid in Example 22. The liquefaction rate at this time was 68.0%. The results are shown in Table 6.

[Example 26]
Instead of glycerin (4) prepared with a weight ratio of glycerin (2) and acetic acid in Example 22 of 14: 1, glycerin (5) prepared with a weight ratio of glycerin (2) and acetic acid of 10: 1 was prepared. did.

  After 3 g of cedar (2) was mixed with 27 g of glycerin (4), 0.18 g of 50 wt% sulfuric acid was added and mixed. The mixture was allowed to stand overnight at room temperature in the atmosphere, and then heated to 210 ° C. by microwave irradiation for 15 minutes to obtain a biomass liquefaction 26. The liquefaction rate at this time was 35.3%. The results are shown in Table 6.

[Example 27]
In the same manner as in Example 26, glycerin (5) was prepared. Instead of adding 0.18 g of 50 wt% sulfuric acid in Example 26, biomass liquefaction 27 was obtained in the same manner as in Example 26, except that 0.24 g of 50 wt% sulfuric acid was added. The liquefaction rate at this time was 65.0%. The results are shown in Table 6.

[Example 28]
In the same manner as in Example 26, glycerin (5) was prepared. Instead of adding 0.18 g of 50 wt% sulfuric acid in Example 26, a biomass liquefaction 28 was obtained in the same manner as in Example 26, except that 0.3 g of 50 wt% sulfuric acid was added. The liquefaction rate at this time was 74.7%. The results are shown in Table 6.

[Example 29]
Instead of glycerin (4) prepared with a weight ratio of glycerin (2) and acetic acid in Example 22 of 14: 1, glycerin (6) prepared with a weight ratio of glycerin (2) and acetic acid of 20: 1 was prepared. did.

  After 3 g of cedar (2) was mixed with 27 g of glycerin (6), 0.18 g of 50 wt% sulfuric acid was added and mixed. The mixture was allowed to stand overnight at room temperature in the atmosphere, and then heated to 210 ° C. by microwave irradiation for 15 minutes to obtain a biomass liquefaction 29. The liquefaction rate at this time was 67.0%. The results are shown in Table 6.

[Example 30]
In the same manner as in Example 29, glycerin (6) was prepared. Instead of adding 0.18 g of 50 wt% sulfuric acid in Example 29, biomass liquefaction 30 was obtained in the same manner as in Example 29, except that 0.24 g of 50 wt% sulfuric acid was added. The liquefaction rate at this time was 68.7%. The results are shown in Table 6.

[Example 31]
In the same manner as in Example 29, glycerin (6) was prepared. After 3 g of cedar (2) was mixed with 27 g of glycerin (6), 0.18 g of 50 wt% sulfuric acid was added and mixed. This mixture was allowed to stand at room temperature for 7 days in the atmosphere, and then biomass liquefaction 31 was obtained by heating at 210 ° C. for 15 minutes by microwave irradiation. The liquefaction rate at this time was 84.2%. The results are shown in Table 6.

  The results of Examples 22 to 31 are summarized in Table 6. “Glycerin (2): acetic acid” in Table 6 indicates “weight ratio of glycerin (2) and acetic acid when glycerin (2) is treated with acetic acid”, and “sulfuric acid concentration [wt%]”. Means the weight part of the added sulfuric acid with respect to 100 weight part of used cedar (2).

[Example 32]
After mixing 10 g of cedar (2) with 90 g of glycerin (1), using a vacuum desiccator, reducing the pressure to 0.0095 MPa to 0.015 MPa and holding at room temperature for 30 minutes, then 0.6 g of 50 wt% sulfuric acid Was added and mixed.

  This mixture was heated at 200 ° C. for 20 minutes by microwave irradiation to obtain a biomass liquefaction 32. The liquefaction rate at this time was 74.6%. From the comparison between Example 32 and Example 5 above, it is considered that the acid catalyst is preferably added before impregnation with glycerol.

[Example 33]
92.2 g of glycerin (1) and 0.91 g of oleic acid were mixed and stirred at 40-50 ° C. for 30 minutes. To this, 10 g of cedar (2) was mixed, and then 0.6 g of 50 wt% sulfuric acid was added and mixed. This mixture was decompressed to 0.065 MPa to 0.15 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated to 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction 33. The liquefaction rate at this time was 79.4%.

[Example 34]
104.1 g of glycerin (1) and 1.02 g of methyl oleate were mixed and stirred for 10 minutes. To this, 10 g of cedar (2) was mixed, and then 0.6 g of 50 wt% sulfuric acid was added and mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated to 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction 34. The liquefaction rate at this time was 72.7%.

[Example 35]
10 g of cedar (2), 83.7 g of glycerin (1), 6.3 g of distilled water, and 0.6 g of 50 wt% sulfuric acid were mixed. The mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated to 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction 35. The liquefaction rate at this time was 82.5%.

(Reference Example 5)
90.1 g of glycerin (1), 7.0 g of distilled water, and 1.0 g of sodium chloride were mixed and stirred at 80 ° C. for 30 minutes. To this, 10 g of cedar (2) was mixed, and then 0.6 g of 50 wt% sulfuric acid was added and mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator and held at room temperature for 30 minutes, and then heated at 200 ° C. for 20 minutes by microwave irradiation. It did not liquefy.

  From Examples 33 to 35 and Reference Example 5, it was found that fatty acids and fatty acid methyls are thought to affect the decrease in the liquefaction rate, but not as much as sodium chloride.

[Example 36]
1 kg of cedar (2), 9 kg of glycerin (1), and 120 g of 25 wt% sulfuric acid were mixed. This mixture was allowed to stand at room temperature for 10 days in the atmosphere to obtain a glycerin impregnated product 36.

  The obtained glycerin impregnated material 36 was heated for 10 minutes while stirring at a stirring speed of 351 rpm in a temperature range of 190 to 210 ° C. using a kettle-type microwave heating reactor.

  After taking out the contents 36 from the kettle-type microwave heating reactor, it was filtered using a centrifugal filter (using a 180-mesh filter cloth) to obtain a biomass liquefaction 36. When the combustion experiment of the obtained biomass liquefaction 36 was conducted, it burned completely without any problem, and the maximum exhaust heat temperature was 833 ° C.

[Example 37]
After mixing 0.2 g sodium chloride, 95.0 g glycerin (1) and 6.4 g distilled water and stirring at 70 ° C. for 20 minutes, 10 g cedar (2) and 0.6 g 50 wt% Sulfuric acid was mixed. The mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated to 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction 37. The liquefaction rate at this time was 14.8%.

[Example 38]
After mixing 0.1 g sodium chloride, 91.0 g glycerin (1) and 6.4 g distilled water and stirring at 60 ° C. for 10 minutes, 10 g cedar (2) and 0.6 g 50 wt% Sulfuric acid was mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated to 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction 38. The liquefaction rate at this time was 59.8%.

[Example 39]
After mixing 0.05 g of sodium chloride, 90.0 g of glycerin (1) and 6.5 g of distilled water and stirring at 60 ° C. for 10 minutes, 10 g of cedar (2) and 0.6 g of 50 wt% Sulfuric acid was mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated at 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction 39. The liquefaction rate at this time was 71.5%.

[Example 40]
After mixing 0.1 g of sodium sulfate, 95.5 g of glycerin (1) and 6.4 g of distilled water and stirring at 60 ° C. for 10 minutes, 10 g of cedar (2) and 0.6 g of 50 wt% Sulfuric acid was mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated to 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction 40. The liquefaction rate at this time was 66.8%.

[Example 41]
After mixing 0.1 g of potassium sulfate, 95.5 g of glycerin (1) and 6.4 g of distilled water and stirring at 60 ° C. for 10 minutes, 10 g of cedar (2) and 0.6 g of 50 wt% Sulfuric acid was mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated to 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction product 41. The liquefaction rate at this time was 67.6%.

[Example 42]
After mixing 0.24 g of sodium sulfate, 91.0 g of glycerin (1) and 6.4 g of distilled water and stirring at 60 ° C. for 10 minutes, 10 g of cedar (2) and 0.6 g of 50 wt% Sulfuric acid was mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated to 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction 42. The liquefaction rate at this time was 40.4%.

[Example 43]
After mixing 0.3 g of potassium sulfate, 91.0 g of glycerin (1) and 6.4 g of distilled water and stirring at 60 ° C. for 10 minutes, 10 g of cedar (2) and 0.6 g of 50 wt% Sulfuric acid was mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator, held at room temperature for 30 minutes, and then heated to 200 ° C. by microwave irradiation for 20 minutes to obtain a biomass liquefaction 43. The liquefaction rate at this time was 46.9%.

(Reference Example 6)
1.0 g sodium chloride, 90.1 g glycerin (1) and 7.0 g distilled water were mixed and stirred at 70 ° C. for 20 minutes, then 10 g cedar (2) and 0.6 g 50 wt% Sulfuric acid was mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator and held at room temperature for 30 minutes, and then heated at 200 ° C. for 20 minutes by microwave irradiation. It did not liquefy.

(Reference Example 7)
10 g of cedar (2), 91.7 g of glycerin (1) and 0.6 g of 50 wt% sulfuric acid were mixed. This mixture was reduced in pressure to 0.0095 MPa to 0.015 MPa using a vacuum desiccator and held at room temperature for 30 minutes, and then an aqueous sodium chloride solution in which 0.2 g of sodium chloride was dissolved in 6.4 g of distilled water was added. Although heating was performed at 200 ° C. for 20 minutes by microwave irradiation, the cedar (2) hardly liquefied.

(Reference Example 8)
After mixing 3.5 g of magnesium chloride hexahydrate, 90.1 g of glycerin (1) and 7.0 g of distilled water and stirring at 70 ° C. for 20 minutes, 10 g of cedar (2) and 0 .6 g of 50 wt% sulfuric acid was mixed. This mixture was decompressed to 0.0095 MPa to 0.015 MPa using a vacuum desiccator and held at room temperature for 30 minutes, and then heated at 200 ° C. for 20 minutes by microwave irradiation. It did not liquefy.

  From the above reference examples, it was found that the liquefaction inhibiting factors were alkali metal salts such as sodium chloride, sodium sulfate and potassium sulfate, and alkaline earth metal salts such as magnesium chloride. For example, when sodium chloride is present, it is considered that the impregnation product and the liquefied product thereof are gelled or polymerized and the liquefaction of cellulose does not proceed sufficiently.

  As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment, A various deformation | transformation is possible.

  DESCRIPTION OF SYMBOLS 10 ... Biomass liquefaction manufacturing plant, 11 ... Grinding processing part, 12 ... Mixing / impregnation processing part, 13 ... Microwave heating processing part, 14 ... Essential oil extraction processing part, 15A ... Organic acid processing part, 15B ... Distillation processing part, 15C ... Ion exchange treatment unit, 20 ... Biodiesel fuel production plant, 21 ... Pretreatment unit, 22 ... Esterification treatment unit, 23 ... Separation treatment unit, 100 ... Biomass liquefaction production system

Claims (19)

The following steps A and B;
A) A step of mixing a cellulose-based biomass raw material obtained by crushing cellulosic biomass and glycerin, impregnating the cellulose-based biomass raw material with the glycerin, and obtaining an impregnated product of glycerin,
B) A process of obtaining a biomass liquefaction by heat-treating the impregnated product in the presence of an acid catalyst and liquefying cellulose in the cellulose-based biomass raw material,
A method for producing a biomass liquefaction comprising:   The method for producing a biomass liquefaction according to claim 1, wherein the impregnation in the step A is performed under reduced pressure.   The method for producing a biomass liquefaction according to claim 1 or 2, wherein the acid catalyst is a liquid and is added at a stage of mixing the cellulosic biomass raw material and the glycerin to obtain a mixture.   The method for producing a biomass liquefaction according to claim 3, wherein the acid catalyst is sulfuric acid.   The method for producing a biomass liquefaction according to any one of claims 1 to 3, wherein the heat treatment in the step B is performed by microwave irradiation. Step A is
A1) Crushing cellulosic biomass to obtain the cellulosic biomass raw material,
A2) A step of immersing the cellulosic biomass raw material in an organic solvent to extract an essential oil component contained in the cellulosic biomass raw material,
A3) A step of mixing the cellulosic biomass raw material and glycerin to obtain a mixture,
The manufacturing method of the biomass liquefaction of any one of Claims 1-5 containing this.   The method for producing a biomass liquefaction according to claim 6, wherein the organic solvent in the step A2 is an organic solvent miscible with glycerin.   The method for producing a biomass liquefaction according to claim 7, wherein the organic solvent is an aliphatic monohydric alcohol having 1 to 10 carbon atoms.   The method for producing a biomass liquefaction according to claim 7, wherein the organic solvent is a monohydric alcohol having 1 to 5 carbon atoms.   The method for producing a biomass liquefaction according to claim 1, wherein the cellulosic biomass is woody biomass.   The method for producing a biomass liquefaction according to claim 10, wherein the woody biomass is derived from a conifer or a broadleaf tree.   The method for producing a biomass liquefaction according to claim 10, wherein the woody biomass is derived from coniferous trees.   The method for producing a biomass liquefaction according to claim 10, wherein the woody biomass contains bark.   The method for producing a biomass liquefaction according to claim 1, wherein the glycerin in the step A is obtained by purifying crude glycerin containing an alkali metal or an alkaline earth metal and water.   The method for producing a liquefied biomass according to claim 14, wherein the crude glycerin further contains a fatty acid, a fatty acid salt or a fatty acid ester.   The method for producing a biomass liquefaction according to claim 14 or 15, wherein the crude glycerin is a by-product of biodiesel fuel produced by transesterification of fats and oils.   The biomass liquefied product according to any one of claims 1 to 16, wherein the biomass liquefied product is used as a biomass liquefied fuel, a chemical raw material, a resin raw material, a caking additive, or a soil modifier. Production method. A biodiesel fuel production plant for producing biodiesel fuel from biomass, a biomass liquefaction production plant for producing biomass liquefaction from cellulosic biomass raw materials,
A biomass liquefaction production system comprising:
The biodiesel fuel production plant supplies waste glycerin obtained as a byproduct of biodiesel fuel to the biomass liquefaction production plant,
The biomass liquefaction manufacturing plant mixes the cellulose-based biomass raw material and the waste glycerin, impregnates the cellulose-based biomass raw material with the waste glycerin to obtain an impregnated waste glycerin, A biomass liquefaction production system characterized by heat-treating in the presence of an acid catalyst to liquefy cellulose in the cellulose-based biomass raw material. The biomass liquefaction manufacturing plant has the following ac:
a) a treatment unit for subjecting the waste glycerin to a distillation treatment to reduce inorganic salts contained in the waste glycerin;
b) a processing unit for treating the waste glycerin with an ion exchange resin in order to reduce inorganic salts contained in the waste glycerin;
c) A processing unit for treating the waste glycerin with an organic acid in order to reduce the fatty acid or fatty acid ester contained in the waste glycerin;
The biomass liquefaction manufacturing system according to claim 18, comprising at least one of the following.

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