JP2009077697A - Method for hydrolyzing biomass, and hydrolyzing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for hydrolyzing biomass with pressurized hot water by which the formation of an overdecomposition product is suppressed and saccharification rate can be increased, and to provide a hydrolyzing device. <P>SOLUTION: The hydrolyzing device 100 is equipped with a first hydrolyzing device 110 and a second hydrolyzing device 120. The first hydrolyzing device 110 is equipped with a raw material vessel 10 into which the biomass is inserted, a saccharification vessel 20 for carrying out the hydrolyzing (saccharifying) treatment, a receiver 30 for collecting a water-soluble component after the hydrolysis, and a solid-liquid separation vessel 40 for collecting a residue after the hydrolysis. The saccharification vessel 20 comprises an inlet through which biomass-containing water slurry flows in, and an outlet which is formed at the opposite side of the inlet opening and from which the residue after the hydrolysis flows out, and a filter 21 installed in the outlet side. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a biomass hydrolysis method and a hydrolysis apparatus using pressurized hot water.

In recent years, the use of biomass, which is renewable energy, has attracted attention from the viewpoint of preventing global warming. In particular, there is increasing interest in the use of bioethanol.
Conventionally, bioethanol (also called biomass ethanol) has been mainly produced from starch, but recently, ethanol has been produced from cellulosic biomass due to the influence of the amount of starch-based biomass and grain prices. Development of a method to do this is underway. As a method for producing ethanol from cellulosic biomass, the conventional fermented ethanol method can be utilized by hydrolyzing (saccharifying) the cellulosic biomass. Therefore, development of hydrolysis (saccharification) technology for cellulosic biomass is important.

As a biomass hydrolysis (saccharification) technique, a method of hydrolyzing in sulfuric acid has been proposed. However, it becomes a complicated process such as removing and neutralizing sulfuric acid before ethanol is obtained. Further, since sulfuric acid is used, there are problems of reactor corrosion and waste liquid treatment.
In addition, technologies for saccharifying biomass using supercritical water or subcritical water are also being studied, but monosaccharides (hexose, pentose) are secondarily decomposed to produce fermentation inhibitors (Okino et al., “Next Development of a generation bioethanol production process ”, see Catalysts, 49 (4), 271-275, (2007)), and there is a problem that the sugar yield decreases.
Therefore, Patent Document 1 and Non-Patent Document 1 describe saccharification treatment with pressurized hot water with a reduced treatment temperature as a means for reducing the treatment temperature to suppress the formation of overdegraded products and increasing the sugar yield. Has been.

Patent Document 1 describes a technique for obtaining a water-soluble oligosaccharide by flowing pressurized hot water through a saccharification tank filled with cellulose powder.
Non-Patent Document 1 describes a method of obtaining xylo-oligosaccharides from hemicellulose by bringing corn stover, which is a raw material, into contact with pressurized hot water.

Patent No. 3041380 Bioresource Technology, 96, 1986-1993 (2005)

  However, cellulosic biomass used as a raw material for bioethanol contains hemicellulose in addition to cellulose, and these have different temperatures optimum for saccharification due to differences in crystallinity. Therefore, with a configuration such as Patent Document 1 or Non-Patent Document 1, a sufficient sugar yield cannot be obtained in saccharification of cellulosic biomass.

  The objective of this invention is providing the hydrolysis method and hydrolysis apparatus of the biomass by the pressurized hot water which can aim at the increase in a saccharification rate while suppressing the production | generation of a hyperdegradation product.

  The biomass hydrolysis method of the present invention is a biomass hydrolysis method carried out with pressurized hot water, wherein water-soluble oligosaccharides and / or simple substances obtained from the saccharification tank in which the hydrolysis reaction is carried out are carried out. Sugar is selectively extracted sequentially.

  In the present invention, water-soluble oligosaccharides and / or monosaccharides obtained by hydrolysis are sequentially extracted from the saccharification tank while the hydrolysis reaction of biomass is ongoing in the saccharification tank. Thereby, it is possible to recover the water-soluble oligosaccharide and / or monosaccharide (hereinafter also referred to as water-soluble oligosaccharide and the like) while suppressing the excessive decomposition of the monosaccharide, and the yield is improved. On the other hand, the water slurry remaining in the saccharification tank has a longer hydrolysis reaction time, so that it is more reliably hydrolyzed and the sugar yield is improved.

In the biomass hydrolysis method of the present invention, it is preferable to selectively sequentially extract water-soluble oligosaccharides and / or monosaccharides with an inorganic separation membrane provided in the saccharification tank.
In the present invention, an inorganic separation membrane is provided in the saccharification tank, and water-soluble oligosaccharides and the like produced by the hydrolysis reaction in the saccharification tank permeate the inorganic separation membrane. Therefore, water-soluble oligosaccharides and the like can be selectively extracted, and the sugar yield can be improved.

In the biomass hydrolysis method of the present invention, it is preferable to separate water-soluble oligosaccharides and / or monosaccharides in a solid-liquid separation tank provided at the outlet of the saccharification tank.
In this invention, the heavy component that has not been hydrolyzed in the saccharification tank is introduced into the solid-liquid separation tank and separated into a solid and a liquid. Since water-soluble oligosaccharides and the like are dissolved in the liquid, the sugar yield is further improved by collecting the liquid.

In the biomass hydrolysis method of the present invention, the hydrolysis reaction is carried out in at least two stages of the saccharification tank, and the heavy components remaining in the saccharification tank after the hydrolysis reaction are continuously introduced into the next saccharification tank. It is preferred that
In this invention, hydrolysis is performed at least twice in at least two stages of saccharification tanks. Accordingly, the heavy component that has not been hydrolyzed by one treatment can be reliably hydrolyzed by introducing it again into the saccharification tank. That is, the sugar yield is improved.

  In the biomass hydrolysis method of the present invention, the biomass is preferably cellulosic biomass. The pressurized hot water in the first saccharification tank is at a temperature of 150 ° C. or higher and 220 ° C. or lower, and the pressurized hot water in the second or subsequent saccharification tank is 220 ° C. or higher and 300 ° C. or higher. It is preferable that the temperature is not higher than ° C.

Cellulose contains hemicellulose and cellulose, and their hydrolysis temperatures are different from each other.
According to this invention, in the first stage saccharification tank, the hydrolysis reaction is performed at a temperature of 150 ° C. or more and 220 ° C. or less of pressurized hot water. Here, hemicellulose is mainly decomposed. In the second and subsequent saccharification tanks, hydrolysis is performed at a temperature of 220 ° C. to 300 ° C. of pressurized hot water. Here, cellulose is mainly decomposed.
Thus, since each hydrolysis is performed at the optimum temperature for each substance to be decomposed, each substance is reliably decomposed, and the formation of overdecomposed products can be suppressed. Moreover, when the heavy component which is hard to be hydrolyzed is introduced again into the saccharification tank, the possibility of being hydrolyzed increases and the sugar yield is improved.

In the biomass hydrolysis method of the present invention, it is preferable that the heavy component from the final stage saccharification tank outlet is cooled to 80 ° C. or lower.
According to this invention, it is possible to suppress excessive decomposition of oligosaccharides and to recover energy from exhaust heat. Moreover, when the heavy part from the last stage saccharification tank exceeds 80 degreeC, there exists a possibility of giving a disorder | damage | failure to saccharification and fermentation by a latter stage enzyme.

In the biomass hydrolysis method of the present invention, the pressurized hot water preferably has a pressure equal to or higher than a saturated water vapor pressure in the saccharification tank. Moreover, it is preferable that the volume-based slurry liquid space velocity (LHSV: Liquid Hourly Space Velocity) with respect to biomass is 0.5 / hr or more and 60 / hr or less. More preferably, it is 1 / hr or more and 10 / hr or less.
Since the hydrolysis reaction is performed under such conditions, the hydrolysis reaction is further promoted and the sugar yield can be improved.

In the biomass hydrolysis method of the present invention, hydrolysis is preferably performed using a solid acid catalyst filled in the saccharification tank.
By using the solid acid catalyst, the hydrolysis reaction in the saccharification tank is further promoted. Therefore, since the sugar yield is high even at low pressure and low temperature, the sugar yield can be improved and the energy can be reduced.
In addition, as a solid acid catalyst, a zeolite, an alumina, etc. can be used, for example.

In the biomass hydrolysis method of the present invention, it is preferable to cause an enzyme to act on the water-soluble oligosaccharide and / or residue obtained after the hydrolysis reaction.
In this invention, an enzyme is allowed to act on the residue remaining after hydrolysis of biomass. Thereby, a residue can be decomposed | disassembled to a monosaccharide and an overall saccharide | sugar yield can be improved.
As the enzyme, for example, cellulase can be used for cellulose.

The biomass hydrolysis apparatus of the present invention includes a saccharification tank that hydrolyzes biomass using pressurized hot water, and an inorganic separation membrane that permeates the water-soluble oligosaccharide and / or monosaccharide hydrolyzed in the saccharification tank. And a solid-liquid separation tank for separating heavy components remaining after hydrolysis in the saccharification tank.
According to this invention, the hydrolysis reaction of biomass proceeds in the saccharification tank, and water-soluble oligosaccharides and the like obtained by this hydrolysis reaction are extracted by the inorganic separation membrane provided in the saccharification tank and remain in the saccharification tank. The residue is further separated by a solid-liquid separation tank, and further water-soluble oligosaccharides can be recovered. Therefore, the sugar yield is improved.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[Configuration of hydrolysis equipment]
FIG. 1 is a schematic view of a hydrolysis apparatus according to an embodiment of the biomass hydrolysis method of the present invention.
As shown in FIG. 1, the hydrolysis apparatus 100 of this embodiment includes a first hydrolysis apparatus 110 and a second hydrolysis apparatus 120.

The first hydrolysis apparatus 110 includes a raw material tank 10 into which raw materials are charged, a saccharification tank 20 that performs hydrolysis (saccharification) treatment of water slurry introduced from the raw material tank 10, and a hydrolysis reaction of the saccharification tank 20. The receiver 30 which collects the obtained water-soluble oligosaccharide etc., and the solid-liquid separation tank 40 which collects the residue of the hydrolysis reaction of the saccharification tank 20 are provided.
The raw material tank 10 and the saccharification tank 20 are connected by a flow path 91, and the water slurry of the raw material tank 10 is introduced into the saccharification tank 20 through the flow path 91. On the flow path 91, the pump 15 which extrudes the water slurry of the raw material tank 10 to the saccharification tank 20, and the heater 16 which adjusts the temperature of the water slurry which flows through the flow path 91 are provided.

Further, the saccharification tank 20 and the receiver 30 are connected by a flow path 92, and the water-soluble oligosaccharide extracted in the saccharification tank 20 is recovered to the receiver 30 through the flow path 92. A cooler 25 that cools the water-soluble oligosaccharide extracted from the saccharification tank 20 and a pressure adjustment valve 26 that adjusts the extraction pressure from the filter 21 in the saccharification tank 20 are provided on the flow path 92.
Further, the saccharification tank 20 and the solid-liquid separation tank 40 are connected by a flow path 93, and the residue after the hydrolysis reaction of the saccharification tank 20 is introduced into the solid-liquid separation tank 40. On the flow path 93, a cooler 27 for cooling the residue after the hydrolysis reaction of the saccharification tank 20 and a pressure adjusting valve 28 for adjusting the pressure in the saccharification tank 20 are provided.
The solid-liquid separation tank 40 and the receiver 30 are connected by a flow path 94.

  Cellulose biomass (or also called lignocellulose) is used as a raw material to be charged into the raw material tank 10. Specifically, it is woody materials such as cedar and beech, and herbaceous materials such as rice straw and corn stover.

  The raw material tank 10 is a tank for producing a lignocellulose-containing water slurry as a raw material. As for the blending amount of lignocellulose, it is preferable to increase the slurry concentration as long as the specifications and capacity of the pump are suitable. Thereby, since heating of water becomes unnecessary, there exists a tendency which becomes an energy saving.

The saccharification tank 20 is a tank that hydrolyzes (saccharifies) the lignocellulose-containing water slurry. The saccharification tank 20 is provided on the inlet 20A into which the lignocellulose-containing water slurry flows, the outlet 20B on the opposite side of the inlet 20A, the outlet 20B from which the residue after hydrolysis flows out, and the outlet 20B. Filter 21 and an outlet 20C for allowing water-soluble oligosaccharide or the like that has passed through the filter 21 to flow out.
The filter 21 is an inorganic separation membrane such as metal or sintered metal, and selectively allows water-soluble oligosaccharides to permeate.

The receiver 30 collects water-soluble oligosaccharides and the like that have passed through the filter 21 in the saccharification tank 20. The solid-liquid separation tank 40 separates the residue after the hydrolysis reaction in the saccharification tank 20 into a solid and a liquid.
The liquid component separated in the solid-liquid separation tank 40 is collected in the receiver 30 through the flow path 94, and the heavy component that has become a solid is introduced into the second hydrolysis apparatus 120.

The pump 15 provided on the flow path 91 introduces the lignocellulose-containing water slurry of the raw material tank 10 into the saccharification tank 20. Similarly, the heater 16 provided on the flow path 91 adjusts the temperature of the lignocellulose-containing water slurry introduced into the saccharification tank 20. Furthermore, the pressure regulating valves 26 and 28 respectively adjust the extraction pressure from the filter 21 in the saccharification tank 20 and the pressure in the saccharification tank 20.
The pump 15, the heater 16, and the pressure regulating valves 26 and 28 are appropriately prepared so that the saccharification tank 20 satisfies the following conditions.

  The temperature is 150 ° C. or higher and 220 ° C. or lower, preferably 150 ° C. or higher and 200 ° C. or lower. If the temperature is lower than 150 ° C., the hydrolysis reaction is slowed, and the sugar yield is lowered, which is not practical. On the other hand, when the temperature exceeds 220 ° C., excessive decomposition may increase and the overall sugar yield may be reduced.

  The pressure is adjusted by the pressure regulating valve 26 or 28 so that the inside of the saccharification tank 20 becomes equal to or higher than the saturated water vapor pressure. In the said temperature range, it is 0.5 MPa or more and 10 MPa or less, for example.

  The liquid hourly space velocity (LHSV) is preferably 0.5 / hr or more and 60 / hr or less, more preferably 1 / hr or more and 10 / hr or less. If the liquid space velocity (LHSV) is less than 0.5 / hr, the treatment time may be long and the economy may be reduced. On the other hand, if it exceeds 60 / hr, the hydrolysis reaction becomes slow, and the sugar yield is lowered, which is not practical.

The saccharification tank 20 may be filled with a solid acid catalyst (not shown). Since the solid acid catalyst is solid, it requires little energy in the hydrolysis reaction of sugar, and can be recovered and reused, so that there is no problem of waste liquid. That is, it is an environmentally friendly catalyst.
Examples of the solid acid catalyst include zeolite and alumina.

The cooler 25 provided on the flow path 92 cools the water-soluble oligosaccharide and the like obtained by the hydrolysis reaction of the saccharification tank 20 to 80 ° C. or lower. And energy recovery is aimed at if necessary. The cooler 27 provided on the flow path 93 adjusts the degree of cooling according to the solid-liquid separation method.
Note that the first hydrolysis apparatus 110 may not include the cooler 27.

Next, the second hydrolysis apparatus 120 will be described.
The second hydrolysis device 120 has substantially the same configuration as the first hydrolysis device 110. That is, a raw material tank 50 into which the heavy component obtained in the first hydrolysis apparatus 110 is charged, a saccharification tank 60 that performs hydrolysis (saccharification) treatment of water slurry introduced from the raw material tank 50, and a saccharification tank And a solid-liquid separation tank 80 for collecting the residue of the hydrolysis reaction in the saccharification tank 60.
The raw material tank 50 and the saccharification tank 60 are connected by a flow path 96, and the water slurry of the raw material tank 50 is introduced into the saccharification tank 60 through the flow path 96. A pump 55 that pushes the water slurry of the raw material tank 50 to the saccharification tank 60 and a heater 56 that adjusts the temperature of the water slurry flowing in the flow path 96 are provided on the flow path 96.

Further, the saccharification tank 60 and the receiver 70 are connected by a flow path 97, and the water-soluble oligosaccharide extracted in the saccharification tank 60 is recovered to the receiver 70 through the flow path 97. A cooler 65 that cools the water-soluble oligosaccharide extracted from the saccharification tank 60 and a pressure adjustment valve 66 that adjusts the extraction pressure from the filter 61 in the saccharification tank 60 are provided on the flow path 97.
Furthermore, the saccharification tank 60 and the solid-liquid separation tank 80 are connected by a flow path 98, and the residue after the hydrolysis reaction of the saccharification tank 60 is introduced into the solid-liquid separation tank 80. On the flow path 98, a cooler 67 for cooling the residue after the hydrolysis reaction in the saccharification tank 60 and a pressure adjusting valve 68 for adjusting the pressure in the saccharification tank 60 are provided.
The solid-liquid separation tank 80 and the receiver 70 are connected by a flow path 99.

  The raw material tank 50 is charged with the heavy component obtained by the first hydrolysis apparatus 110. Further, hot water is supplied from the hot water tank 90 via the flow path 95, and a heavy component-containing water slurry is generated in the raw material tank 50. It is preferable from the viewpoint of energy efficiency that the temperature of the hot water is equal to or higher than the temperature of the heavy component charged into the raw material tank 50. Moreover, hot water is supplied so that the density | concentration of a solid heavy part may become high as long as it meets the specification and capability of a pump.

The configuration of the saccharification tank 60 is the same as that of the saccharification tank 20 described above. The saccharification tank 60 is provided at the inlet 60A into which the heavy component-containing water slurry flows, the outlet 60B from which the residue after hydrolysis is discharged, and the outlet 60B. And the outflow port 60 </ b> C for allowing the water-soluble oligosaccharide or the like that has passed through the filter 61 to flow out.
The filter 61 is an inorganic separation membrane such as a metal or a sintered metal, and selectively transmits water-soluble oligosaccharides.

The receiver 70 has the same configuration as the receiver 30 described above, and collects water-soluble oligosaccharides and the like that have passed through the filter 61 in the saccharification tank 60.
The solid-liquid separation tank 80 has the same configuration as the above-described solid-liquid separation tank 40 and separates the residue after hydrolysis in the saccharification tank 60 into a solid and a liquid.
The liquid component separated in the solid-liquid separation tank 80 passes through the flow path 99 and is collected in the receiver 70 described above.

The pump 55 provided on the flow path 96 introduces the heavy component-containing water slurry of the raw material tank 50 into the saccharification tank 60. Similarly, the heater 56 provided on the flow path 96 adjusts the temperature of the heavy component-containing water slurry introduced into the saccharification tank 60. Furthermore, the pressure regulating valves 66 and 68 regulate the pressure in the saccharification tank 60.
The pump 55, the heater 56, and the pressure adjustment valves 66 and 68 are appropriately prepared so that the inside of the saccharification tank 60 satisfies the following conditions.

  The temperature is 220 ° C. or higher and 300 ° C. or lower, preferably 220 ° C. or higher and 270 ° C. or lower. If the temperature is lower than 220 ° C., the hydrolysis reaction is slowed, and the sugar yield is lowered, which is not practical. On the other hand, when the temperature exceeds 300 ° C., excessive decomposition may increase and the overall sugar yield may be reduced.

  The pressure is adjusted by the pressure regulating valves 66 and 68 so that the inside of the saccharification tank 60 becomes equal to or higher than the saturated water vapor pressure. In the said temperature range, it is 2.5 MPa or more and 10 MPa or less, for example.

The liquid hourly space velocity (LHSV) is preferably 0.5 / hr or more and 60 / hr or less, more preferably 1 / hr or more and 10 / hr or less. If the liquid space velocity (LHSV) is less than 0.5 / hr, the treatment time may be long and the economy may be reduced. On the other hand, if it exceeds 60 / hr, the hydrolysis reaction becomes slow, and the sugar yield is lowered, which is not practical.
Further, the saccharification tank 60 may be filled with the same solid acid catalyst as the saccharification tank 20.

The cooler 65 provided on the flow path 97 cools the water-soluble oligosaccharide and the like obtained by the hydrolysis reaction of the saccharification tank 60 to 80 ° C. or lower. The cooler 65 can suppress excessive decomposition of water-soluble oligosaccharides and the like.
Further, the cooler 67 provided on the flow path 98 cools the heavy component that is a residue after the hydrolysis reaction of the saccharification tank 60. Since water-soluble oligosaccharides and the like that may be partially contained in the heavy component may be excessively decomposed, it is preferable to quickly cool to 80 ° C. or lower. When the residue remaining as a solid content in the solid-liquid separator 80 is separately fermented with an enzyme or the like, energy efficiency is good if the temperature is not lowered to a temperature suitable for the enzyme used for fermentation.

[Operation of hydrolysis equipment]
Next, one aspect of the flow of hydrolysis of biomass by the hydrolysis apparatus 100 will be described.
First, the raw material tank 10 of the first hydrolysis apparatus 110 is charged with biomass lignocellulose and water to adjust the mixed raw material. At this time, the blending amount of lignocellulose is not particularly limited, but is preferably adjusted to 10 to 30% by mass from the viewpoint of the transport ability of the pump 55 and the efficiency of hydrolysis.
Next, the pump 15, the heater 16, and the pressure adjustment so that the temperature in the saccharification tank 20 is 150 ° C. or higher and 220 ° C. or lower, the pressure is saturated water vapor pressure or higher, and the liquid space velocity is 0.5 / hr or higher and 60 / hr or lower. Valves 26 and 28 are adjusted.
Under such conditions, the lignocellulose-containing water slurry is introduced from the raw material tank 10 through the flow path 91 to the saccharification tank 20.

And in the saccharification tank 20, an oligosaccharide produces | generates by a hydrolysis reaction. It is mainly hemicellulose that is degraded under these conditions. The generated oligosaccharide passes through the filter 21 in a state dissolved in water, and is collected in the receiver 30 through the flow path 92.
In the saccharification tank 20, a heavy component containing lignocellulose that has not been hydrolyzed and water-insoluble oligosaccharide remains as a residue and is introduced into the solid-liquid separation tank 40 through the flow path 93.
In addition, before introducing into the solid-liquid separation tank 40, you may introduce this heavy part into the saccharification tank 20 again.
In the solid-liquid separation tank 40, the solid and the liquid are separated, and the liquid is collected in the receiver 30 through the flow path 94 as a water-soluble oligosaccharide or the like.

On the other hand, the heavy component remaining as a solid is introduced into the raw material tank 50 of the second hydrolysis apparatus 120 by, for example, pumping.
The raw water tank 50 is further supplied with hot water from the hot water tank 90 via the flow path 95, and a heavy component-containing water slurry is generated. The mixing ratio of the heavy component is 20% by mass based on the total amount of the heavy component-containing water slurry.
Next, the pump 55, the heater 56, and the pressure adjustment are performed so that the temperature in the saccharification tank 60 is 220 ° C. or more and 300 ° C. or less, the pressure is saturated water vapor pressure or more, and the liquid space velocity is 0.5 / hr or more and 60 / hr or less. Valves 66 and 68 are adjusted.

Under such conditions, the heavy component-containing water slurry is introduced from the raw material tank 50 through the flow path 96 to the saccharification tank 60.
And an oligosaccharide is produced | generated by the hydrolysis reaction in the saccharification tank 60. FIG. It is mainly cellulose that is decomposed here. The oligosaccharide passes through the filter 61 in a state dissolved in water, and is collected in the receiver 70 through the flow path 97.
In the saccharification tank 60, a heavy component containing lignocellulose that has not been hydrolyzed remains as a residue and is introduced into the solid-liquid separation tank 80 through the flow path 98.
The heavy component may be introduced again into the saccharification tank 60 before being introduced into the solid-liquid separation tank 80.
In the solid-liquid separation tank 80, it is separated into a solid and a liquid, and the liquid is recovered as a water-soluble oligosaccharide or the like in the receiver 70 via the flow path 99.
Thus, the oligosaccharides collected in the receiver 30 and the receiver 70 can be used for various applications such as fuel, fiber, composite material, food, etc. by isolating and purifying from aqueous solution by a known method. it can.

Furthermore, a monosaccharide can be produced by decomposing the finally obtained residue. As a method for hydrolyzing the residue into a monosaccharide, an enzyme is preferably used. Examples of the enzyme include cellulase and hemicellulase.
The obtained monosaccharide can be used for alcohol or the like by fermentation.

The present embodiment described above has the following operational effects.
In the present embodiment, since the filter 21 (or filter 61) is provided in the saccharification tank 20 (or saccharification tank 60), water-soluble oligosaccharides and the like generated by the hydrolysis reaction are converted into the saccharification tank 20 (or saccharification tank 60). Can be extracted sequentially. Therefore, the reaction time of the heavy oligosaccharide remaining in the saccharification tank 20 (or saccharification tank 60) can be lengthened, and the sugar yield is improved.
Moreover, excessive decomposition can be suppressed by sequentially extracting the produced water-soluble oligosaccharides and the like.
That is, the yield of sugar can be improved by suppressing the formation of overdegraded products.

  Moreover, since the heavy component which is the residue after hydrolysis is separated from the solid and the liquid in the solid-liquid separation tank 40 (or the solid-liquid separation tank 80) and the liquid is recovered, the sugar yield can be further improved. it can.

  Furthermore, the filter 21 (or filter 61) is provided on the outlet 20B (or outlet 60B) side of the saccharification tank 20 (or saccharification tank 60). The hydrolysis reaction starts from the inlet 20A (or inlet 60A) of the saccharification tank 20 (or saccharification tank 60), and the content of hydrolyzed oligosaccharide is increased in the vicinity of the outlet 20B (or outlet 60B). Therefore, with such a configuration, the yield of oligosaccharide is high.

And the hydrolysis of biomass is performed with the two-stage hydrolysis apparatus from which reaction conditions differ. In the first stage, hydrolysis is performed with pressurized hot water at 150 ° C. or higher and 220 ° C. or lower, so that hemicellulose in the biomass is hydrolyzed. In the second stage, hydrolysis is performed with pressurized hot water of 220 ° C. or higher and 300 ° C. or lower, so that cellulose is hydrolyzed.
Thus, since hydrolysis is performed at the optimum temperature of each substance, each substance is reliably decomposed, the sugar yield is improved, and the formation of overdegraded products can be suppressed.

  Moreover, in this embodiment, since the oligosaccharide etc. which were obtained by the hydrolysis reaction of the 1st hydrolysis apparatus 110 and the 2nd hydrolysis apparatus 120, and the remaining heavy part are aimed at heat recovery, energy efficiency is achieved. Will improve.

  Furthermore, the saccharification tank 20 or the saccharification tank 60 may be filled with a solid acid catalyst as a catalyst for the hydrolysis reaction. By using a solid acid catalyst, the hydrolysis reaction can be carried out without reducing the sugar yield even at a lower pressure and lower temperature. Further, as described above, the solid acid catalyst is an environment-friendly catalyst and can reduce energy.

  And you may decompose | disassemble the residue finally obtained with the hydrolysis apparatus 100 of this embodiment into a monosaccharide with an enzyme. As a result, the overall sugar yield can be increased.

It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
For example, in the present embodiment, the first hydrolysis apparatus 110 and the second hydrolysis apparatus 120 are continuously operated, but a batch type using only the first hydrolysis apparatus 110 may be used. If it is a batch type, an apparatus can be reduced in size and introduction expense can be held down.

  Further, after the hydrolysis reaction of the saccharification tank 20 is completed by the first hydrolysis apparatus 110, the residue remaining in the saccharification tank 20 may be introduced again from the inlet 20A of the saccharification tank 20. Thereby, the hydrolysis reaction time of the biomass which has not yet hydrolyzed and the heavy part becomes long, and it can hydrolyze more. Therefore, the sugar yield is improved.

  In this embodiment, hemicellulose is hydrolyzed in the first stage and cellulose is hydrolyzed in the second stage. However, when only hemicellulose is hydrolyzed, only the first stage of hydrolysis need be performed. . Thus, by selecting the treatment conditions according to the subject of hydrolysis, hydrolysis can be ensured, and the sugar yield is improved.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not restrict | limited at all to the description content of these Examples.

  Hydrolysis was performed using cedar flour (particle size average 152 μm (80 to 120 mesh)) as a raw material, and the mass of the overdecomposed product, water-soluble matter, and water-insoluble matter was measured. In addition, the hydrolysis was performed twice by a batch method using one experimental device, not a continuous saccharification method using two experimental devices shown in the embodiment.

The analysis method of the hyperdegradation product and the solubilization degree is as follows.
<Overly decomposed product>
The super-decomposed product is analyzed by a gel permeation chromatography (GPC) method with a differential refractive index detector (
Analysis was performed using a RID (Refractive Index Detector).
The excessively decomposed product is defined as the peak area ratio of the excessively decomposed product in the total peak area when the water-soluble material is analyzed by the analyzer. Since RID is used, the peak area ratio corresponds to the approximate weight ratio.
Overdecomposed product = (peak area of overdecomposed product) / (peak area of water-soluble matter) × 100
When hemicellulose decomposition is targeted, the peak that flows after the pentose peak is defined as the overdecomposed product.
In addition, not only the hyperdegradation product by the pressurized hot water treatment but also a free product originally contained in the cell can be considered, but no analytical distinction is made.
When cellulose is targeted for decomposition, the peak that flows after the hexose peak is defined as the overdecomposed product.

<Solubility (water-soluble content)>
The solubilization degree is defined by the following equation.
Solubility = (dry weight of raw material−dry weight of residue) / dry weight of raw material × 100
The mass is measured when the sample is stored in a room temperature desiccator for one day and the water content becomes constant.

[Example 1]
The first hydrolysis apparatus 110 described in the above embodiment was used.
A water slurry containing 15% by mass of cedar flour as a raw material was prepared in the raw material tank 10 and flowed into the saccharification tank 20 by the pump 15 (LHSV: 4 / hr). The inside of the saccharification tank 20 was adjusted to an experimental pressure of 4 MPa with the pressure adjusting valves 26 and 28, and adjusted to 190 ° C. with the heater 16. The water slurry was allowed to stay in the saccharification tank 20 for 15 minutes.
After the steady operation, the filter 21 in the saccharification tank 20 was passed through, cooled to 40-60 ° C. by the coolers 25 and 27, and a sample was taken in the receiver 30 and another receiver. Both samples were suction filtered with an aspirator and separated into a precipitate and a filtrate (first-stage hydrolysis treatment).
The precipitate was stored in a desiccator at room temperature for one day before being used as a raw material for the second stage hydrolysis, and the mass when the water content became constant was measured.

Next, this precipitate was adjusted to a 15% by mass water slurry in the raw material tank 10 and flowed into the saccharification tank 20 with the pump 15 (LHSV: 4 / hr). The inside of the saccharification tank 20 was adjusted to an experimental pressure of 4 MPa with the pressure adjusting valves 26 and 28, and adjusted to 240 ° C. with the heater 16. The water slurry was allowed to stay in the saccharification tank 20 for 15 minutes.
After the steady operation, the filter 21 in the saccharification tank 20 was passed through, cooled to 40-60 ° C. by the coolers 25 and 27, and a sample was taken in the receiver 30 and another receiver. Both samples were suction filtered with an aspirator and separated into a precipitate and a filtrate (second stage hydrolysis treatment).
The deposit was stored in a desiccator at room temperature for one day and the mass was measured.

[Comparative Example 1]
Except that the filter 21 was not provided in the saccharification tank 20, the treatment was performed in the same manner as in Example 1, and the water slurry of cedar flour as a raw material was separated into a precipitate and a filtrate.
The above measurement results are evaluated by the mass ratio with respect to the raw material.

  As can be seen from Table 1, in Example 1, the formation of overdecomposed products is suppressed, and the proportion of water-soluble components is large. On the other hand, in Comparative Example 1, a hyperdegradable product is generated, and the proportion of water-soluble components is small. That is, in Example 1, it can be said that hydrolysis was performed efficiently.

  The present invention can be used for fuels, fibers, composite materials, foods, and the like using biomass as a raw material.

BRIEF DESCRIPTION OF THE DRAWINGS Schematic of the saccharification apparatus of one Embodiment in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 ... Hydrolysis apparatus 110 ... 1st hydrolysis apparatus 10 ... Raw material tank 20 ... Saccharification tank 21 ... Filter 30 ... Receiver 40 ... Solid-liquid separation tank 120 ... Second hydrolysis apparatus 50 ... Raw material tank 60 ... Saccharification tank 61 ... Filter 70 ... Receiver 80 ... Solid-liquid separation tank

Claims (12)

A method for hydrolyzing biomass using pressurized hot water,
A method for hydrolyzing biomass comprising selectively sequentially extracting water-soluble oligosaccharides and / or monosaccharides obtained by a hydrolysis reaction from a saccharification tank in which the hydrolysis reaction is performed. The biomass hydrolysis method according to claim 1,
A method for hydrolyzing biomass, wherein the water-soluble oligosaccharide and / or monosaccharide is selectively and sequentially extracted with an inorganic separation membrane provided in the saccharification tank. In the hydrolysis method of the biomass of Claim 1 or Claim 2,
A method for hydrolyzing biomass, wherein the water-soluble oligosaccharide and / or monosaccharide is separated in a solid-liquid separation tank provided at an outlet of the saccharification tank. In the hydrolysis method of the biomass in any one of Claims 1-3,
The hydrolysis reaction is performed in at least two stages of the saccharification tank,
A method for hydrolyzing biomass, wherein a heavy component remaining in the saccharification tank after the hydrolysis reaction is continuously introduced into the next saccharification tank. The biomass hydrolysis method according to claim 4,
The biomass is a cellulosic biomass. The biomass hydrolysis method, wherein the biomass is hydrolyzed. The biomass hydrolysis method according to claim 5,
The pressurized hot water in the first saccharification tank is at a temperature of 150 ° C. or higher and 220 ° C. or lower,
The method for hydrolyzing biomass, wherein the pressurized hot water in at least one saccharification tank in the second and subsequent stages has a temperature of 220 ° C. or higher and 300 ° C. or lower. In the hydrolysis method of the biomass in any one of Claims 4-6,
A method for hydrolyzing biomass, characterized in that the heavy component from the final stage saccharification tank outlet is cooled to 80 ° C or lower. In the hydrolysis method of the biomass in any one of Claims 1-7,
The pressure of the said pressurized hot water is more than the saturated water vapor pressure in the said saccharification tank. The biomass hydrolysis method characterized by the above-mentioned. In the hydrolysis method of the biomass in any one of Claims 1-8,
A volume-based slurry liquid space velocity (LHSV: Liquid Space Velocity) for biomass is 0.5 / hr or more and 60 / hr or less. In the hydrolysis method of the biomass in any one of Claims 1-9,
Hydrolysis using a solid acid catalyst filled in the saccharification tank. A method for hydrolyzing biomass. In the hydrolysis method of the biomass in any one of Claims 1-10,
A method for hydrolyzing biomass, characterized in that an enzyme is allowed to act on water-soluble oligosaccharides and / or residues obtained after a hydrolysis reaction. A saccharification tank for hydrolyzing biomass using pressurized hot water;
An inorganic separation membrane that permeates the water-soluble oligosaccharide and / or monosaccharide hydrolyzed in the saccharification tank;
A biomass liquid hydrolysis apparatus comprising: a solid-liquid separation tank that separates heavy components remaining after hydrolysis in the saccharification tank.

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