JP2010081855A - Method for producing saccharides - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing saccharides by which not only the saccharides are obtained from a ligneous biomass in high yield and high efficiency, but also the saccharides containing pentoses and hexoses, and the saccharides containing the hexoses can separately be collected. <P>SOLUTION: The method for producing the saccharides, including a first slurry heating step (S1) for heat-treating a slurry obtained by adding high-temperature and high-pressure water to the ligneous biomass, a first separation step (S2) for separating the heat-treated slurry into a liquid component and a solid component, a second slurry-heating step (S3) for forming a slurry by adding water to the separated solid component and heat-treating the resultant slurry, a second separation step (S4) for separating the heat-treated slurry into a liquid component and a solid component, a useful component-acquiring step (S5) for acquiring the saccharides by removing water from the separated liquid component, further includes, in addition to the acquirement of the saccharides at the useful component-acquiring step (S5), acquiring the saccharides by removing the water from the liquid component separated at the first separation step (S2). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a production method for recovering saccharides including oligosaccharides, glucose and the like from woody biomass which is a cellulose-containing material.

  Industrial and household waste contains a large amount of biopolymers and synthetic polymers, but most of them are discarded without being reused. These polymers can be valuable chemical raw materials and energy resources, and it is desired to develop a technology capable of processing them in large quantities and effectively using them.

  One of the most promising polymer resources is a large amount of cellulose contained in agricultural and forestry products such as paper, wood and straw. As a technique for obtaining useful components such as saccharides such as glucose from cellulose, various methods such as a thermal decomposition method, a high-temperature hydrolysis method using an acid catalyst, and an enzymatic hydrolysis method have been conventionally known. Yes. However, the thermal decomposition method has a problem that the reaction control is impossible and the production rate of saccharides is low. In addition, in the high-temperature hydrolysis method, since acid is added, problems such as device corrosion due to acid and removal of acid from the product, and in order to avoid such problems, if the concentration of acid is suppressed, sugar formation occurs. There was a problem that the rate was low. Furthermore, the hydrolysis method has a problem that the reaction rate is low at present and cannot be used as an industrial production technique.

Therefore, as a technique for performing hydrolysis without using an acid or an enzyme, for example, Patent Document 1 discloses a method for obtaining a saccharide by decomposing cellulose using supercritical or subcritical water. Has been. Patent Document 2 discloses a method in which cellulose powder is obtained by contacting cellulose powder with 200 to 300 ° C. hot pressurized water to perform hydrolysis. Furthermore, Patent Document 3 discloses a method for obtaining a saccharide with high efficiency by hydrolyzing cellulose or cellulose-containing substance powder by contacting with pressurized hot water at 220 to 270 ° C. in the presence of a lanthanoid ion as a catalyst. Is disclosed.
JP-A-5-31000 Japanese Patent Laid-Open No. 10-327900 JP 2002-85100 A

However, the conventional methods for obtaining saccharides have the following problems.
As described above, when hydrolyzing wood or the like with high-temperature and high-pressure water, the treatment temperature is too high, so there is a risk that the decomposition of the biomass may proceed too much. There is a problem that acid components such as gas components and gas components are generated, and the yield of useful components decreases. On the other hand, when the temperature is lowered, the decomposition rate is deteriorated, the sugar yield is likely to be lowered, and most of the useful component cellulose is recovered as an oligosaccharide which is difficult to use as it is. In addition, an enzyme treatment for saccharification is required.

  Among saccharides to be produced, hexose can be fermented by general yeasts, but pentose requires special yeasts that have been genetically modified, and is easily decomposed. When many sugars coexist, it becomes difficult for pentose sugars to break down. Therefore, when this saccharide is used as a raw material for bioethanol production, it is difficult to separate only the pentose for efficient ethanol fermentation. And saccharides containing hexose and saccharides mainly containing hexose. However, the conventional technique has a problem that the obtained saccharide cannot be separated and recovered mainly into a saccharide containing pentose and hexose and a saccharide mainly containing hexose.

  The present invention has been made in view of the above problems, and its purpose is to obtain saccharides mainly from pentose and hexose in addition to obtaining saccharides from woody biomass with high yield and high efficiency. Another object of the present invention is to provide a saccharide production method capable of separating and recovering saccharides mainly containing hexose.

  The method for producing saccharides according to the present invention is a method for producing saccharides using woody biomass as a raw material. A slurry obtained by adding high-temperature high-pressure water at 150 to 200 ° C. and 1.6 to 3 MPa to the woody biomass is 5 A first slurry heating step for heat treatment for 20 minutes, a first separation step for separating the slurry heat-treated in the first slurry heating step into a liquid component and a solid component, and separation in the first separation step A second slurry in which 2.5 to 20 times the amount of water is added to the resulting solid component to form a slurry, and the slurry is heat-treated for 10 to 120 seconds under the conditions of 250 to 300 ° C. and 11.5 to 15 MPa. Water is removed from the liquid component separated in the heating step, the second separation step of separating the slurry heated in the second slurry heating step into a liquid component and a solid component, and the liquid component separated in the second separation step. And A useful component acquisition step of acquiring a saccharide that is a component for use, and in addition to acquiring the saccharide in the useful component acquisition step, in the useful component acquisition step, further separated in the first separation step Water is removed from the liquid component to obtain saccharides that are useful components.

  According to such a manufacturing method, the production efficiency of saccharides from woody biomass is improved by including the first slurry heating step, the first separation step, the second slurry heating step, the second separation step, and the useful component acquisition step. In addition, the yield of saccharide is improved.

  Furthermore, in the first slurry heating step, the slurry is heat-treated at a relatively low temperature and low pressure, whereby the hemicellulose portion of the woody biomass is hydrolyzed, and most of the pentose and hexose are heated and extracted into water. . Thereby, saccharides mainly containing pentose and hexose (hereinafter referred to as “first saccharide” as appropriate) are produced from the heat-extracted liquid component. Hemicellulose mainly consists of a mixture of pentose and hexose.

  And in a 2nd slurry heating process, the cellulose part of woody biomass is hydrolyzed by heat-processing a slurry by comparatively high temperature and high pressure, and most hexoses are heat-extracted by water. Thereby, saccharides mainly containing hexose (hereinafter referred to as “second saccharide” as appropriate) are produced from this heat-extracted liquid component. Cellulose is mainly composed of hexose.

  According to the method for producing saccharides according to the present invention, saccharides can be produced efficiently from woody biomass with high yield. In addition, since saccharides mainly containing pentose and hexoses and saccharides mainly containing hexoses can be separated and recovered, when the obtained saccharides are used as a raw material for bioethanol production, ethanol Fermentation can be performed efficiently.

  Next, the manufacturing method of the saccharide | sugar which concerns on this invention with reference to drawings is demonstrated in detail. In the drawings to be referred to, FIG. 1 is a flowchart for explaining steps of a method for producing saccharides, FIG. 2 is a schematic diagram showing an example of a hydrolysis reaction apparatus used in the method for producing saccharides, The schematic diagram which shows the outline of a semi-flow-type reaction apparatus, (b) is a schematic diagram which shows the outline of a flow-type reaction apparatus.

≪Method for producing saccharides≫
As shown in FIG. 1, the manufacturing method of saccharides includes a first slurry heating step (S1), a first separation step (S2), a second slurry heating step (S3), and a second separation step (S4). And a useful component acquisition step (S5).
Hereinafter, each step will be described.

<First slurry heating step (S1)>
The first slurry heating step (S1) is a step of preparing a slurry by adding high-temperature high-pressure water at 150 to 200 ° C. and 1.6 to 3 MPa to woody biomass, and subjecting this slurry to heat treatment for 5 to 20 minutes. . Then, by heating the slurry, the hemicellulose portion of the woody biomass is hydrolyzed, and most of the pentose and hexose are heated and extracted into water. In the first slurry heating step (S1), since the cellulose portion is not hydrolyzed, the hexose sugar in the first saccharide can be reduced.

[Woody biomass]
The woody biomass used as a raw material (hereinafter also referred to as “biomass”) is not particularly limited, and woody biomass such as wood powder, wood pieces, chip dust, sawdust, sawdust, and the like can be used. Examples of the wood piece include building demolition waste, thinned wood generated at the time of deforestation, pruned branches such as parks and roadside trees, and the like. As described above, according to the present invention, normally discarded biomass can be effectively used, so that the problem of the treatment plant and the like are solved and the energy problem is also solved.

  The biomass is preferably used after being pulverized. By pulverizing and using biomass, the contact area between biomass and water increases. Therefore, hemicellulose is easily hydrolyzed, and as a result, the yield of saccharide is easily improved. Here, in the first slurry heating step (S1), as will be described later, since a semi-flow reactor can be used, the pulverized biomass (wood flour) is packed in the reactor (reaction tube), and the tree Since high-temperature hot water is circulated through the gaps between the powders, it is preferable to use a relatively coarsely pulverized biomass (particle size of about 0.25 to 1.5 mm) so as not to cause clogging of the filter.

  What is necessary is just to determine the usage-amount of the wood to be used suitably according to the conditions at the time of processing, such as the kind of wood, the amount of water to be used. However, since it is difficult to make a large amount of wood into a slurry at a time, it is preferable to add it within a stirrable range while observing the state of the slurry. As a temporary measure, the biomass content in the slurry is preferably 10% by mass or more, more preferably 13% by mass or more, further preferably 15% by mass or more, and further preferably 20% by mass or more. . When the biomass content is less than 10% by mass, the production efficiency is lowered, and it is difficult to obtain a saccharide at a low cost. The upper limit of the biomass content is not particularly limited as long as the slurry state can be maintained.

[High-temperature high-pressure water]
The water used when preparing the slurry is high-temperature high-pressure water of 150 to 200 ° C. and 1.6 to 3 MPa.
By extracting only the hemicellulose part that is easily decomposed in biomass at a relatively low temperature and low pressure compared to general conditions over time, it is possible to extract pentose and hexose mainly constituting hemicellulose. it can. In addition, since this operation is relatively low temperature and low pressure, the reactor can be an inexpensive one having a heat resistance of about SUS304, is easy to construct in terms of equipment, and has the necessary energy. Less.

  In order to perform such treatment, a semi-flow reactor can be used. By using this semi-circulating reactor, it is possible to use wood powder having a relatively coarse particle size, and at the same time, it is possible to treat biomass without problems even if water wettability is not particularly good. In the first slurry heating step (S1), the water / wood powder ratio becomes high as biomass, but by using a semi-flow reactor, the processing temperature can be lowered and the amount of energy used can be reduced. it can.

  If the temperature of water is less than 150 ° C., the reaction between biomass and water does not occur effectively, and the hydrolysis of hemicellulose does not proceed easily. On the other hand, when it exceeds 200 ° C., hydrolysis of cellulose tends to occur, and there is a possibility that even the hexose of cellulose is extracted.

  When the pressure is less than 1.6 MPa, the liquid phase part is not formed, and the dispersion and solubilization of hemicellulose does not proceed. On the other hand, even if it exceeds 3 MPa, since the dispersion and solubilization of hemicellulose does not proceed any further, it is not economical. Also, from the viewpoint of the pressure resistance of the apparatus, the pressure is 3 MPa or less. For example, if the temperature of the slurry is set to 150 ° C., the pressure is preferably set to 1.6 MPa or more. If the temperature is 200 ° C., the pressure is preferably set to 2.5 MPa or more. In this range, the pressure may be set as appropriate in consideration of the equipment to be used. From the viewpoint of reducing the load on the pump and other devices, a pressure close to the lower limit value at each temperature is adopted. It is preferable to do this.

The heating time (extraction time) of the slurry is 5 to 20 minutes. When the heating time is less than 5 minutes, the hydrolysis of hemicellulose is insufficient. On the other hand, even if it exceeds 20 minutes, hydrolysis does not proceed any further, so that it is not economical.
The biomass may be heat-treated by adding a predetermined amount of high-temperature high-pressure water at a time and heating the biomass at a predetermined amount every minute for 5 to 20 minutes.

  In addition, before moving to a 1st separation process (S2), you may quench this heated slurry to 100 degrees C or less (preferably 30-70 degreeC) by a cooling process, for example. By cooling the slurry in a high temperature state, the subsequent handling becomes easy, and the saccharides (mainly pentose and hexose) produced in the first slurry heating step (S1) are further decomposed by preheating. Can be prevented. In addition, the pressure of the solid-liquid separator can be lowered, and the specification level of valves and the like can be lowered.

<First separation step (S2)>
The first separation step (S2) is a step of separating the slurry heat-treated in the first slurry heating step (S1) into a liquid component and a solid component.
Here, the liquid component means a solution mainly containing pentose and hexose produced by hydrolysis of the hemicellulose portion of biomass, and the solid component means a slurry mainly containing the cellulose portion of biomass. .

The method for separating the slurry into a liquid component and a solid component in the first separation step (S2) is not particularly limited, and for example, a solid-liquid separation filter can be used.
Examples of the filter include paper, cloth, membrane, ceramics, and the like, and the liquid component and the solid component can be separated by passing the slurry after the heat treatment through the filter.

  The mesh size of the filter is not particularly limited as long as solid-liquid separation is possible. For example, a filter having a mesh size of about 100 μm can be used. A plurality of filters to be used may be arranged in parallel. By providing a plurality of filters, the solid-liquid separation performance can be further improved.

  Moreover, it can replace with a solid-liquid separation filter, and can also isolate | separate into a liquid component and a dehydrated solid component using a dehydrator (for example, a filter, a filter press, a belt press, a centrifugal dehydrator, etc.). .

<Second slurry heating step (S3)>
In the second slurry heating step (S3), 2.5 to 20 times the amount of water is added to the solid component separated in the first separation step (S2) to form a slurry, and the slurry is 250 to 300 ° C. This is a step of heat treatment for 10 to 120 seconds under the condition of 11.5 to 15 MPa. Then, by heating the slurry, the cellulose portion of the woody biomass is hydrolyzed, and most of the hexose is heated and extracted into water.

[Solid component]
The solid component is separated from the liquid component in the first separation step (S2). As described above, in the first slurry heating step (S1), the hemicellulose portion of the woody biomass is hydrolyzed and the liquid component is obtained. Therefore, the solid component mainly contains the cellulose portion of the biomass.

[water]
The water used for preparing the slurry may be at ordinary temperature and normal pressure. In addition, it is preferable to prepare a slurry under a normal pressure of less than 100 ° C. from the viewpoint of simplifying the operation of adding the solid component and saving energy. Moreover, you may use high temperature / high pressure water as mentioned above.

  The amount of water to be added is 2.5 to 20 times that of the solid component. If the amount of water is less than 2.5 times, it becomes difficult to slurry the solid component. On the other hand, when the amount exceeds 20 times, the amount of water increases and a lot of energy is required for solid-liquid separation and extraction of components. In addition, by going through the first slurry heating step (S1), the solid component has already been improved in water wettability and the like, and since the decomposition of particles is also progressing, rather than slurrying biomass, It can be slurried with a fairly small amount of water and requires less energy.

And the hydrolysis of a cellulose is performed by heat-processing the slurry prepared as mentioned above on the conditions of 250-300 degreeC and 11.5-15 MPa for 10 to 120 second.
In the second slurry heating step (S3), since the processing temperature is high and the pressure is high, a reactor having a heat resistance of about SUS316 is necessary, but since the reaction time is short, a small reactor is used. It can be used, and the overall equipment cost is also low.

  In addition, in order to perform such a process, a flow-type reaction apparatus can be used. In this flow reactor, the biomass has already been processed by the semi-flow reactor, so the wettability of the wood flour is improved and the particle size is finer, so the water / wood flour ratio is very high. Can handle the low. Therefore, in this flow-type reaction apparatus, the amount of energy consumed can be reduced even at a treatment temperature effective for cellulose decomposition, and the total amount of energy consumed can be reduced.

  Further, the heating process is divided into two times, and the liquid component is separated in the first separation process (S2), so that the component decomposed in the first slurry heating process (S1) is more separated in the second slurry heating process (S3). Can prevent excessive decomposition due to a strong heat history, and improve the total sugar yield (ratio of the total amount of recovered monosaccharides and oligosaccharides relative to holocellulose contained in the original biomass) Can be made.

  When the heating temperature is less than 250 ° C., the reaction between cellulose and water does not occur effectively, and hydrolysis of cellulose hardly proceeds. On the other hand, when the temperature exceeds 300 ° C., the thermal decomposition of saccharides and the like produced by the hydrolysis reaction is more dominant than the decomposition of cellulose, and the yield of the target saccharide (hexose sugar) is reduced.

  When the pressure is less than 11.5 MPa, a liquid phase portion is not formed, and dispersion and solubilization of cellulose does not proceed. On the other hand, even if it exceeds 15 MPa, the dispersion and solubilization of cellulose does not proceed any further, which is not economical. Also, from the viewpoint of pressure resistance of the apparatus, the pressure is set to 15 MPa or less. For example, when the temperature of the slurry is 250 ° C., the pressure is preferably set to 11.5 MPa or more, and preferably 300 MPa or 13 MPa. In this range, the pressure may be set as appropriate in consideration of the equipment to be used. From the viewpoint of reducing the load on the pump and other devices, a pressure close to the lower limit value at each temperature is adopted. It is preferable to do this.

  The heating time (extraction time) of the slurry is 10 to 120 seconds. When the heating time is less than 10 seconds, hydrolysis of cellulose becomes insufficient. On the other hand, even if it exceeds 120 seconds, since hydrolysis does not advance any more, it is not economical.

  In addition, before moving to a 2nd separation process (S4), you may quench this heated slurry by cooling process, for example to 100 degrees C or less (preferably 30-70 degreeC). By cooling the slurry in a high temperature state, the subsequent handling becomes easy, and the saccharide (mainly hexose sugar) produced in the second slurry heating step (S3) is prevented from being further decomposed by preheating. Can do. In addition, the pressure of the solid-liquid separator can be lowered, and the specification level of valves and the like can be lowered.

<Second separation step (S4)>
The second separation step (S4) is a step of separating the slurry heat-treated in the second slurry heating step (S3) into a liquid component and a solid component.
Here, the liquid component refers to a solution mainly containing hexose produced by hydrolysis of the cellulose portion of biomass, and the solid component refers to a slurry mainly including components other than holocellulose of biomass.
Since others are the same as those in the first separation step (S2), description thereof is omitted here.

<Useful component acquisition step (S5)>
The useful component acquisition step (S5) is a step of removing saccharide (second saccharide) which is a useful component by removing water from the liquid component separated in the second separation step (S4).
Moreover, in addition to obtaining the second saccharide, it is a step of obtaining saccharide (first saccharide) which is a useful component by removing water from the liquid component separated in the first separation step (S2). .

  As a method for separating and removing water from the liquid component, a general distillation method, evaporation method (spray drying method or the like), or the like can be used. By separating and collecting water (solid-liquid separation), saccharides can be obtained from the liquid component.

  Examples of the saccharide obtained in the useful component obtaining step (S5) include pentoses such as xylose, ribose, arabinose, and aviose; hexoses such as glucose, fructose, ribulose, galactose, mannose, and talose; and heptoses such as glucoheptose. The oligosaccharide etc. which these 1 type (s) or 2 or more types polymerized about 2-20 are contained. In addition, sugar derivatives such as amino sugars and sugar alcohols may be included.

  The first saccharide is mainly a mixture of pentoses such as xylose and ribose and hexoses such as glucose and fructose, and can be fermented by special yeast that has been genetically modified. The second saccharide is mainly a hexose such as glucose or fructose, and can be fermented with general yeast. As described above, the first saccharide and the second saccharide may include other monosaccharides, oligosaccharides, and the like.

  Thus, the isolated and purified saccharides can be used as functional food materials, raw materials for bioethanol production, and the like. In addition, since saccharides mainly containing pentose and hexoses and saccharides mainly containing hexoses can be separated and recovered, when the obtained saccharides are used as a raw material for bioethanol production, In addition, saccharides containing pentose and hexose sugars are subjected to alcoholic fermentation using genetically modified yeast, and saccharides containing mainly hexose sugars are subjected to alcoholic fermentation using general yeasts. , Ethanol fermentation can be performed efficiently.

  If necessary, in the modified coal acquisition step (S5), saccharides (from the liquid component separated in the first separation step (S2) and the liquid component separated in the second separation step (S4) ( In addition to obtaining the first saccharide and the second saccharide), water may be removed from the solid component separated in the second separation step (S4) to produce a solid fuel (solid fuel obtaining step). . This solid fuel has a lower moisture content and higher calorific value than the raw material biomass, so it can be used as a steam boiler for power generation or blast furnace injection like coal. it can. As a method for separating and removing water from the solid component, a general distillation method or evaporation method can be used as in the modified coal acquisition step (S5) for acquiring saccharides from the liquid component.

  In the acquisition of the first saccharide, the second saccharide, and the solid fuel, these may be acquired at the same time, or any one or two may be acquired first. .

  Next, with respect to the method of sugars according to the present invention, an example of using a semi-flow reactor and a flow reactor will be described with reference to FIG.

<Hemicellulose hydrolysis>
First, the process of hydrolyzing the hemicellulose part of the woody biomass using a semi-flow reactor will be described.

  As shown in FIG. 2 (a), in the hydrolysis of hemicellulose, first, biomass 16 is charged into the reactor 15 of the semi-flow reactor 10, and the reactor 15 is supplied from the water tank 11 through the water pump 12. Water is supplied to make a slurry. At this time, water is heated and supplied by the preheater 13 so that the water temperature is 150 to 200 ° C. in the reactor 15 and the pressure holding valve 20 is closed to control the pressurizing pump 14. The water pressure is set to 1.6 to 3 MPa. And a slurry is heat-processed for 5 to 20 minutes on such conditions. In the semi-flow reactor 10 here, the water pump 12 and the pipe line are connected so that water can be supplied from the water pump 12 to the pipe line that is input to the cooler 17 so that the sample after the heat treatment can be rapidly cooled. Is connected.

  Thereafter, the slurry is discharged from the reactor 15, sent to the cooler 17 to which the cooling unit 18 is attached, and cooled to 100 ° C. or lower. The heat recovered at this time can be reused in the temperature raising process in the reactor 15 and the preheater 13.

  Next, the cooled slurry is separated into a liquid component and a solid component by a solid-liquid separation filter of a solid-liquid separator 19 provided on the downstream side of the cooler 17. A plurality of filters used at this time may be arranged in parallel.

  In place of the filter, a tank (not shown) is provided on the downstream side of the pressure holding valve 20, and the slurry after the heat treatment is dehydrated (for example, a filter, a filter press, a belt press, centrifugal dehydration). Etc.) can also be used to separate the liquid component and the dehydrated solid component.

  The separated liquid component passes through the pressure holding valve 20 and is sent to the gas-liquid separator 22. When the liquid component passes through the pressure holding valve 20, it is rapidly depressurized to the atmospheric pressure, so that the low boiling point component dissolved in the liquid component is vaporized and gas is generated. These liquid component and gas component are separated in the gas-liquid separator 22, and the gas is recovered in the gas bag 21 and the liquid component is recovered in the reaction liquid receiver 23.

The liquid component recovered in the reaction liquid receiver 23 is practically concentrated by a reverse osmosis membrane or the like because the hydrolysis product is diluted with a large amount of water.
Then, saccharides (mainly pentose and hexose) can be obtained from the recovered liquid component by a general distillation method, evaporation method (spray dry method or the like), and the like. On the other hand, the solid component separated by the solid-liquid separator 19 is supplied to the second slurry heating step to hydrolyze the cellulose.

<Hydrolysis of cellulose>
Next, the process of hydrolyzing the cellulose portion of the woody biomass using a flow reactor will be described.

  As shown in FIG. 2 (b), in the hydrolysis of cellulose, first, 2.5 to 20 times the amount of water is added to the solid component in the slurry tank 31 of the flow reactor 30 to form a slurry 32. . Next, a predetermined amount of slurry 32 is supplied from the slurry tank 31 to the reactor 34 by the slurry pump 33, the slurry 32 is heated to 250 to 300 ° C., and the pressure holding valve 38 is closed, so that the slurry pump 33 By controlling the pressure, pressurization is performed in the range of 11.5 to 15 MPa. And a slurry is heat-processed for 10 to 120 second on such conditions.

  After that, a cooling process by the cooling unit 36 and the cooler 35, a solid-liquid separation process by the solid-liquid separator 37, and a gas component separation process by the gas-liquid separator 40, the gas is put into the gas bag 39, and the liquid component is the reaction liquid. It is collected in the receiver 41. The cooling process, the solid-liquid separation process, the gas component separation process, and the like are the same as in the case of using the semi-flow reactor 10 in the above-described hemicellulose hydrolysis, and thus description thereof is omitted here.

The liquid component recovered in the reaction liquid receiver 41 is practically concentrated by a reverse osmosis membrane or the like because the hydrolysis product is diluted with a large amount of water.
Then, saccharides (mainly hexoses) can be obtained from the recovered liquid component by a general distillation method, evaporation method (spray dry method or the like) and the like. On the other hand, the solid component separated by the solid-liquid separator 37 may be discarded as a residue, but can also be used as a solid fuel after dehydration (solid-liquid separation).

  The present invention is as described above. However, in carrying out the present invention, for example, a raw material crushing step for crushing biomass, or garbage, between or before and after each step, within a range that does not adversely affect each step. Other steps such as an unnecessary material removing step for removing unnecessary materials such as a drying step for drying the obtained saccharide may be included.

Next, the method for producing saccharides according to the present invention will be specifically described with reference to examples.
[Example 1]
Using a semi-flow reactor as shown in FIG. 2 (a), 200 g of cedar wood flour having a particle diameter of 1 mm was placed in a reactor and sealed. Thereto, pure water at 180 ° C. was fed at a pressure of 2 MPa at an amount of 200 g per minute for 20 minutes to prepare 4.2 kg of slurry. The slurry was discharged from the reactor, cooled to room temperature with a cooler, and returned to normal pressure. Thereafter, when the slurry was processed by a solid-liquid separator using a 100 μm mesh filter, about 108 g of a solid component and about 4092 g of a liquid component were obtained. The liquid component (Extract 1) was analyzed by high performance liquid chromatography (HPLC) (Shimadzu Corporation LC-VP, (detector: RID-10A SPD-6AV)). The analysis conditions are “column: Shodex KS802, eluent: water, flow rate: 0.5 ml / min, column temperature: 65 ° C.”. The analysis result of this liquid component was in the state shown in FIG. In addition, the other monosaccharide in FIG. 3A is mainly pentose.

  Next, using a flow reactor as shown in FIG. 2B, about 108 g of the solid component was charged into the slurry tank. After adding 900 g of water to this solid component and stirring well to make a slurry, this slurry was pressurized to 15 MPa and fed to a reactor already heated to 280 ° C. by a slurry pump at 50 g per minute. The slurry residence time in the reactor was about 30 seconds. When this slurry was processed by a solid-liquid separator using a 100 μm mesh filter, about 25 g of a solid component and about 983 g of a liquid component were obtained. This liquid component (Extract 2) was analyzed by HPLC under the same conditions as described above. The analysis result of the liquid component was as shown in FIG. In addition, the other monosaccharide in FIG.3 (b) is mainly hexose.

  As a result of obtaining the ratio (sugar yield) of the total amount of monosaccharides and oligosaccharides in Extract 1 and Extract 2 with respect to holocellulose contained in 200 g of the original cedar wood flour from HPLC analysis results, The total amount of sugars was 93 g with respect to 126 g of cellulose, and the sugar yield was about 74%.

[Comparative Example 1]
Using a semi-flow reactor as shown in FIG. 2 (a), 200 g of cedar wood flour having a particle diameter of 1 mm was placed in a reactor and sealed. Thereto, pure water at 300 ° C. was fed at a pressure of 15 MPa in an amount of 200 g per minute for 60 minutes to prepare 12.2 kg of slurry. The slurry was discharged from the reactor, cooled to room temperature with a cooler, and returned to normal pressure. Then, when the slurry was processed with a solid-liquid separator using a 100 μm mesh filter, about 72 g of a solid component and about 12128 g of a liquid component were obtained. This liquid component was analyzed by HPLC under the same conditions as in Example 1 (not shown).

  As a result of obtaining the sugar yield from the analysis result by HPLC in the same manner as in Example 1, the total amount of saccharide was 50 g with respect to 126 g of holocellulose, and the sugar yield was about 40%.

[Comparative Example 2]
Using a flow reactor as shown in FIG. 2 (b), 200 g of cedar wood flour having a particle diameter of 1 mm was charged into the slurry tank. Next, after adding 2000 g of water to 200 g of this cedar wood powder and stirring well to make a slurry, this slurry was pressurized to 15 MPa and already heated to 280 ° C. with a slurry pump every minute. 50g was sent. The slurry residence time in the reactor was about 30 seconds. When this slurry was processed by a solid-liquid separator using a 100 μm mesh filter, about 65 g of a solid component and about 2135 g of a liquid component were obtained. This liquid component was analyzed by HPLC under the same conditions as in Example 1 (not shown).

  From the analysis result by HPLC, the sugar yield was determined in the same manner as in Example 1. As a result, the total amount of sugar was 45 g with respect to 126 g of holocellulose, and the sugar yield was about 36%.

  From the above results, it can be seen that according to the method for producing saccharides according to the present invention, saccharides can be produced efficiently and in high yield from woody biomass. Moreover, it turns out that saccharides mainly containing pentose and hexose sugars and saccharides mainly containing hexose sugars are separated from the obtained saccharides and can be efficiently and easily recovered.

  As mentioned above, although the best embodiment and the example were shown and explained in detail about the manufacturing method of the sugar concerning the present invention, the meaning of the present invention is not limited to the above-mentioned contents, and the scope of the right is a claim. It should be interpreted broadly based on the scope description. Needless to say, the contents of the present invention can be widely modified and changed based on the above description.

It is a flowchart explaining the process of the manufacturing method of the saccharide | sugar which concerns on this invention. It is a schematic diagram which shows an example of the hydrolysis reaction apparatus used for the manufacturing method of the saccharide | sugar which concerns on this invention, (a) is a schematic diagram which shows the outline of a semi-flow-type reaction apparatus, (b) is a flow-type reaction apparatus. It is a schematic diagram which shows an outline. (A), (b) is a graph which shows the result of the HLPC analysis in an Example.

Explanation of symbols

S1 1st slurry heating process S2 1st separation process S3 2nd slurry heating process S4 2nd separation process S5 useful component acquisition process 10 semi-flow type reactor 11 water tank 12 water pump 13 preheater 14 pressure pump 15, 34 reaction Chamber 16 Biomass 17, 35 Cooler 18, 36 Cooling unit 19, 37 Solid-liquid separator 20, 38 Pressure holding valve 21, 39 Gas bag 22, 40 Gas-liquid separator 23, 41 Reaction liquid receiver 30 Flow reactor 31 Slurry tank 32 Slurry 33 Slurry pump

Claims (1)

A method for producing saccharides using woody biomass as a raw material,
A first slurry heating step in which a slurry obtained by adding high temperature and high pressure water of 150 to 200 ° C. and 1.6 to 3 MPa to the woody biomass is heated for 5 to 20 minutes;
A first separation step of separating the slurry heat-treated in the first slurry heating step into a liquid component and a solid component;
To the solid component separated in the first separation step, 2.5 to 20 times the amount of water is added to form a slurry, and the slurry is 10 to 120 under conditions of 250 to 300 ° C. and 11.5 to 15 MPa. A second slurry heating step for second heat treatment;
A second separation step of separating the slurry heat-treated in the second slurry heating step into a liquid component and a solid component;
A useful component acquisition step of removing water from the liquid component separated in the second separation step and acquiring a saccharide which is a useful component;
In the useful component acquisition step, in addition to acquiring the saccharide, in the useful component acquisition step, water is further removed from the liquid component separated in the first separation step to acquire a saccharide that is a useful component. A method for producing a saccharide characterized by comprising:

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