JP2012095576A - Method and apparatus for production of saccharified solution of cellulose-based biomass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a saccharified solution production method and a saccharified solution production apparatus, both of which can produce a saccharified solution from a cellulose-based biomass raw material by an enzymatic saccharification technique with high efficiency.SOLUTION: The apparatus includes: a first enzymatic saccharification device 21 for enzymatically saccharifying fine powder of the cellulose-based biomass raw material 10; a first solid/liquid separation device 31 for separating into a solid material 61 which contains unsaccharified cellulose, hemicellulose, lignin, or the like discharged from the first enzymatic saccharification device 21 and a liquid 63 which contains a hexose; a hot water treatment device 41 for treating the solid material 61, which has been separated by the first solid/liquid separation device 31 and contains unsaccharified cellulose, hemicellulose, lignin, or the like, with hot water while applying a pressure; a second solid/liquid separation device 32 for separating into a solid material 62 which contains undissolved cellulose discharged from the hot water treatment device 41 and a liquid 64 in which lignin and hemicellulose are dissolved; and a second enzymatic decomposition device 22 for enzymatically saccharifying the cellulose contained in the solid material 62 which has been separated by the second solid/liquid separation device 32 to thereby enzymatically decompose the cellulose into a saccharified solution 13 which contains the hexose.

Description

  The present invention relates to a method and an apparatus for producing a sugar liquid that can efficiently produce a sugar liquid that is a raw material for producing, for example, bioalcohols using a cellulose-based biomass raw material.

  Sugarcane, corn, and the like that are currently used as alcohol raw materials are originally provided for food. It is not preferable to use these edible resources as industrial resources because of food shortages.

  For this reason, it is an important issue to effectively use cellulosic resources such as herbaceous biomass and woody biomass that are considered to be useful resources in the future.

  The components of cellulosic biomass are cellulose, hemicellulose, lignin and the like. Cellulose and hemicellulose can be saccharified, and sugar made from cellulose can be fermented with glucose or the like as a raw material for alcohol production. The sugar from hemicellulose is xylose, and fermentation has been difficult in the past, but in recent years, a microbiological technique for fermenting xylose has been developed.

  There are two methods for obtaining the above saccharides: acid treatment and enzyme treatment. The acid treatment method uses sulfuric acid and has a high saccharification rate, but monosaccharides such as glucose are excessively decomposed to reduce the saccharification yield of glucose. On the other hand, saccharification under environmentally friendly and mild conditions is possible with the enzyme treatment method, but the enzyme is difficult to come into contact with cellulose, and the saccharification rate is very bad even if saccharification is performed for a long time.

  Various pretreatments have been proposed for the improvement. Among them, there are methods for separating components into cellulose, hemicellulose, lignin and the like, and a combination of extraction with an alkali or organic solvent and hydrolysis with a dilute acid has been proposed for component separation. However, it has not yet been commercialized on a large scale due to the corrosion of the reaction vessel by acid and the complexity of the neutralization treatment.

  As disclosed in Non-Patent Document 1 below, as a pretreatment for improving enzymatic saccharification, cellulosic biomass is pulverized and the crystal structure of cellulose is degraded, so that the enzyme can easily come into contact with cellulose and saccharification is promoted. It is generally known that However, in addition to the technical problem that it is difficult to finely pulverize uniformly, it is not yet commercialized because it costs more to make it finer.

  The hot water treatment does not require latent heat of vaporization, has a relatively high rate of temperature rise, and hot water has a hydrolytic ability. Further, there is an advantage that the reaction vessel is not corroded or neutralized, such as acid treatment. It is generally known that this treatment promotes component separation, can separate hemicellulose, and can promote enzymatic saccharification. However, with a normal size (about several mm), a sufficient component separation result cannot be obtained unless the hydrothermal treatment temperature is 200 ° C. or higher, and the phenol compound is extracted in that environment, and the enzyme activity is inhibited. There is.

JP 2005-168335 A

A.T.W.M.Hendriks, G. Zeeman: Bioresource Technology 100 (2009) 10-18

  It is generally known that as a pretreatment for improving enzymatic saccharification, cellulosic biomass is pulverized and the crystal structure of cellulose is deteriorated so that the enzyme can easily come into contact with cellulose and saccharification is promoted. However, with a simple pulverization technique that can ensure economic efficiency, the particle size of pulverized biomass is 0.25 to 0.5 mm, and according to the experimental results shown in FIG. 2, the saccharification rate is only about 30% in enzymatic saccharification. It is difficult to obtain a further high saccharification rate.

  In the invention disclosed in Patent Document 1, various cellulosic biomass is hydrothermally treated and saccharified by an enzymatic method. However, in a cellulosic biomass having a normal size (several millimeters), There is a problem that the water treatment condition is a high temperature of 220 ° C. or higher, an enzyme inhibitor is produced from the lignin component and the like, and the enzyme saccharification efficiency is lowered.

The present invention has been made to solve these problems.
Cellulose based on the advantage of enzymatic saccharification of finely pulverized biomass, enzymatic saccharification at a high saccharification rate, and hydrothermal treatment of the remaining unsaccharified biomass under mild conditions that can suppress the production of enzyme inhibitors It is to achieve a high saccharification rate of biomass efficiently.

  An object of this invention is to provide the manufacturing method and apparatus which manufacture an efficient sugar liquid from a cellulose biomass raw material.

  Cellulosic biomass can be pulverized by simple pulverization technology that can ensure economic efficiency, saccharify the components that can be easily enzymatically saccharified by primary enzyme saccharification, separate the saccharified solution, and leave the remaining unsaccharified solid under mild conditions It is intended to provide a production method and apparatus capable of obtaining a high saccharification rate by performing hydrothermal treatment, separating a solution, and subjecting the remaining solid to secondary enzyme saccharification.

  The invention according to claim 1 of the present invention is a first enzyme saccharification step for enzymatically saccharifying fine powder of cellulosic biomass, and a solid containing unsaccharified cellulose, hemicellulose, lignin and the like discharged from the first enzyme saccharification step, A solid-liquid separation step for separating into a liquid containing 6 carbon sugars, a hydrothermal treatment step for subjecting a solid containing unsaccharified cellulose, hemicellulose, lignin and the like separated in the solid-liquid separation step to pressurized hot water treatment, and Cellulosic biomass raw material that has undergone a second enzymatic saccharification step in which a solid containing undissolved cellulose discharged in the hydrothermal treatment step, and a liquid in which lignin and hemicellulose are dissolved are enzymatically saccharified to a sugar solution containing saccharides are used. This is a method for producing a sugar solution.

  The invention according to claim 2 of the present invention includes a hydrothermal treatment step in which a cellulosic biomass raw material having a fine powder size of 1 mm or less is subjected to pressurized hot water treatment under conditions of a reaction temperature of 150 to 180 ° C. and a residence time of 60 minutes or less. Cellulosic biomass raw material that has undergone an enzymatic saccharification step in which a solid containing undissolved cellulose discharged in this hydrothermal treatment step, and a liquid in which lignin and hemicellulose are dissolved are enzymatically saccharified and enzymatically decomposed into a sugar solution containing saccharides are used. This is a method for producing a sugar solution.

  The invention according to claim 3 of the present invention is a first enzyme saccharification device for enzymatic saccharification of fine powder of cellulose biomass raw material, and a solid containing unsaccharified cellulose, hemicellulose, lignin and the like discharged from the first enzyme saccharification device A first solid-liquid separation device that separates into a liquid containing 6 carbon sugars, and a hot water treatment that performs pressurized hot water treatment on a solid containing unsaccharified cellulose, hemicellulose, lignin and the like separated by the first solid-liquid separation device An apparatus, a second solid-liquid separation device that separates the solid containing undissolved cellulose discharged from the hydrothermal treatment device, and a liquid in which lignin and hemicellulose are dissolved, and the solid separated by the second solid-liquid separation device It is in the manufacturing apparatus of the sugar liquid using the cellulosic biomass raw material which comprises the 2nd enzyme decomposing apparatus which carries out the enzymatic saccharification of the cellulose and enzymatically decomposes into the sugar liquid containing 6 carbon sugars.

  The invention according to claim 4 of the present invention is the sugar according to claim 3, wherein the hemicellulose component in the liquid in which lignin and hemicellulose are separated by the second solid-liquid separation apparatus is subjected to an enzyme treatment to contain pentose. An apparatus for producing a sugar liquid using a biomass material comprising a third enzyme decomposition apparatus that decomposes the liquid.

  According to the present invention, cellulosic biomass is finely pulverized and enzymatically saccharified with a simple pulverizer, and unsaccharified biomass is hydrothermally treated at 150 ° C to 180 ° C for 10 to 60 minutes, followed by enzymatic saccharification. Regardless of the type of cellulosic biomass, the saccharification rate of hexose can be stably improved. In addition, by supplying the sugar solution to an existing bioethanol production plant, it is possible to diversify raw materials related to bioethanol production and to reduce costs.

  Since the hydrothermal treatment conditions are relaxed, the excessive decomposition of the hemicellulose component is suppressed, and as a result, it is possible to efficiently recover the pentose component and contribute to effective utilization of the pentose. .

It is a conceptual diagram which shows embodiment of the manufacturing apparatus and method of a sugar liquid using the cellulose biomass raw material of this invention. It is a figure which shows the result of the experiment regarding the relationship between the enzyme saccharification reaction time of a fine powder, and the amount of glucose production. It is a figure which shows the result of the experiment regarding the relationship between the enzyme saccharification reaction time of the fine powder which carried out the hot water process, and the amount of glucose production. It is a figure which shows the result of the experiment regarding the relationship between hydrothermal treatment conditions (temperature and residence time) and glucose production amount. It is a figure which shows the result of the experiment regarding the relationship between pH conditions of enzyme saccharification of a fine powder, and saccharide production.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  As shown in FIG. 1, the sugar liquid production apparatus using the cellulosic biomass raw material according to the embodiment of the present invention uses finely pulverized biomass raw material 10 (in this embodiment, for example, EMPLTY FRUIT BUNCH (EFB)) as water. 11, enzymatically saccharified in the first enzymatic decomposition device 21, transferred to the first solid-liquid separation device 31, and separated into a solid 61 containing unsaccharified cellulose, hemicellulose, lignin and the like and a liquid 63 containing 6 carbon sugars. The solid 61 is mixed with the water 11 and transferred to the hot water treatment device 41 to perform pressurized hot water treatment. After the hot water treatment, it is transferred to the second solid-liquid separator 32 and separated into a solid 62 containing undissolved cellulose and a liquid 64 in which lignin and hemicellulose are dissolved. The solid 62 is enzymatically saccharified by the second enzymatic decomposition device 22 to obtain hexose 13. The liquid 64 obtains the pentose 14 by enzymatic saccharification in the third enzymatic decomposition apparatus 51.

  Here, in this embodiment, as shown in FIG. 3, the content ratio of glucose (hexose) in the solvent of hexose 13 is 90% or more. Further, as shown in FIG. 2, the content ratio of glucose (hexose) in the solvent of the liquid 63 is 65% or more, but the liquid 63 may be obtained as the hexose 12. An enzyme solution containing carbon sugar or liquid 65 may be injected into the second enzyme decomposition apparatus 22.

  The cellulosic biomass raw material 10 is not particularly limited in particle size, but is preferably pulverized to 0.5 mm or less. In this embodiment, EFB was first pulverized to about several mm with a commercially available cutter, and further finely pulverized to 0.5 mm or less with an airflow pulverizer. Any pulverization apparatus can be used as long as it can be finely pulverized to 0.5 mm or less.

  As shown in FIG. 4, the reaction temperature in the hot water treatment apparatus 41 is preferably in the range of 150 to 180 ° C., more preferably 160 to 175 ° C. This is because at a low temperature of less than 150 ° C., the hydrothermal decomposition rate is low and a long decomposition time is required, leading to an increase in the size of the apparatus, which is not preferable. On the other hand, when the temperature exceeds 200 ° C., the decomposition rate becomes excessive, the cellulose component dissolves, the amount of migration from the solid to the liquid side increases, and the excessive decomposition of the hemicellulose-based saccharide is promoted, which is not preferable. The hemicellulose and lignin components are dissolved from about 140 ° C., and the cellulose is dissolved from about 230 ° C., but the cellulose is left on the solid content side, and the hemicellulose component and the lignin component have a sufficient decomposition rate. It is because it is good to set it as the range of 175 degreeC.

  The reaction pressure is preferably 0.1 to 0.3 MPa higher than the saturated vapor pressure of water at each temperature at which the inside of the main body is in the state of pressurized hot water. Moreover, as shown in FIG. 4, it is preferable that reaction time shall be 20 to 30 minutes. This is because if the reaction is carried out too long, the proportion of the overdecomposed product increases, which is not preferable.

  In the first enzyme decomposing apparatus 21, as shown in FIG. 2, the enzyme decomposing time is 24 hours or less, preferably 6 to 8 hours.

  In the second enzyme decomposition apparatus 22, as shown in FIG. 3, the enzyme decomposition time is preferably 48 to 96 hours.

  In the first enzyme decomposing apparatus 21 and the second enzyme decomposing apparatus 22, as shown in FIG. 5, the optimum pH for enzyme activation is preferably pH 4.5 to 6.5.

  Here, the weight ratio between the biomass raw material to be supplied and the pressurized hot water is 1 in the EFB and 5 in the pressurized hot water in this embodiment, preferably 1: 1 to 1: 5. .

  According to the present invention, cellulose (which becomes a 6-carbon sugar solution by enzymatic saccharification) is obtained by enzymatic saccharification of a portion that can be easily enzymatically saccharified and using a hydrothermal decomposition apparatus under a mild condition for biomass containing remaining unsaccharified cellulose. Other reactants (lignin component, hemicellulose component) are dissolved and separated by transferring to pressurized hot water to obtain a biomass solid mainly composed of cellulose. As a result, it is possible to efficiently saccharify cellulose, including cellulose that has been enzymatically saccharified, and to efficiently produce a sugar solution of hexose having a glucose (hexose) content of 90% or more in the solvent. .

  According to the present invention, by using the hydrothermal decomposition apparatus under mild conditions, the excessive decomposition of the hemicellulose component is suppressed, and as a result, the pentose component can be efficiently recovered.

  Here, as the chemical product based on the sugar solution, various organic raw materials such as alcohols, petroleum products, amino acids and the like can be mentioned. Therefore, the biomass-derived sugar liquid becomes a raw material for producing a substitute for a chemical product derived from crude oil, which is a depleted fuel.

  As described above, according to the method and apparatus according to the present invention, an efficient sugar liquid is produced from a cellulosic biomass raw material, and various organic raw materials (for example, alcohols and petroleum substitutes) are used based on the sugar liquid. Products, amino acids, etc.) can be produced efficiently.

10 Finely pulverized biomass raw material
11 water
12, 13 6 Carbohydrate
14 5 Carbohydrate
21, 22 Enzymatic digester
31, 32 Solid-liquid separator
41 Hot water treatment equipment
51 Enzymatic digester
61, 62 solid
63-65 liquid

Claims (4)

A first enzymatic saccharification step for enzymatic saccharification of fine powder of cellulosic biomass;
A solid-liquid separation step for separating into a solid containing unglycosylated cellulose, hemicellulose, lignin and the like discharged in the first enzyme saccharification step and a liquid containing hexose;
A hydrothermal treatment step of subjecting a solid containing unsaccharified cellulose, hemicellulose, lignin and the like separated in the solid-liquid separation step to pressurized hydrothermal treatment;
The solids containing undissolved cellulose discharged in the hydrothermal treatment step, and the liquid in which lignin and hemicellulose are dissolved are subjected to a second enzymatic saccharification step in which enzymatic saccharification is performed to enzymatically decompose into a sugar solution containing saccharides. A method for producing a sugar solution using a cellulosic biomass raw material. A hydrothermal treatment step of subjecting a cellulosic biomass raw material having a fine powder size of 1 mm or less to a pressurized hydrothermal treatment under conditions of a reaction temperature of 150 to 180 ° C. and a residence time of 60 minutes,
Cellulose system characterized by undergoing an enzymatic decomposition step in which a solid containing undissolved cellulose discharged in the hydrothermal treatment step, and a liquid in which lignin and hemicellulose are dissolved are enzymatically saccharified and enzymatically decomposed into a sugar solution containing saccharides A method for producing a sugar solution using biomass raw materials. A first enzymatic saccharification apparatus for enzymatic saccharification of fine powder of cellulosic biomass,
A first solid-liquid separation device for separating solids containing unsaccharified cellulose, hemicellulose, lignin and the like discharged from the first enzyme saccharification device and liquids containing hexose;
A hot water treatment device for treating the solid separated in the first solid-liquid separation device with pressurized hot water,
A second solid-liquid separation device for separating the solid containing undissolved cellulose discharged from the hydrothermal treatment device and the liquid in which lignin and hemicellulose are dissolved;
A saccharide using biomass raw material, comprising a second enzyme decomposing device that enzymatically saccharifies cellulose in the solid separated by the second solid-liquid separating device and enzymatically decomposes it into a sugar solution containing hexose. Liquid production equipment.   A third enzyme decomposing apparatus for decomposing a hemicellulose component in a liquid in which lignin and hemicellulose dissolved by the second solid-liquid separation apparatus are decomposed into a sugar liquid containing pentose is provided. The manufacturing apparatus of the sugar liquid using the biomass raw material of Claim 3.

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