WO2017047830A1

WO2017047830A1 - Reactor for continuously saccharifying biomass

Info

Publication number: WO2017047830A1
Application number: PCT/KR2015/009608
Authority: WO
Inventors: 김태완; 구민수; 주영환; 김동현; 김태승; 구본욱; 성민지
Original assignee: 에스케이이노베이션 주식회사; 에스케이에너지 주식회사
Priority date: 2015-09-14
Filing date: 2015-09-14
Publication date: 2017-03-23

Abstract

The present invention relates to a reactor for saccharifying biomass containing a high concentration of solids, and more particularly, to a reactor for continuously saccharifying biomass comprising: a porous plate in which a nozzle for supplying an additive, containing a saccharifying enzyme, and a sensor are provided on an inner cross-section of a hole; and a stirring means.

Description

Biomass Continuous Glycosylation Reactor

The present invention relates to a reactor for continuous glycosylation of a biomass containing a high concentration of solids, and more particularly, a porous plate having a nozzle and a sensor for supplying an additive containing a glycosylation enzyme at an inner end surface of a hole; It relates to a biomass continuous saccharification reactor comprising a stirring means.

The biofuel production process for producing bioethanol from cellulose is mainly composed of raw material acquisition, pretreatment, saccharification, fermentation, and purification. Pretreatment aimed at effectively separating cellulose and hemicellulose from lignin with complex and rigid structures, especially when using wood-based biomass that is difficult to decompose due to the complex and rigid structure of cellulose, hemicellulose and lignin. The process is essential. Cellulose isolated through this process is endo-β-1,4-glucanase [EC 3.2.1.4], exo-β-1,4-glucanase ( exo-β-1,4-glucanase) [EC 3.2.1.91], beta-glucosidase (EC 3.2.1.21), and three types of enzymes are hydrolyzed to glucose, a typical monosaccharide, and glucose Fermentation produces ethanol.

Enzymatic hydrolysis techniques of cellulose and hemicellulose have long been known, but lead to high catalyst costs, slow reactions, and high equipment investment due to the need for large reactors. In addition, the use of enzymes can increase the rate of saccharification, but there are limitations in efficiency due to the inhibitory action of reaction substrates and products, as well as cost problems, but do not require extreme reaction conditions of high temperature and high pressure, and there are no harmful by-products. Because of the energy saving effect, there is a high demand for the development of saccharification technology using the same.

In order to achieve the commercial economics of cellulose ethanol, ethanol must be produced at a concentration of 5% (w / w), so that ethanol can be separated with little energy during distillation, and this is based on ethanol (theoretical yield: 0.51, actual fermentation). A saccharified solution containing more than 11% (w / w) sugar should be produced with an efficiency of 90%). After pretreatment, saccharification should be initiated at the biomass level (50-70% sugar content) at about 15-20% solids.

However, since the concentration of 15 to 20% of the solid content is similar to kneaded clay or miso, it is difficult to transfer the fluid in the substrate, so that the glycosylated enzyme is evenly distributed or suitable for glycation. Maintaining the reaction temperature is not easy, and because the pH of the saccharified solution is decreased due to the dissociation of the acetyl group present in the biomass during the saccharification process, the basic material (eg, NaOH) is continuously injected during the reaction. However, this also has a problem that it is difficult to maintain an effective saccharification reaction is difficult to mix.

Various mixing tanks have been developed in which cutting technology by a porous plate and mixing technology by stirring means have been adopted for efficient biomass mixing.

EP 0011870A1 discloses a stirring vessel for mixing a solid material including a fixed porous plate and a stirring means and a liquid substance, but one injection hole of the liquid material is provided at the upper or lower portion of the stirring vessel, so that stirring time is required for even mixing. It takes a long time.

US 8617480B2 has a fixed porous plate and a stirring means, and also describes a stirring tank including a spray nozzle in a space partitioned by the porous plate, but the nozzle is mounted on the inner wall of the stirring tank, There is a problem that the mixing of the input material is not easy in the stagnant biomass.

US 4409329A has a feature of mixing the biomass by the porous plate, but the feature is that the gap between the porous plate is very narrow to less than 5 cm for the mixing of biomass of a high concentration of solid components, the addition of the additive is provided at the top of the stirring vessel It is characterized by being made through the inlet.

In summary, although the prior art has many descriptions of a stirrer including a perforated plate and a stirring means, since the nozzles for adding the additives are provided at the agitation tank wall or in the upper and lower parts, the biomass phase from the beginning of the charging. Since the stirring time may be long because the additives such as the enzyme and the acid / base substance for pH adjustment may not be evenly distributed, the energy consumption may need to be improved.

Accordingly, the present inventors have made diligent efforts to develop a reactor capable of increasing the enzyme mixing efficiency required to increase the saccharification efficiency of high-viscosity biomass. As a result, the present inventors have fabricated a continuous saccharification reactor including an improved porous plate and stirring means. Bio is cut through the porous plate by mounting a nozzle to supply additives such as glycosylase, acid or basic substance for pH adjustment, buffer, and surfactant to induction provided at the inner end surface of the hole of the porous plate. The additives were evenly dispersed in the mass, and it was confirmed that the increase in saccharification efficiency and the convenience of operation were increased and the present invention was completed.

발명의 요약Summary of the Invention

An object of the present invention is provided with a nozzle and a sensor for supplying an additive containing a glycosylation enzyme to the inner end surface of the perforated plate hole to efficiently glycosylate a high solids content biomass through efficient mixing of the glycosylase. To provide a continuous saccharification reactor.

Another object of the present invention is to provide a method for saccharifying high viscosity biomass using the continuous saccharification reactor.

In order to achieve the above object, the present invention (a) a rotating shaft rotatable by a separate power; (b) a plurality of stirring means provided on the rotating shaft; And (c) a central glycosylation reactor for a high viscosity biomass composed of a cylindrical saccharification unit, through which a rotating shaft of (a) penetrates and a plurality of stirring means coupled to the rotating shaft are installed at regular intervals; (A) Located inside the cylindrical saccharification unit, a plurality of which is provided between the stirring means partitions the space containing each stirring means, penetrating from the outer peripheral surface of the porous plate to the inner end surface of the hole (hole) The above-described flow path is provided and provides a continuous saccharification reactor including a porous plate having a nozzle in communication with the flow path and in communication with the inner end surface of the hole to supply the additive.

The present invention also (a) when the biomass introduced from the inlet formed in the upper reaches the porous plate by the rotation of the stirring means is added through the nozzle provided in the inner end of the hole (hole) of the porous plate Mixing the additives and biomass by the rotation of the stirring means provided in the lower portion of the porous plate while flowing into the biomass and passing through the holes; And (b) saccharifying the biomass by transporting the biomass downwardly by repeating step (a) by the porous plate and stirring means sequentially installed in the saccharification unit, and the additive supplied to the nozzle is enzyme, pH control. It provides a continuous saccharification method characterized in that the acid / base material and the surfactant for supplying through different nozzles.

1 is a schematic diagram showing the structure of a porous plate and a hole provided therein mounted in a continuous saccharification reactor for high viscosity biomass.

FIG. 2 is a conceptual diagram of a saccharification reactor composed of a continuous saccharification reactor for a high viscosity biomass, a supply part of an additive included therein, and a low viscosity saccharifier.

발명의 상세한 설명 및 구체적인 Detailed description and specifics of the invention 구현예Embodiment

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Hereinafter, the present invention will be described in detail.

Enzymatic saccharification of high viscosity biomass with a solid content of 10-30%, which is essential for the previous stage of ethanol fermentation, is difficult to transfer fluid into biomass, so that it is difficult to maintain enzyme mixture, saccharification temperature and pH by simple agitation. There is a problem with efficiency.

The present inventors intend to improve the enzyme mixing efficiency required to increase the glycosylation efficiency of high-viscosity biomass, through the inner end of the hole of the porous plate for cutting high-viscosity biomass, A continuous saccharification reaction tank was introduced in which an additive containing an acid or basic substance, a buffer, and a surfactant was sprayed. That is, while high viscosity biomass passes through the porous plate and the stirring means sequentially, the glycosylation enzyme is evenly and quickly dispersed, and the cutting of the biomass and the mixing of the enzyme and the additive by the hole and the stirring means of the porous plate are repeated. While the saccharification efficiency was improved by efficient enzyme mixing.

Accordingly, the present invention in one aspect, (a) a rotating shaft rotatable by a separate power; (b) a plurality of stirring means provided on the rotating shaft; And (c) a central glycosylation reactor for a high viscosity biomass composed of a cylindrical saccharification unit, through which a rotating shaft of (a) penetrates and a plurality of stirring means coupled to the rotating shaft are installed at regular intervals; (A) Located inside the cylindrical saccharification unit, a plurality of which is provided between the stirring means partitions the space containing each stirring means, penetrating from the outer peripheral surface of the porous plate to the inner end surface of the hole (hole) The above-described flow path is formed, and it relates to a continuous saccharification reactor including a porous plate having a nozzle in communication with the flow path and in communication with the inner end surface of the hole to supply the additive.

The rotary shaft of the continuous saccharification reactor of the present invention is mounted to penetrate through the central portion of the device integrally from the top to the lower portion of the saccharification unit, the agitation means of the saccharification unit may be attached to agitate the biomass by coaxial rotation. .

The number of stirring means provided in the saccharification portion of the continuous saccharification reactor of the present invention may be one or more, the number can be easily adjusted by those skilled in the art.

The porous plate provided in the saccharification section of the continuous saccharification reactor of the present invention may be fixed to the inner wall of the saccharification section, or may be attached to a rotating shaft, and may be mounted to be capable of rotating or rotating. The porous plate serves to mix the raw materials, and the mixing effect may be reduced when the upper and lower porous plate holes are vertically aligned. In addition, when the porous plate is fixed, raw materials that are not mixed around the holes of the porous plate may be stagnant or secondary reactants may be deposited. Therefore, it is desirable to minimize the deposition of stagnant raw materials or side reactants by rotating the porous plate. In addition, when the viscosity of the raw material is high, the mixing and the movement to the lower side are slowed, so it is preferable to move the porous plate up and down to promote the mixing and the movement of the raw material to the lower portion.

In the present invention, the mixing effect can be maximized by adjusting the number and / or size of the holes of the porous plate. For example, when the size of the holes of the porous plate is large or the number is small, the mixing efficiency is low, and when the size or the number is small, the mixing efficiency is increased, and thus can be adjusted by the choice of those skilled in the art.

In the continuous saccharification reactor of the present invention, in particular, the number of holes may be characterized in that 10 to 90%, preferably 50 to 80% of the area of the porous plate, The diameter may be characterized in that 0.1 ~ 100cm, the diameter of the lower side may be 0.01 ~ 2cm smaller than the upper side diameter.

The size of holes formed in one porous plate may be the same or different from each other, and the diameter may be easily adjusted by those skilled in the art.

In addition, the size of holes formed in each porous plate may be the same or different, and the diameter may be easily adjusted by those skilled in the art.

Therefore, the diameter of the hole of each porous plate can be manufactured so that the hole of the porous plate installed on the upper side is larger than that provided in the lower portion of the saccharification unit. The raw material is introduced at the top and mixed toward the bottom to cause a reaction. At this time, the viscosity of the upper raw material is high, but the lower part is mixed with the reactants to lower the viscosity, therefore, the high viscosity of the upper part to install a large hole size plate, the lower viscosity of the lower hole to install a small plate size It is desirable to keep the moving speed of the raw material constant. In addition, since the size difference of the hole is lowered down to have a small size and a large amount of holes, the mixing of the raw materials has an advantage that can occur better.

The shape of the hole formed in the perforated plate may be circular, square, triangular, pentagonal, hexagonal, 24-pentagonal, and polygonal. In one perforated plate, holes of the same shape or holes of different shapes are formed. ) May be formed together.

In the continuous saccharification reactor of the present invention, since the saccharification unit is cylindrical, the gravity is used to transfer the biomass and the mixing effect by the porous plate can reduce the number of stirring means that should be normally installed. As a result, the amount of strategy needed for rotation can be significantly reduced.

In one embodiment, the porous plate has at least one flow passage penetrating from its outer circumferential surface to an inner end surface of the hole, and has a nozzle communicating with each flow passage for supplying an additive, or in a flow passage without a nozzle. Additional configurations, such as pH sensors and temperature sensors, can be communicated to check the status of the biomass. When the nozzle is attached to the reactor wall, the enzyme is fed to the side of the raw material so that the raw material has to be mixed while moving down a certain distance to be completely mixed with the raw material. In order to solve this drawback, a structure is installed inside the reactor, and then a device for supplying additives from the structure is often used. However, the additive supplying device, the higher the viscosity of the raw material acts as a factor that hinders the movement of the raw material, thereby increasing the risk of breakage. Therefore, it is preferable to provide a nozzle on the inner surface of the hole provided in the perforated plate, and the nozzle can supply additives uniformly to the raw material without disturbing the flow of the raw material. Moreover, it is preferable to install a sensor in the flow path in which a nozzle is not provided and to measure the state of a raw material.

Ends of the outer peripheral surface side flow path of the porous plate may be connected to an additive supply device, a pH reader, a temperature instrument panel, and the like, but are not limited thereto.

In the continuous saccharification reactor of the present invention, the nozzle and the additional configuration may be provided together in the same porous plate, or may be mounted on different porous plates so that the stock solutions of the additives do not directly contact each other.

In the continuous saccharification reactor of the present invention, the porous plates are installed at regular intervals in the saccharification unit, and a stirring means is mounted therebetween to partition a space including each stirring means, and the holes of the porous plates. By varying the type, concentration, combination, etc. of the additives introduced through the, it is possible to control the enzymatic reaction environment between each porous plate different.

In the continuous saccharification reactor of the present invention, the agitation means of the saccharification unit may be one or more selected from the group consisting of a bar, a disc, a paddle, and a scraper. A scraper may be installed in each compartment with additional agitating means, and more preferably the agitating means is mounted close to the top of the perforated plate, so as to not only agitate the biomass in the compartment but also stay in the top of the perforated plate. Can be forced to the lower part.

Since the continuous saccharification reactor of the present invention is a continuous type of saccharification reactor capable of continuously processing high viscosity biomass, in the case of a bioprocess, the initial investment cost is high due to the low concentration of the target substance, and compared to the capacity of the facility. While the productivity is low, the initial investment is reduced, productivity is increased, and operation convenience is improved.

According to another aspect of the present invention, (a) when the biomass introduced from the inlet formed in the upper reaches the porous plate by the rotation of the stirring means is supplied through a nozzle provided in the inner end surface of the hole of the porous plate Mixing the additives with the biomass by rotation of the stirring means provided in the lower portion of the porous plate while the additives are introduced into the biomass and pass through the holes; And (b) saccharifying the biomass by transporting the biomass downwardly by repeating step (a) by the porous plate and stirring means sequentially installed in the saccharification unit, and the additive supplied to the nozzle is enzyme, pH control. It is characterized in that for the acid / base material and the surfactant is supplied through different nozzles.

In the present invention, the porous plate may be equipped with a pH sensor and a temperature sensor in addition to the hole of the porous plate is not provided as a specific example, to confirm the physical and chemical state of the biomass have.

In the present invention, in one embodiment, the enzyme and the basic material supplied to the nozzle may be supplied by a nozzle in communication with the induction formed in the inner end surface of the different holes to prevent enzyme denaturation.

In the present invention, the basic material may be sodium hydroxide (NaOH), but is not limited thereto.

In the present invention, when passing through the porous plate in the process of transporting the biomass to the bottom, the biomass is distributed and at the same time the additive including the glycosylase supplied through the nozzle can be evenly dispersed throughout the biomass, the next porous plate It is continuously mixed by the stirring means until reaching, and since this mixing-stirring action is repeated until it is transferred to the lower part of the saccharification part, the mixing effect of the additive can be maximized.

In the present invention, the enzyme is at least one enzyme selected from the group consisting of exo-glucanase, endo-glucanase, and beta-glucosidase (β-glucosidase) Features may be, but are not limited to such. For example, beta glucanase (endo-1,3 (4) -beta-glucanase), laminarinase; Exo-1,2-1,6-alpha-mannosidase, alpha-N-arabinofuranosidase, ferroyl esterase, Endo-alpha-arabinanase (endo-1,5-alpha-arabinanase), pectinase, polygalacturonase, pectin esterase, aspartic protease protease, metallo protease, endo- (1,4) -mannanase, phytase, glucuronidase (alpha-glucuronidase, beta-glucuronidase) Hexenuronidase, alkaline phosphatase, acid phosphatase, alpha-galactosidase, beta-galactosidase, beta-mannosidase beta-mannosidase, or alpha-fucosidase, and the liver may use enzymes.

In the present invention, exo-glucanase and / or endo-glucanase is supplied through the holes of the upper porous plate, and through the holes of the lower porous plate. It may be to supply a beta-glucosidase (β-glucosidase).

In the continuous saccharification method of the present invention, when the viscosity of the biomass decreases while the saccharification reaction occurs, the low-viscosity biomass is quickly transferred downward through the porous plate, while the biomass having the relatively high viscosity is the porous plate. As the transfer is slowed down and thus the enzyme is continuously mixed while staying on the upper part of the saccharification unit, the saccharification continues, so that the saccharification efficiency can be improved. Therefore, in order to smoothly transfer the biomass, the size of the hole of the porous plate installed in the upper part of the reaction vessel may be large and the size of the hole of the porous plate installed in the lower part may be controlled to be small, or holes between the respective porous plates. By varying the size of, by artificially adjusting the residence time, it is possible to maximize the saccharification efficiency.

Continuous glycosylation reactor for the high-viscosity biomass according to the present invention and biomass treatable by the method is characterized in that the solid content of 10 ~ 30wt%.

The continuous saccharification reactor for high viscosity biomass according to the present invention is characterized in that evenly injecting glycosylase, maintaining temperature during saccharification, and pH can be smoothly controlled for high solids content biomass.

Wood-based biomass is composed mainly of cellulose, hemicellulose, and lignin, but the composition and content of chemical components of wood are different depending on conifers, hardwoods, species, and age. It is also called as cellulose-based biomass because it contains polysaccharide cellulose which is the main component of cell wall of wood or herbal biomass.

Therefore, the biomass of the present invention can be used in combination with cellulose-based biomass, wood-based biomass, lignocellulosic biomass, and wood-based biomass.

Biomass according to the present invention may include, for example, crops such as starch containing grains and refined starch; For example, rice, wheat, rye, oats, barley, rapeseed, cane from sugar cane, bagasse, straw; For example, conifers of Pinus sylvestris, Pinus radiate; For example, Alix spp. Hardwood of Eucalyptus spp; For example, beets, bulbs such as potatoes; For example, it may include biomass derived from rice, wheat, rye, oats, barley, rapeseed, sugar cane, cereal from corn or the like.

In the present invention, 'glycosylation' is a process in which the cellulose component is converted into glucose by the action of an enzyme, and a process in which cellulase is adsorbed on the reaction surface of cellulose to convert cellulose into cellobiose and thus produced cells Bios can be divided into the process of conversion to glucose by the enzymatic reaction of? -Glucosidase (β-glucosidase).

Unless otherwise defined in the technical and scientific terms used in the present invention, those having ordinary skill in the art to which the present invention pertains generally have the meanings that are commonly understood, and the gist of the present invention in the following description and the accompanying drawings. Descriptions of well-known functions and configurations that may unnecessarily blur are omitted.

Explanation of the sign

100: high viscosity continuous saccharifier

110: stirring means

120: upper perforated plate

121: hall

122: rotation axis

123: Euro

124: lower perforated plate

130: high viscosity continuous saccharification motor mixing motor

140: valve

150: additive pump

In the continuous saccharification reactor according to the present invention, since the porous plate having the enzyme supply nozzle and the sensor communicating with the induction formed in the inner end surface of the porous plate hole is mounted in a plurality of spaces at regular intervals, the biomass is Since the additive supplied from the nozzle can be evenly and quickly dispersed while being shredded by the porous plate, it is very easy to maintain the enzymatic activity condition by the sensor, thereby increasing the saccharification efficiency, which is useful for producing bioethanol.

Claims

(a) a rotating shaft rotatable by a separate power;

(b) a plurality of stirring means provided on the rotating shaft; And

(c) a continuous saccharification reactor for a high viscosity biomass consisting of a cylindrical saccharification unit, through which a rotating shaft of (a) penetrates and a plurality of stirring means coupled to the rotating shaft are installed at regular intervals;

(A) Located inside the cylindrical saccharification unit, a plurality of which is provided between the stirring means partitions the space containing each stirring means, penetrating from the outer peripheral surface of the porous plate to the inner end surface of the hole (hole) The above-described flow path is formed, the continuous saccharification reactor comprising a porous plate having a nozzle in communication with the flow path and in communication with the inner end surface of the hole for supplying additives.
The continuous saccharification reactor according to claim 1, wherein the porous plate is fixed to one or more of the rotating shafts to enable coaxial rotation or shanghai movement.
The continuous saccharification reactor of claim 1, wherein the porous plate is fixed to one or more inner walls of the saccharification unit.
The continuous saccharification reactor according to claim 1, wherein a diameter of the hole provided in the porous plate is 0.1 to 100 cm.
The continuous glycosylator according to claim 4, wherein the holes provided in the porous plate have a difference in diameter of 0.01 cm to 2 cm in the lower side compared to the upper side diameter.
6. The continuous saccharification reactor according to claim 5, wherein the holes provided in the porous plate have a difference in diameter of 0.05 to 50 cm from the diameter of the lower side compared to the diameter of the upper side.
6. The continuous saccharification reactor according to claim 5, wherein a diameter of a hole of the porous plate is larger than a hole of the porous plate disposed above the lower portion of the saccharification unit.
The continuous saccharification reactor according to claim 1, wherein the stirring means is at least one selected from the group consisting of a bar, a disc, a paddle and a scraper.
The continuous glycosylation reactor according to claim 8, wherein the scraper is installed in close proximity to or in contact with an upper portion of the perforated plate of the saccharification unit.
The continuous saccharification reactor according to claim 1, wherein a sensor for measuring pH and temperature is further provided in the passage.
Continuous saccharification method for high viscosity biomass using the continuous saccharification reactor of claim 1 comprising the following steps:

(a) When the biomass introduced from the inlet formed in the upper reaches the porous plate by the rotation of the stirring means, the additive supplied through the nozzle provided in the inner end of the hole of the porous plate is added to the biomass. Mixing the additives and the biomass by the rotation of stirring means provided in the lower portion of the porous plate while being introduced and passing through the holes; And

(b) in the step of saccharifying while transferring the biomass downward while repeating the step (a) by the porous plate and the stirring means sequentially installed in the saccharification unit,

The additive supplied to the nozzle is a continuous glycosylation method, characterized in that the enzyme, acid / base material for pH adjustment and the surfactant is supplied through different nozzles.
The continuous saccharification method according to claim 11, wherein the hole of the porous plate which is not provided with a nozzle is further equipped with a pH sensor and a temperature sensor to check the physicochemical state of the biomass.
The method of claim 11, wherein the enzyme is at least one enzyme selected from the group consisting of exo-glucanase, endo-glucanase, and beta-glucosidase. Continuous glycosylation method, characterized in that.
12. The method of claim 11, wherein exo-glucanase and / or endo-glucanase are supplied through holes in the upper perforated plate and beta-glucose through holes in the lower perforated plate. Continuous glycosylation method, characterized in that the supply of (sid-glucosidase).