KR20130137568A - A method of simultaneous implementation of pretreatment process and separation process for processing biomass and biochemicals made thereof - Google Patents

Abstract

The present invention provides a method for simultaneously performing a pretreatment process and a separation process for processing biomass; a method for purifying (or preparing) biomass derived chemicals using the same; a device for performing the above methods; and high purity biochemicals including xylose and specific by-products and the likes which are purified (or prepared) by the above methods. The method for simultaneously performing a pretreatment process and a separation process for processing biomass according to the present invention can pretreat the biomass and obtain purified biochemicals (xylose and specific by-products) at the same time, thereby achieving two purposes at the same time. In addition, the method for simultaneously performing a pretreatment process and a separation process for processing biomass according to the present invention does not require additional processes such as isolation and purification or non-toxicity of by-products which are required for processing by-products in products of conventional pretreatments. The present invention can obtain high concentration xylose in which specific by-products are isolated and obtain expensive furfural and acetic acid by isolating specific by-products collected in gas state without extra energy consumption. [Reference numerals] (AA) Simultaneously performing a pretreatment process and a separation process;(BB) Biomass;(CC) Acid saccharification;(DD) Fermentation

Description

A method of simultaneous implementation of pretreatment process and separation process for processing biomass and biochemicals made according to the present invention

The present invention provides a method for simultaneously performing a pretreatment process and a component separation process for biomass treatment; Using this method to purify (or manufacture) biomass-derived chemicals; An apparatus for implementing the method; And it provides a high-purity biochemical containing xylose and certain by-products purified (or prepared) by the above method.

Pretreatment refers to a process that enables to improve the rate and yield of enzymatic hydrolysis of biomass, especially lignocellulosic biomass. The ultimate goal of pretreatment is to reduce the crystallinity of cellulose to increase the accessibility of enzymes, to increase the specific surface area of biomass, and to increase the amount of effective enzymes. For example, the pretreatment process is considered an essential step in converting biomass into biofuels.

Pretreatment methods can be largely divided into physical and chemical biological methods depending on the treatment method. Typical physical methods include milling or steam explosion, chemical methods such as dilute acid pretreatment, soaking in Aqueous Ammonia (SAA) and ammonia recycled leaching (Ammonia Recycled). Percolation, ARP), and biological methods include methods using microorganisms such as molds.

The pretreatment process is divided into batch and continuous processes according to the device type. The two processes are the same in terms of chemical reaction between substrate and catalyst by applying heat and pressure for a certain time, but compared to a batch process where the reaction is completed in a single condition in a single reactor, various reaction conditions using one or a connected device are used. As a continuous process capable of continuous pretreatment can be advantageously applied in terms of scale up and cost, in recent years, research on a continuous process, particularly a continuous extrusion process, has been actively conducted.

The continuous extrusion process has various process variables such as screw rotation speed and arrangement, shape of the injection part, barrel temperature, biomass feed rate and feed amount, and dependent variables such as viscosity, bed, rolling speed, Due to the wide range of internal pressure, power requirements, residence time, and temperature of internal materials, extensive research on biomass pretreatment conditions is possible. In addition, the continuous extrusion process can increase the specific surface area (SSA) of the biomass to which enzymes can be adsorbed due to the synergistic effect of heating, shearing, and mixing. Pretreatment efficiency can be increased with only a short residence time, and it is evaluated to be suitable for use as a continuous process for pretreatment of biomass.

Wood-based biomass consists of 15-20 wt% lignin, 40-50 wt% cellulose, and 25-35 wt% hemicellulose. Lignin is a large molecular weight polymer containing a large amount of aromatic compounds polymerized with methoxylated p-coumacyl alcohol, coniferyl alcohol, synapyl alcohol, and the like. It is considered to be the most difficult to decompose among the existing natural compounds, and cellulose is a polysaccharide connected to ß-1,4 bonds with glucose, and is known to have a strong physical and chemical structure because it has a stable structure with a linear structure. Hemicellulose is a polysaccharide that has a lower degree of polymerization than cellulose, and is mainly composed of a polymer of xylose, which is a five-saccharide sugar. In addition, hemicellulose is composed of polymers such as arabose, a five-saccharide sugar, mannose, galactose, and glucose. have.

Xylan (the polymer of xylose), which is the main component of hemicellulose, has a low degree of polymerization compared to cellulose, and thus hydrolysis is relatively easy by physicochemical treatment. The importance of the technology of converting xylose obtained through hydrolysis into ethanol, chemical products or bio-products has been emphasized several times, and the process for producing xylitol from xylose has been developed early and used commercially. Xylose is usually reduced to xylitol by the process of adding hydrogen in the presence of Raney Nickel catalyst. Xylitol produced is widely used in dentistry by inhibiting tooth corrosion by inhibiting the growth of bacteria using tooth enamel. In addition, it has low calorie content, gastrointestinal resistance, insulin independent, etc. and thus is applied to food or medical process.

By-products produced in the pretreatment process using wood based biomass are the furfural and 5-hydroxymethylfurfural resulting from the over decomposition of xylose or glucose, phenolic compounds derived from lignin, and the structural degradation of wood based biomass. Acetic acid produced by These by-products are known to have a negative effect on fermentation efficiency, and as a detoxification method to remove them, adsorption method using activated carbon and ion exchange resin or precipitation method through overliming have been developed. For example, furfural, etc., has a high value-in-use, and research on the process of producing from wood-based biomass has also been conducted. Furfural is a furan-based colorless liquid having a molecular formula of C ₅ H ₄ O ₂ and a boiling point of 161.8 ° C. and is also referred to as α-furanaldehyde furfural. The annual production of furfural is about 250,000 Mt and the market price is about $ 1,000 / Mt. It is widely used in various fields such as oil refining process, plastics, food, medicine, etc. It is also used as a component of P-series fuels or liquid alkanes. Furfural is generally produced by hydrolysis of hemicellulose, a constituent of wood-based biomass, which undergoes one or two steps. In the first step, xylose is obtained by hydrolyzing pentosan, a polysaccharide containing pentose sugar as a constituent molecule, and then xylose is converted to furfural through dehydration in the same reactor. In the two-stage process, furfural is produced after hydrolysis and dehydration are performed in different reactors. The first stage process has a very low yield of furfural (0.7-3.3%), and the second stage process has a relatively high yield of furfural, while the remaining solids after the reaction can be used only as a source for fuel production. After the reaction, the remaining solid can be used as a source for the production of cellulose, glucose and ethanol, mainly producing furfural using a two-step process. For industrial production of furfural, woody biomass is pressurized and treated with water vapor, or diluted sulfuric acid or hydrochloric acid catalysts are mainly used.These methods are expensive due to expensive purification process and waste water. It is causing environmental problems, and the chemical technology for producing furfural while improving it is required.

Acetic acid is a colorless liquid with a molecular formula CH ₃ COOH and a boiling point of 118.1 ° C. and has the simplest molecular formula among carboxylic acids. The global production of acetic acid is about 6.5 Mt per year, 1.5 Mt of which is produced by regeneration and the rest from petrochemical or biological sources. Acetic acid has a wide range of uses, and is used in the chemical industry to produce polyethylene telephthalate for soft drinks, cellulose acetate for photographic films, and polyvinylacetate for glue and synthetic fibers. In addition, it is used in various fields such as pharmacy, plastics, and food. However, acetic acid produced during the pretreatment of biomass has been removed through detoxification because it has a low production rate and is evaluated as a material that inhibits fermentation. In addition, the separate separation method developed to date is mostly a method for non-toxicization, and little research has been conducted on the method of efficiently separating and purifying acetic acid generated in the pretreatment process.

The inventors have found that pretreatment specific by-products such as furfural and acetic acid are mostly present in the gas phase under pretreatment reaction conditions, and are collected separately at the same time as the pretreatment or after the pretreatment before cooling the product, thereby allowing biotechnology such as xylose, furfural and acetic acid. It was confirmed that mass derived biochemicals can be obtained at high concentrations (FIG. 3).

In addition, it was confirmed that specific by-products (furfural and acetic acid, etc.), which were previously subjected to expensive separation purification or non-toxicity, were easily separated in a pretreatment process and recovered separately.

The present invention is based on this.

A first aspect of the invention provides a method for producing a chemical reaction product from biomass by pretreatment of the biomass under any reaction conditions; And a second step of separating a specific product in a gaseous state from the chemical reaction product with another product in a liquid or solid state simultaneously with or after the first step.

A second aspect of the present invention provides a method for producing a chemical reaction product, comprising: a first step of pretreating the biomass under any reaction conditions to produce a chemical reaction product from the biomass; And a second step of separating the specific gaseous product in the chemical reaction product from other products in the liquid or solid state simultaneously with or after the first step, and in the liquid or other product in the solid state. Provided is a method for preparing xylose to separate the loss.

According to a third aspect of the present invention, there is provided a method for producing a specific by-product produced during wood-based biomass pretreatment, wherein the specific by-product is subjected to pre-treatment of the wood-based biomass to produce a specific by-product under reaction conditions in which the specific by-product is present in the gas phase. a step; And a step b of collecting the specific by-product from the step a product at the same time as or after the step a in a gas phase, wherein the specific by-product is furfural, acetic acid, formic acid, levulinic acid and 5-hydride. It provides a method for producing a specific by-product that includes any one or more selected from the group consisting of oxymethylfurfural.

According to a fourth aspect of the present invention, there is provided a wood based biomass pretreatment apparatus comprising: a reactor for pretreating wood based biomass; And a gas collecting unit located above the reactor, and the gas collecting unit is for separating a specific gaseous product from the chemical reaction product generated during the woody biomass pretreatment.

The fifth aspect of the present invention provides xylose prepared by the method for producing xylose according to the second aspect.

A sixth aspect of the present invention is a specific by-product comprising any one or more selected from the group consisting of furfural, acetic acid, formic acid, levulinic acid and 5-hydroxymethylfurfural prepared by the preparation method according to the third aspect. To provide.

Hereinafter, the present invention will be described in detail.

By-products produced during the pretreatment of biomass are known as furfural and acetic acid. As shown in FIG. 1, conventional biofuel production requires a separate non-toxic process for removing them, and a problem such as xylose is also disposed of together.

Furthermore, as shown in FIG. 2, a separate separation / purification process was further required to obtain xylose from the product of the pretreatment process.

The present inventors found that, under the pretreatment reaction conditions of the pretreatment process, the gaseous specific products generated during the biomass pretreatment are collected in the gas phase based on the fact that most of the gaseous products exist as specific by-products such as furfural and acetic acid. In addition to the step of, as shown in Figure 3, it is characterized by obtaining by separating the xylose and certain by-products.

That is, a simultaneous pretreatment / separation process for simultaneously performing the pretreatment process and the component separation process may be provided. Thus, as shown in FIG. 3, the present invention can obtain various useful biochemicals at economical and high yields without the need for the non-toxicization process or the separation / purification process, which is essential in the conventional biomass conversion process.

Furthermore, the present invention can fractionate specific products that are collected in the gaseous state, thereby obtaining specific by-products such as purified furfural and acetic acid without additional energy input. Since the specific by-products are collected in the gas phase and recovered, there is no need for a separate energy input for fractional distillation of them, and also in the petroleum industry, each of the furfural, acetic acid, etc., which has been treated as a by-product to be disposed of in the past, is recovered in a separated / purified form. It can be used as a useful raw material. Since these specific by-products are expensive compounds, the present invention can be a high value-added process which is distinguished from the conventional one even in economic terms.

The term 'simultaneous pretreatment / separation process' or 'pretreatment / separation process' used in the present invention is in contrast to the biomass conversion process, which requires an additional separation / purification process following the conventional pretreatment process. It means a special novel process only of the present invention to proceed simultaneously with the pre-process and the component separation process. Thus, the biomass treatment method of the present invention can obtain purified biochemicals with pretreatment of biomass without additional procedures or devices.

The biomass treatment method according to the present invention comprises: a first step of producing a chemical reaction product from the biomass by pretreatment of the biomass under any reaction conditions; And a second step of separating the specific product in the gaseous state from the chemical reaction product with another product in the liquid or solid state simultaneously with or after the first step.

The first step is a step of producing a chemical reaction product in the gas, liquid, or solid state from the biomass under a chemical pretreatment reaction process. Specifically, when the biomass is wood-based biomass, the chemical reaction product may contain xylose and certain byproducts. The pretreatment reaction and the process of the biomass is carried out with various chemical reactions as well as the hydrolysis reaction of the biomass, and also the resulting product can be produced not only xylose and specific by-products, but also various substances. Furthermore, depending on the specific type of biomass, various substances can be produced in the gas, liquid or solid state in addition to xylose and certain by-products.

The first step may be initiated by introducing biomass into the reactor. Preferably, the biomass may be preheated to 50 ℃ to 100 ℃ before input to the reactor.

In the present invention, the biomass is energy, electricity, plastics, polymers, nutrients (human and animal), proteins, biomolecules, drugs (such as ethanol, hydrocarbons, gasoline, natural gas, methane, biodiesel and hydrogen gas) Human and livestock), fertilizers, or any combination of materials or organic ingredients that can be used in production systems to produce other products. The biomass, which is a pretreatment target of the present invention, is not particularly limited, and may include wood-based biomass and algae baomai (green algae, brown algae, red algae), and the like, and may preferably be wood-based biomass, but is not limited thereto. no.

The wood-based biomass refers to wood, herbaceous plants containing cellulose, and may include products derived from them or wastes thereof, that is, wood, waste wood, paper, and the like. The wood-based biomass may be composed of three wood components of cellulose, hemicellulose, lignin, extracts such as rosin, and ash. Non-limiting examples of the wood-based biomass may be rapeseed, barley, sawdust, EFB (Empty Fruit Bunch) or a mixture thereof, but is not particularly limited.

The pretreatment of the biomass of the first step may change the binding state between the components in the biomass, and the components may be decomposed to produce a chemical reaction product in gas, liquid, or solid state. Further, the pretreatment of the biomass may include changes in molecular structure, oxidation of components in the biomass, change in average molecular weight, change in average crystallinity, change in surface area, change in polymerization degree, change in porosity, change in degree of branching, grafting, A change in the crystalline region size, or a change in the overall region size.

In one embodiment of the present invention, in the pretreatment of biomass, hemicellulose and cellulose as constituents may be separated from the biomass, and further, hemicellulose may be decomposed to generate xylose and certain by-products. In order to carry out this pretreatment reaction, a catalyst for separating and decomposing hemicellulose and cellulose can be used. The catalyst may be an acid that may be used for chemical pretreatment, preferably the acid may be sulfuric acid, but is not limited thereto.

The catalyst may be preheated to 150 ℃ to 300 ℃ before input to the reactor.

As used herein, the term 'by-product' refers to a product comprising furfural, 5-hydroxymethylfurfural, phenolic compounds derived from lignin, and acetic acid, etc., except for xylose, produced during biomass pretreatment. Means. The amount of by-products produced is less than that of other products, and also, since they were conventionally subjected to detoxification or separation / purification after the pretreatment process, the expression “by-products” was often used as a term for this.

In the present invention, the specific by-products of interest may include any one or more selected from the group consisting of furfural, acetic acid, formic acid, levulinic acid and 5-hydroxymethylfurfural. The present inventors have confirmed that the specific product, which is a gaseous state generated in the biomass pretreatment, is mainly composed of the specific by-products, thereby separating the pretreatment process and the component separation process at the same time.

The present invention can be carried out under any reaction conditions, ie it means reaction conditions in general biomass pretreatment and is not particularly limited. However, it can be carried out under reaction conditions in which certain by-products are present in the gas phase, such that the desired by-products are contained in the particular product in the gaseous state. That is, the reaction condition in which the specific by-products exist in the gas phase may be a reaction temperature higher than the boiling point of the specific by-products, and the reaction temperature in the reactor may be controlled to correspond thereto. The reaction temperature is primarily determined as a temperature higher than the boiling point of a specific by-product, but may be determined in consideration of the types and yields of products according to specific types of biomass. Therefore, the reaction temperature may be appropriately selected by those skilled in the art according to the type of biomass used as the raw material, and is not particularly limited as long as it is higher than the boiling point temperature of a specific by-product. More specifically, the reaction temperature of the reaction conditions may be generally 150 ℃ to 250 ℃, but is not particularly limited as described above. By satisfying the above reaction conditions, the specific by-products generated may exist as a specific product in the gaseous state, and further, the specific product in the gaseous state may be collected and separated in the gas phase in the second step.

The first step may be carried out in a continuous or batch reactor, and the type, size, etc. of the possible reactors are not limited and may be appropriate to those skilled in the art according to the type, amount, reaction conditions, and yield of the desired product. Can choose.

The second step is to collect and separate a specific product in a gaseous state from the chemical reaction product generated through the first step. Through the biomass pretreatment of the first step, the gas generated from the biomass is filled in the reactor in which the first step is performed, and it may be separated from other products in a liquid or solid state. This gaseous specific product may be mainly composed of the desired specific by-products by adjusting the reaction conditions of the first step. Thus, by capturing the gas (specific product in gaseous state) present in the reactor, specific by-products can be easily collected.

When the second step is carried out in a batch reactor, it is possible to capture a specific product in a gaseous state by attaching a gas collecting unit on the upper part of the reactor. Specifically, the gas collecting unit may include a pipe connected to the upper portion of the reactor and a pressure valve attached thereto, thereby opening the valve to recover a specific product in a gaseous state in the reactor.

Even when the second step is performed in a continuous reactor, a gaseous specific product may be collected by attaching a gas collecting unit to the upper part of the reactor. Specifically, the gas collecting unit may be attached to be located at the rear end of the reactor while the upper portion is perpendicular to the product flow direction. The pressure pump attached to the gas collecting unit may be used to recover a specific product in a gaseous state in the reactor.

By separating the gaseous specific product in the gas phase through the second step, the remaining liquid or solid product can be obtained. By separating the gaseous specific product, preferably in the gas phase, it is possible to obtain a liquid or solid product in which a particular by-product is separated, thus eliminating the need for a separate special separation / purification or non-toxic process.

Since the gaseous specific products (containing certain by-products) are separated during the first and second steps, the remaining products may be in the form of liquids, solids or slurries whose distinction is not clear. The form of the remaining product from which the specific product in the gaseous state is separated may be variously adjusted according to the conditions such as the catalyst concentration and the input amount, the reaction temperature and the reaction time in the first step.

The 'chemical reaction product' of the present invention includes 'gaseous specific product', 'liquid other product' and 'solid other product'. The specific product in the gaseous state is generated from the pretreatment of the biomass, and may consist mainly of the specific by-products, and is the same as described above. Liquid and solid products are those in which gaseous, biomass, catalysts, and other solvents, including water, undergo a 'simultaneous pretreatment / separation process' corresponding to the first and second stages. Means the remaining product from which the product is excluded. Thus, the previously described xylose is contained in the product in the liquid or solid state.

In addition, the solid product may include biomass that has not been reacted or has been completely decomposed. Particularly in the case of recovered solid products, biofuels can be prepared by saccharifying and fermenting them separately. At this time, since a specific by-product is separated through the second step, there is no need to go through a separate non-toxicization process.

Furthermore, the xylose is mainly contained in the liquid product, but may be contained in the solid product.

The biomass treatment method according to the present invention may further comprise a third step after the second step of recovering any one or more of the liquid or solid other products from which the gaseous specific product is separated.

When the remaining product from which the gaseous specific product is separated includes both liquid and solid products, by separating the double liquid products, the liquid and solid products are separated and recovered. Can be.

By recovering the product in the liquid and / or solid state in the third step, it is possible to prepare a high concentration xylose through one process without additional separation and purification.

In one embodiment of the present invention, the product recovered through the first and second steps contain a high concentration of xylose produced by the decomposition of hemicellulose, most of the specific by-products (furfural and acetic acid, etc.) It was confirmed to be separated.

In one embodiment of the present invention, when the third step of recovering any one or more of the remaining liquid product and the solid product is separated from the xylose-containing product in a batch reactor, the reactor bottom The product was attached to a mesh to filter the solid product, and the liquid product was separated and recovered.

In one embodiment of the present invention, when the third step is performed in a continuous reactor, by attaching a cooler to the reactor end to cool the remaining product, it can be recovered through the outlet. Additionally, a mesh or solid / liquid separator may be attached at the end of the reactor to filter out the solid state product and to separate and recover the liquid state product.

As described above, in the method for preparing xylose through the first to third steps, each step is sequentially performed through one process, and at the same time as the pretreatment of biomass, the generated xylose and the specific by-product are separated. You can. That is, it is possible to reduce the degree of crystallization of cellulose, increase the accessibility of enzymes, increase the specific surface area of biomass and achieve xylose production, and additionally, by-products can be easily separated in the middle of the process. The purpose can be achieved.

The process for preparing xylose according to the second aspect of the present invention comprises: a first step of pretreating the biomass under any reaction conditions to produce a chemical reaction product from the biomass; And a second step of separating the specific gaseous product in the chemical reaction product from other products in the liquid or solid state simultaneously with or after the first step, and in the liquid or other product in the solid state. To separate Ross.

In the xylose manufacturing method of the present invention, the first step and the second step are the same as described in the first embodiment. The first and second stages may yield a liquid or other product in which gaseous specific products have been separated, from which xylose can be separated to obtain purified xylose excluding certain byproducts. have.

More specifically, it is as described above that the xylose is contained in the liquid product among the other liquid or solid products. Purified xylose may be obtained through a conventional separation method using the liquid product by distillation or solubility difference. In addition, in the case of the product in the solid state, xylose can obtain purified xylose using a method of washing with water using a property that is well soluble in water.

Furthermore, in the method for preparing xylose of the present invention, after the second step, the gaseous specific product may further include a third step of recovering any one or more of the liquid or solid other products separated from the gaseous specific product. This is also the same as described above in the first aspect.

Method for producing a specific by-product produced during the pretreatment of the wood-based biomass according to the third aspect of the present invention, a method for producing a specific by-product by pre-treating the wood-based biomass under the reaction conditions in which the specific by-product is present in the gas phase step; And a step b of collecting the specific by-product from the step a product in a gas phase simultaneously with or after step a. The specific by-product may include any one or more selected from the group consisting of furfural, acetic acid, formic acid, levulinic acid, and 5-hydroxymethylfurfural.

Step a is the same as the first step described above. Specifically, by adjusting the reaction conditions of the first stage so that the specific by-products can be present in the gas phase, a specific product in the gaseous state consisting mainly of the specific by-products can be produced from the wood-based biomass. Preferably, the reaction condition in which a specific by-product is present in the gas phase may be a reaction temperature higher than the boiling point of the specific by-product, and the reaction temperature in the reactor may be controlled to correspond thereto. More specifically, the reaction temperature of the reaction conditions may be generally 150 ℃ to 250 ℃, but is not particularly limited as described above.

Step b is the same as step 2 described above. However, the second step relates to a biomass treatment method, which focuses on simply separating a gaseous specific product from other products, whereas the step b relates to a method for preparing a specific by-product. It should be noted that the focus is on the capture and recovery of certain by-products contained in certain gaseous products.

By collecting the specific by-products in the gas phase through step b, specific desired by-products can be obtained, and there is no need for an additional separation / purification process to obtain them separately as in the prior art. The collection of the specific by-product may be achieved through the separation of the specific product in the gaseous state of the second step.

The method of preparing a specific by-product of the present invention may further include a step c of fractionating the specific by-product collected after step b without additional energy input.

The step c is a step of obtaining each component by fractionating a specific by-product collected in a gas state without additional energy input, and furfural, acetic acid, and the like may be recovered in a separated state.

In step c, the specific by-product collected in the gaseous state in step b may be introduced into a recovery tower for fractionation. The principle of separating the specific by-products is fractional distillation, by cooling the specific by-products recovered in the gas phase, each component is sequentially liquefied according to the boiling point, it can be separated by each component.

Alternatively, by-products can be cooled and liquefied without fractionating specific by-products, thereby obtaining a by-product solution containing various components.

According to a fourth aspect of the present invention, there is provided a wood based biomass pretreatment apparatus comprising: a reactor for pretreating wood based biomass; And a gas collecting unit located above the reactor, and the gas collecting unit is for separating a specific gaseous product from the chemical reaction product generated during the woody biomass pretreatment.

The biomass treatment method of the first aspect of the present invention, the production method of xylose of the second aspect, and the production method of the specific by-product of the third aspect can be performed through the apparatus of the third aspect.

The device according to the invention may be a continuous or batch reaction device.

In a batch reaction device according to one embodiment of the present invention, in a batch reaction device usually used for pretreatment of biomass, a gas collecting unit is further provided at the top of the reactor.

More specifically, the apparatus comprises a batch reactor for pretreating woody biomass to produce xylose or to produce specific byproducts in the gas phase; A gas collecting unit located above the reactor; A liquid holding tank connected to the bottom of the reactor to collect and store a liquid product; It may include a catalyst tank (catalyst reservoir) and a manipulator connected to the reaction tank for introducing the catalyst. In addition, a heater capable of maintaining a constant reaction temperature may be mounted outside the reactor, and a screen wire mesh may be mounted at the bottom of the reactor to separate liquid and solid products. In addition, a sampling valve and a sampling port may be installed between the bottom of the reactor and the liquid reservoir to enable real-time sampling of the liquid product during the reaction (FIG. 4).

The gas collecting unit may include a pressure valve, a gas collecting port, and a gas capture tank, which are attached to a pipe connected to the upper part of the reactor, and thus, a specific product having a gas state generated inside the reactor after the reaction. (Specific by-products) can be recovered by adjusting the pressure valve.

In the continuous reaction apparatus according to the embodiment of the present invention, in the continuous reaction apparatus usually used for pretreatment of biomass, a gas collecting unit is additionally provided at the top of the reactor. Preferably, the continuous reaction device may be a biaxial coaxial continuous device capable of thermo-mechanical compression molding.

More specifically, the apparatus comprises a continuous reactor for pretreating woody biomass to produce xylose or to produce specific byproducts in the gas phase; A gas collecting unit located above the reactor; A cooler located at the end of the reactor connected to the gas collecting unit and capable of cooling the product; A barrel providing an appearance of the reactor; A screw / shaft positioned in the reactor for transferring, mixing and reacting woody biomass; A raw material input unit connected to the reaction tank and into which wood-based biomass is input; A catalyst input unit connected to the reaction tank and into which a catalyst is introduced; A heater mounted outside the reactor and capable of maintaining a constant reaction temperature; A drive motor providing rotational power to the screw / shaft; And an outlet for discharging any one or more of the remaining liquid product and the solid product from which the specific by-product is removed from the xylose-containing product (FIG. 5).

As shown in FIG. 6, the screw may include a combination of a forwarding screw, a forward kneading block, and a reverse kneading block. And the screw is a conveying zone (conveying zone) for transporting the biomass and catalyst to the kneading block, kneading block zone for mixing the biomass and catalyst, and reacted the mixed reactants at the temperature and internal pressure of the barrel The main can be divided into a reaction zone and a compression zone to reduce the pitch size of the screw to pressurize the reactants to perform an efficient pretreatment reaction.

The gas collecting portion may be attached to be located at the rear end (end) of the reactor while being vertical to the product flow direction. The pressure pump attached to the gas collecting unit may be used to collect gaseous by-products in the reactor. However, the position of the gas collecting unit does not necessarily need to be the rear end of the reaction tank, and may be attached at an appropriate position on the upper part of the reaction tank, and two or more may be attached.

The above batch and continuous reactors are exemplary, and any type of batch and continuous reactors capable of satisfying the simultaneous pretreatment / separation process of the present invention may be included in the present invention. It is free to select the size and configuration of the reaction apparatus and reactor according to the products desired by one of ordinary skill in the art.

The fifth aspect of the present invention provides xylose prepared by the method according to the second aspect.

As described above in the second aspect, the biomass-derived purified xylose may be obtained through the first and second steps.

A sixth aspect of the present invention provides a specific by-product comprising at least one selected from the group consisting of furfural, acetic acid, formic acid, levulinic acid and 5-hydroxymethylfurfural prepared by the method according to the third aspect. to provide.

As described above in the third aspect, the above-mentioned steps a and b may yield a specific biomass-derived by-product. Furthermore, by going through step c, certain by-products can be fractionated without additional energy input to obtain furfural, acetic acid, formic acid, levulinic acid and 5-hydroxymethylfurfural in purified form.

The biomass treatment method in which the pretreatment process and the component separation process are carried out at the same time of the present invention can obtain purified biochemicals (xylose and specific by-products) at the same time as the biomass is pretreated, and thus can achieve both purposes simultaneously. It has an effect. In addition, there is an effect that an additional process such as separation purification or non-toxicization of the by-products for treating the by-products in the conventional pretreatment product is unnecessary.

The present invention can obtain a high concentration of xylose from which specific by-products are separated, and further, expensive furfural and acetic acid can be obtained by fractionating specific by-products collected in the gas phase without additional energy input.

1 is a schematic diagram showing a process of pre-treating conventional wood-based biomass and producing biofuels through a non-toxic process of by-products.
FIG. 2 is a schematic diagram showing a process of producing biofuel and xylose by pretreatment of conventional wood-based biomass and separation / purification of by-products.
3 is a schematic diagram illustrating a process for producing xylose, certain by-products and other biochemicals from woody biomass through a simultaneous pretreatment / separation process according to the present invention.
4 is a schematic diagram showing a batch reaction apparatus in which a simultaneous pretreatment / separation process according to the present invention can be performed.
5 is a schematic diagram showing a continuous reaction apparatus in which a simultaneous pretreatment / separation process according to the present invention can be performed.
6 is a schematic view showing a screw that can be applied to the continuous reaction apparatus according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for illustrating the present invention, and the scope of the present invention is not construed as being limited by these embodiments.

In the embodiment of the present invention, the experiment was performed using the following experimental materials, apparatus, and analysis method.

1. Experimental material

1.1 Substrate

In the embodiment of the present invention, rapeseed, barley, sawdust, EFB (Empty Fruit Bunch, a kind of palm by-product) was used as a substrate. Each substrate was ground using a ball mill and then powdered into a mesh, and the powdered substrates were dried in a dryer at 45 ± 5 ° C. for 24 hours.

1.2 Batch  Pretreatment / Separation Unit

As a batch reaction device for the simultaneous pretreatment / separation process of the present invention, a batch pretreatment / separation device composed of a SUS316L material reaction tank, a liquid storage tank, a gas collection tank, two catalyst tanks, and a manipulator was used. The reactor was manufactured with a diameter of 70 mm and a height of 275 mm with a capacity of 885 mL. The outside of the reactor was equipped with a heating jacket (maximum temperature 300 ° C.) of 5 KW / h capable of maintaining a constant reaction temperature. The inside of the reactor was equipped with a stirrer for efficient heat transfer, and the temperature sensor (thermocouple, KQXL-18G-12, Omega Eng. Inc., Stamford, CT) was installed to observe the temperature inside the reactor. In addition, a screen wire mesh made of SUS316L was mounted to separate a liquid product from a solid product. The reaction tank is connected to the liquid reservoir to allow the finished liquid product to be filtered through the mesh and separated into the liquid reservoir, and equipped with a sampling valve and a sampling port to collect the liquid product in real time during the reaction. In order to recover the gas (furfural, acetic acid, etc.) generated in the reactor after the reaction by installing a gas collecting unit including a pressure valve, a gas collecting port and a collecting tank on the upper part of the reactor. It was. The two catalyst tanks were also equipped with a heating device, so that a single catalyst or two catalysts could be used. In the operation device, a timer and a digital temperature controller for controlling the reaction time were installed to enable the temperature confirmation and control of the reaction tank and the catalyst tank. The schematic diagram of a batch pretreatment / separation apparatus is shown in FIG.

1.3 continuous pretreatment / separation unit ( Continuous Twin Screw - driven Reactor , CTSR )

As a continuous reaction device for the simultaneous pretreatment / separation process of the present invention, a biaxial coaxial continuous device capable of thermal compression molding was used by itself. The continuous reactor was composed of a barrel, a screw / shaft, a raw material input unit, a catalyst input unit, and a driving motor, which provided the appearance of the reactor, and the material of the barrel and screw was SUS316. The screw consists of a combination of a forwarding screw, a forward kneading block, and a reverse kneading block. The total length of the screws used is 1000 mm and the diameter is 36.0 mm, the ratio of length to diameter (L / D ratio) was 27.78. The screw is used to transfer the raw material (substrate) and catalyst to the kneading block, the mixing zone for mixing the raw material and the catalyst, the reaction zone for reacting the mixed reactants at the temperature and internal pressure of the barrel, and the pitch size of the screw. It is divided into compression zones that pressurize the sample so that it can be pretreated and separated. The schematic diagram of the continuous pretreatment / separation apparatus is shown in FIG. 5, and the schematic diagram of the screw is shown in FIG.

1.4 Pretreatment / Separation Process Conditions

In the embodiment of the present invention, the experimental conditions were determined in consideration of the yield of xylose and the amount of by-products produced. Specifically, the experimental conditions were determined in consideration of the yield of xylose in the case of using a batch device, and the experimental conditions were determined in consideration of the amount of specific by-products including furfural and acetic acid in the case of using a continuous device. Decided.

Sulfuric acid was diluted by concentration (0.4 to 4.5 (w / v, H ₂ SO ₄ )%) and used as a pretreatment reaction catalyst.The reaction temperature was 150 to 180 ° C and the reaction time was 5 to 21 minutes. Time 7.2 minutes).

1.5 Recovery of Pretreatment Reaction By-Products

The wood-based biomass-derived pretreatment by-products produced through batch and continuous reaction processes were discharged to specific gaseous products due to temperature and pressure differences inside and outside the apparatus, which were collected and cooled to room temperature and recovered as liquid. .

2. Method of Analysis

2.1 Carbohydrate Analysis

0.3 ± 0.01 g of sample (recovered liquid and / or solid product) and 3 mL of 72.0 (w / v)% sulfuric acid were added to the test tube, and stirred at 15 ± 20 minutes for 60 minutes at 30 ± 3 ° C. Reacted (first hydrolysis). 84 mL of distilled water was added to the reacted sample to lower the acid concentration to 4.0 (w / v)%, followed by 60 at 121 ° C. using a high pressure reactor (Thermo Scientific Co.- Napco 8000-DSE Autoclave, Frederick, MD, USA). The reaction was carried out for minutes (secondary hydrolysis). After completion of the reaction, the sample was cooled to room temperature, neutralized with calcium carbonate, centrifuged at 16099 g for 20 minutes, and the supernatant was collected and filtered using a syringe filter (Gelman, 0.2 μm pore size). The filtrate was analyzed by high performance liquid chromatography (Breeze HPLC system, Waters Co., USA) equipped with a refractive index detector (Waters 2414, Waters Co., Milford, Mass., USA). As a standard for correcting the amount of sugar decomposed during the reaction, a standard of Sigma-Aldrich was used. Sugar recovery standards (SRS) were prepared similar to the sugar concentration in the sample, followed by secondary hydrolysis with the first hydrolyzate of the sample by adding 10 mL of 348 μl of 72.0 (w / v)% sulfuric acid. It was.

2.2 Hydrolyzate  And recovered byproducts analysis

The hydrolyzate and recovered by-products after hydrolysis are neutralized and centrifuged if necessary (neutralized with calcium carbonate in the case of hydrolyzate, centrifuged for 20 minutes at 16099 g for 20 minutes), and the supernatant is taken out of a syringe filter (Gelman, 0.2 μm pore size). ) Was filtered. The filtrate was analyzed by high performance liquid chromatography (Breeze HPLC system, Waters Co., USA) equipped with a refractive index detector (Waters 2414, Waters Co., Milford, Mass., USA).

Example  One: Batch  With device Rapeseed  Pretreatment / Separation Process

A pretreatment / separation process was carried out using a batch apparatus to obtain high concentrations of xylose and specific byproducts isolated from the rapeseed. First, 560 mL of 1.8 (w / v)% sulfuric acid aqueous solution was added to the catalyst tank and preheated to 200 ° C., and 40 g of the sample was put into a reactor of the batch reactor and preheated to 70 ° C. The pre-heated sulfuric acid solution was moved to the reactor by opening the control valve, and the reaction was started when the temperature of the reactor reached 153 ° C. The reaction time was 21 minutes. After the reaction, the pressure valve of the reactor was opened to collect and recover the by-products present in the gaseous state. After the collection and recovery of the by-products, the control valve connected to the liquid reservoir was opened to separate the liquid product into the liquid reservoir. Co., Milford, MA, USA) was analyzed by high performance liquid chromatography (Breeze HPLC system, Waters Co., USA) (simultaneous pretreatment / separation process).

In addition, the experiment was carried out under the same conditions as above, but the recovered product was analyzed by recovering the liquid product without recovering the gaseous product (by-product).

The two results are compared and shown in Table 1 below.

Product type Product concentration analyzed without collection (g / L) Product concentration analyzed after collection (g / L) Concentration or recovery
(%)
Liquid product Liquid product Weather byproducts Xylose 8.99 57.86 - 643.6 Formic acid 1.09 - 0.71 65.1 Acetic acid 3.01 - 2.70 89.7 Levulinic acid 0.08 - ND - 5-HMF 0.05 - ND - Furfural 1.12 - 1.12 98.2

* ND: Not Detected

As can be seen from Table 1, the formic acid was separated and recovered to 0.71 g / L for acetic acid, 2.70 g / L for acetic acid and 1.12 g / L for furfural as compared with the result of not collecting by-products separately. By-products were recovered up to 98.2% through the capture process.

The concentration of xylose in the liquid product recovered after the by-product collection was 57.86 g / L, about 6.4 times higher than the concentration of xylose (8.99 g / L) in the liquid product recovered without the collection. (Concentration: 643.6%). In the case of levulinic acid or 5-hydroxymethylfurfural, the amount produced during the pretreatment / separation process is insignificant. However, accurate analysis may be difficult. It was considered possible.

Example  2: Batch  Barley straw pretreatment / separation process

Barley straw was used as a biomass to perform a batch pretreatment / separation process. The reaction temperature was set to 150 ° C., the concentration of sulfuric acid solution was 1.0 (w / v)%, and the reaction time was set to 15 minutes. Reactor operation and by-product recovery method was the same as in Example 1, and the recovered liquid product and gaseous by-products were analyzed in the same manner as in Example 1. The experiment was carried out under the same conditions as above, but the liquid product was collected and analyzed without separately collecting the produced gas product (by-product).

The two results are compared and shown in Table 2 below.

Product type Product concentration analyzed without collection (g / L) Product concentration analyzed after collection (g / L) Concentration or recovery
(%)
Liquid product Liquid product Weather byproducts Xylose 11.97 57.81 - 483.0 Formic acid 0.19 - 0.10 52.6 Acetic acid 1.54 - 1.36 88.3 Levulinic acid ND - ND - 5-HMF 0.12 - 0.05 41.7 Furfural 1.01 - 0.98 97.0

* ND: Not Detected

The concentration of xylose produced during the pretreatment of barley straw was 11.97 g / L, and the concentrations of by-products were found to range from 0.12 to 1.54 g / L. However, after the collection process, the concentration of xylose was 4.8 times concentrated to 57.81 g / L, and the recovered byproduct concentrations were 0.10 g / L for formic acid, 1.36 g / L for acetic acid, and 5-hydr. In the case of oxymethylfurfural, 0.05 g / L and furfural showed 0.98 g / L, indicating a recovery of 41.7 to 97.0%. The reason why the levulinic acid was not produced was because the levulinic acid was a glucose-derived superdegradable product, which focused on the purification of xylose separation (xylose yield: 83.5%), and almost no glucose was decomposed under the above reaction conditions. In severe cases, the production of by-products such as levulinic acid could be increased.

Example  3: Batch  With device Empty Fruit Bunch (EFB Pretreatment / separation process

The pretreatment / separation process was carried out using Empty Fruit Bunch (EFB). The pretreatment / separation conditions were 180 ° C., sulfuric acid solution 0.4 (w / v)% and reaction time 5 min. The reactor operation and by-product recovery method were the same as in Example 1, except that the sulfuric acid solution added to the catalyst tank was preheated to 230 ° C. and adjusted so that the sulfuric acid solution was introduced into the reaction tank so as to quickly reach the reaction temperature. . The recovered liquid products and gaseous by-products were analyzed in the same manner as in Example 1. The experiment was carried out under the same conditions as above, but the liquid product was collected and analyzed without separately collecting the produced gas product (by-product).

The two results are compared and shown in Table 3 below.

Product type Product concentration analyzed without collection (g / L) Product concentration analyzed after collection (g / L) Concentration or recovery
(%)
Liquid product Liquid product Weather byproducts Xylose 12.58 58.40 - 464.2 Formic acid 0.98 - 0.73 74.8 Acetic acid 1.09 - 1.00 91.7 Levulinic acid 0.31 - 0.05 16.1 5-HMF 0.05 - 0.03 60.0 Furfural 0.46 - 0.41 89.1

As can be seen in Table 3, the concentration of xylose in the liquid product analyzed after the collection process was 58.40 g / L, indicating a concentration of 464.2% (in the liquid product recovered only through the pretreatment process). Xylose concentration: 12.58 g / L), the by-products recovery was 74.8% formic acid, 91.7% acetic acid, 16.1% levlinic acid, 60.0% 5-hydroxymethylfurfural, 89.1% furfural.

The rapeseed, barley straw, and EFB-derived xylose produced during the pretreatment / separation process using a batch system showed a high concentration of 56.7 to 58.4 g / after the collection process, which is 4.6 to 6.4 times higher than the simple pretreatment without the collection process. The results were confirmed, which was judged to be due to the concentration of the liquid product in the process of collecting the gaseous product by opening the pressure valve to recover the by-products. In addition, in Examples 1 to 3, the test conditions (xylose yield of 76.6 to 83.5%) were tested in consideration of the yield of xylose first, so that the amount of generated by-degradation products, that is, by-products during the pretreatment / separation process, was relatively high. Although it was low, it was found that the result was a relatively high recovery rate (particularly, a maximum recovery rate of 98.2 and 89.7% for acetic acid and furfural).

Example  4: using a continuous device Rapeseed  Pretreatment / Separation Process

The rapeseed was applied to a continuous device to carry out the pretreatment / separation process. At this time, the biomass input amount was 0.5 g / min, 3.5 (w / v)% sulfuric acid solution to 4.5 mL / min, and the reaction temperature was 165. ℃, screw rotation speed was set to 20 rpm and the residence time of the biomass reactor was 7.2 minutes. In order to collect the gaseous by-products generated during the pretreatment / separation process, a vapor collecting device was installed at the sample outlet part, and the by-products were collected by using a pressure pump. The collected by-products were allowed to be recovered in the liquid state through the cooling device. The remaining liquid state was cooled by cooling two barrels mounted at the end of the continuous device to confirm the concentration of xylose and the recovery of the collected by-products. The product was recovered and analyzed (simultaneous pretreatment / separation process).

In addition, the experiment was carried out under the same conditions as above, but the recovered product was analyzed by recovering the liquid product without recovering the gaseous product (by-product).

The two results are compared and shown in Table 4 below.

Product type Product concentration analyzed without collection (g / L) Product concentration analyzed after collection (g / L) Concentration or recovery
(%) Liquid product Liquid product Weather byproducts Xylose 7.87 56.70 - 720.5 Formic acid 3.64 - 3.63 99.7 Acetic acid 5.37 - 5.36 99.8 Levulinic acid 0.78 - 0.78 100.0 5-HMF 0.04 - 0.03 75.0 Furfural 5.73 - 5.75 100.3

As shown in Table 4, the concentration of xylose was found to be 720.5% (7.87 g / L without the collection process, 56.70 g / L after the collection process), and by-products (formic acid, acetic acid, levulinic acid, 5-hydroxymethylfurfural) showed a high recovery rate of 99.7% or more except for 5-hydroxymethylfurfural. However, in the case of 5-hydroxymethylfurfural, the concentration produced in the pretreatment / separation process is very small (0.04 g / L when not collected and 0.03 g / L after being collected). Was judged to be somewhat unreasonable. Therefore, it could be judged that a considerable recovery was made for all the by-products analyzed.

Example  5: Pretreatment / Separation Process of Sawdust Using Continuous Apparatus

Continuous pretreatment / separation was performed using sawdust, reaction temperature of 180 ° C., catalyst concentration of 3.5 (w / v, H ₂ SO ₄ )%, and other specific conditions and methods were the same as in Example 4. It was. The result of performing the pretreatment / separation process of collecting the generated gaseous product (by-product) and the result of performing the pretreatment without collecting it are shown in Table 5 below.

Product type Product concentration analyzed without collection (g / L) Product concentration analyzed after collection (g / L) Concentration or recovery
(%) Liquid product Liquid product Weather byproducts Xylose 8.14 57.57 - 707.2 Formic acid 4.36 - 3.32 76.1 Acetic acid 6.62 - 6.03 91.1 Levulinic acid 0.64 - 0.06 9.4 5-HMF 0.09 - ND - Furfural 7.06 - 7.36 104.2

* ND: Not Detected

As can be seen in Table 5, the concentration of xylose (57.57 g / L) after the collection process is about 7.1 times higher than the concentration of xylose (8.14 g / L) without the collection process. It was found that the concentration ratio similar to that of Example 4 was observed. Among the by-products, acetic acid and furfural recovery rate was high (acetic acid 91.1%, furfural 104.2%). The recovery of furfural was more than 100%, and it was judged that an error occurred in the analysis. The reason for the low recovery rate of levulinic acid was that the levulinic acid had a boiling point of 245 to 246 ° C. 117.8 ℃, 5-hydroxymethylfurfural 114 ~ 116 ℃, furfural 161.8 ℃) had a very high boiling point, it was determined that the recovery was difficult without a separate distillation.

Example  6: using a continuous device Empty Fruit Bunch (EFB Pretreatment / separation process

The pretreatment / separation process of EFB was carried out using a continuous apparatus.

Process conditions were the reaction temperature of 175 ℃, sulfuric acid aqueous solution concentration 3.0% (w / v), the reaction time (retention time) 7.2 minutes, and other specific conditions and methods were the same as in Example 4. The result of performing the pretreatment / separation process of collecting the generated gaseous product (by-product) and the result of performing the pretreatment without collecting it are shown in Table 6 below.

Product type Product concentration analyzed without collection (g / L) Product concentration analyzed after collection (g / L) Concentration or recovery
(%) Liquid product Liquid product Weather byproducts Xylose 11.13 57.47 - 516.4 Formic acid 3.37 - 2.65 78.6 Acetic acid 5.55 - 5.38 97.0 Levulinic acid 0.38 - ND - 5-HMF 0.25 - ND - Furfural 7.06 - 6.24 88.4

* ND: Not Detected

As can be seen in Table 6, after collecting, xylose showed a concentration of 57.47 g / L (concentration of 516.4%), recovery of formic acid 78.6%, acetic acid 97.0%, and furfural 88.4%. In the case of, levulinic acid and 5-hydroxymethylfurfural, it could be confirmed that it was not recovered.

The production concentrations of the biomass-derived by-products produced by using the continuous device showed up to 17.5 times higher than those using the batch device, which was set in the range of xylose yield (44.8 ~ 46.3%). Pretreatment / fractionation conditions are considered, taking into account the amount of by-products produced rather than by deliberate increase). The rapeseed, sawdust, and EFB-derived xylose produced during the pretreatment / fractionation process using a continuous device showed a high concentration of 56.7 ~ 57.6 g / L after the collection process, up to 7.2 times higher than without the collection process. The concentration was 720.1%). The reason for the higher concentration of xylose in the continuous device than in the case of a batch device (xylose concentration in the batch device: 464.2 to 643.6%, xylose concentration in the continuous device: 516.4 to 720.5%) ), The liquid and solid products produced at the sample outlet of the continuous unit are directly exposed to external temperatures (in the case of batch units, the exposure valve is opened to capture the vapors in the reactor at different pressures). The steam collected in the collecting device is cooled by the difference between the external temperature and the internal temperature. In addition, the internal and external pressure difference of the device is also considered to be larger than that of the batch device. On the other hand, in the case of pretreatment / separation using a continuous apparatus, as in the case of pretreatment / separation using a batch apparatus, it was confirmed through 1 to 6 that the recovery of by-products such as acetic acid and furfural was efficiently performed. Could.

Example  7: Partial recovery of recovered byproducts

A fractionation process was performed on rapeseed derived gaseous by-products collected in Example 4 above. Two recovery towers were used to separate the by-products, and each recovery tower was connected with a circulator to flow a constant temperature antifreeze to the recovery tower to cool the by-products in the vapor state. Table 7 below shows the set circulator temperature and the recovery tower actual temperature.

Condition number Recovery tower temperature (circulator temperature) (℃) Recovery tower 1 Recovery tower 2 One 40.1 (40.0) 19.4 (10.0) 2 39.0 (30.0) 17.3 (10.0) 3 36.0 (30.0) 16.9 (5.0) 4 34.9 (25.0) 13.1 (5.0) 5 32.6 (25.0) 12.1 (0.0) 6 30.2 (20.0) 8.3 (0.0) 7 28.3 (20.0) 5.8 (-5.0) 8 24.9 (15.0) 4.0 (-5.0)

The concentration, recovery amount and recovery rate of each by-product fractionated through recovery towers 1 and 2 are shown in Tables 8 and 9 below.

Condition number Byproduct Concentration (g / L) Formic acid Acetic acid Levulinic acid 5-HMF Furfural Recovery tower 1 Recovery tower 2 Recovery tower 1 Recovery tower 2 Recovery tower 1 Recovery tower 2 Recovery tower 1 Recovery tower 2 Recovery tower 1 Recovery tower 2 One 1.51 1.62 2.01 2.78 0.0 0.0 0.0 0.0 1.54 2.98 2 1.70 1.46 2.14 2.50 0.0 0.0 0.0 0.0 1.68 3.11 3 1.78 1.40 2.20 2.64 0.0 0.0 0.01 0.0 1.71 2.88 4 1.83 1.43 2.88 2.06 0.0 0.0 0.0 0.0 1.88 2.50 5 1.98 1.21 2.75 2.11 0.0 0.0 0.02 0.0 2.14 2.99 6 2.02 1.19 2.91 2.26 0.0 0.18 0.01 0.0 2.50 2.88 7 2.43 1.08 2.98 2.27 0.0 0.23 0.0 0.0 2.50 2.92 8 2.59 0.95 2.99 2.20 0.23 0.11 0.02 0.0 2.78 2.96

Condition number by-product Formic acid Acetic acid Levulinic acid 5-HMF Furfural Recovery
(g / L) Recovery
(%) Recovery
(g / L) Recovery
(%) Recovery
(g / L) Recovery
(%) Recovery
(g / L) Recovery
(%) Recovery
(g / L) Recovery
(%) One 3.13 86.2 4.79 89.4 0.0 0.0 0.0 0.0 4.52 78.6 2 3.16 87.1 4.64 86.6 0.0 0.0 0.0 0.0 4.79 83.3 3 3.18 87.6 4.84 90.3 0.0 0.0 0.01 33.3 4.59 79.8 4 3.26 89.8 4.94 92.2 0.0 0.0 0.0 0.0 4.69 81.6 5 3.19 87.9 4.86 90.7 0.0 0.0 0.02 33.7 5.13 89.2 6 3.21 87.6 5.17 96.5 0.18 23.1 0.01 33.3 5.39 93.6 7 3.51 96.7 5.25 97.9 0.23 29.5 0.0 0.0 5.42 94.3 8 5.54 97.5 5.19 96.8 0.34 43.6 0.01 33.6 5.28 91.8

As the temperature of the recovery towers 1 and 2 decreased, the concentrations of by-products such as formic acid, acetic acid, and furfural collected in the recovery tower 1 increased, and the concentration in the recovery tower 2 tended to decrease. This is because the liquefaction rate of by-products such as formic acid, acetic acid, and furfural increased as the temperature of the tower 1 decreased, and the amount collected in the recovery tower 2 increased as the amount collected in the recovery tower 1 increased. It seems to have decreased. In addition, as the temperature of the recovery towers 1 and 2 decreased, the amount of by-products recovered gradually increased, from 86.2% to 96.7% for formic acid, 89.4% to 97.7% for acetic acid, and 78.6% for furfural. The recovery rate of up to 94.2% was confirmed (Table 9), and the difference in the recovery rate may be due to the difference in boiling point of each specific by-product. In the case of levulinic acid and 5-hydroxymethylfurfural, the concentration itself was very low, so the separation using the recovery tower was difficult. Especially, in the case of levulinic acid, the boiling point was much higher than that of the by-products. I think it was not done well.

<Description of the major reference numerals>
210: raw material input unit
120: batch reactor, 220: continuous reactor
221: barrel, 222: screw / shaft
130, 230: catalyst input unit
131: first and second catalyst baths
140, 240: gas collecting unit
250: discharge part
150: liquid reservoir
151: sampling valve
152: sampling port
260: drive motor

Claims (14)

Under any reaction conditions, a first step of pretreating the biomass to produce a chemical reaction product from the biomass; And
And a second step of separating a specific product in a gaseous state in the chemical reaction product from another product in a liquid or solid state simultaneously with or after the first step.
The method of claim 1, wherein the other product in the liquid or solid state is a xylose containing product.
The method of claim 2, further comprising a third step of recovering any one or more of the other products in the liquid or solid state.
The method of claim 1, wherein the reaction temperature of the reaction conditions is 150 ℃ to 250 ℃.
The process of claim 1 wherein the first step is carried out in a continuous or batch reactor.
The method of claim 1, wherein the gaseous specific product comprises any one or more selected from the group consisting of furfural, acetic acid, formic acid, levulinic acid, and 5-hydroxymethylfurfural.
The method of claim 1, wherein the first step is carried out in the presence of a catalyst,
Wherein said catalyst is an acid.
Under any reaction conditions, a first step of pretreating the biomass to produce a chemical reaction product from the biomass; And
A second step of separating the specific product in gaseous state from the chemical reaction product from other products in liquid or solid state simultaneously with or after the first step,
A method for preparing xylose, wherein the xylose is separated from the other product in the liquid or solid state.
In the method for producing a specific by-product produced during the wood-based biomass pretreatment,
A step of pre-treating woody biomass to produce a specific byproduct under reaction conditions in which the specific byproduct is present in a gas phase; And
A step b of collecting the specific by-product from the step a product at the same time as or after step a, in a gas phase,
Wherein the specific by-product comprises at least one selected from the group consisting of furfural, acetic acid, formic acid, levulinic acid and 5-hydroxymethylfurfural.
The method according to claim 9, wherein the reaction temperature of the reaction conditions is 150 ℃ to 250 ℃.
The method of claim 9, further comprising the step c of fractionating the specific by-products collected without additional energy input.
The method of claim 11, wherein the fractionation of step c is performed by adding collected specific by-products to a recovery tower.
In the wood-based biomass pretreatment apparatus,
A reactor for pretreating woody biomass; And
And a gas collecting unit located above the reactor,
The gas collection unit is for separating a gaseous specific product from the chemical reaction product generated during the wood-based biomass pretreatment.
The apparatus of claim 13, wherein the reactor is a batch or continuous reactor.

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