JP2014000071A - Device and method for manufacturing cellulosic biomass hydrolysate by two-step acid treatment process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a device and method for manufacturing glucose and xylose from cellulose and hemicellulose by two-step acid treatment process.SOLUTION: The device includes: a primary percolation reactor vessel 1 for converting cellulosic biomass into an oligomer form through primary hydrolysis; a first solvent feeding device 2 for feeding a primary solvent to the primary reactor vessel, having a first solvent tank 21 and a first solvent pump 22; a second solvent feeding device 3 for feeding water to the primary-hydrolyzed solution in the primary reactor vessel so as to lower the acid concentration in the secondary hydrolysis, having a second solvent tank 31 and a second solvent pump 32; a secondary tube-type flow reactor 4 for converting the primary-hydrolyzed solution diluted with the second solvent feeding device into carbohydrate in a monomer form through a tube-type flow reaction for the secondary hydrolysis; a storage tank 5 for storing the hydrolysate produced from the secondary reactor vessel; and a pressure supply device 6 for maintaining the inner pressure of the primary reactor vessel 1 and the secondary reactor vessel.

Description

  The present invention relates to an apparatus and a method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process. More specifically, the present invention relates to a method and an apparatus for producing glucose and xylose from cellulose and hemicellulose, which are main components of cellulosic biomass, by a flow type acid treatment process. In particular, an acid solvent is supplied to a high temperature primary reactor to induce primary hydrolysis to extract an oligomeric liquid carbohydrate, and a secondary water addition of an oligomeric carbohydrate in a low temperature secondary reactor. The invention relates to an apparatus and method comprising inducing degradation to produce a final monomeric form of carbohydrate.

  With the growing concern about resource depletion and environmental pollution due to excessive use of fossil fuels, new renewable alternative energy that can produce energy stably and continuously has become a global topic. ing. As one of the developments of such alternative energy, a technology for producing bioenergy and chemical products from biomass has attracted attention.

  Meanwhile, the main part of the bioconversion process with biomass is to efficiently produce carbohydrates and sugars.

  “Biomass” refers to a carbon assimilation process in which carbon dioxide is fixed using sunlight, that is, a saccharide biosynthesized by a photosynthesis process and an organism including the same. For example, one of the most abundant and renewable plant resources on the earth is a woody resource, lignocellulose, which is one of cellulosic biomass. Lignocellulose is a complex of lignin, a hard-to-decompose aromatic polymer, cellulose (cellulose) and hemicellulose (hemicellulose), and is called biomass in a narrow sense. (Perlack et al., 2005).

  In addition, various fuels such as alcohol, diesel, and hydrogen produced from biomass are generally referred to as bioenergy.

  Cellulose, which is an important component of lignocellulose, is a polysaccharide with a stable linear structure in which glucose is linked by β-1,4 bonds, and has a helical structure in which glucose is linked by α-1,4 bonds. It has a structure that is physically and chemically stronger than amylose in the natural state.

  Hemicellulose, which is another main polysaccharide constituting lignocellulose, is a polysaccharide having a lower degree of sugar polymerization than cellulose. Hemicellulose is mainly composed of a polymer of xylose, which is a pentose, but in addition, arabinose, which is a pentose, mannose, galactose, which is a hexose, It is composed of a polymer such as glucose. Such hemicellulose is characterized by a lower degree of polymerization and lower structural regularity than cellulose, and is relatively easily decomposed by physicochemical treatment.

  Lignin is a polymer that is hydrophobic and has a large molecular weight and a complex structure. Lignin is believed to be produced in order to protect plants from various biochemical attacks and access from outside, for example, microorganisms such as mold and insects. Lignin has a natural or chemical durability, and is considered to be the most difficult substance to decompose among natural compounds existing in nature.

  FIG. 4 shows the general structure of lignocellulose. As shown in the figure, in lignocellulose, lignin is covalently bonded to hemicellulose, and hemicellulose is hydrogen bonded to cellulose. Therefore, as a whole, linear cellulose microfibrils are surrounded by hydrogen bonds in hemicellulose, and lignin is surrounded by covalent bonds in hemicellulose. That is, lignocellulose is in a form for protecting cellulose, which is the main carbohydrate of plants.

  In order to produce bioenergy and other compounds using lignocellulose as a raw material, it is necessary to convert the polysaccharide component constituting lignocellulose into a fermentable sugar in a fermentable state, a so-called sugar platform. is there. From fermentable sugars, liquid acids such as ethanol and butanol, and organic acids that are monomers of biopolymers such as polylactic acid and various amino acids can be produced. The concept of such a sugar platform was first proposed by the US Department of Energy. An important process for converting to a sugar platform is the pretreatment or fractionation process of lignocellulose.

  Biomass pretreatment methods are roughly classified into physical methods, chemical methods, and biological methods.

  Typical physical methods include milling and steam explosion. First, milling is a method of bringing about structural changes by crushing lignocellulose particles into very fine particles with a milling machine. However, milling is not currently used due to its low effectiveness. On the other hand, in the steam explosion method, after lignocellulose is steamed for a certain period of time in a high-pressure container containing high-temperature steam, the container valve is opened in a very short time, so that the structure of lignocellulose can be instantaneously formed like popcorn. This is a method of opening the substrate so that the enzyme can be easily accessed.

  In order to perform such a physical method more effectively, a physicochemical method combining chemical methods has also been studied. As a typical method, there is a dilute acid hydrolysis method. In the dilute acid hydrolysis method, lignocellulose is immersed in a sulfuric acid solution of 2% (w / w) or less, and then, as in the case of the steam explosion method, high-temperature steam at 160 to 200 ° C. is used for 60 seconds to 10 seconds. By steaming for a minute, hemicellulose is hydrolyzed into monosaccharide and oligosaccharide forms by a catalytic reaction with acid, and a part thereof is decomposed into furfural. That is, the dilute acid hydrolysis method has the effect of mainly hydrolyzing hemicellulose to decompose the bond between cellulose, hemicellulose, and lignin on lignocellulose, and can obtain a monomeric form of carbohydrate. The dilute acid hydrolysis method can easily hydrolyze hemicellulose, but cannot hydrolyze the cellulose component. The process with a strong acid can hydrolyze cellulose into glucose, but hemicellulose produces a toxic substance that inhibits microorganisms in the fermentation process, such as furfural, through a hyperlysis reaction of xylose.

  On the other hand, as a typical biomass separation method using alkali instead of acid, there is a method called AFEX (Ammonia fiber explosion) developed by Bruce Dale et al. Of Michigan State University in the United States. In this method, ammonia is mixed with biomass at a ratio of about 1: 1 to 1: 3, then treated at a high temperature of 70 to 180 ° C. for 5 to 30 minutes, and reduced to normal pressure in a short time. As a result, gaseous ammonia is recovered, and physical and chemical changes of the biomass structure are brought about to improve the saccharification rate by the enzyme. On the other hand, unlike dilute acid hydrolysis method, hemicellulose is hardly hydrolyzed and lignin is mainly dissolved out, so that lignin can be separated from cellulose and hemicellulose, and cellulose and hemicellulose can be separated later in enzymatic saccharification step Saccharose and pentoses such as xylose can be obtained together by saccharification.

  However, such an alkali separation method separates and removes only lignin, and cannot separate cellulose and hemicellulose. In particular, xylose components derived from hemicellulose cannot be recovered.

  Further, the above-described physicochemical fractionation method is disadvantageous in terms of cost because the reaction is carried out at a high temperature of 170 ° C. or more, which requires a large amount of energy. In addition, since solid raw materials are handled under extreme conditions, after developing a laboratory-scale process, the scale will be expanded, mixing in the reactor, moving and transporting reactants and products, etc. Problems often occur.

  On the other hand, the biological fractionation method mainly uses mold (white rot fungi) that grows using sugar produced by decomposing lignocellulose like wood, and pretreats under mild conditions. Although it has not yet been put into practical use, research on a laboratory scale has just begun.

  The present invention has been devised to solve such problems of the prior art, and by hydrolyzing any of lignin, cellulose and hemicellulose from cellulosic biomass by two-step acid treatment, It is an object to provide an apparatus and a method for producing glucose and xylose from hemicellulose.

  The apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to the present invention for solving the above-described problems is a leaching type primary that hydrolyzes cellulosic biomass into primary oligomers. A first solvent supply device comprising a reactor, a first solvent tank for supplying a primary solvent to the primary reactor and a first solvent pump, and water in the hydrolyzed solution hydrolyzed by the primary reactor. A second solvent supply device having a second solvent tank and a second solvent pump for lowering the acid concentration in the secondary hydrolysis, and a primary hydrolyzed solution diluted by the second solvent supply device is a tube type A tubular flow type secondary reactor that undergoes secondary hydrolysis in a flow reaction to convert it into a monomeric carbohydrate, a storage tank that stores the hydrolyzate obtained from the secondary reactor, and the primary reaction Vessel and said It includes a pressure source for maintaining the internal pressure of the following reactions, the.

  According to another aspect of the present invention, there is provided an apparatus for producing a hydrolyzate of cellulosic biomass using a two-stage acid treatment process, wherein a transfer pipe is disposed between the secondary reactor and the storage tank to recover lignin. It is filled with an adsorbent or an adsorber is further provided.

  According to still another aspect of the present invention, there is provided an apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process, wherein the first solvent pump stores water for adjusting the concentration of the first solvent. A third solvent supply device including a solvent tank and a third solvent pump is further provided.

  In the cellulosic biomass hydrolyzate production apparatus using a two-stage acid treatment process according to still another aspect of the present invention, the solvent stored in the first solvent tank is an aqueous sulfuric acid solution.

  In the apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to still another aspect of the present invention, the concentration of the first solvent is 3 to 15 wt%.

  According to still another aspect of the present invention, in the apparatus for producing a hydrolyzate of cellulosic biomass by the two-stage acid treatment process, the solvent stored in the second solvent tank is water.

  In the apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to still another aspect of the present invention, the second solvent dilutes the concentration of the first solvent to 1 to 5 wt%.

  According to still another aspect of the present invention, there is provided an apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process, wherein a preheater or a steam generator is provided between the first solvent pump and the primary reactor. Is further provided.

  An apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to still another aspect of the present invention includes a device between the primary reactor and the secondary reactor, and the secondary reactor. One or more of a cooler and a heat exchanger are provided between the storage tanks.

  According to still another aspect of the present invention, there is provided an apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process, wherein the primary reactor has a reaction temperature of 100 to 170 ° C. and a reaction pressure of 150 to 280 psi. It is.

  According to still another aspect of the present invention, there is provided an apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process, wherein the secondary reactor has a reaction temperature of 70 to 120 ° C. and a reaction pressure of 150 to 280 psi. It is.

  A method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to the present invention for solving the above-described problems includes a first step of supplying cellulosic biomass to a leaching type primary reactor, A second stage in which glucan and xylan are extracted from biomass by supplying a first solvent from a first solvent supply device so that cellulose and hemicellulose are primarily hydrolyzed in a secondary reactor, and extracted in the primary reactor. A third stage for supplying a second solvent for diluting the first solvent from the second solvent supply device so that the transported glucan and xylan are converted into glucose and xylose by secondary hydrolysis; And a fourth stage in which glucan and xylan supplied to the secondary reactor are subjected to secondary hydrolysis by a tubular flow reaction to convert them into glucose and xylose.

  According to another aspect of the present invention, the method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process collects the hydrolyzate produced by the secondary reactor in a storage tank after the four stages. Immediately before the step, the method further includes a fifth step of adsorbing so as to separate and recover the lignin.

  In the method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to still another aspect of the present invention, the first solvent is an aqueous sulfuric acid solution.

  In the method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to still another aspect of the present invention, the concentration of the first solvent is 3 to 15 wt%.

  In the method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to still another aspect of the present invention, the second solvent is water.

  In the method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to still another aspect of the present invention, the concentration of the first solvent is diluted to 1 to 5 wt%.

  According to another aspect of the present invention, there is provided a method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process, wherein the primary reactor has a reaction temperature of 100 to 170 ° C. and a reaction pressure of 150 to 280 psi. It is.

  In the method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to still another aspect of the present invention, the secondary reactor has a reaction temperature condition of 70 to 120 ° C. and a reaction pressure of 150 to 280 psi.

  According to still another aspect of the present invention, there is provided a method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process, wherein after the leaching reaction in the second stage, a cooling and heat exchange process is performed, To induce the reaction in the secondary reactor.

  The present invention continuously uses flow-type two-stage reaction conditions so that any of lignin, cellulose and hemicellulose can be hydrolyzed from cellulosic biomass. That is, first, a hydrolysis step is performed in which cellulose and hemicellulose are hydrolyzed into glucan and xylan, and then converted into monosaccharides. Thus, effective saccharification is possible, and any of lignin, cellulose and hemicellulose can be hydrolyzed from cellulosic biomass, and glucose and xylose can be produced from cellulose and hemicellulose.

  In the conventional method for hydrolysis of cellulose biomass using acidic solvent, cellulose can be converted to glucose in strong acid and high temperature process, but hemicellulose undergoes a hyperlysis reaction from xylose and, like furfural, fermentation process. Produces toxic substances that have an inhibitory effect on microorganisms. On the other hand, the weak acid and the low temperature process have a problem that only hemicellulose can be hydrolyzed to xylose. The present invention solves the above problems by inducing high and low temperature processes by a two-stage leaching reaction and a flow reaction.

  In addition, since most of the hydrolyzate (carbohydrate) produced is glucose and xylose, the present invention can be applied to the fermentation process through a quick or simple neutralization process or solvent removal process. , Process costs can be reduced.

  The two-stage hydrolysis method according to the present invention eliminates the need for a process for obtaining a carbohydrate that can be fermented by an enzymatic saccharification process, that is, a saccharified solution, from the biomass obtained by the conventional pretreatment process, at low process cost, and Glucose and xylose can be produced effectively in a short time. As a result, when the saccharification process of cellulose is performed using enzymes by other pretreatment and fractionation processes, the cost of using the enzyme, which has occupied a large part for the production of ethanol, butanol and chemical substances using biomass, is eliminated. At the same time, a saccharified solution (hydrolyzate) can be obtained at a high reaction rate, and as a result, the amount of saccharification produced can be increased.

FIG. 1 is a view showing a two-stage acid treatment hydrolysis apparatus according to an embodiment of the present invention. FIG. 2 is a flowchart showing a hydrolysis process of a two-stage acid treatment according to an embodiment of the present invention. FIG. 3 is a drawing showing changes in the structure of lignocellulose by hydrolysis according to an embodiment of the present invention. FIG. 4 is a drawing showing a general structure of lignocellulose.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the accompanying drawings. In the description of the present invention, when it is determined that a specific description related to a known function or a known configuration hinders understanding of the gist of the present invention, a detailed description thereof will be omitted.

  The present invention uses flow-type two-stage reaction conditions continuously so that any of lignin, cellulose and hemicellulose can be hydrolyzed from cellulosic biomass. First, from glucan and xylan from cellulose and hemicellulose. And then inducing a hydrolysis step that converts it to a monosaccharide. That is, the present invention relates to an apparatus and method for hydrolyzing an acid by appropriately inducing a high-temperature process and a low-temperature process by leaching reaction and flow reaction in two stages for effective saccharification.

  FIG. 1 is a diagram illustrating a two-stage acid treatment hydrolysis apparatus according to an embodiment of the present invention, and FIG. 2 is a flowchart illustrating a two-stage acid treatment hydrolysis process according to an embodiment of the present invention. is there.

  As shown in the drawing, a two-stage acid treatment hydrolysis apparatus according to an embodiment of the present invention includes a leaching type primary reactor 1 that primarily hydrolyzes cellulosic biomass into an oligomer form, A first solvent supply device 2 including a first solvent tank 21 and a first solvent pump 22 for supplying a primary solvent to a leaching type primary reactor, and high-concentration hydrolysis subjected to primary hydrolysis in the primary reactor A second solvent supply device 3 having a second solvent tank 31 and a second solvent pump 32 for supplying water to the solution to lower the acid concentration of the secondary hydrolysis, and the primary hydrolysis diluted by the second solvent supply device A tubular flow secondary reactor 4 in which the decomposition solution is subjected to secondary hydrolysis by a tubular flow reaction at a low temperature of 70 to 120 ° C. and converted to a carbohydrate in a monomer form, and a tubular flow secondary reaction Store hydrolyzate obtained from vessel 4 A storage tank 5 includes a pressure supply device 6 for maintaining the internal pressure of the secondary reactor primary reactor 1 and tubular flow type of leaching type.

  The leaching type primary reactor 1 has a structure in which biomass is filled and a solvent can flow. This is a method of leaching the carbohydrate that is hydrolyzed by the solvent from solid biomass to the outside of the reactor in a liquid state, and it is a reactor that can solve the problem of carbohydrate overdegradation reaction that occurs in batch reaction. is there.

  The tubular flow type secondary reactor 4 has a coiled tube structure, and converts a carbohydrate in an oligomer form generated by a primary reaction in a leaching type to a carbohydrate in a monomer form while maintaining a constant temperature. A reactor that can be induced.

  Meanwhile, the hydrolysis apparatus according to an embodiment of the present invention provides a third solvent supply including a third solvent tank 71 and a third solvent pump 72 that store water for adjusting the concentration of the first solvent for primary hydrolysis. A device 7 may be further included, in which case the third solvent supply device 7 is connected to the first solvent pump 22.

  The first solvent may be, for example, an aqueous sulfuric acid solution (or an inorganic acidic solvent containing sulfuric acid or hydrochloric acid), and the second solvent may be, for example, water.

  Further, either the preheater 8a or the steam generator 8b may be provided between the first solvent pump 22 and the leaching type primary reactor 1. Thereby, in the leaching type primary reactor 1, the time to reach the reaction temperature during the reaction can be shortened.

  Between the leaching primary reactor 1 and the tubular flow secondary reactor 4 or between the tubular flow secondary reactor 4 and the storage tank 5, a cooler 9a or heat exchange is provided. A vessel 9b may be provided. In addition, a pressure supply device 6 may be connected to the storage tank 5.

  Such an apparatus is used for conducting a leaching reaction and passing through a cooling and heat exchange process, or for supplying a second solvent and guiding it to a tubular flow type secondary reactor. Such an addition reaction can be prevented.

  The hydrolysis apparatus according to the present invention functions as a reverse pressure regulator between the first solvent pump 21 and the storage tank 5 in order to maintain the high-pressure conditions necessary for the reaction in the leaching type primary reactor 1. The pressure supply device 6 can be further connected. Alternatively, a pressure supply device 6 that is a reverse pressure regulator for maintaining the pressure at 150 to 280 psi by flowing high-pressure nitrogen into the second solvent pump 32 can be further connected.

  Further, the hydrolysis apparatus according to the present invention is provided between a tubular flow type secondary reactor 4 and a storage tank 5 for storing a hydrolyzate obtained through the tubular flow type secondary reactor 4. In order to collect lignin, the inside of the transfer pipe is filled with an adsorbent, or an adsorption device 10 is further provided. In this case, the adsorbent may be activated carbon, for example. Further, the adsorption device 10 may be an adsorption device filled with activated carbon.

  Next, a method for producing a hydrolyzate of cellulose biomass according to the present invention using the above-described hydrolysis apparatus will be described.

  The method for producing a hydrolyzate of cellulosic biomass according to the present invention includes a step of hydrolyzing cellulosic biomass twice using a leaching type primary reactor 1 and a tubular flow type secondary reactor 4. The liquid which finally passes through the tubular flow type secondary reactor 4 and is collected in the storage tank is monomeric carbohydrates, that is, glucose and xylose.

  Specifically, in the method for producing a hydrolyzate of cellulosic biomass according to the present invention, the first stage of supplying cellulosic biomass to a leaching type primary reactor (S100), so that cellulose and hemicellulose are primarily hydrolyzed. In the second stage (S200) of supplying glucan and xylan from biomass by supplying the first solvent of the first solvent supply device to the leaching type primary reactor, extracted and transferred from the leaching type primary reactor. The third stage (S300) for supplying the second solvent for diluting the first solvent from the second solvent supply device so that the glucan and xylan to be subjected to secondary hydrolysis and conversion with glucose and xylose are obtained, a tubular flow type The secondary hydrolysis reaction of the glucan and xylan supplied to the secondary reactor of No. 2 by the tubular flow reaction (oligomeric glucan and xylan in monomer form) Over scan and the reaction is converted to xylose) is in a fourth step (S400) of converting to glucose and xylose.

  Furthermore, in the method for producing a hydrolyzate of cellulosic biomass according to the present invention, after the fourth stage, before the hydrolyzate produced by the tubular flow type secondary reactor is collected in a storage tank ( Immediately before, it may further comprise a fifth step (S500) in which lignin is adsorbed to be separated and recovered.

  The reason why such five steps are necessary is that while the acid hydrolysis process is being performed, the lignin component that is soluble in acid is also present in the aqueous carbohydrate solution, but such lignin and lignin derivatives are produced carbohydrates. This is because there is a possibility of causing problems in terms of the quality of (saccharified solution). Therefore, it is desirable that the inside of the transfer pipe between the tubular flow type secondary reactor and the storage tank be filled with an adsorbent, or further include an adsorption step.

  The adsorbent used in such an adsorption process needs to efficiently adsorb and remove lignin and lignin derivatives. As the adsorbent, for example, a low-cost and reusable activated carbon is desirable.

  In the first stage, the cellulosic biomass can be supplied, for example, in the form of pellets or chips. As raw materials for cellulosic biomass, hardwood, softwood, recycled paper, waste paper, wood fragments, pulp, paper waste, waste wood, thinned wood, corn stick, corn core, straw, rice husk, wheat straw, sugarcane stick, Examples include, but are not limited to, bagasse and mixtures thereof.

  In the first stage, the leaching primary reactor is filled with biomass, and hydrolysis is performed according to the present invention to remove residual biomass that is a solid component in the leaching primary reactor. Therefore, in the next step, the step of filling the leaching type primary reactor with biomass again is discontinuously performed.

  In the second stage, in the leaching type primary reactor, it is desirable that the reaction temperature is 100 to 170 ° C. and the reaction pressure is 150 to 280 psi. The reason for limiting to such conditions is that the present invention depends on the hydrolysis reaction temperature using sulfuric acid and the concentration of the sulfuric acid solution, but the reaction temperature under the conditions where the sulfuric acid concentration is 1 to 20 wt% is the temperature described above. This is because, in order to induce a solid / liquid reaction, the pressure for preventing vaporization of the liquid solvent falls within the above temperature range.

  In the second stage, the first solvent for primary hydrolysis is an aqueous sulfuric acid solution that can convert high molecular cellulose and hemicellulose into oligomeric glucan and xylan. An inorganic acidic solvent containing sulfuric acid and hydrochloric acid can also be used.

  The concentration of the first solvent is not particularly limited, but the concentration of the sulfuric acid aqueous solution is desirably 3 to 15 wt%.

  The primary hydrolysis step in the second stage can convert cellulose and hemicellulose in hard polymer form into oligomeric form. By performing such primary hydrolysis, 60 to 90 wt% of the cellulose present in the initial biomass is converted to a liquid oligomer form, and 70 to 95 wt% of hemicellulose is converted to a liquid oligomer form. In addition, the solid biomass remaining in the leaching type primary reactor decreases in proportion to the liquefied oligomeric liquid that is leached out.

  In addition, the second solvent in the third stage is not particularly limited as long as it is a solvent capable of diluting the first solvent, but preferably water (distilled water) is used. At this time, the flow rate of the second solvent is preferably equal to or less than the supply flow rate of the first solvent (5 to 10 ml / min) and applied in a certain direction.

  That is, the second solvent using water can dilute the liquid reactant in the acidic atmosphere that is produced from the leaching reaction into a weak acid. Here, the weak acid desirably refers to a weakly oxidizing atmosphere of 1 to 5 wt% when the first solvent is an aqueous sulfuric acid solution.

  In the fourth stage, it is desirable to maintain a flow-type reaction so that oligomeric glucan and xylan are converted to glucose and xylose in a weakly oxidizing atmosphere diluted with the second solvent.

  At this time, it is desirable that after the leaching reaction is performed and the cooling and heat exchange steps are performed, or the second solvent is supplied to be guided to the tubular flow type secondary reactor.

  Further, the concentration of the solvent in the weak sulfuric acid atmosphere used as the second solvent is preferably 3 to 5 wt%, the reaction temperature is 70 to 120 ° C., and the reaction pressure is 150 to 280 psi. The reason for limiting the numerical values in this way is as described above.

  Here, both pressure conditions provided to the leaching primary reactor and the tubular flow reactor can be adjusted by the pressure supply device 6.

  Finally, the liquid hydrolyzate produced by the fourth stage is collected in a storage tank, but most of the collected hydrolyzate is glucose and xylose and is fed to the initial leaching reactor. Based on biomass, the yield of glucose was 55 to 90 wt% and the yield of xylose was 65 to 95 wt%. Such a yield is the final conversion yield that is not related to the fifth stage, which is the adsorption process.

  As described above, the present invention provides a method for producing biofuel that obtains alcohol using extracted glucose and xylose. As a result, liquid carbohydrate components (glucose and xylose) obtained from the reactor can be fermented to obtain chemical substances such as ethanol and butanol. Furthermore, chemicals such as HMF and furfural can be obtained through thermal decomposition and chemical catalytic processes. A substance can be obtained.

  Further, alcohol (ethanol, butanol), alkane chemicals, C3-C6 chemical raw materials and organic acids, which are biofuels, can be produced using the produced glucose and xylose.

  FIG. 3 is a drawing showing changes in the structure of lignocellulose by hydrolysis according to an embodiment of the present invention. As shown in the figure, when the above-described process is performed using the production apparatus according to the present invention, all of lignin, cellulose and hemicellulose are hydrolyzed from cellulosic biomass, and further, glucose and xylose are converted from cellulose and hemicellulose. Can be produced.

  Hereinafter, preferred embodiments of the present invention will be described.

  First, the leaching type primary reactor 1 was filled with biomass, the reaction temperature was maintained at 150 ° C., and the pressure was maintained at 200 psi.

  A 10% sulfuric acid aqueous solution was supplied from the first solvent tank 21 to the leaching type primary reactor 1 and subjected to primary hydrolysis for 5 minutes. At this time, 70 wt% of cellulose was converted into a liquid oligomer form, and 85 wt% of hemicellulose was converted into a liquid oligomer form.

  Next, water was supplied from the second solvent tank 31 to the tubular flow type secondary reactor 4 to convert the oligomeric carbohydrate (saccharified solution) into the monomerized saccharified solution and collected in the storage tank 5. .

  Ultimately, the glucose yield was 65 wt% and the xylose yield was 80 wt%. This means that the yield of glucose increased from a maximum of 35 wt% to 65 wt% as compared with the acid hydrolysis of biomass by the conventional primary acid hydrolysis apparatus. Moreover, the yield of xylose is also 80 wt%, which is different from the conventional high temperature and long reaction time in which xylose is excessively decomposed to show a low yield of 60%. Thus, the xylose overdegradation process was eliminated, the production of furfural as a fermentation inhibitor was reduced, and a high yield of xylose was obtained.

  In addition, by filling activated carbon capable of adsorbing lignin between the tubular flow type secondary reactor 4 and the storage tank 5 for collecting the final carbohydrate, 58 wt% of lignin and lignin derivatives are removed. It was. In the conventional primary acid hydrolysis apparatus, the yield of ethanol in the fermentation process is greatly affected by the phenol compound derived from lignin due to high temperature and long reaction time. In contrast, the present invention greatly increases the efficiency of the fermentation process by filling activated carbon and removing the phenol compound.

  The preferred embodiment according to the present invention has been described above. However, the present invention is not limited to this embodiment, and any person who has ordinary knowledge in the technical field of the present invention can understand the scope and spirit of the present invention. It is obvious that various modifications and changes can be made without departing from the above.

  A cellulosic biomass carbohydrate production apparatus and method according to an embodiment of the present invention employ a continuous reaction system. That is, glucose and xylose can be produced from cellulose biomass by continuously supplying the first solvent and the second solvent to the leaching type primary reactor and the tubular flow type secondary reactor. Therefore, without performing the enzymatic saccharification step, it is possible to cause the reaction quickly and minimize the overdegradation reaction. In addition, since the two main steps are continuously performed, the efficiency of the process is excellent, and a high concentration of glucose and xylose can be obtained with high efficiency. Therefore, the industrial utility value is high.

DESCRIPTION OF SYMBOLS 1 Leaching type primary reactor 2 1st solvent supply apparatus 3 2nd solvent supply apparatus 4 Tube-type flow type secondary reactor 5 Storage tank 6 Pressure supply apparatus 7 3rd solvent supply apparatus 8a Preheater 8b Steam generator 9a Cooler 9b Heat exchanger 10 Adsorber 21 First solvent tank 22 First solvent pump 31 Second solvent tank 32 Second solvent pump 71 Second solvent tank 72 Second solvent pump

Claims (20)

A leaching-type primary reactor for primary hydrolysis of cellulosic biomass to form an oligomer;
A first solvent supply device comprising a first solvent tank for supplying a primary solvent to the primary reactor and a first solvent pump;
A second solvent supply device including a second solvent tank and a second solvent pump for supplying water to the hydrolyzed solution hydrolyzed in the primary reactor to lower the acid concentration in the secondary hydrolysis;
A tubular flow secondary reactor in which the primary hydrolysis solution diluted by the second solvent supply device is subjected to secondary hydrolysis by a tubular flow reaction and converted into a carbohydrate in a monomer form;
A storage tank for storing the hydrolyzate obtained from the secondary reactor;
A pressure supply device for maintaining the internal pressure of the primary reactor and the secondary reaction;
An apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process.   2. The apparatus according to claim 1, wherein the transfer pipe is filled with an adsorbent in order to collect lignin between the secondary reactor and the storage tank, or an adsorption device is further provided. An apparatus for producing a hydrolyzate of cellulosic biomass by an acid treatment step.   The first solvent pump is further provided with a third solvent supply device including a third solvent tank storing water for adjusting the concentration of the first solvent and a third solvent pump. An apparatus for producing a hydrolyzate of cellulosic biomass by the two-stage acid treatment process described.   The apparatus for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to claim 1, wherein the solvent stored in the first solvent tank is an aqueous sulfuric acid solution.   The apparatus for producing a hydrolyzate of cellulosic biomass according to claim 4, wherein the concentration of the first solvent is 3 to 15 wt%.   The apparatus for producing a hydrolyzate of cellulosic biomass according to claim 1, wherein the solvent stored in the second solvent tank is water.   The said 2nd solvent dilutes the density | concentration of a 1st solvent to 1-5 wt%, The production apparatus of the hydrolyzate of the cellulosic biomass by the two-step acid treatment process of Claim 6 characterized by the above-mentioned.   The cellulosic biomass is hydrolyzed by the two-stage acid treatment process according to claim 1, wherein a preheater or a steam generator is further provided between the first solvent pump and the primary reactor. Decomposition production equipment.   One or more of a cooler or a heat exchanger is provided between the primary reactor and the secondary reactor, and between the secondary reactor and the storage tank. An apparatus for producing a hydrolyzate of cellulosic biomass by the two-stage acid treatment process according to claim 1.   The hydrolyzate of cellulosic biomass by the two-stage acid treatment process according to claim 1, wherein the primary reactor has a reaction temperature of 100 to 170 ° C and a reaction pressure of 150 to 280 psi. Production equipment.   The hydrolyzate of cellulosic biomass by the two-stage acid treatment process according to claim 1, wherein the secondary reactor has a reaction temperature of 70 to 120 ° C and a reaction pressure of 150 to 280 psi. Production equipment. A first stage of supplying cellulosic biomass to a leaching primary reactor;
A second stage in which glucan and xylan are extracted from biomass by supplying a first solvent from a first solvent supply device so as to primarily hydrolyze cellulose and hemicellulose in the primary reactor;
A second solvent for diluting the first solvent is supplied from the second solvent supply device so that the glucan and xylan extracted and transferred in the primary reactor are secondarily hydrolyzed and converted into glucose and xylose. Stages,
A fourth stage in which glucan and xylan supplied to a tubular flow type secondary reactor are converted into glucose and xylose by secondary hydrolysis in a tubular flow reaction;
And a method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process.   5. The method according to claim 5, further comprising a fifth step of adsorbing the hydrolyzate produced by the secondary reactor immediately after collecting the lignin in a storage tank after the four steps. Item 13. A method for producing a hydrolyzate of cellulosic biomass by the two-stage acid treatment process according to Item 12.   The method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to claim 12, wherein the first solvent is an aqueous sulfuric acid solution.   The method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to claim 14, wherein the concentration of the first solvent is 3 to 15 wt%.   The method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to claim 12, wherein the second solvent is water.   The method for producing a hydrolyzate of cellulosic biomass by a two-stage acid treatment process according to claim 16, wherein the second solvent is diluted with a concentration of the first solvent to 1 to 5 wt%.   The hydrolyzate of cellulosic biomass by the two-stage acid treatment process according to claim 12, wherein the primary reactor has a reaction temperature of 100 to 170 ° C and a reaction pressure of 150 to 280 psi. Production method.   The hydrolysis of cellulosic biomass by the two-stage acid treatment process according to claim 12, wherein the secondary reactor has a reaction temperature condition of 70 to 120 ° C and a reaction pressure of 150 to 280 psi. How to produce things.   The two-stage according to claim 12, wherein after the leaching reaction in the second stage, a cooling and heat exchange process is performed, and the second solvent is supplied to induce a reaction in the secondary reactor. A method for producing a hydrolyzate of cellulosic biomass by an acid treatment step.

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