KR101417836B1 - Apparatus for producing cellulosic biomass hydrolysis material by Two-step acid treatment process and method thereof - Google Patents

Abstract

The present invention relates to an apparatus and a method for producing a hydrolyzed substance of a cellulosic biomass through a two-stage acid treatment process, and its object is to hydrolyze lignin, cellulose and hemicellulose from a cellulosic biomass through a two- And an apparatus and a method for producing glucose and xylose from cellulose and hemicellulose.
The present invention relates to a leachable primary reactor (1) for converting a cellulosic biomass into an oligomer form through primary hydrolysis; A first solvent supply device (2) for supplying a primary solvent to the leached primary reactor; A second solvent supply device 3 for supplying water to the high concentration hydrolysis solution which has been primarily hydrolyzed in the reactor to lower the acid concentration of the secondary hydrolysis; A tubular flow-type secondary reactor (4) for converting the diluted primary hydrolysis solution through the second solvent supply device into a monomer-type carbohydrate through a secondary hydrolysis in a tubular flow reaction at a low temperature; A reservoir 5 for storing the hydrolyzate obtained through the tubular flow reactor; And a pressure supply device (6) for maintaining the internal pressures of the leach type primary reactor and the tubular flow type secondary reactor, and a device for producing a hydrolyzate of cellulosic biomass through a two- The production method used is characterized by the invention.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and a method for producing a hydrolyzed substance of a cellulosic biomass through a two-

The present invention relates to an apparatus and a method for producing a hydrolyzed substance of a cellulosic biomass through a two-stage acid treatment process. Specifically, cellulose and hemicellulose, which are the main components of a cellulosic biomass, The present invention relates to a method and an apparatus for producing an oligosaccharide, and more particularly, to a process for producing an oligosaccharide-type liquid carbohydrate by a process comprising the steps of extracting an oligomeric liquid carbohydrate by inducing primary hydrolysis by supplying an acid solvent to a high- And inducing secondary hydrolysis of the carbohydrate to produce carbohydrate in the form of the final monomer.

As the global exhaustion of fossil fuels and concerns about environmental pollution increase, the concept of renewable and alternative energy that produces stable and sustainable energy is becoming a hot topic. As part of such alternative energy development, technologies for producing bioenergy and chemical products from biomass are attracting attention.

A major part of this biomass-based bio conversion process is the production of efficient carbohydrates, sugars.

Biomass refers to a carbon assimilation process in which carbon dioxide is fixed using sunlight, that is, a saccharide biosynthesized through a photosynthesis process and a whole organism including the biosubstance. The biomass refers to a cellulosic plant represented by plant resources that are most abundant on the planet and can be regenerated without exhaustion There is lignocelluloses, one of the biomass of woody resources. Lignocellulose is a complex of lignin, a degradable aromatic polymer, and carbohydrates, cellulose and hemicellulose, and is called a biomass in a narrow sense (Perlack et al., 2005).

Generally, bioenergy is a generic term for various fuel such as alcohol, diesel, and hydrogen produced from such biomass.

Cellulose, which is an important component in lignocellulose, is a linear polysaccharide of a stable form in which glucose is linked by a β1,4 bond. It is physically and chemically much more natural in nature than a helical amylose in which glucose is linked by α1,4 bonds It has a strong structure.

Hemicellulose, another major polysaccharide constituting lignocellulose, is a polysaccharide whose degree of polymerization is lower than that of cellulose. It is mainly composed of a polymer of 5-valent xylose, and also contains 5-valent arabinose It is composed of polymers such as 6-valent phosphorus mannose, galactose, and glucose. It has a lower polymerization degree and lower regularity of the structure than cellulose, and is decomposed relatively easily by physicochemical treatment.

Lignin is a polymer with a complex structure with a large molecular weight that is hydrophobic. Lignin is presumed to be produced for the purpose of protecting plants from various kinds of biochemical attack and access from the outside, that is, microorganisms such as fungi and insects. Such lignin is naturally or chemically resistant and is considered to be the most difficult to decompose among natural compounds present in the natural world.

As shown in FIG. 4, lignocellulose has a structure in which lignin is bonded to hemicellulose through a covalent bond and hemicellulose is connected to cellulose via a hydrogen bond. As a whole, the structure of the lignocellulose is a linear straight-shaped microfibril ) And hemicellulose wrapped around a hydrogen bond. This hemicellulose is surrounded by a covalent linkage of lignin. It has a form to protect cellulose, which is the main carbohydrate of plants.

In order to produce bioenergy and various compounds using lignocellulose as a raw material, the polysaccharide constituting lignocellulose should be converted into a fermentable sugar, a so-called platform, capable of fermenting. From this fermentable sugar, it is possible to produce a variety of amino acids and organic acids, which are monomers of biopolymers such as ethanol and butanol, and biopolymers such as polylactic acid, Was created. Therefore, an important process for going to this platform is the pretreatment or fractionation process of lignocellulose.

Biomass pretreatment methods can be largely divided into physical, chemical and biological methods.

Representative methods by physical methods include milling or steam explosion. First, milling is a method of inducing a structural change while crushing lignocellulosic particles to very fine particles using a milling machine, which is not effective at present. In addition, the steam explosion method is a method in which the lignocellulose is steamed for a certain time in a high-pressure vessel containing a high-temperature steam, and then the valve of the vessel is opened instantaneously to instantaneously open the structure of the lignocellulose like popcorn, So that it becomes a substrate of a certain type.

Many physicochemical methods that combine chemical methods have been studied to make such physical discrimination methods more effective. Typically, lignocellulose is immersed in a sulfuric acid solution of 2% (w / w) or less by diluteacid hydrolysis, and then steamed in a high-temperature steam of 160 to 200 ° C for 60 seconds to 10 Minute, the hemicellulose is hydrolyzed to the monosaccharide and oligosaccharide form through the catalytic reaction by the acid, and some is decomposed into the furfural. That is, the weakly acidic hydrolysis fractionation method mainly hydrolyzes hemicellulose to obtain the effect of dissolving the bond of cellulose, hemicellulose and lignin on the lignocellulose, thereby obtaining a monomeric carbohydrate. The weak acid hydrolysis method can easily hydrolyze hemicellulose, but the cellulose component can not be hydrolyzed. The strong acid process is capable of hydrolyzing cellulose to glucose, but hemicellulose produces a toxic substance which undergoes hyper-degradation reaction in xylose and inhibits microorganisms during the fermentation process such as furfural.

On the other hand, a representative example of biomass fractionation method using alkaline instead of acid is AFEX (ammonia fiber explosion) method developed by Bruce Dale of Michigan State University. In this method, ammonia is mixed with biomass at a ratio of about 1: 1 to 1: 3, treated at a high temperature (70 to 180 ° C) for 5 to 30 minutes, and pressure is immediately dropped at normal pressure to recover gaseous ammonia And physicochemical changes of the biomass structure are induced to improve the glycation rate by enzymes. Unlike the weak acid hydrolysis method, hemicellulose is hardly hydrolyzed and mainly dissolves lignin to separate lignin from cellulose and hemicellulose Thus, cellulose and hemicellulose can be saccharified in a subsequent enzymatic saccharification process to obtain pentoses such as glucose and xylose.

However, this alkaline fractionation method has a disadvantage in that it can not separate cellulose and hemicellulose by removing only lignin by fractionation. In particular, it is impossible to recover the xylose component derived from hemicellulose.

Moreover, since the above-mentioned physicochemical fractionation techniques are carried out at a high temperature of 170 ° C or higher, the energy consumption is large, which is disadvantageous from a cost point of view. Since raw materials in a solid form are treated under extreme conditions, In the case of scale-up, problems often arise in mixing in the reactor, transporting and transporting the reactants and products, and the like.

On the other hand, the biological fractionation method is a pretreatment under mild conditions using mainly fungi (white dead fungi) that grow using sugar produced by degrading lignocellulose such as wood, and research has been started on a laboratory scale .

DISCLOSURE OF THE INVENTION An object of the present invention to solve the above problems is to provide an apparatus and a method for producing glucose and xylose from cellulose and hemicellulose by hydrolysis of lignin, cellulose and hemicellulose from cellulose biomass through two- .

In order to achieve the above-mentioned object and to solve the problems of the prior art, the present invention relates to a leachate type primary reactor for converting a cellulosic biomass into an oligomer through primary hydrolysis;

A first solvent supply device comprising a first solvent tank for supplying a primary solvent to the leachable primary reactor and a first solvent pump;

A second solvent supply device composed of a second solvent tank and a second solvent pump for lowering the acid concentration of the second hydrolysis by supplying water to the first concentrated hydrolysis solution in the reactor;

A tubular flow type secondary reactor for converting the diluted primary hydrolysis solution through the second solvent supply device into a secondary hydrolysis reaction at a low temperature in a tubular flow reaction to form a monomeric carbohydrate;

A reservoir for storing the hydrolyzate obtained through the tubular flow reactor;

And a pressure supply device for maintaining the internal pressures of the leachable primary reactor and the tubular flow type secondary reactor. The apparatus for producing a hydrolyzed substance of cellulose-based biomass according to claim 1, ≪ / RTI >

In a preferred embodiment of the present invention, the adsorbent may be charged or adsorbed in the transfer pipe to recover lignin between the tubular flow type secondary reactor and the storage tank.

In the present invention, the first solvent pump may further include a third solvent supply device including a third solvent tank and a third solvent pump, the third solvent tank carrying water for adjusting the concentration of the first solvent.

In a preferred embodiment of the present invention, the solvent stored in the first solvent tank may be an aqueous sulfuric acid solution.

In a preferred embodiment of the present invention, the concentration of the first solvent may be 3 to 15 wt%.

In a preferred embodiment of the present invention, the solvent stored in the second solvent tank may be water.

The present invention is a preferred embodiment, and the second solvent can dilute the concentration of the first solvent to 1 to 5 wt%.

In a preferred embodiment of the present invention, a preheating device or a steam generating device may be installed between the first solvent pump and the leachable first reactor.

In a preferred embodiment of the present invention, at least one of a cooler or a heat exchanger device may be installed between the leach type first reactor and the tubular flow second reactor, and between the tubular flow second reactor and the storage tank.

In a preferred embodiment of the present invention, the reaction temperature in the leachable first reactor is 100 to 170 ° C, and the reaction pressure is 150 to 280 psi.

In a preferred embodiment of the present invention, the reaction conditions of the tubular flow type secondary reactor are 70 to 120 ° C, and the reaction pressure may be 150 to 280 psi.

The present invention also provides, in another embodiment, a process for producing cellulose-based biomass comprising: a first step of providing a cellulosic biomass to a leachable primary reactor;

A second step of extracting glucan and xylan from the biomass by supplying a first solvent of the first solvent supply device to primary hydrolysis of cellulose and hemicellulose to the leachable primary reactor;

A third step of injecting a second solvent, which is extracted in the first leach type reactor and dilutes the first solvent so as to convert the glucan and the xylan to be transferred into the glucoside and xylose by secondary hydrolysis, through a second solvent supply device ; And

And a fourth step of subjecting the glucan and the xylan supplied to the tubular flow type secondary reactor to secondary hydrolysis by tubular flow reaction to convert the glucan and xylose into glucose and xylose. By providing a method for producing a hydrolyzate of the biomass.

In a preferred embodiment of the present invention, the method further comprises the fifth step of adsorbing the lignin so as to separate and recover the lignin just before collecting the hydrolyzate produced through the tubular flow type secondary reactor after the fourth step into the reservoir .

In a preferred embodiment of the present invention, the first solvent may be an aqueous sulfuric acid solution.

In a preferred embodiment of the present invention, the concentration of the first solvent may be 3 to 15 wt%.

The present invention is a preferred embodiment, and the second solvent may be water.

The present invention is a preferred embodiment, and the second solvent can dilute the concentration of the first solvent to 1 to 5 wt%.

In a preferred embodiment of the present invention, the reaction temperature in the leachable first reactor is 100 to 170 ° C, and the reaction pressure is 150 to 280 psi.

In a preferred embodiment of the present invention, the reaction conditions of the tubular flow type secondary reactor are 70 to 120 ° C, and the reaction pressure may be 150 to 280 psi.

The present invention is a preferred embodiment. After the leaching reaction of the second step, the reaction may be induced in a tubular flow type secondary reactor by supplying a second solvent after cooling and heat-exchanging processes.

As described above, the present invention is a process for continuously using two-step flow-type reaction conditions so that lignin, cellulose and hemicellulose are all hydrolyzed from cellulose-based biomass. That is, hydrolysis is firstly carried out in the form of glucan and xylan from cellulose and hemicellulose, and secondary conversion into monosaccharide is induced, so that effective saccharification is possible and hydrolysis of lignin, cellulose and hemicellulose from cellulose biomass The advantage of being able to produce glucose and xylose from cellulose and hemicellulose,

In addition, the present invention can convert cellulose into glucose in a strong acid and high temperature process, which is a problem that occurs in the conventional method of hydrolyzing cellulose biomass using an acidic solvent. However, hemicellulose has a hyperfractionation reaction in xylose, The present invention relates to a process for producing a toxic substance which inhibits microorganisms in a fermentation process such as furfural and furfural. In contrast, in a weak acid and a low temperature process, only hemicellulose can be hydrolyzed into xylose, The advantages of solving the problems of acid hydrolysis process by inducing high temperature and low temperature process,

Since the produced hydrolyzate (carbohydrate) is mostly glucose and xylose, the present invention can be applied to a fermentation process through a simple neutralization process or a solvent removal process,

Further, the two-stage hydrolysis method according to the present invention is a method for hydrolyzing biomass obtained through a conventional pretreatment process to a fermentable carbohydrate through an enzyme saccharification process, that is, And xylose. Therefore, in the case of applying the other pre-treatment and fractionation process and performing the saccharification process of cellulose by using enzymes, the cost of using enzymes, which occupied a large part for the production of ethanol, butanol and chemicals using biomass, (Hydrolytic substance) can be obtained at a high rate of reaction at the same time as the saccharification solution (hydrolysis substance) can be ultimately increased.

1 is a schematic diagram of a two-stage acid-hydrolysis apparatus according to an embodiment of the present invention,
2 is a flowchart of a two-stage acid-hydrolysis process according to an embodiment of the present invention,
3 is a schematic diagram showing a structural change of lignocellulose by hydrolysis according to an embodiment of the present invention,
4 is a schematic view showing the structure of a general lignocellulose.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

The present invention relates to a process for the hydrolysis of cellulose and hemicellulose from cellulosic biomass to hydrolysis of cellulose and hemicellulose in the form of glucan and xylan from cellulose and hemicellulose, , And inducing a hydrolysis process to convert the hydrolysis process into a hydrolysis process and a hydrolysis process in which a high temperature and a low temperature process are suitably induced through a two-step leaching reaction and a flow reaction.

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

As shown in the drawings, the two-stage acid hydrolysis apparatus using the cellulosic biomass according to one embodiment of the present invention includes a leachate type primary hydrolysis apparatus for converting cellulosic biomass into an oligomer form through primary hydrolysis A reactor (1);

A first solvent supply device 2 composed of a first solvent tank 21 and a first solvent pump 22 for supplying a primary solvent to the leaching type primary reactor;

A second solvent supply device 3 (see FIG. 3) composed of a second solvent tank 31 and a second solvent pump 32 for lowering the acid concentration of the second hydrolysis by supplying water to the first hydrolyzed high- )Wow;

A tubular flow-type secondary reactor 4 for converting the diluted primary hydrolysis solution through the second solvent supply device into a secondary hydrolysis in a tubular flow reaction at a low temperature of 70 to 120 ° C to form a monomer-like carbohydrate; ;

A reservoir 5 for storing the hydrolyzate obtained through the tubular flow reactor;

And a pressure supply device (6) for maintaining the internal pressures of the leach type primary reactor and the tubular flow type secondary reactor.

The leaching-type primary reactor has a structure in which biomass is filled in a reactor and a solvent is flowed. This type of reaction is a method in which a carbohydrate hydrolyzed by a solvent from a solid biomass is leached out of the reactor as a liquid phase It is a reactor that can overcome the problem of hyperproliferation reaction of carbohydrate in batch reaction.

The tubular flow-type secondary reactor is a reactor capable of inducing the conversion of an oligomer-type carbohydrate produced by a leaching-type primary reaction into a monomer-type carbohydrate while maintaining a constant temperature in a coil tube structure.

The acid treatment hydrolytic device comprises a third solvent supply device 7 composed of a third solvent tank 71 carrying water and a third solvent pump 72 for adjusting the concentration of the first solvent for primary hydrolysis, To the first solvent pump.

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

Further, in the present invention, at least one of the preheating device 8a or the steam generating device 8b may be additionally provided between the first solvent pump and the leachable first reactor. This is a device that can reduce the time to reach the reaction temperature in the leaching reactor.

At least one of a cooler 9a and a heat exchanger 9b may be further provided between the leachable first reactor and the tubular flow second reactor or between the tubular flow second reactor and the storage tank, A pressure supply device 6 may be connected to the reservoir.

Such a device prevents the addition reaction such as overdispersion by heat in order to induce the second solvent after the cooling and heat exchange process after the leaching reaction or the second solvent to the tubular flow type second reactor.

The present invention is characterized in that a pressure supply device 6, which is a back pressure regulator, is connected between the first solvent pump 21 and the reservoir 5 to maintain a high pressure condition for reaction in the leaching reactor, Or a pressure supply device 6, which is a back pressure regulator for maintaining the pressure at 150 to 280 psi by introducing high-pressure nitrogen into the second solvent pump 32, may be connected or added.

The present invention also relates to a process for the adsorption of an adsorbent in a transfer pipe to recover lignin between a tubular flow type secondary reactor 4 and a storage tank 5 for storing a hydrolyzed substance obtained through a tubular flow reactor, As shown in FIG. The adsorbent may be activated carbon. Further, the apparatus may be an adsorption apparatus filled with activated carbon.

The hydrolysis reaction from the cellulose-based biomass according to an embodiment of the present invention through the two-stage acid hydrolysis apparatus can be carried out by using a leaching type primary reactor and a tubular flow type secondary reactor, The biomass is hydrolyzed twice and finally the liquid phase which passes through the tubular reactor and is collected in the reservoir is composed of the step of producing the carbohydrates of the monomer, glucose and xylose.

Specifically, the present invention provides a method for producing cellulose-based biomass, comprising: a first step (SlOO) of providing a cellulosic biomass to a leachable primary reactor;

A second step (S200) of extracting glucan and xylan from the biomass by supplying a first solvent of the first solvent supply device to primary hydrolysis of cellulose and hemicellulose to the leachable first reactor;

A third step of injecting a second solvent, which is extracted in the first leach type reactor and dilutes the first solvent so as to convert the glucan and the xylan to be transferred into the glucoside and xylose by secondary hydrolysis, through a second solvent supply device (S300); And

The reaction of the glucan and the xylan fed into the tubular flow type second reactor is subjected to a secondary hydrolysis in a tubular flow reaction (a reaction of converting the oligomeric form of glucan and the xylan into the monomeric form of glucose and xylose) to produce glucose and xylose (S400).

Further, the present invention may further include a fifth step (S500) of adsorbing the lignin to recover and recover the lignin immediately before collecting the hydrolyzate produced through the tubular flow type secondary reactor in the storage tank.

The reason why such a five-step process is necessary is that during the acid hydrolysis process, acid-soluble lignin components are also present in the aqueous carbohydrate solution, and such lignin and lignin derivatives provide quality problems of the carbohydrates It is preferable to fill the adsorbent in the transfer pipe between the tubular flow type secondary reactor and the storage tank or add an adsorption process.

The adsorbent used in this adsorption process must be able to efficiently adsorb and remove lignin and lignin derivatives. As the adsorbent to be used at this time, a low-cost reusable activated carbon is preferable.

In the first step, the cellulosic biomass may be supplied in the form of, for example, pellets or chips. Raw materials of cellulose-based biomass include hard wood, soft wood, recycled paper, waste paper, wood chips, pulp and paper waste, paper lumber, lumber, cornstalks, cornstalks, rice straw, Sorbitol, sugar cane, and mixtures thereof, but are not limited thereto.

After the biomass is charged into the leachate first reactor of the first stage, the hydrolysis is carried out according to the present invention and the residual biomass which is a solid component in the leachable first reactor is removed, Which means that the process of charging biomass into the reactor is performed discontinuously.

In the second step, the reaction temperature in the leachable primary reactor is 100 to 170 ° C, and the reaction pressure is 150 to 280 psi. The reasons for this numerical limitation are that the present invention depends on the hydrolysis temperature and the concentration of the sulfuric acid solution using sulfuric acid. The reaction temperature is in the range of 1 to 20 wt%, and the solid / liquid reaction The reason for this is that the pressure for preventing vaporization of the liquid solvent is 150-280 psi in the above temperature range.

The first solvent for primary hydrolysis in the second step is an aqueous sulfuric acid solution capable of converting polymeric cellulose and hemicellulose into oligomeric glucan and xylan. Inorganic acidic solvents containing sulfuric acid and hydrochloric acid may also be used.

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

The second stage of the primary hydrolysis process can convert the rigid polymeric form of cellulose and hemicellulose into oligomeric form. Through this primary hydrolysis, 60 ~ 90wt% of cellulose present in the initial biomass is converted into liquid oligomer form, and hemicellulose 70 ~ 95wt% is converted into liquid oligomer form. At the same time, the solid biomass remaining in the leachable primary reactor decreases in proportion to the liquid phase in the form of the oligomer which is leached out.

In addition, the second solvent in the third step may be a solvent capable of diluting the first solvent, and preferably water (distilled water) is used. At this time, it is preferable to apply the flow rate in the direction of constant flow below the input flow rate of the first solvent (5 to 10 ml / min).

That is, the second solvent using water can dilute the liquid reaction product in the acidic atmosphere through the leaching reaction into weak acid. As a preferable example, the weak acid means a weak acid atmosphere of 1 to 5 wt% when the first solvent is an aqueous sulfuric acid solution.

In the fourth step, it is preferable to maintain the flow type reaction so that the oligomer type glucan and the xylan can be converted into glucose and xylose in a weak acid atmosphere diluted as the second solvent.

At this time, it is preferable to induce the leaching reaction to the tubular flow type secondary reactor after the cooling and heat exchange processes or after supplying the second solvent.

The concentration of the weak sulfuric acid solvent used as the second solvent is 3 to 5 wt%, the reaction temperature is 70 to 120 DEG C, and the reaction pressure is 150 to 280 psi. The reasons for the numerical limitation are as described above.

Here, the pressure conditions provided to the leachable primary reactor and the tubular flow reactor, respectively, are regulated by one pressure supply device 6.

 Finally, the hydrolyzed material produced through the fourth step is collected in a storage tank. Most of the hydrolyzable material obtained is glucose and xylose. When the biomass introduced into the initial leaching reactor is used as a starting material, the yield of glucose 55 to 90 wt%, and the yield of xylose was 65 to 95 wt%. This yield is the final conversion yield regardless of the fifth step of the adsorption process.

In the subsequent process of the present invention as described above, there is provided a method for producing an alcohol using glucose extracted with the above-described method and xylose, wherein a liquid carbohydrate component (glucose and xylose ) Can be fermented to obtain chemicals including ethanol and butanol, and chemical substances such as HMF and furfural can be obtained through pyrolysis and chemical catalytic processes.

Alcohols (ethanol, butanol), alkane-based chemicals and C3C6-based chemical materials and organic acids, which are biofuels, can be produced using the glucose and xylose produced above.

FIG. 3 is a schematic diagram showing a structural change of lignocellulose by hydrolysis according to an embodiment of the present invention. When a process using the apparatus according to the present invention is performed, lignin, cellulose, and hemicellulose are all converted from cellulose- It is possible to produce glucose and xylose from cellulose and hemicellulose in a subsequent process.

Hereinafter, it is a preferred embodiment of the present invention.

[Example 1]

The process using the two-stage acid treatment hydrolysis apparatus according to the above-described FIG. 1 will be described.

First, the biomass was charged into the leachate first reactor (1) and the reaction temperature of the first leach reactor (1) was maintained at 150 캜 and the pressure of 200 psig.

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

Then, water is supplied from the second solvent tank 31 to the tubular flow type secondary reactor 4 to convert the oligomer type carbohydrate (glycated liquid) into a monomeric glycated liquid and collect it in the reservoir 5.

The yield of this final glucose was 65 wt%, and the yield of xylose was 80 wt%. The yield of final glucose increased from 35wt% to 65wt% compared with the acid hydrolysis of biomass through the existing primary acid hydrolysis unit. The yield of xylose was also 80wt% In contrast to the fact that xylose was overdosed by the reaction time and showed a low yield of 60%, the production of fufural, which is a fermentation inhibitor, was lowered and the recovery rate of xylose was higher than that of xylose.

In addition, 58 wt% of the lignin and lignin derivatives were removed by filling activated carbon which can adsorb lignin between the tubular flow type secondary reactor and the storage tank for capturing the final carbohydrate. In the first acid hydrolysis device, the phenolic compounds derived from lignin by high temperature and long reaction time had a great effect on the ethanol yield in the fermentation process. However, The efficiency of the system can be greatly increased.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents. Of course, such modifications are within the scope of the claims.

The apparatus and method for producing carbohydrates of cellulosic biomass according to preferred embodiments of the present invention are characterized by using a series of reaction systems and using a leachable first reactor and a first solvent and a tubular flow second reactor and a second solvent continuously , It is possible to produce glucose and xylose from the cellulosic biomass, so that it is possible to perform a rapid reaction without enzymatic saccharification and to minimize the decomposition reaction, and the two main steps are a series of reactions Therefore, it has an excellent industrial value because it has an advantage of being excellent in fairness and capable of obtaining high concentration of glucose and xylose with high yield.

Description of the Related Art
(1): leachable first reactor (2): first solvent supplier
(3): Second solvent supply device (4): Tubular flow type secondary reactor
(5): reservoir (6): pressure supply device
(7): Third solvent supply device (8a): Preheating device
(8b): steam generator (9a): cooler
(9b): Heat exchanger (10): Adsorption device
(21): first solvent tank (22): first solvent pump
(31): second solvent tank (32): second solvent pump
(71): third solvent tank (72): third solvent pump

Claims (20)

A leachable primary reactor (1) for converting cellulosic biomass into an oligomer form through primary hydrolysis;
A first solvent supply device 2 composed of a first solvent tank 21 and a first solvent pump 22 for supplying a primary solvent to the leaching type primary reactor;
A second solvent supply device 3 (see FIG. 3) composed of a second solvent tank 31 and a second solvent pump 32 for lowering the acid concentration of the second hydrolysis by supplying water to the first hydrolyzed high- )Wow;
A tubular flow type secondary reactor (4) for converting the diluted primary hydrolysis solution through the second solvent supply device to a secondary hydrolysis in a tubular flow reaction at a low temperature to convert to a monomeric carbohydrate;
A reservoir 5 for storing the hydrolyzate obtained through the tubular flow reactor;
And a pressure supply device (6) for maintaining the internal pressures of the leachable primary reactor and the tubular flow type secondary reactor. The hydrolysis of the cellulosic biomass through a two-stage acid treatment process Material production equipment.
The method according to claim 1,
Characterized in that the adsorbent in the transfer pipe is charged or adsorbed in order to recover lignin between the tubular flow type secondary reactor (4) and the storage tank (5), and the adsorbent of the cellulosic biomass Decomposition material production equipment.
The method according to claim 1,
Wherein the first solvent pump is further provided with a third solvent supply device composed of a third solvent tank and a third solvent pump each of which carries water for controlling the concentration of the first solvent, Apparatus for producing hydrolysis products of biomass.
The method according to claim 1,
Wherein the solvent contained in the first solvent tank is an aqueous solution of sulfuric acid, wherein the hydrolysis product of cellulose-based biomass is produced through a two-step acid treatment process.
The method of claim 4,
Wherein the concentration of the first solvent is 3 to 15 wt%. The apparatus for producing hydrolyzed cellulose-based biomass according to claim 1, The method according to claim 1,
Wherein the solvent contained in the second solvent tank is water. 2. The apparatus for producing a hydrolyzed cellulosic biomass according to claim 1, wherein the solvent is water.
The method of claim 6,
Wherein the second solvent is diluted to a concentration of 1 to 5 wt% of the first solvent.
The method according to claim 1,
Wherein a preheating device or a steam generating device is further installed between the first solvent pump and the leachable first reactor.
The method according to claim 1,
Wherein at least one of a cooler or a heat exchanger is installed between the leachable first reactor and the tubular flow second reactor and between the tubular flow second reactor and the storage tank, the cellulosic biomass Of the hydrolysis product.
The method according to claim 1,
Wherein the reaction temperature in the leachable first reactor is 100 to 170 ° C. and the reaction pressure is 150 to 280 psi.
The method according to claim 1,
Wherein the reaction conditions of the tubular flow type second reactor are 70-120 ° C and the reaction pressure is 150-280 psi. 2. The apparatus for producing a hydrolyzed cellulosic biomass according to claim 1,
A first step of providing the cellulosic biomass to the leachable primary reactor;
A second step of extracting glucan and xylan from the biomass by supplying a first solvent of the first solvent supply device to primary hydrolysis of cellulose and hemicellulose to the leachable primary reactor;
A third step of injecting a second solvent, which is extracted in the first leach type reactor and dilutes the first solvent so as to convert the glucan and the xylan to be transferred into the glucoside and xylose by secondary hydrolysis, through a second solvent supply device ; And
And a fourth step of converting the glucan and the xylan fed into the tubular flow type second reactor into a glucose and xylose by a second hydrolysis reaction in a tubular flow reaction. A method for producing hydrolysates of cellulosic biomass.
The method of claim 12,
And a fifth step of adsorbing the lignin to recover and recover lignin immediately before collecting the hydrolyzate produced through the tubular flow type secondary reactor after the fourth step into a storage tank. ≪ / RTI > wherein the biodegradable polymer is a biodegradable polymer.
The method of claim 12,
Wherein the first solvent is an aqueous solution of sulfuric acid. 2. The method for producing a hydrolyzed cellulosic biomass according to claim 1, wherein the first solvent is a sulfuric acid aqueous solution. 15. The method of claim 14,
Wherein the concentration of the first solvent is 3 to 15 wt%. 2. The method for producing a hydrolyzed cellulosic biomass according to claim 1, wherein the concentration of the first solvent is 3 to 15 wt%.
The method of claim 12,
Wherein the second solvent is water. ≪ RTI ID = 0.0 > 11. < / RTI >
18. The method of claim 16,
Wherein the second solvent dilutes the concentration of the first solvent to 1 to 5 wt%. The method for producing the hydrolyzed cellulosic biomass according to claim 1,
The method of claim 12,
Wherein the reaction temperature in the leachable first reactor is 100-170 ° C. and the reaction pressure is 150-280 psi.
The method of claim 12,
Wherein the tubular flow type secondary reactor has a reaction temperature of 70 to 120 ° C and a reaction pressure of 150 to 280 psi. 2. The method for producing a hydrolyzed cellulosic biomass according to claim 1,
The method of claim 12,
Hydrolysis of cellulosic biomass through a two-stage acid treatment process characterized in that after the leaching reaction in the second stage, the reaction is induced in a tubular flow type secondary reactor after cooling and heat exchange processes are performed and then a second solvent is supplied Material production method.

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