KR101039792B1 - Pretreatment device for fabricating of bio fuel and bio chemical material, and pretreatment process and fabricating process of bio fuel and bio chemical material using the same - Google Patents

Abstract

An immersion tank into which biomass is introduced to remove soluble substances; A feeder for mixing the biomass from which the soluble material has been removed and selected from the group consisting of water, acid, alkali, ionic liquid, and combinations thereof; A reactor for reacting the mixed mixture in the feeder; And a saccharification reactor for hydrolyzing the product obtained in the reactor, wherein the reactor includes a rotary decay valve maintaining a predetermined pressure, and further, a pretreatment apparatus for preparing biofuels and biochemicals is provided. A pretreatment process using a pretreatment device and a process for producing biofuels and biochemicals are provided.

Biomass, Biofuel, Bio Chemicals, Pretreatment

Description

Pretreatment device for the production of biofuels and biochemicals, and pretreatment process using the same and manufacturing process of the biofuel and biochemicals TECHNICAL MATERIAL, AND PRETREATMENT PROCESS AND FABRICATING PROCESS OF BIIO MATERIAL USING THE SAME}

The present disclosure provides a pretreatment apparatus for producing biofuels and biochemicals, a pretreatment process using the same, and a process for producing biofuels and biochemicals.

Biofuels and biochemicals produced from biomass are competitive, economical and relatively clean alternatives. The development of processes to convert biomass from agriculture, fisheries, industry and forestry into higher value materials has been intensive in many countries where research on the use of biomass has been conducted in the face of high grain prices and waste disposal issues. It's going on.

Most of the biomass and biochemical production processes known to date are operated with low concentrations of biomass for improved treatment efficiency and continuous process operation, but this has not led to large commercialization processes due to low economics.

One aspect of the present invention is to provide a pre-treatment apparatus for manufacturing biofuels and biochemicals having economical efficiency by enabling the operation of a continuous process while using a high concentration of biomass, reducing the amount of wastewater generated.

Another aspect of the present invention is to provide a pretreatment process using the pretreatment device for producing biofuels and biochemicals.

Another aspect of the present invention is to provide a process for producing a biofuel using the pretreatment process.

Another aspect of the present invention is to provide a process for producing a biochemical using the pretreatment process.

One aspect of the present invention is the immersion tank for introducing the biomass to remove the soluble material; A feeder for mixing the biomass from which the soluble material has been removed and selected from the group consisting of water, acid, alkali, ionic liquid, and combinations thereof; A reactor for reacting the mixed mixture in the feeder; And a saccharification reactor for hydrolyzing the product obtained in the reactor, wherein the reactor includes a rotary decay valve that maintains a predetermined pressure.

The pretreatment apparatus may further include a stirrer for mixing the acid treated product obtained in the reactor with the alkali treated product obtained in the reactor.

The concentration of the biomass may be 20 to 50% by weight / volume.

The residence time of the mixture in the reactor may be 10 to 180 minutes, the internal temperature of the reactor may be 100 to 200 ℃.

The rotary explosion valve may maintain a pressure of 1 to 50 kg / cm ² .

The pretreatment apparatus may further include a recovery unit for recovering the alkali from the alkali treated product.

Another aspect of the present invention is an immersion step of removing the soluble material by the introduction of biomass into the immersion tank; Mixing at the feeder a biomass from which the soluble material has been removed and selected from the group consisting of water, acid, alkali, ionic liquid and combinations thereof; Reacting the mixture mixed in the feeder in a reactor including a rotary spark valve; And it provides a pre-treatment process for producing biofuels and biochemicals comprising the step of hydrolyzing the product obtained in the reactor in the saccharification reactor.

The pretreatment process may further include mixing the acid treated product obtained in the reactor with the alkali treated product obtained in the reactor in a stirrer.

A mixed weight ratio of the acid treated product and the alkali treated product may be 1: 5 to 1:50.

The biomass is agricultural by-products of rice straw, barley straw, sweet potato stem, rapeseed stem, cassava stem; Waste paper, solid waste of fluff; Thinning wood, waste wood, processing by-product wood; Seaweed, algae, aquatic plants; And it may be selected from the group consisting of a combination thereof.

The immersion process may be to remove the soluble material by mixing the biomass and the selected from the group consisting of water, acid, alkali and combinations thereof.

Another aspect of the present invention is to prepare a biofuel comprising a step of preparing a biofuel selected from the group consisting of alkanes, alkenes, alcohols and combinations thereof using the products obtained in the pretreatment process described above. Provide a process.

Another aspect of the present invention is to prepare a biochemical selected from the group consisting of amino acid based material, organic acid based material, enzyme based material, biodegradable polymer based material and combinations thereof using the product obtained in the above pretreatment process. It provides a process for producing a biochemical comprising a process to.

Other specific details of embodiments of the present invention are included in the following detailed description.

It is possible to operate a continuous pretreatment process using a high concentration of biomass, and it is possible to secure economical efficiency in the post-treatment process by eliminating a separate process for cleaning and neutralizing chemicals, and to reduce the amount of wastewater generated. A pretreatment apparatus for producing a material, and a pretreatment process using the same, and a process for producing biofuels and biochemicals are provided.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

According to one embodiment of the present invention, there is provided a pretreatment apparatus and process for producing biofuels and biochemicals.

The biofuels and biochemicals are manufactured using a high concentration of biomass. First, the biomass will be described.

The biomass is agricultural by-products such as rice straw, barley straw, sweet potato stem, rapeseed stem, cassava stem; Solid waste such as waste paper and fluff; Wood such as thinning wood, waste wood, and processed byproducts; Aquatic plants such as algae and algae may be used, and these may be mixed with each other.

According to one embodiment of the present invention, only one type of biomass may be used, or two or more types may be used.

Cellulose, hemicellulose, and lignin, which are the major constituents of biomass, differ in composition ratio according to the type and site of biomass and are tightly bonded to form a basic structure of a plant.

The cellulose is a glucose polymer connected to each other by β-1,4-glucoside bonds and exists in plants in the form of fine fiber bundles. The cellulose accounts for 20 to 50% by weight of the total amount of biomass, which is an important component that is converted into biofuels and biochemicals through the saccharification process and into glucose and fermentation.

The hemicellulose is a heterogeneous polysaccharide composed of numerous monomers such as D-galactose, D-mannose, D-xylose, L-arabinose and the like. This is also an important component to be converted into biofuels and biochemicals, such as cellulose, accounting for about 10 to 35% by weight of the total biomass.

The lignin is a complex network formed by the polymerization of phenyl propane units, and the constituent monomers of the lignin are methoxylatio p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. It binds to hemicellulose and acts to protect plants from microorganisms and chemical degradation. However, during the saccharification process, the enzyme may affect the surface area that can be adsorbed to cellulose and hemicellulose, and also directly binds to the enzyme, thereby limiting the enzymatic hydrolysis of cellulose and hemicellulose, thereby reducing the effective enzyme degree. It is a substance that slows down and must be removed through pretreatment.

Cellulose and hemicellulose are made up of hydrogen bonds, and hemicellulose and lignin are made up of covalent bonds.

The carbohydrate component of seaweed in biomass varies from 40 to 70% by weight depending on its type. Among them, red algae, which contain the most carbohydrates, is composed of cellulose, a fibrous component, and agar, a major component, and agar has a low content of agarose and sulfate groups. It consists of high agaropectin.

The agarose is composed of D-galactose and 3,6-anhydro-L-galactose (3,6-anhydro-L-galactose). It consists of Ross, D-glucuronic acid and a small amount of Pyruvic acid.

The polysaccharide agar can be degraded using enzymes or by physical or chemical methods.

Pretreatment processes required to convert biomass into biofuels and biochemicals are classified into physical, chemical, and biological methods according to various types of biomass.

Specific examples include steam decay method, alkali treatment method, sulfur dioxide treatment method, hydrogen peroxide treatment method, supercritical ammonia treatment method, weak acid extraction treatment method, ammonia bombardment method, and ionic liquid treatment method. And chemical pretreatment with acid.

1 to 4 is a schematic view showing a part of a pre-treatment apparatus for producing biofuels and biochemicals according to an embodiment of the present invention, respectively, through which a pre-treatment apparatus and a pretreatment process will be described together.

The pretreatment process can be broadly divided into a dipping process, a process of removing a substance that is not required for saccharification fermentation using a high concentration of biomass, and a process of converting a high concentration of biomass mixture into sugars through enzymatic hydrolysis.

As shown in Figures 1 to 4, the immersion process in the immersion tank 10, the process of removing the substances that are not required for the saccharification fermentation process in the feeder 30 and the reactor 44, converting to the monosaccharides May be performed in the saccharification reactor 60.

The immersion tank 10 is a place where the biomass is introduced, where the soluble material is removed to control the size and efficiency of the feeder 30 and the reactor 44 which will be described later. As such, the process of removing the soluble material by introducing biomass into the immersion tank 10 may also be referred to as an immersion process.

Specifically, in the dipping process, a material selected from the group consisting of biomass pulverized to a size of 1 to 20 mm and water, an acid, an alkali, and a combination thereof is supplied to the immersion tank 10 and stirred to elute the soluble material. Let's do it.

At this time, the biomass concentration may be a high concentration of biomass as 20 to 50% by weight / volume.

The water may be used a medium / hot water of 50 to 80 ℃.

Since the immersion process is a preliminary process for removing the primary soluble material and destructive the structure of the biomass, the acid or alkali may be used lower than the concentration of each acid or alkali flowing into the feeder described later.

The acid may be an organic acid such as sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, or the like, and the alkali may be ammonia, sodium hydroxide, calcium compound, or the like.

The sulfuric acid may have a concentration of 1 M or less, specifically 0.3 M or less, and the ammonia may be used in a concentration of 15 weight / vol% or less, specifically 11 weight / vol% or less.

The stirring may be performed for 1 to 6 hours, specifically, for 3 hours.

Elution amount of the soluble material may be 8 to 14% by weight of the total amount of biomass.

The solids content of the biomass from which the soluble material is removed after the immersion process may be 30% by weight or more, specifically 40% by weight or more.

The biomass is dehydrated to have a retained moisture of 50 to 70% by weight.

Next, a step of removing a substance that is not required for saccharification fermentation using a high concentration of biomass, wherein the soluble substance is removed, dehydrated biomass, water, acid, alkali, ionic liquid and a combination thereof After the mixture selected inflow into the feeder 30 and mixed, the mixture is introduced into the reactor 44 and reacted.

Specifically, the mixture is transferred and mixed in the high pressure transfer section 42 through a pump 40 which pushes the mixture toward the reactor 44, and then the reactor 44 heats steam, a thermal jacket, or the like. It is reacted by supplying.

The process carried out in the feeder 30 and the reactor 44 disrupts the structure of the biomass and removes lignin that is not converted to the final product.

The water may be a hot water of 80 ℃ or more.

The acid and alkali are the same as the kinds of acid and alkali used in the immersion step.

The ionic liquid may be an imidazolium-based compound. Examples of the imidazolium-based compound include 1-ethylacrylate-3-methylimidazolium chloride and 1-butyl-3-methylimidazolium chloride (1-buthyl- 3-methylimidazolium chloride), 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate (1-butyl- 3-methylimidazolium hexafluoro phosphate), 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium acetate (1-ethyl- 3-methylimidazolium acetate), 1-benzyl-3-methylimidazolium chloride, 1,3-dimethylimidazolium methyl sulfate, and the like. And preferably 1-butyl-3-methylimidazolium chloride And 1-ethyl-3-methylimidazolium acetate and the like.

The reactor 44 is equipped with a rotary attenuating valve 48 that can continuously remove the high viscosity biomass while maintaining a predetermined pressure at the rear end, thereby amplifying the biomass in the reaction is completed by the pressure difference In this case, the structure of the biomass is further deteriorated by a sudden pressure change, and a constant supply of biomass is possible. This makes it possible to forcibly explode and discharge the high viscosity biomass after passing through the feeder 30 to use a high concentration of biomass.

That is, in the conventional pretreatment apparatus, especially the continuous detonation apparatus, the ON / OFF valve or the pressure control valve is used, but when using a high concentration of biomass, the effect of the solids in the valve closing portion is reduced, the effect of the present invention The pretreatment apparatus according to the embodiment may use a high concentration of biomass by being equipped with a rotary attenuation valve 48 capable of forcibly discharging.

The rotary explosion valve 48 may maintain a pressure of 1 to 50 kg / cm ² .

The residence time of the mixture in the reactor 44 may be 10 to 180 minutes, specifically 10 to 120 minutes, specifically 10 to 30 minutes.

The internal temperature of the reactor 44 may be 100 to 200 ℃. Specifically, the acid treatment by mixing the biomass, water and acid may be 100 to 200 ℃, specifically 145 to 175 ℃. In addition, the alkali treatment by mixing the biomass, water and alkali may be 170 ℃ or less, specifically, may be 120 to 145 ℃. In addition, in the case of the ionic liquid treatment by mixing the biomass and the ionic liquid may be 170 ℃ or less, specifically 140 to 160 ℃.

The internal pressure of the reactor 44 can be operated at up to 35 kg / cm ² .

Next, as a process for converting a high concentration of the biomass mixture into saccharide through enzymatic hydrolysis, the product obtained in the reactor 44 is hydrolyzed in the saccharification reactor 60.

In this case, the obtained product may be directly transferred to the saccharification reactor 60 or may be transferred through the stirrer 50. That is, the pretreatment device may further include a stirrer 50.

As a specific example, when the biomass and water are mixed, the product obtained may be directly transferred to the saccharification reactor 60 and hydrolyzed. Also the acid treated products obtained in the reactor 44, i.e. the products obtained by mixing the biomass, water and acid and the alkali treated products obtained in the reactor, i.e. the biomass, water and alkali After mixing the products obtained by mixing with each other in the stirrer 50, it can be transferred to the saccharification reactor 60 can be hydrolyzed.

The mixed weight ratio of the acid treated product and the alkali treated product in the stirrer 50 may be 1: 5 to 1:50, and specifically 1:10 to 1:20. At this time, the mixed mixture may be adjusted to a pH of 4.5 to 5.5. If the mixing weight ratio and the pH of the mixture is within the above range it can be adjusted to show the optimal activity of the hydrolase.

The product obtained from the biomass may be hydrolyzed in the saccharification reactor 60, which may be an enzyme such as cellulase, betaglucosidase, beta galactosidase as enzymatic hydrolysis.

The hydrolysis is carried out in a saccharification reactor 60 equipped with a screw-type impeller 62, and as the high-concentration product obtained from the high concentration biomass is hydrolyzed due to the mounting of the screw-type impeller 62, The high viscosity liquid obtained can be mixed efficiently, and uniform mixing can be made as a whole.

The hydrolysis may be performed up to 24 hours, specifically, up to 11 hours, when the viscosity decreases due to enzymatic action in the reactor.

The hydrolysis conditions may vary depending on the enzyme conditions to be used. In addition, the hydrolysis product may provide properties suitable for various processes such as batch, continuous, semi-continuous, and fed-batch, which are processes for producing biofuels and chemicals as subsequent processes.

The degree of hydrolysis may be 70 to 90%.

The pretreatment apparatus may further include a recovery unit 70 for recovering the alkali from the alkali treated product.

That is, the solids (B) remaining after removing the lignin and the alkaline liquid from the alkali-treated product are transferred to the above-described stirrer 50 and mixed with the acid-treated product, and some of the remaining desorption liquid is transferred to the desorption liquid storage tank 71. And recovers the alkali (A) through the recovery unit 70, the other part is transferred to the concentrator 73, the condensed process water (C) is reused in the process, the recovered alkali (A) is again It is reused in the pretreatment process, specifically, it is introduced into the feeder 30 described above.

The recovery of the alkali can be adjusted to pH 11 to 13, specifically pH 11 to 11.2 by using one or more of the calcium compound and sodium hydroxide, recovering the alkali (A) by concentration under reduced pressure in the alkali recovery tank 72 do.

At this time, the degree of reduced pressure is 300 to 760 mmHg, specifically 500 to 700 mmHg, the temperature may be 80 to 95 ℃, specifically 80 to 92 ℃.

The concentration of the alkali (A) thus recovered may be 25% by weight or more.

At this time, the solid (D), which is a non-fermentable substance such as lignin deposited on the lower part of the desorption liquid storage tank 71, may be sent to the boiler room at regular intervals and used as a heat source.

Some devices used in the recovery process of the alkali may also be used in the recovery process of the ionic liquid. After washing the product treated with the ionic liquid and leaching the material rich in agarose and cellulose using a ketone-based organic solvent in the process of leaching, the leached solid is transferred to the aforementioned saccharification reactor (60). Some of the remaining desorption liquid is transferred to the desorption liquid storage tank 71 to recover the ketone-based organic solvent through the recovery part 70, and the other part is transferred to the concentrator 73 so that the condensed process water C is transferred to the process. Recycled, the recovered ionic liquid is reused in the pretreatment process, specifically to the feeder 30 described above.

At this time, the decompression degree of the concentration process is 300 to 760 mmHg, specifically 500 to 700 mmHg, the temperature may be 80 to 95 ℃, specifically 80 to 92 ℃.

In this case, the filtered solid material may be sent to the boiler room at regular intervals and used as a heat source.

1 to 4 have been described with respect to the pre-treatment apparatus and process for the production of biofuels and biochemicals, hereinafter shows an example of a more specific pre-treatment process through FIGS.

FIG. 5 is a schematic process diagram illustrating a pretreatment process for preparing biofuels and biochemicals using one type of biomass according to one embodiment, and FIG. 6 is a biofuel using two types of biomass according to another embodiment. FIG. 7 is a schematic process diagram illustrating a pretreatment process for manufacturing a biochemical, and FIG. 7 is a schematic process diagram illustrating a pretreatment process for preparing a biofuel and a biochemical using an ionic liquid according to another embodiment.

As shown in FIG. 5, first, the soluble material is removed as the biomass is selected from the group consisting of water, acid, alkali, and a combination thereof in the immersion tank. The desorption solution from which the soluble material has been removed is dewatered, wherein the dewatering solution from which the soluble material has been removed can be reused in the dipping process, thereby reducing the amount of wastewater generated.

Next, the biomass, water and sulfuric acid from which the soluble material has been removed are mixed in a feeder and reacted in a reactor including a rotary attenuation valve to explode the biomass to obtain an acid treated product. The biomass, water and ammonia from which the solubles have been removed are also mixed in the feeder and reacted in a reactor comprising a rotary attenuation valve to detonate the biomass to obtain an alkali treated product.

The acid treated product and the alkali treated product are then mixed with each other in a stirrer to adjust to pH 4.5 to 5.5, and the product obtained in the stirrer is hydrolyzed in a saccharification reactor.

Meanwhile, some of the alkali treated products are transferred to a recovery unit to recover ammonia, and the recovered ammonia is again introduced into a feeder and reused in a pretreatment process. Others are condensed with water and reused in the process.

FIG. 6 is the same as the process using two types of biomass as shown in FIG. 5 except that the two types of biomass are used in comparison with FIG.

In addition, as shown in FIG. 7, first, the soluble material is removed as the biomass and water are mixed and immersed in an immersion tank. The desorption solution from which the soluble material has been removed is dewatered, wherein the dewatering solution from which the soluble material has been removed can be reused in the dipping process, thereby reducing the amount of wastewater generated.

Next, the biomass, water and ionic liquid from which the soluble material has been removed are mixed in a feeder and reacted in a reactor including a rotary attenuation valve to amplify the biomass to obtain a product treated with the ionic liquid.

Subsequently, the product treated with the ionic liquid is washed with a ketone-based organic solvent in a washing and dehydration process to leach agarose and cellulose-rich materials, and then the leached solid is hydrolyzed in a saccharification reactor.

On the other hand, some of the product treated with the ionic liquid is transferred to the recovery unit to recover the ketone-based organic solvent, the recovered ketone-based organic solvent is again introduced into the washing and dehydration process is reused in the process. The other part is condensed to recover the ionic liquid and water for reuse in the process.

According to another embodiment of the present invention, there is provided a process for producing a biofuel comprising a process for producing a biofuel using the product obtained in the above-described pretreatment process.

Specifically, the biofuel may be prepared by culturing the strain using the product obtained in the aforementioned pretreatment step as a hydrolysis solution.

The strains include saccharomyces cerevisiae, pichia stipitis, candida brassicae, zymomonas moilis, clostridium acetobutylli Combs (clostridium acetobutylicum) and combinations thereof may be used.

The biofuel may be selected from the group consisting of alkanes, alkenes, alcohols, and combinations thereof. In this case, the alkanes are C1 to C10 alkanes, the alkenes are C1 to C10 alkenes, and the alcohols are C1 to C10 alcohols.

The concentration of bioethanol in the biofuel prepared according to the biofuel manufacturing process may be 70 g / L or more, and the concentration of bio butanol may be obtained in an amount of 15 g / L or more. This may vary slightly depending on the type of biomass, and higher concentrations may be obtained under the optimization conditions for each type.

According to another embodiment of the present invention, there is provided a process for producing a biochemical including a process for producing a biochemical using the product obtained in the above-described pretreatment process.

Specifically, the bio-compound can be prepared by culturing the strain using the product obtained in the above-described pretreatment step as a hydrolysis solution.

The strain may be selected from the group consisting of clostridium tyroburyricum, lactobacillus axidophilus, and combinations thereof.

The biochemicals may be selected from the group consisting of amino acid materials, organic acid materials, enzyme materials, biodegradable polymer materials, and combinations thereof.

The concentration of bio butyric acid may be 20 g / L or more in the biochemicals prepared according to the biochemical preparation, and the concentration of bio lactic acid may be 8 g / L or more. This may vary slightly depending on the type of biomass, and higher concentrations may be obtained under the optimization conditions for each type.

As described above, according to the pre-treatment apparatus and process for producing biofuels and biochemicals as an embodiment of the present invention, it is possible to continuously remove lignin or the like that inhibits hydrolysis from the biomass mixture, and to treat wastewater and subsequent The economics of the process can be secured, and the economics of process operation are improved by recovering and reusing alkali and process water.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following examples.

[Example]

Example 1 Pretreatment Process Using One Type of Biomass

Barley straw with a dry weight of 100 kg was crushed to an average size of 2 mm, added with 300 L of hot water at 70 ° C. in an immersion tank, stirred for 3 hours, and filtered through a compression filter. The total amount of filtrate was 175 kg and the total amount of solids contained in the filtrate was 10 kg.

The dehydrated barley straw was mixed in the feeder and in the reactor at a ratio of 85.5 kg (95 wt%) and 4.5 kg (5 wt%) of dilute sulfuric acid, respectively.

The ammonia treatment was added with 100 kg of 28% ammonia water and stirred for 20 minutes at 145 ° C. and 30 kg / cm ² in the reactor after stirring, and then bombed with a rotary explosion valve. After ammonia treatment, the product was subjected to compression filtration, washing and pressing to obtain ammonia-treated products. The ammonia-treated product had a dry weight of 55 kg and a water content of 50%, and a part of ammonia was present.

Dilute sulfuric acid treatment was taken 22.36kg of 3.3% dilute sulfuric acid solution, pretreated at 160 ℃ 6kg / cm ² , 10 minutes and then exploded with a rotary valve and mixed with the ammonia-treated product in a stirrer. The pH after mixing was 5.1 and the solids concentration was 32%.

Cellulase 20FPU and betaglucosidase 30CbU were taken and hydrolyzed in the saccharification reactor at 48 hours and 50 ° C. The final glucose concentration was 140 g / L.

Example 2 Pretreatment Process Using Two Kinds of Biomass

Barley straw with a dry weight of 100 kg was crushed to an average size of 2 mm, added with 300 L of hot water at 70 ° C. in an immersion tank, stirred for 3 hours, and filtered through a compression filter. At this time, the weight of the solid was 225 kg and the moisture content was 60%.

106 kg of 28 wt / vol% ammonia water was added to the filtered solids, mixed in a feeder, and then agitated for 30 minutes at 145 ° C. and 30 kg / cm ² in a reactor, followed by aeration with a rotary explosion valve. After ammonia treatment, the product was subjected to compression filtration and washing / filtration steps to obtain ammonia-treated products. The ammonia-treated product had a dry weight of 58.5 kg of water and some ammonia.

The dry weight 10kg cassava stem was crushed to an average size of 2mm and added with 30L of hot water at 85 ° C. in an immersion tank, stirred for 2 hours, and filtered through a compression filter. At this time, the weight of the solid was 24.2 kg and the moisture content was 61%.

Thereafter, 46 kg of 3.3 wt / vol% dilute sulfuric acid was added thereto, and the resultant was pulverized with a rotary valve after holding at 175 ° C. for 15 minutes in a reactor to obtain a sulfuric acid treated product.

The ammonia-treated product and the sulfuric acid-treated product were added to a stirrer, and after stirring, the pH was 4.9 and the concentration of the solid was 30.4 wt%.

Cellulase 20FPU and betaglucosidase 30CbU were taken and hydrolyzed in the saccharification reactor at 48 hours and 50 ° C. The final glucose concentration was 137 g / L.

Example 3 Pretreatment Process Using Seaweed Biomass

100 kg of red algae were crushed to an average size of 2 mm and filtered through a compression filter. The dry weight of the solid was 40 kg and the moisture content was 50%.

Add 200 kg of 1-ethyl-3-methylimidazolium acetate as an ionic liquid to the filtered solid, mix in a feeder, and stir for 30 minutes at 150 ° C and 5 kg / cm ² in a reactor. Fired with a rotary fired valve. The product treated with the ionic liquid was subjected to compression filtration and washing / filtration steps after treatment with the ionic liquid. Solid concentration of the treated product was 31.2% by weight.

200 U / ml of beta galactosidase was taken and hydrolyzed in a saccharification reactor at 72 hours and 38 ° C. The final glucose concentration was 87 g / L.

Example 4: Biofuel Preparation

Example 4-1 Preparation of Bioethanol

Ethanol was prepared by culturing Saccharomyces cerevises (KCTC 11250 BP) strain, an ethanol production industry strain, using the hydrolysis solution of 140 g / L prepared in Example 1.

After 24 hours of incubation with Saccharomyces cerevisiae strain, the initial sugar concentration of 140 g / L was completely consumed. At this time, the prepared ethanol concentration was 70 g / L.

Example 4-2 Preparation of Bio Butanol

Butanol was prepared by batch culturing the Clostridium acetobutylicum (ATCC 824) strain in a 5.0 L bioreactor using the diluted 140 g / L hydrolysis solution prepared in Example 1 to 40 g / L. It was.

Culture conditions were the initial concentration of 40 g / L, the initial pH 6.0, the culture temperature 37 ℃ and stirring speed 150 rpm. In addition, CO ₂ or N ₂ was supplied to maintain the anaerobic state, and the pH of the culture was adjusted to 5.0 or more using a 28% weight / vol% ammonia solution. After 70 hours of incubation with ATCC 824 strain, the initial sugar concentration of 40 g / L was completely consumed. The butanol concentration prepared was 15 g / L.

Example 5: Biochemical Preparation

Example 5-1 Preparation of Bio Butyric Acid

Butyl acid was prepared by batch culturing the Clostridium tyrobutyricum (ATCC 25755) strain in a 5.0L bioreactor using the diluted 140 g / L hydrolysis solution prepared in Example 1 to 40 g / L. Prepared.

Culture conditions were the initial concentration of sugar 40g / L, the culture temperature 37 ℃ and stirring speed 150rpm. In addition, CO ₂ or N ₂ was supplied to maintain the anaerobic state, and the pH of the culture was adjusted to 6.0 using a 28% weight / vol% ammonia solution. After 22 hours of incubation with ATCC 25755 strain, 40 g / L of initial sugar concentration was completely consumed. At this time, the butyric acid concentration was 25 g / L.

Example 5-2 Preparation of Bio Lactic Acid

Using the diluted solution of 140 g / L hydrolyzate prepared in Example 1 to 20 g / L to inoculate 3 mL strain culture in 200 mL dilution in 500 mL flask of Lactobacillus axidophilus (NCFM) strain Lactic acid was prepared by culturing.

Culture conditions were adjusted to an initial concentration of 20 g / L, pH 6.0. The culture was carried out in an anaerobic incubator capable of temperature control, the culture temperature was adjusted to 37 ℃. After 24 hours of incubation 10 g / L of glucose was consumed. In this case, the prepared lactic acid concentration was 8 g / L.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the range of.

1 to 4 are schematic diagrams each showing a part of a pretreatment apparatus for producing a biofuel and a biochemical according to one embodiment.

5 is a schematic process diagram illustrating a pretreatment process for preparing biofuels and biochemicals using one kind of biomass according to one embodiment.

6 is a schematic process diagram illustrating a pretreatment process for preparing biofuels and biochemicals using two kinds of biomass according to another embodiment.

7 is a schematic process diagram illustrating a pretreatment process for preparing biofuels and biochemicals using an ionic liquid according to another embodiment.

DESCRIPTION OF THE REFERENCE NUMERALS OF THE DRAWINGS

10: immersion tank 30: feeder

40: pump 42: high pressure transfer unit

44: reactor 46: collection tank

48: rotary aeration valve 50: stirrer

60: saccharification reactor 62: screw-type impeller

70: recovery part 71: desorption liquid storage tank

72: alkali recovery tank 73: concentrator

Claims (14)

An immersion tank into which biomass is introduced to remove soluble substances; A feeder for mixing the biomass from which the soluble material has been removed and selected from the group consisting of water, acid, alkali, ionic liquid, and combinations thereof; A reactor for reacting the mixed mixture in the feeder; And A glycosylation reactor for hydrolyzing the product obtained in the reactor, The reactor is a pre-treatment device for producing biofuels and biochemicals that includes a rotary explosion valve to maintain a predetermined pressure. The method of claim 1, The pretreatment device further comprises a stirrer for mixing the acid treated product obtained in the reactor and the alkali treated product obtained in the reactor with each other. The method of claim 1, The concentration of the biomass is 20 to 50% by weight / volume% pre-treatment device for producing biofuels and biochemicals. The method of claim 1, The residence time of the mixture in the reactor is 10 to 180 minutes, the pre-treatment device for producing biofuels and biochemicals. The method of claim 1, The internal temperature of the reactor is 100 to 200 ℃ the pre-treatment device for producing biofuels and biochemicals. The method of claim 1, The rotary explosion valve is a pre-treatment device for producing biofuels and biochemicals to maintain a pressure of 1 to 50 kg / cm ² . The method of claim 1, The pretreatment device further comprises a recovery unit for recovering the alkali or ionic liquid from the alkali or ionic liquid treated product. An immersion process in which biomass is introduced into an immersion tank to remove soluble substances; Mixing at the feeder a biomass from which the soluble material has been removed and selected from the group consisting of water, acid, alkali, ionic liquid and combinations thereof; And Reacting the mixture mixed in the feeder in a reactor comprising a rotary spark valve Pretreatment process for producing biofuels and biochemicals comprising a. The method of claim 8, The pretreatment process further comprises the step of mixing the acid-treated product obtained in the reactor and the alkali-treated product obtained in the reactor with each other in a stirrer. 10. The method of claim 9, The mixed weight ratio of the acid treated product and the alkali treated product is 1: 5 to 1:50 pre-treatment process for producing biofuels and biochemicals. The method of claim 8, The biomass is agricultural by-products of rice straw, barley straw, sweet potato stem, rapeseed stem, cassava stem; Waste paper, solid waste of fluff; Thinning wood, waste wood, processing by-product wood; Seaweed, algae, aquatic plants; And combinations thereof. Pretreatment process for producing biofuels and biochemicals. The method of claim 8, The immersion process is a pre-treatment process for producing biofuels and biochemicals to remove the soluble material by mixing the biomass and the selected from the group consisting of water, acid, alkali and combinations thereof. A biofuel comprising a process for producing a biofuel selected from the group consisting of alkanes, alkenes, alcohols and combinations thereof using the product obtained in the pretreatment process according to any one of claims 8 to 12. Manufacture process. A biochemical selected from the group consisting of amino acid based materials, organic acid based materials, enzyme based materials, biodegradable polymeric materials and combinations thereof using the products obtained in the pretreatment process according to any one of claims 8 to 12. A process for producing a biochemical comprising a process for producing.

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