KR101595004B1 - Continuous pretreatments system of biomass - Google Patents

Abstract

The present invention relates to a feed passage for a raw material, comprising: a feed part having a first hollow part formed therein; A raw material supply unit disposed at one side of the transfer unit and supplied with the raw material; A first conveying device disposed in the first hollow portion and having a screw shape to provide a conveying driving force of the raw material by shaft rotation; And a discharge port disposed on the other side of the transfer unit for discharging the raw material; And a second conveying device in the form of a screw is arranged in parallel with the first conveying device on one side of the first hollow part to crush and extrude the raw material .
The present invention relates to a biomass pretreatment method for pretreating biomass using the biomass pretreatment system.

Description

{Continuous pretreatment system of biomass}

The present invention relates to a biomass continuous pretreatment system, and more particularly, to a system for increasing the recovery rate of carbohydrates by making the cell walls of the biomass and the tightly bonded cellulosic structure flexible through continuous mechanical and chemical treatment.

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 a part of the development of such alternative energy, technologies for producing bio-energy such as alcohol, diesel, hydrogen, and the like from biomass are attracting attention.

Here, biomass refers to a carbon assimilation process for fixing carbon dioxide using sunlight, that is, a saccharide biosynthesized through a photosynthesis process, and a whole organism including the same. Representative examples include lignocelluloses, represented by plant resources that are the most abundant and reproducible on the planet.

The lignocellulosic biomass is required to have a pretreatment process for improving its structural characteristics, that is, the cellulose that can be used as a raw material is surrounded by hemicellulose and lignin, and the accessibility of the saccharifying enzyme is restricted.

As a pretreatment method, various physical and chemical methods such as steam explosion, alkali treatment, sulfur dioxide treatment, hydrogen peroxide treatment, supercritical ammonia treatment, acid treatment, ammonia freeze-thawing and organic solvent treatment are known depending on the kind of biomass , And these methods are practically used alone or in combination. In general, physical methods are slow in process, low in economic efficiency due to high energy consumption, chemical methods are expensive due to use of strong acids or strong alkaline compounds, are unsuitable for large-scale processes, produce byproducts, It is necessary to develop a continuous pretreatment process which is economic, effective, and accessible to the commercialization process without causing environmental problems.

KR 10-1190647 (registration number)

The present invention seeks to provide a biomass pretreatment system for a continuous pretreatment process that is accessible to commercialization processes.

The present invention relates to a feed passage for a raw material, comprising: a feed part having a first hollow part formed therein; A raw material supply unit disposed at one side of the transfer unit and supplied with the raw material; A first conveying device disposed in the first hollow portion and having a screw shape to provide a conveying driving force of the raw material by shaft rotation; And a discharge port disposed on the other side of the transfer unit for discharging the raw material; And a second conveying device in the form of a screw is arranged in parallel with the first conveying device on one side of the first hollow portion to crush and extrude the raw material .

The present invention provides a biomass pretreatment method for pretreating biomass using the biomass pretreatment system.

The continuous pre-treatment system of the present invention includes a transfer part that can easily feed and transport biomass under high pressure conditions generated during the pretreatment, so that a large amount of sugar can be continuously supplied and fermentable.

BRIEF DESCRIPTION OF THE DRAWINGS Fig.
Figure 2 is a flow diagram of a process according to the present invention.

The present invention relates to a biomass pretreatment system, and more particularly, to a biomass pretreatment system comprising: a feed part having a first hollow part formed therein as a feed passage for a raw material; A raw material supply unit disposed at one side of the transfer unit and supplied with the raw material; A first conveying device disposed in the first hollow portion and having a screw shape to provide a conveying driving force of the raw material by shaft rotation; And a discharge port disposed on the other side of the transfer unit for discharging the raw material; And a second conveying device in the form of a screw is arranged in parallel with the first conveying device on one side of the first hollow portion to crush and extrude the raw material.

In particular, the predetermined region means a region corresponding to the raw material supplying portion, and may be, for example, 80%, 90%, or 100% of the length of the raw material supplying portion. In another embodiment, the predetermined area may be an area corresponding to a length of 20 to 40% corresponding to the entire length of the first transfer device.

The term biomass refers to biomass, which is derived from energy such as ethanol, hydrocarbons, gasoline, natural gas, methane, biodiesel and hydrogen gas, electricity, plastics, polymers, nutrients (human and animal), proteins, Humans, and livestock), fertilizers, or other products, or a combination of these materials.

Also, the term biomass pretreatment refers to making a form that is easily decomposed into monosaccharides by changing the bonding state between constituent components in the biomass. For example, the chemical bonding, arrangement, or stereomorphism of the constituents may be changed to remove the non-sugar moieties to facilitate subsequent saccharification of the enzyme. Further, it is also possible to change the molecular structure, oxidize the constituent components in the biomass, change the average molecular weight, change the average crystallinity, change the surface area, change the degree of polymerization, change porosity, change branching degree, , Or a change in overall area size.

The raw material supplying portion of the present invention includes a hopper into which the raw material is injected; A valve connected to the lower end of the hopper on one side and a feed valve connected to the feeder on the other side for delivering the feed to the feeder; And a vibration supply device installed in the hopper and applying vibration thereto; .

Also, the first transfer device may include a thread, and a part of the thread may include at least one discontinuity to withstand back pressure.

Here, a plurality of the cut-off portions may be formed at positions close to the discharge port, and may be formed so as to communicate with neighboring fog acids when viewed from the front, and may be formed so as not to communicate with neighboring threads.

In addition, the biomass pretreatment system of the present invention includes a reaction unit connected to the discharge port to inject a biomass raw material and a solvent into the extruded biomass, And a recovery unit connected to the other side of the reaction unit to recover the reactants generated in the reaction unit. The reaction unit may include a mixing reaction tank in which a solvent supply unit is connected and mixes the extruded raw material and a solvent; And a tubular reaction vessel connected to the mixing reaction tank and including heating means for applying heat to the mixture.

In particular, the mixing tank may include a first motor installed at an upper portion of the upper cover to provide a rotational force; A first rotating shaft connected to the motor; A first stirring blade coupled to a lower end of the rotating shaft and rotated about the rotating shaft to mix the raw material and the solvent; . ≪ / RTI >

In addition, the tubular reaction tank may have a second hollow portion formed therein, and the second hollow portion may include a screw-shaped third transfer device that provides a transfer driving force of the mixture by shaft rotation.

In particular, the heating means includes an oil jacket for enclosing the outer surface of the tubular reaction vessel so as to be heat-treated; A heating block connected to the oil jacket to apply heat to the oil jacket; . ≪ / RTI >

In addition, the recovery unit of the present invention includes a top cover to which a nitrogen storage tank for boosting the pressure inside the recovery unit is connected; A second motor installed on the upper cover to provide a rotational force; A second rotation shaft connected to the second motor; A second stirring blade coupled to a lower end of the second rotation shaft and rotating about the second rotation axis to mix reactants; And at least two discharge valves at a lower end of the recovery section; . ≪ / RTI >

In the present invention, the solvent can be used for an alkali, and can be, for example, NaOH.

The present invention also relates to a biomass pretreatment method for pretreating biomass using a biomass pretreatment system.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

FIG. 1 is a view showing a transfer unit according to an embodiment of the present invention. FIG. 2 is a view showing a biomass pretreatment system according to an embodiment of the present invention. FIG. This is a graph showing the rate of glycyrrhizia.

Hereinafter, the biomass pretreatment system of the present invention will be described in detail with reference to FIGS. 1 to 3 and Examples.

The present invention relates to a continuous biomass pretreatment system (10), and more particularly to a system capable of pre-treating carbohydrates required for ethanol production from cellulose biomass with high efficiency.

1, the biomass pretreatment system 10 of the present invention includes a transfer unit 100, a reaction unit 300, and a recovery unit 400.

First, the conveyance unit 100 refers to a conveyance passage for the raw material, and one side may be connected to the raw material supply unit 200, and the other side may be connected to the discharge port 130. The raw material supply unit 200 refers to a portion for supplying raw material of biomass in powder form, and the discharge port 130 refers to a portion where the raw material is discharged.

In particular, the transfer unit 100 may include a first hollow portion, and the first hollow portion may include a screw-type first transfer device 110 that provides a transfer driving force of the raw material by shaft rotation. The first transfer device 110 can transfer the biomass by the axial rotation of the screw, and the shaft rotation can be provided with the driving force by the motor connected to the screw. Alternatively, the raw material can be continuously moved through a conveyor belt or the like. In addition, in order to more easily transfer the raw material, a part of the thread 111 formed in the first transfer device 110 may include a cut-off part 112 so as not to be connected to each other. As shown in FIG. 1, the cut-off portion may be formed in the thread 111 formed on the other side of the first transfer device 110, and may be formed so as not to be adjacent to each other when viewed from the front. This may be for controlling the first conveying apparatus 110 such that the raw material can not flow back by the pressure in the reaction unit 300, which will be described later.

In addition, a screw-type second transfer device may be formed in a predetermined area on one side of the first hollow part, and the second transfer device may be disposed in parallel with the first transfer device 110. The second transfer device may be a device for transferring the raw material and crushing and extruding the raw material.

More specifically, the first conveying device 110 and the second conveying device 120 are arranged in parallel and engaged, whereby the raw material can be crushed.

Here, the predetermined region means a region corresponding to the raw material supply unit 200, and may be, for example, 80%, 90%, or 100% corresponding to the length of the raw material supply unit. In another embodiment, the predetermined area may be an area of 20 to 40% of the entire length of the first transfer device 110.

The raw material supply unit 200 supplies the biomass raw material and includes a hopper 210 through which the biomass flows into the one side and a hopper 210 through which the raw material is connected to the transfer unit 100, And a vibration supply device installed on the hopper 210 for applying vibration. At this time, the raw material supplied to the raw material supplying unit 200 may be a biomass raw material crushed to 2 mm or less, and may contain 15 to 25% moisture.

2, the discharge port 130 formed in the transfer unit 100 may be connected to the reaction unit 300 of the present invention. In the reaction unit 300, the powdered biomass raw material and the solvent may be introduced to perform the reaction.

Particularly, the reaction unit 300 may include a mixing reaction tank 310 and a tubular reaction tank 320.

More specifically, the mixing tank 310 may be connected to a solvent supply unit. In order to efficiently extract the carbohydrate from the biomass, the solvent may be mixed to further weaken the binding force of each component of the reaction product. The solvent may be an allylic solvent and may be, for example, NaOH.

In the mixing tank 310, the raw material and the solvent may be introduced by the transfer unit 100 and the solvent supply unit to produce a mixture. More specifically, the mixing tank 310 may include a cover at an upper portion thereof, and may include a first motor 311 disposed at an upper portion of the upper cover 410 to provide rotational force, a first motor 311, And a first stirring blade 313 for stirring the mixture in conjunction with the rotation shaft 312. The first stirring blade 313 and the second stirring blade 313 are connected to each other.

The upper end of the first rotation shaft 312 is connected to the first motor 311 and the lower end of the first rotation shaft 312 is accommodated in the upper part of the mixing reaction tank 310 through the upper cover. And rotates to transmit the rotational force to the first stirring blade 313.

The first stirring blade 313 is connected to a lower end of the first rotation shaft 312 and extends radially around the first rotation shaft 312 to stir the reactants stored in the reaction tank to be evenly mixed.

The mixed mixture in the mixing reaction tank 310 is transferred to the tubular reaction tank 320 and the tubular reaction tank 320 includes a heating means so as to uniformly heat the raw material, So that the pretreatment efficiency can be greatly improved.

More specifically, the tubular reactor 320 has a second hollow portion formed therein, and the second hollow portion includes a screw-shaped third transfer device 331 that provides a transfer driving force of the mixture by the rotation of the shaft .

Particularly, the heating means includes an oil jacket 330 for covering the outer surface of the tubular reaction vessel 320 so as to be heat-treated, a heating block 331 connected to the oil jacket 330 to apply heat to the oil jacket 330, ; . ≪ / RTI >

The oil jacket 330 surrounds the outer surface of the tubular reaction tank 320. The oil jacket 330 is filled with oil and the temperature can be uniformly distributed to the entire area of the oil jacket 330. A heating block 331 is coupled to the oil jacket 330. The heating block 331 is heated by electricity to heat the oil contained in the oil jacket 330. The oil jacket 330 can prevent the heat of the tubular reaction vessel 320 of the present invention from escaping to the outside. At this time, the temperature of the heating block 331 can be adjusted to 200 to 300 ° C, and the temperature of the oil jacket 330 is raised to 150 to 250 ° C by the heat transmitted by the heating block 331, And may be transferred to the tubular reaction vessel 320. At this time, the temperature of the inside of the tubular reaction vessel 320 may be 120 to 180 ° C.

In this case, the internal pressure of the tubular reaction tank 320 may be 0.1 to 7 bar. For example, when the temperature of the tubular reaction tank 320 is 145 ° C, Lt; / RTI > That is, the tubular reaction tank 320 can control the pressure by controlling the temperature without additionally providing a pressure regulating device.

This is because when the biomass raw material and the liquid alkaline solvent undergo hydrolysis under high temperature and high pressure, the reactant is swollen to weaken the binding force of each component of the reactant. That is, the binding force of lignin, cellulose, and hemicellulose, which are components of the biomass, weakens, so that the binding force of components of the biomass can be further weakened.

The reactant discharged from the tubular reactor 320 enters the recovery vessel, and the introduced reactants are stirred until a certain amount of the reactant is collected. Specifically, the recovery unit 400 of the present invention includes a second motor 420 installed at an upper portion of the upper cover 410 to provide a rotational force; A second rotation shaft 430 connected to the second motor 420; A second stirring vane 440 coupled to the lower end of the second rotation shaft 430 and rotating about the second rotation shaft 430 to mix the reactants; , The collected reaction product can be stirred. The upper cover 410 may be connected to a nitrogen storage tank for increasing the pressure inside the collecting part 400. The collecting part 400 may include at least two discharge valves 450 . More specifically, a space can be formed between the two valves to allow the reactants to remain therein, so that the reactants can be discharged while maintaining a certain amount of pressure through the two discharge valves (45).

In addition, the biomass pretreatment system 10 of the present invention further includes a control unit to control the motor speed of the mixed reaction tank 310 of the present invention, the temperature control of the tubular reaction tank 320, and the valve control of the recovery unit 400 It can be possible.

Hereinafter, in order to facilitate understanding of the present invention, experimental examples will be described in detail. It should be understood, however, that the following examples are illustrative only and are not intended to limit the scope of the present invention. Experimental examples of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

< Experimental Example >

Experimental Example  One. Biomass  Pretreatment of aquatic plants using a continuous pretreatment system

In order to pre - treat the biomass, we used the 'Giant Weed No. 1' harvested from the second year packaging. The water content of the larvae 1 was packaged at 5 to 10%, dried and ground to 3 mm with a forage cutter. Distilled water was added so that the moisture content was 23%, and the mixture was well stirred and stored at room temperature.

The pulverized crude oil was placed in the raw material supply unit 200 and the stirrer provided in the hopper 210 of the raw material supply unit 200 was mixed with the sample at a rate of 6 Hz and discharged through the valve 220 to the transfer unit 100.

At this time, the frequency of the vibration supply device provided in the raw material supply part 200 was adjusted so that the raw material was discharged to the transfer part 100 at a constant rate of 15 g / minute. Particularly, the raw material is finely pulverized by the first transfer device 110 and the second transfer device provided in the transfer part 100, and after the raw material is pulverized, the raw material is transferred to the first transfer device 110 so as to withstand reverse pressure of 3 bar or less to keep the raw material from flowing back into the mixing tank 310 during operation.

At the same time, the mixed reaction tank was supplied with a sodium hydroxide (NaOH) solvent at a rate of 120 ml / min from a solvent supply portion, passed through a heater heated at 80 ° C and supplied to a mixing tank 310, and then mixed with a raw material in a blender by an agitator. In particular, the caustic soda was supplied so that the ratio of the raw material to the solvent was 1: 8.

The mixed reaction product in the mixing reaction tank 310 was passed through the tubular reaction tank 320. More specifically, the hydrolysis reaction occurred while passing the raw material through the tubular reactor 320 for about 8 minutes under the conditions of 100 to 180 DEG C and 0.1 to 7 bar.

The reactants having passed through the tubular reaction tank 320 were transferred to the recovery unit 400. The reactants were mixed with the stirrer provided in the recovery unit 400 and the automatic operation of the two valves installed at the lower end of the recovery tank at intervals of about 30 minutes Lt; / RTI &gt;

The final pretreated reaction product was washed with water until neutral, and the recovered solid was used for saccharification and fermentation.

Experimental Example  2. Biomass  Analysis of ingredients before and after continuous pretreatment

The component content of the biomass continuous pretreatment was determined based on the NREL (National Renewable Energy Laboratory) standard analysis method. The contents of cellulose, hemicellulose and lignin were 40.5%, 23.8% and 24.1%, respectively (Table 1).

Composition cellulose(%) Hemicellulose (%) Lignin (%) Before pretreatment 40.5 23.8 24.1

The raw material was treated according to the concentration of caustic soda (NaOH) by the biomass pretreatment system 10 of the present invention according to O.5M, 1.0M, 1.5M, and the cellulosic content of the recovered solids was 62.6% , 69.4% and 78.6%, respectively, and lignin was 8.2%, 7.7% and 8.1%, respectively (Table 2)

By concentration Cellulose content (%) Lignin (%) 0.5 M NaOH 62.6 8.2 1.0 M NaOH 69.4 7.7 1.5M NaOH 73.8 8.1

The water content of the recovered solid after pretreatment was about 70%, and the recovery rate relative to the raw material was about 40%. As a result, the content of lignin before and after pretreatment decreased from 24.1% to 3.2%. More specifically, the subsequent saccharification enzyme reaction is affected by lignin. Therefore, it is necessary to remove as much as possible by pretreatment with continuous pretreatment. As a result of the pretreatment, lignin is reduced to 86.7% of the raw material, .

Therefore, it was confirmed that the pretreatment process of the biomass using the biomass continuous pretreatment system of the present invention is suitable for the process for producing bio-energy.

Experimental Example  3. Biomass Pretreatment Rate  black

FIG. 3 is a graph showing the glycation rate of a sample pretreated with the herbicide through the continuous pretreatment system of the present invention. FIG. More specifically, the glycation rate of the untreated raw sample was 8.1%, and the glycation rate of the pretreated product treated with 0.5M to 1.5M sodium hydroxide (NaOH) was as high as 91.8%. As a result of pretreatment experiment with concentration of caustic soda (NaOH) As a result, it was confirmed that the apparatus developed through the present invention not only can be continuously treated as a pre-treatment but also has excellent pretreatment efficiency even under a low concentration of caustic soda solvent. In particular, in terms of the concentration of glycosylation enzymes, which accounts for a large portion of the cost of commercial ethanol production, it was found that 91.8% glycosylation was obtained using a low concentration of enzyme 10FPU. In addition, It is confirmed that the continuous pretreatment is possible.

10: Biomass pretreatment system
100:
110: first transfer device 111: threaded
112: Disconnecting portion 130:
200:
210: hopper 220: valve
300: reaction part
310: mixing tank 311: first motor
312: first rotating shaft 313: first stirring blade
320: tubular reaction tank 321: third feed device
330: Oil jacket 331: Heating block
400:
410: upper cover 420: second motor
430: second rotating shaft 440: second stirring blade
450: discharge valve

Claims (11)

A conveyance portion having a first hollow portion formed therein as a conveyance passage for the raw material;
A raw material supply unit disposed at one side of the transfer unit and supplied with the raw material;
A first conveying device disposed in the first hollow portion and having a screw shape to provide a conveying driving force of the raw material by shaft rotation;
A discharge port disposed on the other side of the transfer section for discharging the raw material; And
A reaction unit connected to the discharge port to inject the extruded biomass raw material and a solvent to perform a reaction; / RTI &gt;
Wherein the first transfer device includes a screw thread and at least one of the threaded portions on the other side of the first transfer device is formed with at least one cut-off portion to withstand the back pressure from the reaction portion,
And one side of the first hollow portion is disposed in parallel with the first transfer device in a screw-shaped second transfer device in a length range of 20 to 40% of the entire length of the first transfer device to crush and extrude the raw material A biomass pretreatment system characterized by. The method according to claim 1,
The raw material supply portion
A hopper into which the raw material is injected;
A valve connected to the lower end of the hopper on one side and a feed valve connected to the feeder on the other side for delivering the feed to the feeder; And
A vibration supply device installed in the hopper for applying vibration; Biomass pretreatment system. delete The method according to claim 1,
The biomass pretreatment system
A recovery unit connected to the other side of the reaction unit to recover the reactants generated in the reaction unit; Further comprising a biomass pretreatment system. 5. The method of claim 4,
The reaction part
A mixing tank in which a solvent supply device is connected and mixing the extruded raw material and the solvent to produce a mixture; And
And a tubular reaction tank connected to the mixing tank and including heating means for applying heat to the mixture. 6. The method of claim 5,
The mixing tank
A first motor installed at an upper portion of the upper cover to provide a rotational force;
A first rotating shaft connected to the motor;
A first stirring blade coupled to a lower end of the rotating shaft and rotated about the rotating shaft to mix the raw material and the solvent; Biomass pretreatment system. 6. The method of claim 5,
The tubular reactor
Wherein a second hollow portion is formed in the second hollow portion, and the second hollow portion includes a screw-shaped third transfer device for providing a transfer drive force of the mixture by shaft rotation. 6. The method of claim 5,
The heating means
An oil jacket for enclosing the outer surface of the tubular reaction tank so as to be heat-treated;
A heating block connected to the oil jacket to apply heat to the oil jacket; Wherein the biomass pretreatment system comprises a biomass pretreatment system. 5. The method of claim 4,
The collecting unit
A top cover to which a nitrogen storage tank for pressurizing the pressure inside the recovery unit is connected;
A second motor installed on the upper cover to provide a rotational force;
A second rotation shaft connected to the second motor;
A second stirring blade coupled to a lower end of the second rotation shaft and rotating about the second rotation axis to mix reactants; And
At least two discharge valves at the lower end of the recovery part; Biomass pretreatment system. The method according to claim 1,
Wherein the solvent is an alkaline solvent. A pretreatment method for biomass by pretreatment of biomass using the biomass pretreatment system according to any one of claims 1, 2 and 4 to 10.

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