KR101754465B1 - Bio-oil from macroalgae and method for producing thereof - Google Patents

Abstract

The present invention relates to a bio-oil derived from a large algae and a process for producing the bio-oil, comprising: a drying step of drying a macro alga; A bio-oil production step of producing a bio-oil by using the dried macro-algae in supercritical alcohol; And separating and recovering the product material produced after the production step.
According to the present invention, by using a supercritical alcohol as a solvent, liquefaction and deoxygenation from a large algae can provide a bio oil with high yield, high energy and economy, and a method for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a bio-oil derived from giant algae and a method for producing the bio-

The present invention relates to a bio-oil derived from giant algae and a process for producing the same.

Recent interest in the production of renewable, sustainable and environmentally friendly fuels and chemical materials based on non-fossil fuels is increasing as concerns over exhaustion of energy resources and environmental pollution due to overuse of fossil fuels increase. Unlike fossil raw materials, biomass is a renewable energy source and has attracted worldwide attention because it has carbon-nutral characteristics that re-absorb carbon dioxide generated after use.

Among biofuels, bioethanol using sugar-based raw materials and biodiesel using vegetable oils are commercially produced. However, these first-generation biofuels have a fundamental limitation in competition with food resources, The energy content is low when compared with gasoline, jet fuel and diesel starting from the existing fossil raw materials. As a result, much attention has been focused on the production of biofuels ("drop-in" biofuels), which do not compete with food resources and which contain little or no oxygen in the molecular structure.

Among various non-food biomass, macroalgae that occur in the ocean are very fast, have excellent ability to absorb and fix carbon dioxide, have high photosynthetic yield, (Bioresource Tech. 2008, 99, 6494-6504; Singh et al., Applied Energy, 2011, 88, 3548-3555), Milledge et al. Energies, 2014, 7, 7194-7222; Maceira et al., Applied Energy, 2011, 88, 3318-3323).

Conventional methods for producing liquid fuels from large algae can be divided into biological conversion methods and thermochemical conversion methods.

The biological conversion method is a method of converting organic matter present in a large algae mainly by using microorganisms or enzymes, and has a disadvantage that the reaction time is very long and the reaction yield is very low, making economical production of biofuels difficult.

The thermochemical conversion method can be divided into fast pyrolysis and hydrothermal liquefaction. The rapid pyrolysis is a method of rapidly heating the biomass to a temperature of 500-600 ° C to generate highly volatile organic material by cranking reaction of the biomass, and condensing the generated organic material to produce a bio-oil. Unlike the rapid pyrolysis of woody biomass, in the case of rapid pyrolysis of giant algae, the yield of bio-oil produced is low (15-50 wt%), there is a limit to the removal of oxygen present in large algae (O / C ratio (HHV) = 18-26 MJ / kg), it is difficult to directly produce the bio-oil, and in order to improve the bio-oil, There has been a disadvantage in that an excessive amount of hydrogen and a long reaction time are added to the graining process, and costs such as catalyst development are increased.

On the other hand, in case of hydrothermal liquefaction using water of high temperature and high pressure such as subcritical water or supercritical water, the yield of bio oil is comparable or slightly higher than that of the rapid thermal decomposition process, (O / C ratio = 0.10-0.15), and the energy content of the produced bio-oil is high (high calorific value, high heating value, HHV = 25-36 MJ / kg). However, the supercritical and asymptotic coefficients are higher than those of other solvents due to the high corrosiveness of the process equipment. In addition to the decomposition reaction of the biomass to produce the liquid material, the production of solid materials such as 촤 / tar Condensation or repolymerization reactions are simultaneously accompanied by a low yield of bio-oil, resulting in low economical efficiency of the bio-fuel production process and difficulty in securing energy efficiency of a large-scale liquefaction process.

Meanwhile, a process using an organic solvent instead of water at a high temperature and a high pressure has been proposed as a limit of the source of the biomass liquefaction process based on water at a high temperature and a high pressure. However, the yield, oxygen removal rate and energy content . Therefore, bio-oil yield is high by using renewable and sustainable giant algae as a raw material, the ability to remove oxygen contained in giant algae is high, and the energy content of bio-oil produced is high, so that an economical and efficient giant algae conversion process It is necessary to develop.

Accordingly, it is an object of the present invention to provide a bio-oil having a low oxygen content and a high energy content from a large algae at a high yield using a supercritical alcohol as a solvent.

It is another object of the present invention to provide a bio-oil production method in which bio-oil is produced from macro-algae by liquefaction and deoxygenation using supercritical alcohols.

According to an aspect of the present invention, there is provided a bio-oil production method comprising: drying a large algae; And a bio-oil production step of producing the bio-oil by using the dried macro-algae in a supercritical alcohol.

The giant algae may comprise at least one of brown algae, red algae or green algae.

The brown algae may be selected from the group consisting of Ascophyllum nodosum , Dictyota dichotoma , Fucus serratus , Laminaria digitata , Laminaria hyperborea , At least one of Saccharina japonica ( Saccharina latissima ), Stragularia clavata , Macrocystis pyrifera or Undaria pinantifida , at least one of which is at least one of Saccharina japonica ( Saccharina latissima ), Undaria pinantifida One can be included.

After the drying step, the moisture content of the macro algae may be 2 to 60 wt%.

The bio-oil production step may include a step of mixing the dried large algae with an alcohol solvent in a reactor, and then adjusting the temperature and pressure to produce a bio-oil from the supercritical alcohol.

The reactor may comprise a batch or continuous reactor.

The alcohol solvent may be at least one selected from the group consisting of methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutanol, 2-butanol, tert-butanol, n- pentanol, isopentyl alcohol, Methyl-1-pentanol, 3-methyl-1-pentanol, 2-methyl-1-pentanol, Methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3- Dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 2-ethyl 1-butanol, 1-heptanol, 2-heptanol, 3-heptanol or 4-heptanol.

In addition, the mixing ratio of the dried algae and the alcohol solvent may be in the range of the large algae: alcohol ratio of 0.1 to 60:40 to 99.9.

The reaction temperature of the alcohol solvent may be 300 to 600 ° C, and the reaction pressure may be 30 to 600 bar.

The supercritical alcohol may be methanol (critical temperature = 239 DEG C, critical pressure = 81 bar), ethanol (critical temperature = 241 DEG C, critical pressure = 63 bar), propanol (critical temperature = (critical pressure = 45 bar), isobutanol (critical temperature = 275 ° C, critical pressure = 45 bar), isopropyl alcohol (critical temperature = Butanol (critical temperature = 233 DEG C, critical pressure = 40 bar), n-pentanol (critical temperature = 307 DEG C, critical pressure = 39 DEG C), 2-butanol (critical temperature = 263 DEG C, critical pressure = 42 bar) (critical pressure = 39 bar), 2-methyl-1-butanol (critical temperature = 302 캜, critical pressure = 39 bar), neopentyl alcohol (critical temperature = 276 캜 (Critical pressure = 40 bar), diethylquinol (critical temperature = 286 占 폚, critical pressure = 39 bar), methyl propylenol (critical temperature = 287 占 폚, critical pressure = 37 bar) (Critical temperature = 337 [deg.] C, Critical pressure = 40 bar), dimethylethylquinol (critical temperature = 271 [deg.] C; critical pressure = 37 bar), 1-hexanol 34 bar), 2-hexanol (critical temperature = 310 캜, critical pressure = 33 bar), 3-hexanol (critical temperature = 309 캜, critical pressure = 34 bar) Temperature = 331 DEG C, critical pressure = 35 bar), 3-methyl-1-pentanol (critical temperature = 387 DEG C, critical pressure = 30 bar) (Critical pressure = 36 bar), 3-methyl-2-pentanol (critical temperature = 333 占 폚, critical pressure = 36 bar) 4-methyl-2-pentanol (critical temperature = 301 DEG C; (Critical pressure = 35 bar), 2-methyl-3-pentanol (critical temperature = 303 캜, critical pressure = 35 bar) (Critical pressure = 35 bar), 2,3-dimethyl-1-butanol (critical temperature = 331 캜, critical pressure = 35 bar), 2,3-dimethyl- (Critical pressure = 35 bar), 3-dimethyl-1-butanol (critical temperature = 331 캜, (Critical temperature = 307 DEG C, critical pressure = 34 bar), 1-heptanol (critical temperature = 360 DEG C, critical pressure = 31 bar), 2-heptanol (critical temperature = 335 DEG C, (Critical pressure = 30 bar) or 4-heptanol (critical temperature = 329 ° C; critical pressure = 30 bar), and the alcohol Critical temperature and critical pressure.

The yield of the bio-oil produced by the bio-oil production method of the present invention may be 60 to 90% by weight according to the following formula (2).

&Quot; (2) "

In addition, the bio-oil produced by the bio-oil production method may have an oxygen content of 5 to 20% by weight and an O / C (oxygen / carbon) ratio of 0.05 to 0.16.

The high calorific value (HHV) of the bio-oil may be 30 to 45 MJ / kg according to the following equation (4).

&Quot; (4) "

In Equation (4), C, H, N, S and O are weight ratios of carbon, hydrogen, nitrogen, sulfur and oxygen present in bio oil.

The carbon recovery rate of the bio-oil may be 50 to 200% according to Equation (6).

&Quot; (6) "

The energy efficiency of the bio-oil may be 50 to 150% according to Equation (7).

&Quot; (7) "

(Where m ₁ is the weight of the large algae, m ₂ is the weight of the alcohol, C _ps is the average specific heat of dried giant algae (1.25 kJ / kg · K), C _palc is the specific heat of the alcohol, the yield of bio-oil, OC _raw is the content of the organic matter contained in the large bird (82 wt%), OC _oil is the content of the organic material contained in the bio-oil (about 95 wt%), HHV _raw is a large bird senior heating value, HHV _oil is the high calorific value of bio-oil)

The bio-oil according to the present invention has advantages of low oxygen content and high energy content by preparing supercritical alcohol from macro algae.

In addition, bio-oils that have undergone liquefaction and deoxygenation of macro algae in supercritical alcohols can be used as fuels for conventional heavy oil power generation, and when applied in relatively mild conditions, gasoline, diesel, There are advantages that can be used as aviation oil.

In addition, there is an advantage in that the economical efficiency of the conversion process can be secured by increasing the energy efficiency of the macro algae conversion process through the production method of bio oil containing high yield and high energy.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

The present invention relates to a bio-oil from a large algae and a method for producing the same, and more particularly, to a bio-oil containing a high yield and a high energy from a large alga recovered from the ocean and a process for producing the same.

A method for producing a bio-oil derived from a giant algae according to the present invention comprises: a step (S10) of drying a giant algae; (S20) a bio-oil production step of producing a bio-oil using the supercritical alcohol in the dried large algae; And a step (S30) of separating and recovering the product material produced after the manufacturing step.

Each step of the method for producing a large-scale algae-derived bio oil according to an embodiment of the present invention will be described in detail.

First, the giant alga used in the production of the bio-oil of the present invention is an alga growing in the ocean, and any of brown algae, red algae or algae can be used without limitation. Brown algae are multi-cellular bodies and are best differentiated among algae. Examples of the brown algae include Ascophyllum nodosum , Dictyota dichotoma , Fucus serratus , Laminaria digitata , Laminaria hyperborea , Saccharina japonica ( Saccharina latissima ), Stragularia clavata , Macrocystis pyrifera , Undaria pinantifida and the like are used. The saccharine or yaffonica has a by-product content of 18% by weight, and the organic substance includes 66% by weight of carbohydrate, 10.6% by weight of protein, 1.6% by weight of lipid %.

Red algae is one of the largest flocks in the deepest algae, and is almost multicellular, except for some single-celled species. The red algae may be selected from the group consisting of Ahnfeltia plicata , Corallina officinalis , Caulacanthus ustulatus , Chondrus crispus , Palmaria palmata , and the like may be used, but the present invention is not limited thereto. There are many kinds of green algae such as unicellular, multicellular, noncellular, and chlorophyll. The green algae may be selected from the group consisting of Cladophora rupestris , Monostroma grevillei , Ulva compressa , Ulva lactuca , Ulva rigida C Agardh) may be used, but the present invention is not limited thereto.

Next, the drying step (S10) for drying the large algae of the present invention is a step of removing water present in the large algae after recovering from the ocean, and natural drying or the like may be used. The content of water present in the giant algae after drying may be 2-60% by weight. Preferably from 10 to 40% by weight, and more preferably from 15 to 30% by weight. When the moisture content is less than 2% by weight, energy required for drying is excessively consumed. When the moisture content exceeds 60% by weight, an effective liquefaction and deoxygenation reaction can not proceed.

In addition, the bio-oil production step (S20) of producing the bio-oil using the supercritical alcohol in the dried large algae may include introducing the dried large algae and the alcohol solvent into the reactor to increase the temperature and pressure, It is the step of producing the bio-oil with the alcohol of the state. The liquefaction and deoxygenation reaction in supercritical alcohols leads to a very high yield of bio-oil produced from macro-algae and an effective oxygen-elimination reaction, thereby providing excellent quantity and quality of bio-oil.

Conventional bio oil production processes using rapid pyrolysis and hydrothermal liquefaction from large alga have been problematic in that yield and oxygen removal ability are low. However, since the process using the supercritical alcohol according to the present invention is capable of stabilizing the reaction intermediate having high reactivity in the liquefaction of a large alga due to the hydrogen generated by itself without providing hydrogen from the outside, It is possible to inhibit condensation or repolymerization reactions which produce solid residues such as tar and also to reduce decarboxylation, decarbonylation and hydrodeoxygenation, Since the reaction is excellent in the ability to remove oxygen present in the large algae, the O / C (oxygen / carbon) ratio of the bio-oil produced can be lowered, and the energy content of the bio-oil can be increased. In addition, unstable anion intermediates that occur when decomposing organic substances in large algae, such as esterification, alkylation, and alkoxylation, which are unique chemical reactions of supercritical alcohols, Can be stabilized and the yield of the bio-oil can be increased.

The alcohol solvent to be introduced into the reactor in the bio-oil production step (S20) may be any alcohol for alcohol containing at least one hydroxyl group in the main chain having 1 to 10 carbon atoms, but is not limited thereto. Preferably, an alcohol having at least one hydroxyl group bonded to the main chain having 1 to 7 carbon atoms may be used, but is not limited thereto. For example, the alcohol solvent may be methanol (critical temperature = 239 DEG C, critical pressure = 81 bar), ethanol (critical temperature = 241 DEG C; critical pressure = 63 bar), propanol (critical temperature = 52 bar), isopropyl alcohol (critical temperature = 307 캜, critical pressure = 41 bar), butanol (critical temperature = 289 캜, critical pressure = 45 bar), isobutanol (Critical pressure = 42 bar), tert-butanol (critical temperature = 233 占 폚, critical pressure = 40 bar), n-pentanol (critical temperature = 307 占 폚, critical pressure = 39 bar), isopentyl alcohol (critical temperature = 306 캜, critical pressure = 39 bar), 2-methyl-1-butanol (critical temperature = 302 캜, critical pressure = 39 bar), neopentyl alcohol (Critical pressure = 40 bar), diethylquinol (critical temperature = 286 캜, critical pressure = 39 bar), methylpropylenevanol (critical temperature = 287 캜, critical pressure = 37 bar), methyl (Critical pressure = 39 bar), dimethylethyl ketone (critical temperature = 271 占 폚, critical pressure = 37 bar), 1-hexanol (critical temperature = 337 占 폚, critical pressure = 34 bar), 2-hexanol (critical temperature = 310 캜, critical pressure = 33 bar), 3-hexanol (critical temperature = 309 캜, critical pressure = 34 bar) Temperature = 331 DEG C, critical pressure = 35 bar), 3-methyl-1-pentanol (critical temperature = 387 DEG C, critical pressure = 30 bar) (Critical pressure = 36 bar), 3-methyl-2-pentanol (critical temperature = 333 占 폚, critical pressure = 36 bar) 4-methyl-2-pentanol (critical temperature = 301 DEG C; (Critical pressure = 35 bar), 2-methyl-3-pentanol (critical temperature = 303 캜, critical pressure = 35 bar) (Critical pressure = 35 bar), 2,3-dimethyl-1-butanol (critical temperature = 331 캜, critical pressure = 35 bar), 2,3-dimethyl- (Critical pressure = 35 bar), 3-dimethyl-1-butanol (critical temperature = 331 캜, (Critical temperature = 307 DEG C, critical pressure = 34 bar), 1-heptanol (critical temperature = 360 DEG C, critical pressure = 31 bar), 2-heptanol (critical temperature = 335 DEG C, A solvent composed of 3-heptanol (critical temperature = 332 ° C; critical pressure = 30 bar) or 4-heptanol (critical temperature = 329 ° C; critical pressure = 30 bar). More preferably, it may contain at least one of methanol, ethanol or butanol. The supercritical condition of the alcohol is not less than the critical temperature and the critical pressure of the alcohol.

In addition, the reactor used in the bio-oil production step (S20) of the present invention is not particularly limited to the reactor configuration, but a batch type or continuous type reactor may be used.

In the bio-oil production step (S20), the mixture ratio of the dried macro alga introduced into the reactor and the alcohol solvent may be in the range of macro algae: alcohol ratio of 0.1 to 60:40 to 99.9. That is, the concentration of the macro alga can be 0.1 to 60 wt%, preferably 1 to 40 wt%. When the concentration of the macro algae in the alcohol is less than 0.1 wt%, the concentration is too lean and the amount of the bio oil produced in a unit time is too small to be economical. When the amount of the macro algae exceeds 60 wt% There is a possibility that an effective liquefaction and deoxygenation reaction can not be carried out from the seaweed algae, and the uniformity is deteriorated and the quality is deteriorated.

In the bio-oil production step (S20), the reaction temperature of the macro algae and the alcohol may be 300 to 600 ° C. Preferably 350 to 550 ° C, and more preferably 380 to 520 ° C. When the reaction temperature is less than 300 ° C, effective liquefaction and deoxygenation do not occur, and the yield of the bio-oil may be lowered and the oxygen content may be increased. When the reaction temperature is higher than 600 ° C, cracking reaction occurs vigorously, There is a problem that the yield of the bio oil is lowered due to the possibility of gasification of the large algae and the economical efficiency of the conversion process of the bio oil of the large algae is decreased.

In addition, in the bio oil production step (S20), the reaction pressure between the macro alga and the alcohol may be 30 to 600 bar. Preferably 100 to 550 bar, and more preferably 350 to 500 bar. If the reaction pressure is less than 30 bar, the liquefaction and deoxygenation ability of the supercritical alcohol may be lowered, thereby lowering the yield of the bio-oil and increasing the oxygen content. If the reaction pressure exceeds 600 bar, There is a problem of rising.

In addition, in the bio-oil production step (S20), the reaction time of the macro alga and the alcohol is not particularly limited, but may be 30 seconds to 120 minutes. Preferably from 10 minutes to 100 minutes, and more preferably from 30 minutes to 90 minutes. If the reaction time is less than 30 seconds, the liquefaction and deoxygenation ability of the supercritical alcohol may be lowered, thereby lowering the yield of the bio oil and increasing the oxygen content. If the reaction time exceeds 120 minutes, the high temperature and high pressure should be maintained for a long time There is a problem that the process cost is increased.

Next, a step S30 of separating and recovering the product material produced after the bio-oil production step is a step of separating and recovering the product material by lowering the temperature and pressure after the oil production step. That is, the gaseous products such as carbon dioxide, carbon monoxide, methane, ethane, and ethylene are discharged through the decompression device located at the outlet of the reactor and the by-products of the deoxygenation reaction. , And solid / residue / inorganic material. At this time, the separation of gaseous products can be performed by separating gas and liquid by lowering the temperature and pressure, and the solid phase separation can be separated by solid and liquid separation using a filter, a cyclone, or the like. A mixture of bio-oils and alcohols can be separated from each other by fractional distillation.

Next, the conversion rate of the macro algae to bio-oil according to the bio-oil production method may be 60 to 90%, preferably 70 to 85%, according to the following equation (1).

[Equation 1]

The bio-oil conversion rate refers to the weight ratio between the reactants and the products (liquid and vapor) when the solid algae are converted into liquid and vapor phases.

In addition, the yield of the bio-oil produced by the above production method may be 60 to 90 wt%, preferably 70 to 85 wt%, according to the following formula (2).

&Quot; (2) "

The bio-oil yield refers to the weight ratio of the reactant to the product (liquid phase) when the solid algae convert to the liquid phase.

The yield of the solid residue produced according to the bio oil production process may be 15 to 30% by weight, preferably 20 to 25% by weight, according to the following formula (3).

&Quot; (3) "

Next, the oxygen content of the bio-oil produced according to the bio-oil production method may be 5 to 20% by weight, and preferably 8 to 15% by weight.

In addition, the O / C (oxygen / carbon) molar ratio of the bio oil may be 0.05 to 0.16, preferably 0.05 to 0.14.

The high calorific value (HHV) of the bio-oil may be 30 to 45 MJ / kg, preferably 35 to 40 MJ / kg according to the following equation (4).

&Quot; (4) "

In Equation (4), C, H, N, S and O are weight ratios of carbon, hydrogen, nitrogen, sulfur and oxygen present in the bio-oil.

In addition, the total carbon recovery rate in the gaseous, liquid, and solid products produced by the above production method may be 100 to 200%, preferably 130 to 180% according to the following equation (5) .

&Quot; (5) "

In addition, the carbon recovery rate of the bio oil produced by the above production method may be 50 to 200%, preferably 100 to 180%, according to the following equation (6).

&Quot; (6) "

In addition, the energy efficiency of the bio-oil produced by the above-described method may be 50 to 150%, preferably 90 to 130%, according to Equation (7).

&Quot; (7) "

In the above equation (7), m ₁ represents the weight of the large algae, m ₂ represents the weight of alcohol, C _ps represents the average specific heat of dried large algae (1.25 kJ / kg · K), C _palc represents the specific heat of alcohol kJ / kg · K), Y is the yield of bio-oil, OC _raw is the content of the organic matter contained in the large bird (82 wt%), OC _oil is the content of the organic material contained in the bio-oil (about 95%), HHV _raw is the high calorific value of large algae, and HHV _oil is the high calorific value of bio oil.

Hereinafter, the present invention will be described in detail with reference to the following examples and comparative examples. However, the present invention is not intended to limit the scope of protection defined by the appended claims.

Example  - hydrogenation in supercritical fluids and Deoxygenation  reaction

Example  One

Biofuels were prepared using Saccharina japonica , a large alga recovered from Jeollanamdo, Korea, and ethanol as a supercritical fluid.

The saccharin or yoponica used in the present invention has an ash content of 18% by weight and an organic substance of 66% by weight of carbohydrate, 10.6% by weight of protein and 1.6% by weight of lipid.

The giant algae were dried in a vacuum oven maintained at 70 ° C prior to the reaction. A large algae and ethanol were introduced at a concentration of 10% by weight in a batch type reactor having a volume of 140 ml, and then a bio oil was prepared at 400 캜 for 45 minutes. The reaction pressure was maintained at 400 bar. The gaseous products were collected by using a Tedlar bag, and the solid and liquid products were separated using a filter. The separation of bio-oil and alcohol in the liquid phase was evaluated by evaluating the characteristics of the bio-oil prepared by fractional distillation, and the results are shown in Tables 1 and 2.

Example  2

The bio-oil was prepared from macro algae in the same manner as in Example 1, except that supercritical methanol was used as the supercritical fluid. The bio-oil was evaluated in the same manner as in Example 1, Table 2 shows the results.

Example  3

The bio-oil was prepared from macro algae in the same manner as in Example 1 except that supercritical butanol was used as the supercritical fluid. The bio-oil was evaluated in the same manner as in Example 1, Table 2 shows the results.

Example  4

The bio-oil was prepared from macro algae in the same manner as in Example 1, except that the reaction time was 1 hour in the batch reactor. The bio-oil was evaluated in the same manner as in Example 1, Table 2 shows the results.

Example  5

The bio-oil was prepared from macro algae in the same manner as in Example 1, except that the concentration of the large algae was adjusted to 20 wt%. The bio-oil was evaluated in the same manner as in Example 1, 1 and Table 2, respectively.

Comparative Example  1 - Bio-oil production using supercritical water

A bio-oil was prepared from macro algae in the same manner as in Example 1 except that supercritical fluid was used in supercritical state at 400 ° C and 400 bar instead of supercritical ethanol. The bio-oils were evaluated in the same manner and the results are shown in Tables 1 and 2.

Comparative Example  2 - Weighing factor  Bio-oil production using

A bio-oil was prepared from macro algae in the same manner as in Comparative Example 1, except that water having a subcritical state of 300 DEG C and 100 bar was used instead of supercritical water as a thermochemical liquefying fluid. The bio-oils were evaluated in the same manner and the results are shown in Tables 1 and 2.

<Characteristic analysis of bio-oil>

In the above Examples and Comparative Examples, the conversion rates of the great algae and the final yield of bio oil were calculated from the weights of the respective components in accordance with the following equations (1) to (7).

[Equation 1]

&Quot; (2) &quot;

&Quot; (3) &quot;

&Quot; (4) &quot;

(C, H, N, S, and O in Equation (4) are the weight ratio of carbon, hydrogen, nitrogen, sulfur and oxygen present in bio oil)

&Quot; (5) &quot;

&Quot; (6) &quot;

&Quot; (7) &quot;

(Where m ₁ is the weight of the large algae, m ₂ is the weight of the alcohol, C _ps is the average specific heat of dried giant algae (1.25 kJ / kg · K), C _palc is the specific heat of the alcohol , Y is the yield of bio-oil, OC _raw is the amount of organic matter contained in the giant algae (82 wt%), OC _oil is the amount of organic matter contained in the bio-oil (about 95 wt% , HHV _raw is the high calorific value of large algae, and HHV _oil is the high calorific value of bio oil)

The conversion rates of giant algae to bio-oils and the yields of gaseous, liquid and solid materials calculated according to the above equations are shown in Table 1 below.

Supercritical
Fluid reaction
Temperature
(° C) reaction
pressure
(bar) reaction
time
(minute) Conversion Rate
(%) Bio oil yield (wt%) Solid residue yield
(wt%) Meteorological material yield
(wt%) Example 1 Supercritical
ethanol 400 400 45 77.4 78.1 22.6 11.1 Example 2 Supercritical
Methanol 400 400 45 76.2 76.2 23.8 10.7 Example 3 Supercritical
Butanol 400 400 45
74.7 70.8 25.3 9.5 Example 4 Supercritical
ethanol 400 400 60 79.0 79.6 21.0 42.8 Example 5 Supercritical
ethanol 400 400 45 77.5 78.5 22.5 12.7 Comparative Example 1 Supercritical water factor 400 400 45 91.5 47.2 8.5 1.13 Comparative Example 2 Subcounter 300 100 45 87.0 74.1 13.0 0.17

As shown in Table 1 above, supercritical ethanol, supercritical methanol, and supercritical butanol were used as supercritical fluid in Examples 1 to 3, and a reaction was performed to prepare bio oil using macro algae as a raw material , The conversion rates of giant algae were very high at 75-78% at 400 ℃ and 400 bar, respectively.

On the other hand, the yield of the solid residue was 23-25% by weight, and almost all of the organic matter contained in the giant algae was converted into vapor and liquid when the content of inorganic matter contained in the giant algae was considered to be 18% by weight. On the other hand, a major amount of vapor phase material was mainly CO2, carbon monoxide, methane, ethane, ethylene and the like. The yield of these vapor phase materials was detected as 10-11% by weight and the yield of bio oil was 70-78 weight %.

Therefore, it was found that, in Examples 1 to 3, it is very effective to convert an organic matter in which supercritical alcohols exist in a giant algae to bio-oil as a liquid substance. This is because supercritical alcohols can effectively provide hydrogen, thereby suppressing condensation or repolymerization reaction that produces solid residue, and can be used for esterification, alkylation, It is considered that alkylation, alkoxylation, etc. effectively proceeded, stabilizing the unstable intermediate which occurs upon decomposition of the organic matter present in the giant algae, and thus increasing the yield of bio-oil.

When the reaction time was increased to 60 minutes in Example 4, it was found that the conversion rate of the great algae was 79.0% and that of the solid residue was 21.0% by weight, indicating that most of the organic matter present in the great algae was converted into vapor and liquid phase . On the other hand, the yield of the vapor phase material was 42.8 wt%, and the yield of bio oil was 79.6 wt%. As compared with Example 1, it was found that the gasification reaction of bio-oil was actively progressed as the reaction time was prolonged at a high temperature because the yield of the gaseous material increased.

In addition, when the concentration of the large algae was increased to 20% by weight as in Example 5, it was found that most of the organic matter present in the large algae was converted to bio oil, similar to Example 1.

Table 2 below shows the characteristics of the bio-oil obtained through Examples and Comparative Examples of the present invention.

C
(wt%) O
(wt%) H
(wt%) N
(wt%) S
(wt%) O / C ratio HHV
(MJ / kg) Carbon recovery rate of bio-oil (%) Total carbon
Recovery rate
(%) Energy efficiency
(%) Giant algae 33.6 36.5 5 One 0.5 0.81 14.6 - - Example 1 74.5 12.0 9.8 1.7 0.3 0.12 36.6 140 156 106 Example 2 74.4 11.0 9.2 1.5 0.3 0.11 35.9 122 145 104 Example 3 75.2 13.2 10.6 1.2 0.2 0.13 37.7 141 152 99 Example 4 71.2 9.0 10.4 1.2 0.8 0.09 36.6 135 166 109 Example 5 75.5 11.2 9.5 1.2 0.2 0.11 37.0 137 150 114 Comparative Example 1 60.2 13.1 8.2 2.5 0.5 0.16  29.2 71 74 65 Comparative Example 2 45.3 28.5  7.1 1.5 0.5 0.48  19.8 80 93 80

As shown in Table 2, the bio-oil prepared in Examples 1 to 4 had an oxygen content of 9-13% by weight and an O / C molar ratio of 0.11-0.13, which was significantly lowered I could. It can be seen that the supercritical alcohol can effectively remove the oxygen contained in the giant algae due to the hydrogen generated by itself. The HHV of the bio-oil prepared in Examples 1 to 3 was 36-38 MJ / kg, which was higher than the HHV of 14.6 MJ / kg of the large algae, indicating that the energy content of the bio-oil was greatly increased . On the other hand, the bio-oil has a carbon recovery rate of 120-140% and the carbon recovery rate of the total product (gaseous, liquid and solid) is 140-170%, which means that more carbon is produced than the amount of carbon present in the giant algae . This is because the esterification, alkylation and alkoxylation, which are the unique chemical reactivity of supercritical alcohols, effectively proceed and some of the alcohols are effectively combined with the bio-oil intermediates, . On the other hand, in Examples 1 to 3, it was found that the energy efficiency of the giant algal liquefaction process was 99% or more.

Further, it was found that when the concentration of the macro algae was increased to 20 wt% in Example 5, the energy content of the produced bio oil was high, and the carbon recovery and energy efficiency were high, similarly to Example 1.

On the other hand, in Comparative Example 1, when the giant tidal liquefaction was carried out at supercritical water conditions of 400 ° C and 400 bar instead of the supercritical alcohol, the yield of the bio-oil was as low as 47.2% by weight, the O / C molar ratio was as high as 0.16, HHV was 29.2 MJ / kg, which was relatively low. In addition, it was found that the carbon recovery rate of the produced bio-oil was as low as 71%, and the energy efficiency was 65%, indicating that the deoxidation reaction of the large algae did not proceed.

Also, in Comparative Example 2, when macrophage liquefaction was carried out using an ash factor of 300 ° C and 100 bar instead of supercritical water, the yield of bio-oil was as high as 74.1% by weight, but the O / C molar ratio was very high as 0.48 , And HHV was as low as 19.8 MJ / kg. Therefore, it was found that the effective deoxygenation did not proceed when liquefying the large algae in the subcycle.

The configuration of the present invention has been proved to be superior through the above-described embodiments, but is not necessarily limited to the above configuration, and various permutations, modifications and variations are possible without departing from the technical idea of the present invention. Therefore, the above description does not limit the scope of the present invention, which is defined by the limitations of the following claims.

Claims (16)

A drying step to dry giant algae; And
Preparing a bio-oil by mixing the dried macro-algae and an alcohol solvent in a reactor, and then preparing a bio-oil using supercritical alcohols produced by controlling the reaction temperature to 400 ° C and the reaction pressure to 400 bar; Method for manufacturing bio oil. The method according to claim 1, wherein the large algae comprises at least one of brown algae, red algae or green algae. The method of claim 2, wherein the brown algae is selected from the group consisting of Ascophyllum nodosum , Dictyota dichotoma , Fucus serratus , Laminaria digitata , ( Laminaria hyperborea ), Saccharina japonica ( Saccharina latissima ), Stragularia clavata , Macrocystis pyrifera , or Undaria pinantifida ). &lt; / RTI &gt; The method for producing a bio-oil according to claim 1, wherein the moisture content of the macro algae is 2 to 60 wt% after the drying step. delete 2. The method of claim 1, wherein the reactor comprises a batch or continuous reactor. The method according to claim 1, wherein the alcohol solvent is at least one selected from the group consisting of methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutanol, 2-butanol, tert-butanol, n-pentanol, isopentyl alcohol, , Neopentyl alcohol, diethyl ketone, methyl propyl ketone, methyl isopropyl ketone, dimethyl ethyl ketone, 1-hexanol, 2-hexanol, Methyl-2-pentanol, 4-methyl-2-pentanol, 4-methyl-1-pentanol, Butanol, 2,3-dimethyl-1-butanol, 2,3-dimethyl-2-butanol and 3,3-dimethyl- -Butanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol or 4-heptanol. delete [2] The method of claim 1, wherein the mixing ratio of the dried algae to the alcohol solvent is in the range of 0.1 to 60:40 to 99.9. The method of claim 1, wherein the supercritical alcohol is selected from the group consisting of methanol (critical temperature = 239 ° C., critical pressure = 81 bar), ethanol (critical temperature = 241 ° C., critical pressure = 63 bar), propanol (Critical pressure = 45 bar), isobutanol (critical temperature = 275 DEG C, critical pressure = 52 bar), isopropyl alcohol (critical temperature = 307 DEG C; critical pressure = 41 bar) (Critical pressure = 45 bar), 2-butanol (critical temperature = 263 캜, critical pressure = 42 bar), tert-butanol (critical temperature = 233 캜, critical pressure = 40 bar), n-pentanol (Critical pressure = 39 bar), isopentyl alcohol (critical temperature = 306 캜, critical pressure = 39 bar), 2-methyl-1-butanol (Critical pressure = 40 bar), diethylquinol (critical temperature = 286 캜, critical pressure = 39 bar), methyl propyl cinnol (critical temperature = 287 캜, critical pressure = 37 bar)(Critical pressure = 397 bar), dimethylethylquinol (critical temperature = 271 캜, critical pressure = 37 bar), 1-hexanol (critical temperature = 337 캜, critical pressure = Critical pressure = 33 bar), 3-hexanol (critical temperature = 309 캜, critical pressure = 34 bar), 2-methyl-1-pentanol Critical temperature = 331 占 폚, Critical pressure = 35 bar), 3-methyl-1-pentanol (critical temperature = 387 占 폚, critical pressure = 30 bar), 4-methyl-1-pentanol (critical temperature = 330 占 폚; (Critical pressure = 30 bar), 2-methyl-2-pentanol (critical temperature = 286 캜, critical pressure = 36 bar) , 4-methyl-2-pentanol (critical temperature = 301 DEG C; (Critical pressure = 35 bar), 2-methyl-3-pentanol (critical temperature = 303 캜, critical pressure = 35 bar) (Critical pressure = 35 bar), 2,3-dimethyl-1-butanol (critical temperature = 331 캜, critical pressure = 35 bar), 2,3-dimethyl- (Critical pressure = 35 bar), 3-dimethyl-1-butanol (critical temperature = 331 캜, (Critical temperature = 307 DEG C, critical pressure = 34 bar), 1-heptanol (critical temperature = 360 DEG C, critical pressure = 31 bar), 2-heptanol (critical temperature = 335 DEG C, Wherein the alcohol comprises at least one alcohol selected from the group consisting of 3-heptanol (critical temperature = 332 DEG C, critical pressure = 30 bar) or 4-heptanol (critical temperature = 329 DEG C; critical pressure = 30 bar) And a method for producing a biofuel having a critical pressure or more. The method of claim 1, wherein the yield of the bio-oil produced by the bio-oil production method is 60 to 90% by weight according to the following formula (2).
&Quot; (2) &quot;

A bio oil produced by the method of any one of claims 1 to 4, 6, 7, and 9 to 11. 13. The bio oil according to claim 12, wherein the bio oil has an oxygen content of 5 to 20% by weight and an O / C (oxygen / carbon) molar ratio of 0.05 to 0.16. 13. The bio oil according to claim 12, wherein the high heating value (HHV) of the bio oil is 30 to 45 MJ / kg according to the following formula (4).
&Quot; (4) &quot;

(Wherein C, H, N, S, and O are the weight ratio of carbon, hydrogen, nitrogen, sulfur, and oxygen present in bio oil) 13. The bio-oil according to claim 12, wherein the bio-oil has a carbon recovery rate of 50 to 200% according to the following formula (6).
&Quot; (6) &quot;

13. The bio-oil according to claim 12, wherein the energy efficiency of the bio-oil is 50 to 150% according to the following formula (7).
&Quot; (7) &quot;

(Where m ₁ is the weight of the large algae, m ₂ is the weight of the alcohol, C _ps is the average specific heat of dried giant algae (1.25 kJ / kg · K), C _palc is the specific heat of the alcohol, the yield of bio-oil, OC _raw is the content of the organic matter contained in the large bird (82 wt%), OC _oil is the content of the organic material contained in the bio-oil (95 wt%), HHV _raw is a large bird senior heating value, HHV _oil Is the high calorific value of bio-oil)