KR20210108132A - Method of converting biomass-degraded oil - Google Patents

Abstract

Disclosed is a method for converting biomass-degraded oil. The method reduces the acid value of the biomass-degraded oil by removing acid contained in the biomass-degraded oil or converting the acid into a useful substance by sequentially performing a first hydrogenation reaction, an esterification reaction and a second hydrogenation reaction of the biomass-degraded oil.

Description

METHOD OF CONVERTING BIOMASS-DEGRADED OIL

Disclosed herein is a method for converting biomass cracking oil.

Global warming and depletion of fossil fuels are major issues of social and technological attention, which must be addressed quickly to reduce greenhouse gas production while meeting energy demand. Among the continuously available resources for producing energy and chemicals that support the global economy, biomass resources are promising resources that can simultaneously produce energy and chemicals, similar to petroleum.

Biodiesel produced from lipid-based raw materials and bioethanol produced from sugars are mass-produced and used as petroleum alternative fuels, and research on non-edible biomass raw materials is being actively conducted to avoid conflicts with food supply. In particular, lignocellulosic biomass (lignocellulose), such as wood and grass, is a non-edible biomass resource that can be used as a raw material for sugar and other carbon-rich chemical products.

In the case of using lignocellulosic biomass to produce sugar-based bioalcohol, the main goal was to develop biofuel through saccharification of cellulose. We encountered a technical limitation in not being able to use the ingredients.

Biomass decomposition oil or pyrolysis oil obtained through thermochemical decomposition of biomass has an advantage in that all biomass components can be utilized regardless of their chemical characteristics. Biomass cracked oil is a mixture composed of complex compounds and can be used as a petroleum-like fuel as a carbon source, but organic acids such as acetic acid present in a high proportion among the components increase the acid value of biomass cracked oil, destabilizing the oil and poor storage properties. do. In addition, there is a problem in that it is difficult to completely replace petroleum resources by corroding the device when applying the engine.

Removal or conversion of these organic acids in the conversion technology of biomass cracked oil is an important technical task, and various conversion methods have been proposed. For example, the organic acid is directly neutralized using a base, the organic acid is removed through hydrogenation, or the organic acid is extracted and purified using an extraction solvent. Although various technologies have been proposed as described above, technologies such as conversion, utilization, and refining of organic acids contained in biomass decomposed oil are still being developed from various viewpoints.

KR 10-2019-0006385 A

In one aspect, the present disclosure aims to provide a biomass cracking oil conversion method comprising a cascade reaction.

In one aspect, the present disclosure provides a first hydrogenation reaction for hydrotreating a biomass cracked oil; an esterification reaction of esterifying the first hydrogenation product; And it provides a biomass cracking oil conversion method comprising a second hydrogenation reaction of hydrotreating the esterification reaction product.

In an exemplary embodiment, the method may be to reduce the total acid number of biomass decomposed oil.

In an exemplary embodiment, the biomass cracked oil, which is a reactant of the first hydrogenation reaction, may have an organic acid concentration of 10% by weight or more.

In an exemplary embodiment, the first hydrogenation reaction may be carried out at 50 to 200 °C.

In an exemplary embodiment, the first hydrogenation reaction may be carried out under a hydrogen pressure of 1 bar or more.

In an exemplary embodiment, the esterification reaction may be condensation of an alcohol and a carboxylic acid.

In an exemplary embodiment, the esterification reaction may be carried out in the presence of an acid catalyst or in the absence of a catalyst.

In an exemplary embodiment, the esterification reaction may be performed by further mixing the second hydrogenation product with the first hydrogenation product.

In an exemplary embodiment, the esterification reaction may be carried out at 50 to 200 °C.

In an exemplary embodiment, the esterification reaction may be carried out at atmospheric pressure.

In an exemplary embodiment, the second hydrogenation reaction may be carried out at 100 to 400 °C.

In an exemplary embodiment, the second hydrogenation reaction may be carried out under a hydrogen pressure of 1 to 100 bar.

In an exemplary embodiment, the second hydrogenation product may include alcohol in an amount of 20% by weight or more based on the total weight of the product.

In one aspect, the technology disclosed in the present disclosure has the effect of providing a biomass cracking oil conversion method. The method reduces the acid value of the biomass cracked oil by sequentially performing a first hydrogenation reaction, an esterification reaction, and a second hydrogenation reaction of the biomass cracked oil to remove or convert the acid contained in the biomass cracked oil into useful substances It has the effect of making

1 shows a flowchart of a biomass cracking oil conversion method according to an embodiment. Hydrogenation refers to a first hydrogenation reaction, and hydrocracking refers to a second hydrogenation reaction.
2 and 3 show GC/MS results of products of each step of the biomass cracking oil conversion method according to an embodiment. The hydrogenation product means the first hydrogenation reaction product, and the hydrocracking product means the second hydrogenation reaction product.

Hereinafter, the present disclosure will be described in detail.

In one aspect, the present disclosure provides a first hydrogenation reaction for hydrotreating a biomass cracked oil; an esterification reaction of esterifying the first hydrogenation product; And it provides a biomass cracking oil conversion method comprising a second hydrogenation reaction of hydrotreating the esterification reaction product.

The present disclosure provides an acid value of biomass cracked oil by continuously performing a first hydrogenation reaction, an esterification reaction, and a second hydrogenation reaction of the biomass cracked oil to remove or convert the acid contained in the biomass cracked oil into useful substances. provide a way to reduce it.

The present disclosure has the effect of reducing the total acid value and stabilizing the biomass cracked oil by converting carboxylic acids and other organic-derived acids included in the biomass cracked oil into alcohol.

In an exemplary embodiment, the biomass may be a plant including wood, herbs, or seaweed. The biomass is meant to include processing materials and wastes thereof using the plant.

In an exemplary embodiment, the biomass is lignocellulosic biomass (lignocellulose), cellulose (cellulose), hemicellulose (hemicellulose), lignin (lignin), vegetable oil (lipid), seaweed (macroalgae), microalgae (microalgae) And it may be one or more selected from the group consisting of carbohydrates.

In an exemplary embodiment, the carbohydrate may be a saccharide compound.

In the present disclosure, "biomass decomposition oil" means a liquid product obtained by decomposition of biomass.

In an exemplary embodiment, the biomass decomposition oil is a material obtained by thermally decomposing a biomass raw material at a temperature of 300 ° C. or higher by a method such as pyrolysis, hydrothermal liquefaction, solvothermal liquefaction, etc. it could be Through this thermal decomposition, sugars and sugar-derived low-molecular compounds, aromatic compounds, phenol-based compounds, fats and oils, and fats and oils-derived compounds, and oligomers or high molecular weight compounds obtained by polymerization of these low-molecular compounds can be obtained.

In an exemplary embodiment, the biomass cracked oil may be biomass pyrolysis oil.

In an exemplary embodiment, the method may be to reduce the total acid number of biomass decomposed oil.

In an exemplary embodiment, the method may be to reduce the carboxylic acid number of biomass decomposed oil.

The first hydrogenation reaction is a hydrogenation reaction in which hydrogen is added to a compound, and in one aspect, may refer to a reaction in which hydrogen is added to a carbonyl compound to reduce it to an alcohol.

In an exemplary embodiment, the biomass cracked oil, which is a reactant of the first hydrogenation reaction, may have an organic acid concentration of 10% by weight or more.

In an exemplary embodiment, the first hydrogenation reaction may be performed by mixing biomass cracking oil, hydrogen, and a catalyst for the first hydrogenation reaction.

In an exemplary embodiment, the catalyst for the first hydrogenation reaction may use a catalyst generally used for a hydrogenation reaction in the art, for example, the catalyst for the first hydrogenation reaction is a metal catalyst it could be

In an exemplary embodiment, the catalyst for the first hydrogenation reaction may include one or more of a transition metal and a noble metal.

In an exemplary embodiment, the catalyst for the first hydrogenation reaction may include one or more metals selected from the group consisting of Mo, Ni, Co, Cu, Pt, Pd, Ru, Rh and Ir.

In an exemplary embodiment, the metal catalyst may be a supported metal catalyst in which a metal is supported on a support.

In an exemplary embodiment, the carrier may be at least one selected from the group consisting of carbon, silica, alumina, silica-alumina, magnesium oxide, zeolite, zirconia and titania.

In an exemplary embodiment, the metal may include at least one of a transition metal and a noble metal.

In an exemplary embodiment, the metal may include one or more metals selected from the group consisting of Mo, Ni, Co, Cu, Pt, Pd, Ru, Rh, and Ir.

In an exemplary embodiment, the first hydrogenation reaction may be carried out at 50 to 200 °C. Accordingly, it is possible to prevent the hydrogenation reaction from occurring because the reaction temperature is too low, or from the reaction such as hydrodeoxygenation or carbonization in addition to the desired hydrogenation reaction because the reaction temperature is too high.

In an exemplary embodiment, the first hydrogenation reaction may be carried out at atmospheric pressure. The first hydrogenation reaction may sufficiently occur even at atmospheric pressure.

In an exemplary embodiment, the first hydrogenation reaction may be carried out under a hydrogen pressure of 1 bar or more. The hydrogen pressure was measured at room temperature. If the hydrogen pressure is less than 1 bar, the hydrogenation reaction may occur at a very slow rate, which may reduce efficiency and may make it difficult to obtain a desired product.

In an exemplary embodiment, the first hydrogenation reaction may be carried out under a hydrogen pressure of 1 to 100 bar. In another exemplary embodiment, the first hydrogenation reaction is 1 bar or more, 10 bar or more, 20 bar or more, 30 bar or more, 40 bar or more, or 50 bar or more, and 100 bar or less, 90 bar or less, 80 bar or less. , 70 bar or less, 60 bar or less, or 50 bar or less may be carried out under a hydrogen pressure.

The esterification reaction means that an alcohol and an organic acid react to lose water and condensate to produce an ester compound.

In an exemplary embodiment, the esterification reaction may be condensation of an alcohol and a carboxylic acid.

In an exemplary embodiment, the alcohol participating in the esterification reaction may be one or more of ethanol, diol, phenol, benzyl alcohol, and other hydrocarbon compounds including alcohol groups.

In an exemplary embodiment, the carboxylic acid participating in the esterification reaction may be at least one of acetic acid, propionic acid, butyric acid, and other hydrocarbon compounds containing a carboxyl group.

In an exemplary embodiment, the esterification reaction may be carried out in the presence of an acid catalyst.

In an exemplary embodiment, the acid catalyst may be a solid acid. The solid acid is a substance whose surface is acidic in a solid state, that is, a property of giving a hydrogen ion or a property of accepting an electron pair. For example, the solid acid may be a metal oxide or a zeolite.

In an exemplary embodiment, the metal oxide may be at least one selected from the group consisting of silica, alumina, silica-alumina, magnesium oxide, zirconia, and titania.

In an exemplary embodiment, the zeolite may be one or more selected from the group consisting of H-Y, H-ZSM-5, and H-β as a zeolite ion-exchanged with hydrogen.

In an exemplary embodiment, the acid catalyst may be at least one selected from the group consisting of Amberlyst-15, Nafion, and zeolite.

In an exemplary embodiment, the esterification reaction may be carried out without using a catalyst.

In an exemplary embodiment, the esterification reaction may be performed by further mixing the second hydrogenation product with the first hydrogenation product.

In an exemplary embodiment, the esterification reaction may be carried out at 50 to 200 °C.

In an exemplary embodiment, the esterification reaction may be carried out at atmospheric pressure.

In the biomass decomposition oil conversion method according to the present disclosure, if the first hydrogenation reaction and the second hydrogenation reaction are performed without the esterification reaction, alcohol is not generated and the second hydrogenation reaction cannot be smoothly performed.

The second hydrogenation reaction refers to a hydrogenolysis reaction, and in one aspect, an alcohol compound may be produced by decomposing an ester compound through a decomposition reaction of a compound by hydrogenation treatment.

In an exemplary embodiment, the second hydrogenation reaction may be performed by mixing an esterification product, hydrogen, and a catalyst for the second hydrogenation reaction.

In an exemplary embodiment, the catalyst for the second hydrogenation reaction may be a metal catalyst.

In an exemplary embodiment, the catalyst for the second hydrogenation reaction may include one or more of a transition metal and a noble metal.

In an exemplary embodiment, the catalyst for the second hydrogenation reaction may include one or more metals selected from the group consisting of Mo, Ni, Co, Cu, Pt, Pd, Ru, Rh and Ir.

In an exemplary embodiment, the catalyst for the second hydrogenation reaction may preferably include Cu in terms of catalytic reaction efficiency.

In an exemplary embodiment, the metal catalyst may be a supported metal catalyst in which a metal is supported on a support.

In an exemplary embodiment, the carrier may be at least one selected from the group consisting of carbon, silica, alumina, silica-alumina, magnesium oxide, zeolite, zirconia and titania.

In an exemplary embodiment, the metal may include at least one of a transition metal and a noble metal.

In an exemplary embodiment, the metal may include one or more metals selected from the group consisting of Mo, Ni, Co, Cu, Pt, Pd, Ru, Rh, and Ir.

In an exemplary embodiment, the second hydrogenation reaction may be carried out at 100 to 400 °C. Accordingly, it is possible to prevent the occurrence of side reactions such as additional carbonization in addition to the desired hydrogenation reaction because the reaction temperature is too low and the hydrogenation reaction does not occur or the burn temperature is too high.

In an exemplary embodiment, the second hydrogenation reaction may be carried out under a hydrogen pressure of 1 bar or more. The hydrogen pressure was measured at room temperature. If the hydrogen pressure is less than 1 bar, the hydrogenation reaction may occur at a very slow rate, which may reduce efficiency and may make it difficult to obtain a desired product. On the other hand, when the hydrogen pressure is too high, exceeding 100 bar, the hydrodeoxygenation reaction becomes strong and it may be difficult to obtain an alcohol product.

In an exemplary embodiment, the second hydrogenation reaction may be preferably carried out under a hydrogen pressure of 1 to 100 bar. In another exemplary embodiment, the second hydrogenation reaction is 1 bar or more, 10 bar or more, 20 bar or more, 30 bar or more, 40 bar or more, or 50 bar or more, and 100 bar or less, 90 bar or less, 80 bar or less. , 70 bar or less, 60 bar or less, or 50 bar or less may be carried out under a hydrogen pressure.

In an exemplary embodiment, the second hydrogenation reaction may be carried out under the same hydrogen pressure as the first hydrogenation reaction or lower than the first hydrogenation reaction. In this case, the first hydrogenation reaction may be carried out under a hydrogen pressure of 50 to 100 bar.

In an exemplary embodiment, the second hydrogenation product may not include acetic acid.

In an exemplary embodiment, the second hydrogenation product may include alcohol.

In an exemplary embodiment, the alcohol content included in the second hydrogenation product may vary depending on the concentration of the organic acid of the biomass cracking oil, which is the first raw material, but, for example, the second hydrogenation product is the total weight of the product. Based on 20% by weight or more, or 20 to 50% by weight of alcohol may be included.

In an exemplary embodiment, the alcohol may include ethanol and cyclohexanol.

In an exemplary embodiment, esters, carboxylic acids, etc. may hardly exist after the second hydrogenation reaction.

In an exemplary embodiment, the second hydrogenation product may not contain an organic acid or the concentration of the organic acid may be 1 wt% or less.

In an exemplary embodiment, the second hydrogenation product may be utilized by adding a large amount of ethanol and cyclohexanol to the esterification reaction.

Hereinafter, the present disclosure will be described in more detail through examples. These examples are only for illustrating the present disclosure, and it will be apparent to those of ordinary skill in the art that the scope of the present disclosure is not to be construed as being limited by these examples.

Test Example 1. First hydrogenation reaction

The first hydrogenation reaction of biomass cracked oil was performed using a _{Ni/TiO 2 catalyst.} A cylinder-type stationary reactor was used, and 18.8 g of Ni/TiO ₂ catalyst was installed in the reactor. The pyrolysis oil obtained through pyrolysis of biomass was introduced into a continuous flow stationary reactor at a flow rate of 10 g/h to perform a reaction. Hydrogen gas used for the reaction was introduced at 0.6 L/h, and the inside of the reactor was maintained at 100 bar. During the reaction, the reaction temperature was maintained at 150 °C. After the reaction, the product was collected in a liquid state and analyzed by GC/MS and GC-FID.

Test Example 2. Esterification Reaction

The esterification reaction was performed in a batch reactor using the product produced through the first hydrogenation reaction of biomass cracked oil in Test Example 1 as a reactant. 50 g of the product of Test Example 1 was put into a reactor, and 5 g of Amberlyst-15 was mixed as a solid acid catalyst. The reaction temperature was fixed at 120 °C, and the reaction was carried out for 1 hour while the reaction pressure was maintained at normal pressure. After the reaction, the product was analyzed by GC/MS and GC-FID.

test example 3. Second hydrogenation reaction

A second hydrogenation reaction was performed in a continuous reaction using a fixed bed reactor using the product that had undergone the esterification reaction in Test Example 2 as a reactant. 18 g of Cu/Zn/Al ₂ O ₃ catalyst was added into the reactor. In addition, the product of Test Example 2 was introduced into the reactor at a flow rate of 6 g/h. Hydrogen gas was introduced at a flow rate of 0.6 L/h. The reaction temperature was fixed at 250 °C, and the reaction pressure was maintained at 50 bar. After the reaction, the product was analyzed by GC/MS and GC-FID.

Table 1 below shows the results of measuring the yield, carboxylic acid number (CAN), and total acid value (TAN) of the products of each step of the first hydrogenation, esterification, and second hydrogenation reactions.

characteristic reactants and products for each step Biomass Pyrolysis Oil Step 1: First hydrogenation Step 2: Esterification Step 3: Second Hydrogenation Step yield (wt%) - 90 75 59 CAN (mg KOH/g oil) 400 350 360 10 TAN (mg KOH/g oil) 590 400 430 15

Table 2 below shows the results of elemental analysis of the products of the first hydrogenation, esterification, and second hydrogenation reactions.

characteristic Composition (wt%) Biomass Pyrolysis Oil Step 1: First hydrogenation Step 2: Esterification Step 3: Second Hydrogenation C 59.25 61.2 60.04 66.95 H 7.52 7.9 7.76 15.09 O 31.88 29.73 30.47 15.31 H/C (atom/atom) 1.52 1.55 1.55 2.7 O/C (atom/atom) 0.4 0.36 0.38 0.17

Table 3 below shows the results of analysis of compounds and compositions of products of each step of the first hydrogenation, esterification, and second hydrogenation reactions.

product Composition (wt%) Biomass Pyrolysis Oil Step 1: First hydrogenation Step 2: Esterification Step 3: Second Hydrogenation Ethanol 0 0.3 0 18.8 Acetone 1.4 0.4 0.3 0 Acetic acid 35.7 32.6 31.8 0 Furfural 1.4 0 0 0 Cyclohexanol 0 0.3 0.1 4.4 Phenol 2.8 2.7 2.9 0.5 Cyclohexyl acetate 0 0.2 0.2 0 water ¹ 15.8 15.3 12.8 40.6

¹ Moisture determination by Karl-Fischer method.

As shown in Table 1 above, it can be seen that the total acid value decreased from 590 mg KOH/g oil to 15 mg KOH/g oil, and the carboxylic acid value decreased from 400 mg KOH/g oil to 10 mg KOH/g oil. there was. As described above, through the first hydrogenation, esterification and second hydrogenation of the biomass cracked oil, acid compounds such as acetic acid were removed and the total acid value and the carboxylic acid value were rapidly reduced, thereby significantly reducing the acid value of the biomass cracked oil. Confirmed. On the other hand, it was confirmed that alcohol was not produced when the first hydrogenation reaction and the second hydrogenation reaction were performed without the esterification reaction.

Above, specific parts of the present disclosure have been described in detail, for those of ordinary skill in the art, these specific techniques are only preferred embodiments, and it is clear that the scope of the present disclosure is not limited thereby. something to do. Accordingly, it is intended that the substantial scope of the present disclosure be defined by the appended claims and their equivalents.

Claims (13)

a first hydrogenation reaction for hydrotreating the biomass cracked oil;
an esterification reaction of esterifying the first hydrogenation product; and
A biomass cracking oil conversion method comprising a second hydrogenation reaction of hydrotreating the esterification reaction product.
The method of claim 1,
The method is to reduce the total acid number (total acid number) of the biomass cracked oil conversion method for biomass cracked oil.
The method of claim 1,
The biomass cracked oil, which is a reactant of the first hydrogenation reaction, has an organic acid concentration of 10% by weight or more, biomass cracking oil conversion method.
The method of claim 1,
The first hydrogenation reaction is carried out at 50 to 200 ℃, biomass cracking oil conversion method.
The method of claim 1,
The first hydrogenation reaction is carried out under a hydrogen pressure of 1 bar or more, biomass cracking oil conversion method.
The method of claim 1,
The esterification reaction is to condense alcohol and carboxylic acid, biomass decomposition oil conversion method.
The method of claim 1,
The esterification reaction is carried out in the presence of an acid catalyst or in the absence of a catalyst, biomass cracking oil conversion method.
The method of claim 1,
Wherein the esterification reaction is carried out by further mixing the second hydrogenation reaction product with the first hydrogenation reaction product, biomass cracking oil conversion method.
The method of claim 1,
The esterification reaction is to be carried out at 50 to 200 ℃, biomass decomposition oil conversion method.
The method of claim 1,
The esterification reaction is carried out at atmospheric pressure, biomass decomposition oil conversion method.
The method of claim 1,
The second hydrogenation reaction is to be carried out at 100 to 400 ℃, biomass cracking oil conversion method.
The method of claim 1,
The second hydrogenation reaction is carried out under a hydrogen pressure of 1 to 100 bar, biomass cracking oil conversion method.
The method of claim 1,
Wherein the second hydrogenation reaction product comprises alcohol in an amount of 20% by weight or more, based on the total weight of the product, biomass cracking oil conversion method.

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