KR102231862B1 - Catalysts for bio-oil hydrotreating - Google Patents

Abstract

In the present specification, a catalyst for a hydrogenation reaction in which ruthenium (Ru) metal and nickel (Ni) metal are supported on a metal oxide support, a method of preparing the catalyst, and a hydrogenation-treated bio with improved chemical stability with reduced oxygen content and acidity. A method of making an oil is disclosed.

Description

Catalysts for bio-oil hydrotreating {Catalysts for bio-oil hydrotreating}

In the present specification, a catalyst for a hydrogenation reaction in which ruthenium (Ru) metal and nickel (Ni) metal are supported on a metal oxide support, a method of preparing the catalyst, and a hydrogenation-treated bio with improved chemical stability with reduced oxygen content and acidity. A method of making an oil is disclosed.

Due to the global climate change resulting from the depletion and increasing use of fossil fuels, there is a significant increase in interest in the development of renewable and sustainable energy sources at present. Among them, bioenergy produced from biomass, an organic organism existing on the planet, is emerging as a new energy source that can replace existing fossil fuels in terms of being carbon-neutral and sustainable.

Among bio-energy, bio-oil produced through thermal decomposition of biomass is a liquid product, so it has the advantage of increasing the energy density of biomass and enabling transport and storage. However, because bio-oil is composed of various oxygen-containing compounds such as aldehydes, ketones, carboxylic acids, phenols, etc. derived from the main constituents of biomass, it has a high oxygen content, so it is well mixed with hydrocarbon-based fuels. And the quality and stability of the bio-oil are deteriorated.

In order to reduce the high oxygen content of the bio-oil and saturate the unsaturated compounds, the hydrogenation reaction of bio-oil using a catalyst carrying palladium (Pd), ruthenium (Ru), or platinum (Pt) as a support under a hydrogen gas atmosphere. Research has been conducted on. However, since the catalyst is severely deactivated and an expensive noble metal is used as an active material, there is a problem in that the treatment cost is high. Accordingly, there is a need to develop a new catalyst capable of reducing treatment costs while the hydrogenation reaction of bio-oil proceeds stably.

KR 10-2015-0100398 A

In one aspect, the present specification aims to provide a catalyst for hydrogenation reaction in which ruthenium (Ru) metal and nickel (Ni) metal are supported on a metal oxide support.

In another aspect, the present specification aims to provide a method of preparing the catalyst for the hydrogenation reaction.

In another aspect, an object of the present specification is to provide a method for producing a hydrogenation-treated bio-oil having improved chemical stability with reduced oxygen content and acidity by using the hydrogenation catalyst.

In one aspect, the technology disclosed herein includes a metal oxide support; And it provides a catalyst for hydrogenation reaction comprising a ruthenium (Ru) metal and nickel (Ni) metal supported on the support.

In an exemplary embodiment, the catalyst may be a catalyst for hydrogenation reaction of bio-oil.

In an exemplary embodiment, the metal oxide support may be one or more selected from the group consisting of titanium oxide, silicon oxide, and zirconium-tungsten oxide.

In an exemplary embodiment, the ruthenium metal may be included in an amount of 0.5 to 4% by weight based on the total weight of the catalyst.

In an exemplary embodiment, the nickel metal may be included in an amount of 1 to 20% by weight based on the total weight of the catalyst.

In an exemplary embodiment, the mixing weight ratio of the ruthenium metal and the nickel metal may be 1: 2 to 5.

In another aspect, the technology disclosed in the present specification is a method for preparing the catalyst for the hydrogenation reaction, including preparing a binary metal-supported metal oxide catalyst in which ruthenium (Ru) metal and nickel (Ni) metal are supported on a metal oxide support. It provides a method for producing a catalyst for hydrogenation reaction.

In an exemplary embodiment, the manufacturing method comprises: 1) heating an aqueous solution containing a metal oxide support; 2) adding and stirring a precipitant solution containing nickel (Ni) metal precursor solution and sodium carbonate (Na ₂ CO ₃ ) to the heated aqueous solution, and evaporating the solvent to obtain a precipitate; 3) drying and firing the precipitate to prepare a nickel-supported metal oxide catalyst; 4) adding a ruthenium (Ru) metal precursor solution to the nickel-supported metal oxide catalyst, stirring, and evaporating the solvent to prepare a concentrate; And 5) drying the concentrate.

In an exemplary embodiment, the firing in 3) may be performed at 500 to 900°C.

In an exemplary embodiment, the firing in 3) may be performed for 1 to 5 hours in an air atmosphere.

In another aspect, the technology disclosed in the present specification provides a method for producing a bio-oil subjected to a hydrogenation reaction, including the step of performing a hydrogenation reaction by adding bio-oil to the catalyst for the hydrogenation reaction.

In an exemplary embodiment, the manufacturing method comprises: a) reducing the catalyst for hydrogenation in a hydrogen gas atmosphere, b) performing a hydrogenation reaction by adding hydrogen gas and bio-oil to the catalyst for hydrogenation, and c) hydrogenation. It may include cooling and recovering the reaction-completed bio-oil.

In an exemplary embodiment, the hydrogenation reaction in b) may be performed at a temperature of 150 to 200°C.

In an exemplary embodiment, the hydrogenation reaction in b) may be performed at a pressure of 50 to 100 bar.

In an exemplary embodiment, the supply rate of the bio-oil in b) may be 0.2 to 1 hr ^-1 of Liquid Hourly Space Velocity (LHSV).

In one aspect, the technology disclosed in the present specification has the effect of providing a catalyst for hydrogenation reaction in which a ruthenium (Ru) metal and a nickel (Ni) metal are supported on a metal oxide support.

In another aspect, the technology disclosed in the present specification has the effect of providing a method of preparing the catalyst for the hydrogenation reaction.

In another aspect, the technology disclosed in the present specification has an effect of providing a method for producing a hydrogenation-treated bio-oil having improved chemical stability with reduced oxygen content and acidity by using the hydrogenation catalyst.

Hereinafter, the present invention will be described in detail.

The catalyst according to the present specification is an inexpensive binary metal supported catalyst capable of replacing a catalyst for hydrogenation reaction in which an expensive metal, such as palladium (Pd) metal or platinum (Pt) metal, is supported on a conventional carbon support. Supported on a metal oxide support, there is an effect of improving the catalytic activity and reproducibility of the hydrogenation reaction of the bio-oil while being inexpensive.

The catalyst for the hydrogenation reaction of bio-oil has high activity against the hydrogenation reaction, and carbon deposition and cracking reactions on the surface of the catalyst must be suppressed. Noble metals such as palladium (Pd) or platinum (Pt) have high hydrogenation activity, but are not preferable because carbon is easily deposited, promotes the cracking reaction of carbon bonds, and the cost of producing a catalyst is high.

In one aspect, the technology disclosed herein includes a metal oxide support; And it provides a catalyst for hydrogenation reaction comprising a ruthenium (Ru) metal and nickel (Ni) metal supported on the support.

In the present specification, "bio-oil" refers to a liquid having a dark brown fluidity produced by thermal decomposition of biomass, and refers to a mixture of oxygen-containing organic compounds produced by the decomposition reaction of major constituents of biomass.

In the present specification, "hydrotreating" refers to a reaction of reducing the oxygen functional group of the oxygenated organic compound contained in the bio-oil and improving the saturation of the unsaturated compound.

In an exemplary embodiment, the catalyst may be a catalyst for hydrogenation reaction of bio-oil.

In an exemplary embodiment, the catalyst may be a catalyst for hydrogenation reaction for the production of bio-oil having a reduced oxygen content.

In an exemplary embodiment, the metal oxide support may be one or more selected from the group consisting _{of titanium oxide (TiO 2} ), silicon oxide (SiO ₂ ), and zirconium-tungsten oxide (W-ZrO _{2 ).} The carbon support, which is currently most widely used, has a high specific surface area, which is advantageous for supporting active materials, but it is difficult to regenerate the catalyst due to poor stability due to long-term operation.

The support of the catalyst should disperse the active material evenly on the surface, minimize carbon deposition, and facilitate regeneration. In this respect, in an exemplary embodiment, the metal oxide support may be preferably titanium oxide as a binary metal support support of Ru and Ni.

The catalyst for the hydrogenation reaction according to the present specification is specifically designed to reduce treatment costs while stably and efficiently proceeding the hydrogenation reaction of bio-oils composed of various types of oxygen-containing compounds such as aldehydes, ketones, carboxylic acids, phenols, etc. There is an effect of providing a bio-oil with improved quality and stability by supporting binary metals of metal, ruthenium (Ru) metal, and nickel (Ni) metal.

In an exemplary embodiment, the ruthenium metal may be included in an amount of 0.5 to 4% by weight based on the total weight of the catalyst.

In another exemplary embodiment, the ruthenium metal is 0.5% by weight or more, 1% by weight or more, 1.5% by weight or more, 2% by weight or more, 2.5% by weight or more, or 3% by weight or more, based on the total weight of the catalyst, and 4 It may be less than or equal to 3.5%, less than or equal to 3%, less than or equal to 2.5%, or less than or equal to 2% by weight. Preferably, the ruthenium metal is 1 to 3% by weight based on the total weight of the catalyst may be preferred in terms of the hydrogenation reaction activity of the bio-oil, carbon deposition and cracking inhibition.

In an exemplary embodiment, the nickel metal may be included in an amount of 1 to 20% by weight based on the total weight of the catalyst.

In another exemplary embodiment, the nickel metal is 1% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more, 5% by weight or more, 6% by weight or more, 7% by weight based on the total weight of the catalyst. % Or more, 8% or more, 9% or more, or 10% or more, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14 It may be less than or equal to 13%, less than or equal to 12%, less than or equal to 11%, less than or equal to 10%, less than or equal to 9%, less than or equal to 8%, less than or equal to 7%, less than or equal to 6%, or less than or equal to 5% by weight. have. Preferably, the nickel metal may be preferably 1 to 10% by weight, 5 to 10% by weight, or 5 to 8% by weight based on the total weight of the catalyst in terms of the hydrogenation activity of the bio-oil. If the nickel metal content is too high, the active point of the ruthenium metal may be blocked and the sintering phenomenon of the nickel particles may be accelerated, resulting in a decrease in catalytic activity.

In an exemplary embodiment, the mixing weight ratio of the ruthenium metal and the nickel metal may preferably be 1: 2 to 5, 1 to 2 to 4, or 1 to 2 to 3. The catalyst for the hydrogenation reaction not only has high activity against the hydrogenation reaction, but also suppresses carbon deposition and cracking reactions on the surface of the catalyst, thereby providing excellent effects.

In another aspect, the technology disclosed in the present specification is a method for preparing the catalyst for the hydrogenation reaction, including preparing a binary metal-supported metal oxide catalyst in which ruthenium (Ru) metal and nickel (Ni) metal are supported on a metal oxide support. It provides a method for producing a catalyst for hydrogenation reaction.

In an exemplary embodiment, the manufacturing method comprises: 1) stirring and heating an aqueous solution containing a metal oxide support; 2) a precipitant solution containing nickel (Ni) metal precursor solution and sodium carbonate (Na ₂ CO ₃ ) was added to the stirred and heated aqueous solution, stirred, and the solvent was evaporated to obtain a precipitate; 3) drying and firing the precipitate to prepare a nickel-supported metal oxide catalyst; 4) adding a ruthenium (Ru) metal precursor solution to the nickel-supported metal oxide catalyst, stirring, and evaporating the solvent to prepare a concentrate; And 5) drying the concentrate.

In an exemplary embodiment, the heating in 1) may be 80 to 90°C, more specifically to 85°C.

In an exemplary embodiment, 2) may be stirred for 1 to 3 hours and then filtered and washed to obtain a precipitate.

In an exemplary embodiment, drying in 3) may be performed at 100 to 120°C, more specifically 100 to 105°C or 105 to 110°C.

In an exemplary embodiment, the firing in 3) may be performed at 500 to 900°C.

In an exemplary embodiment, the firing in 3) may be performed for 1 to 5 hours in an air atmosphere of 100 ml/min.

In an exemplary embodiment, 4) may be to obtain a concentrate by stirring for 1 to 3 hours and then concentrating under reduced pressure at 60 to 70°C.

In an exemplary embodiment, drying in 5) may be performed at 100 to 120°C, more specifically 100 to 105°C or 105 to 110°C.

In another aspect, the technology disclosed in the present specification provides a method for producing a bio-oil subjected to a hydrogenation reaction, including the step of performing a hydrogenation reaction by adding bio-oil to the catalyst for the hydrogenation reaction.

In an exemplary embodiment, the raw material for producing the bio-oil may be a by-product of a wood processing process or a forestry by-product.

In an exemplary embodiment, the manufacturing method comprises: a) reducing the hydrogenation catalyst to a temperature of, for example, about 450°C under a hydrogen gas atmosphere, and b) adding hydrogen gas and bio-oil to the hydrogenation catalyst to perform a hydrogenation reaction. And c) cooling and recovering the bio-oil for which the hydrogenation reaction has been completed.

In an exemplary embodiment, the hydrogenation reaction may be to perform the hydrogenation reaction by introducing bio-oil while flowing hydrogen gas into the reactor after adjusting the temperature and pressure of the reactor.

In an exemplary embodiment, the hydrogenation reaction may be preferably a mild hydrogenation reaction. In general, the hydrogenation reaction of bio-oil is carried out at a temperature of 300° C. and a pressure of 150 bar or more, but the method of manufacturing the method for producing a bio-oil subjected to the hydrogenation reaction according to the present specification is relatively low temperature and pressure conditions. There is an effect of providing a bio-oil with improved quality and stability by carrying out a mild hydrogenation reaction using a Ru/Ni binary metal supported catalyst.

In an exemplary embodiment, the hydrogenation reaction in b) may be performed at a temperature of 150 to 200°C. If the hydrogenation reaction temperature is too high, the cracking reaction of the bio-oil may be accelerated to reduce the yield of the product, and if the hydrogenation reaction temperature is too low, the hydrogenation reaction may not be initiated.

In an exemplary embodiment, the hydrogenation reaction in b) may be performed at a pressure of 50 to 100 bar. In the mild hydrogenation reaction, as the pressure of the hydrogen gas increases, the solubility of hydrogen in the bio-oil is improved and mass transfer between the catalyst and hydrogen is promoted. Therefore, it may be desirable to have a high hydrogenation pressure.

In an exemplary embodiment, the supply rate of the bio-oil in b) may be 0.2 to 1 hr ^-1 of Liquid Hourly Space Velocity (LHSV).

In another exemplary embodiment, in b), the bio-oil is ^{supplied at a liquid hourly space velocity (LHSV) of 0.2 to 0.5 hr -1} , thereby reducing the residence time in the reactor of the bio-oil as a reactant and is hydrogenated. It is effective in preventing problems in which the reaction may not proceed sufficiently.

The method for producing the bio-oil subjected to the hydrogenation reaction can continuously produce bio-oil with improved chemical stability.

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

Experimental example 1. Of bio oil Mild Hydrogen Preparation of catalyst for reaction

20 g of titanium oxide (TiO ₂ ) and 300 ml of distilled water were heated to 85° C. while stirring. A nickel precursor aqueous solution in which 24.77 g of nickel nitrate hexahydrate was dissolved in 100 ml of distilled water and an aqueous precipitant solution in which 9 g of sodium carbonate was dissolved in 100 ml of distilled water were slowly added dropwise to the above mixture. Stir for 2 hours. The mixture after stirring was filtered under reduced pressure to evaporate moisture. The obtained solid residue was dried at 105° C. for 12 hours, and then calcined at 600° C. (heating rate 2.5° C./min) for 2 hours in an air atmosphere of 100 ml/min. An aqueous solution obtained by dissolving 0.84 g of ruthenium chloride hydrate in 200 ml of distilled water was added to the calcined solid residue, followed by stirring for 2 hours. Thereafter, the pressure was reduced using a rotary evaporator to evaporate moisture at 60 to 70° C. and concentrated. The concentrate concentrated under reduced pressure was completely dried at 105° C. for 12 hours to prepare a catalyst for mild hydrogenation of bio-oil.

The catalyst shown in Table 1 was prepared by varying the concentration of the metal precursor as an active material and the type of metal oxide as the support according to the method for preparing the catalyst.

Experimental example 2. Bio oil Mild Hydrogen reaction

Using each of the catalysts prepared in Experimental Example 1, a mild hydrogenation reaction of bio-oil was performed. The reaction was carried out at a reaction temperature of 150° C., a reaction pressure of 100 bar, and a liquid supply rate of bio-oil (LHSV) of 0.43 hr ^-1 . The catalytic activity was compared through elemental analysis and acidity analysis of the bio-oil before and after the mild hydrogenation reaction, and the results are summarized in Table 1 below.

In the case of Comparative Example 1 and Comparative Example 2, when the mild hydrogenation reaction was performed, the oxygen content of the bio-oil was 25.97% and 32.12%, respectively, and the total acidity was 246 mg KOH/g-bio-oil and 355 mg KOH/g, respectively. -Bio-oil, but in the case of Examples 1 to 8, it was confirmed that the oxygen content was similar or significantly lower and the total acidity was low when compared with Comparative Examples 1 and 2. Particularly, in the case of Example 4, it was confirmed that the hydrogenation reaction activity was highest after the mild hydrogenation reaction with 18.08% oxygen content and 209 mg KOH/g-bio-oil total acidity.

C
(wt%) H
(wt%) O
(wt%) H/C
(atom/
atom) O/C
(atom/
atom) Total acidity
(mg KOH/
g-bio-oil Bio oil 54.39 6.26 39.36 1.38 0.54 419 Comparative Example 1 5 wt% Ru/C 65.73 8.30 25.97 1.52 0.30 246 Comparative Example 2 5 wt% Pd/C 61.14 6.73 32.12 1.32 0.39 355 Example 1 (2 wt% Ru/20 wt% Ni)/TiO ₂ 66.29 7.65 26.06 1.38 0.29 228 Example 2 (2 wt% Ru/20 wt% Ni)/SiO ₂ 66.66 7.43 25.91 1.34 0.29 239 Example 3 (2 wt% Ru/20 wt% Ni)/WZr 71.76 7.84 20.41 1.31 0.21 246 Example 4 (2 wt% Ru/5 wt% Ni)/TiO ₂ 73.19 8.73 18.08 1.43 0.19 209 Example 5 (2 wt% Ru/10 wt% Ni)/TiO ₂ 71.43 8.08 20.48 1.36 0.22 228 Example 6 (1 wt% Ru/20 wt% Ni)/TiO ₂ 68.98 7.80 23.22 1.36 0.25 210 Example 7 (1.5 wt% Ru/20 wt% Ni)/TiO ₂ 69.81 8.31 21.88 1.43 0.24 220 Example 8 (3 wt% Ru/20 wt% Ni)/TiO ₂ 74.02 7.04 18.94 1.14 0.19 260

As described above, specific parts of the present invention have been described in detail, and for those of ordinary skill in the art, these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereby. It will be obvious. Therefore, it will be said that the practical scope of the present invention is defined by the appended claims and their equivalents.

Claims (15)

As a catalyst for a hydrogenation reaction, the catalyst,
Titanium oxide support; And
Including ruthenium (Ru) metal and nickel (Ni) metal supported on the support,
The ruthenium metal is included in an amount of 2 to 3% by weight based on the total weight of the catalyst,
The nickel metal is included in 5 to 6% by weight based on the total weight of the catalyst,
The catalyst has a purpose of reducing the acidity of the bio-oil, a catalyst for the hydrogenation reaction of bio-oil.
delete delete The method of claim 1,
The ruthenium metal is contained in an amount of 2% by weight based on the total weight of the catalyst, a catalyst for the hydrogenation reaction of bio-oil.
The method of claim 1,
The nickel metal is included in an amount of 5% by weight based on the total weight of the catalyst, a catalyst for hydrogenation reaction of bio-oil.
The method of claim 1,
The ruthenium metal is included in 2% by weight based on the total weight of the catalyst,
The nickel metal is included in an amount of 5% by weight based on the total weight of the catalyst, a catalyst for hydrogenation reaction of bio-oil.
A method for producing a catalyst for hydrogenation reaction of bio-oil according to any one of claims 1, 4 to 6,
A method for producing a catalyst for hydrogenation reaction of bio-oil, comprising preparing a binary metal-supported titanium oxide catalyst in which ruthenium (Ru) metal and nickel (Ni) metal are supported on a titanium oxide support.
The method of claim 7,
The manufacturing method,
1) heating an aqueous solution containing a titanium oxide support;
2) adding and stirring a precipitant solution containing nickel (Ni) metal precursor solution and sodium carbonate (Na ₂ CO ₃ ) to the heated aqueous solution, and evaporating the solvent to obtain a precipitate;
3) drying and firing the precipitate to prepare a nickel-supported titanium oxide catalyst;
4) adding a ruthenium (Ru) metal precursor solution to the nickel-supported titanium oxide catalyst, stirring, and evaporating the solvent to prepare a concentrate; And
5) A method for producing a catalyst for hydrogenation reaction of bio-oil, comprising drying the concentrate.
The method of claim 8,
In the above 3), the sintering is carried out at 500 to 900° C., a method for producing a catalyst for hydrogenation reaction of bio-oil.
The method of claim 8,
In the above 3), the sintering is carried out for 1 to 5 hours in an air atmosphere, a method for producing a catalyst for hydrogenation reaction of bio-oil.
A method for producing a bio-oil subjected to a hydrogenation reaction, comprising the step of performing a hydrogenation reaction by adding bio-oil to the catalyst for the hydrogenation reaction of the bio-oil according to any one of claims 1, 4 to 6.
The method of claim 11,
The manufacturing method,
a) reducing the catalyst for the hydrogenation reaction of bio-oil under a hydrogen gas atmosphere,
b) Hydrogenation reaction is performed by adding hydrogen gas and bio-oil to a catalyst for hydrogenation reaction of bio-oil, and
c) A method for producing a bio-oil subjected to a hydrogenation reaction, comprising cooling and recovering the bio-oil on which the hydrogenation reaction has been completed.
The method of claim 12,
In the above b), the hydrogenation reaction is carried out at a temperature of 150 to 200° C., a method for producing a bio-oil subjected to a hydrogenation reaction.
The method of claim 12,
In the above b), the hydrogenation reaction is carried out at a pressure of 50 to 100 bar, a method for producing a bio-oil subjected to a hydrogenation reaction.
The method of claim 12,
In the above b), the supply rate of the bio-oil is 0.2 to 1 hr ^-1 of a liquid hourly space velocity (LHSV), a method for producing a bio-oil subjected to a hydrogenation reaction.