WO2014112712A1

WO2014112712A1 - Method for producing ring-shaped hydrocarbon from lignin-transforming substance using noble metal supported catalyst

Info

Publication number: WO2014112712A1
Application number: PCT/KR2013/010802
Authority: WO
Inventors: 이관영; 홍윤기; 엄희준; 이대원
Original assignee: 고려대학교 산학협력단
Priority date: 2013-01-18
Filing date: 2013-11-26
Publication date: 2014-07-24

Abstract

The present invention relates to a catalyst for producing a ring-shaped hydrocarbon represented by Formula 1 or Formula 2, and a method for producing a ring-shaped hydrocarbon from a lignin-transforming substance by a hydrodeoxygenation or hydrogenation reaction using the catalyst. [Formula 1] M/MoO_x/γ-Al₂O₃; [Formula 2] M/WO_x/γ-Al₂O₃, wherein M is Pd, Pt, Ru, or Rh.

Description

Process for producing cyclic hydrocarbons from lignin converting materials using catalysts loaded with precious metals

The present invention relates to a process for producing cyclic hydrocarbons from lignin converting materials using catalysts loaded with precious metals.

Recently, due to the limited reserves of fossil fuels, biomass has been in the spotlight as a feedstock of organic chemicals as well as fuels. Among them, lignin is a by-product produced in the pulp process and is burned and used as a lower fuel. Usually, lignin is converted into gaseous or liquid phase through pyrolysis and used as fuel or feedstock. In the case of liquid, it is called “bio-oil” and it is an oxygen-rich (about 40%) aromatic compound. consist of.

Therefore, in order to use biooil as a feedstock for chemicals, it is important to properly remove oxygen contained in biooil. Recently, hydrodeoxygenation using a catalyst can be converted into a high yield of aromatic chemicals by appropriately removing oxygen from a lignin converting material, and thus many studies have been conducted.

US Pat. No. 4,647,704 describes a process for converting lignin into an aromatic phenol via hydrodeoxygenation. The catalyst is a zero-valent or sulfide tungsten-based catalyst, nickel was used as an additive, and the reaction was carried out using silica-alumina or silica-alumina-phosphate as a carrier. In addition, Korean Patent No. 10-0587248 discloses that tungsten or molybdenum-based catalysts include phosphorus, nickel, cobalt, iron, ruthenium, and the like, or cobalt, palladium, nickel, platinum catalysts are zinc, rhenium, selenium, tin, germanium, lead, and the like. A method for obtaining phenol from benzene diol using a catalyst comprising was described.

When hydrogen is added in the deoxygenation reaction, the sulfide catalyst becomes active. Therefore, the prior art has dealt with a method of converting guaiacol into aromatic compounds such as phenol and benzene using a lignin model material, guaiacol, as a reactant, and a sulfide catalyst. In particular, the aromatic substances of the sulfide molybdenum The catalysts can be prepared by aromatic chemicals such as phenol and benzene through a hydrogenated deoxygenation reaction, nine under the catalyst of CoMo or NiMo / Al ₂ O ₃ there was added sulfur child ahkol The conversion reaction of was studied.

Guaicol is converted into an aromatic chemical through a continuous reaction in the presence of hydrogen and sulfide catalysts, as shown in Scheme 1 below, and converted to cyclohexane as the benzene ring is hydrogenated.

Scheme 1

However, recent studies have found that sulfur from sulfide catalysts not only deactivates the catalyst, but also contaminates the product and requires high temperature and pressure conditions. Precious metal catalysts are being studied. Unlike the sulfide catalyst, the noble metal catalyst is first converted into cyclohexane through hydrogenation and hydrodeoxygenation, as shown in Scheme 2 below.

Scheme 2

The present invention is a Group 8 precious metal (Pd, Pt, Ru or Rh) supported by gamma alumina in order to obtain a high yield of cyclic hydrocarbons produced after hydrodeoxygenation and hydrogenation from lignin conversion materials containing aromatic hydrocarbons. It is an object to use this contained tungsten oxide or molybdenum oxide catalyst.

It is also an object of the present invention to provide a method for producing a cyclic hydrocarbon from a lignin converting material using the catalyst.

In order to achieve the above object,

The present invention provides a catalyst for producing a cyclic hydrocarbon represented by the following formula (1) or (2).

[Formula 1]

M / MoO _x / γ-Al ₂ O ₃

[Formula 2]

M / WO _x / γ-Al ₂ O ₃

M is Pd, Pt, Ru or Rh.

The present invention also provides a method for preparing a cyclic hydrocarbon from the lignin conversion material using the catalyst.

The catalyst of the present invention enables the production of cyclic hydrocarbons from lignin convertors in high yields and can be used without sulfur treatment to produce cyclic hydrocarbons under relatively simple conditions without contaminating the product.

1 is a graph showing the conversion rate of the guai alcohol according to the type of catalyst.

FIG. 2 is a graph showing the production rate of cyclic hydrocarbons converted from guaiacol according to the amount of tungsten added.

3 is a graph showing the results of repeated measurements 10 times to determine the durability of the catalyst of the present invention.

Figure 4 is a graph showing the production rate of the cyclic hydrocarbon when the catalyst of the present invention using the lignin converting material, guaiacol, anisol, catechol and phenol as the reactant.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a catalyst for producing a cyclic hydrocarbon represented by the following formula (1) or (2).

[Formula 1]

M / MoO _x / γ-Al ₂ O ₃

[Formula 2]

M / WO _x / γ-Al ₂ O ₃

M is Pd, Pt, Ru or Rh.

The catalyst for producing a cyclic hydrocarbon of the present invention is a molybdenum oxide or tungsten oxide catalyst containing a Group 8 noble metal (Pd, Pt, Ru or Rh) supported by gamma alumina. The catalyst uses lignin convertors as reactants to produce cyclic hydrocarbons.

The catalyst for producing a cyclic hydrocarbon of the present invention uses alumina having a gamma phase structure as a carrier, and molybdenum oxide (MoO _x ) or tungsten oxide (WO _x ) is preferably 10 to 45 to the weight of the alumina carrier. It is included in weight percent. Molybdenum oxide or tungsten oxide contained in the alumina carrier is called molybdenum oxide alumina or tungsten oxide alumina, and is represented by the following formula (3) or (4).

[Formula 3]

MoO _x / γ-Al ₂ O ₃

[Formula 4]

WO _x / γ-Al ₂ O ₃

In addition, Group 8 precious metals (Pd, Pt, Ru or Rh) is included in 1 to 5% by weight relative to the weight of the formula (3) or formula (4).

The present invention relates to a method for producing a cyclic hydrocarbon from the lignin conversion material using the catalyst for producing a cyclic hydrocarbon of formula (1) or (2). The lignin converting material is converted into a cyclic hydrocarbon through hydrodeoxygenation and hydrogenation.

Examples of the lignin converting material include guaiacol, anisol, catechol and phenol, and preferably guaiacol is most used. The guiacol may be dissolved in an organic solvent, and hexane (n-hexane), decane (n-decane), paraxylene (p-xylene), and the like are preferable.

Filling the catalyst for producing a cyclic hydrocarbon of formula (1) or formula (2) with guai acol as a reactant, the reaction is carried out for 1 to 3 hours at a temperature of 200 to 400 ℃ and a pressure of 5 to 10 MPa . Through the above reaction, guaiacol is mainly converted to cyclohexane, and also to cyclohexanol and methoxycyclohexanol.

Example 1 Pd10WA Catalyst 조article

Ammonium metatungstate (Sigma Aldrich) of 10% by weight relative to the weight of the alumina carrier was added to the alumina carrier by the initial wetness method (Incipient Wetness method) and then dried at 80 ° C. for 12 hours. The dried material was calcined at 500 ° C. to obtain tungsten alumina (WO _× / γ-Al ₂ O ₃ , 10WA) in powder form. Thereafter, the pore volume of tungsten alumina was measured, and palladium of 2 wt% based on the weight of the tungsten alumina was added by an initial wet method. At this time, palladium is added in an aqueous palladium nitrate solution. Thereafter, the mixture was calcined at 500 ° C. to prepare a Pd / WO _x / γ-Al ₂ O ₃ (Pd10WA) catalyst.

Example 2. Preparation of Pd20WA Catalyst

A Pd / WO _x / γ-Al ₂ O ₃ (Pd20WA) catalyst was prepared in the same manner as in Example 1 except that 20% by weight of ammonium metatungstate was added to the alumina carrier.

Example 3. Preparation of Pd35WA Catalyst

A Pd / WO _x / γ-Al ₂ O ₃ (Pd35WA) catalyst was prepared in the same manner as in Example 1, except that 35% by weight of ammonium metatungstate was added to the alumina carrier.

Comparative Example 1. WO _xx / γ-Al ₂₂ O ₃₃ (35WA) catalyst manufacturing

Ammonium metatungstate (Sigma Aldrich) of 35% by weight relative to the weight of the alumina carrier was added to the alumina carrier by the initial wetness method (Incipient Wetness method) and then dried at 80 ° C. for 12 hours. The dried material was calcined at 500 ° C. to obtain tungsten alumina (WO _× / γ-Al ₂ O ₃ , 35WA) in powder form.

Comparative Example 2. Pd / γ-Al ₂₂ O ₃₃ (PdAl) Catalyst Preparation

A Pd / γ-Al ₂ O ₃ (PdAl) catalyst was prepared by adding an aqueous solution of palladium nitrate of 2% by weight based on the weight of the alumina carrier and firing at 500 ° C.

Comparative Example 3. CoMo-S Catalyst Preparation

5 vol% of CoMo (Criterion Co., Ltd.) catalyst was injected with H ₂ S / H ₂ gas and reacted at 400 ° C. for 3 hours to prepare a CoMo-S catalyst.

Comparative Example 4. SiO ₂₂ -Al ₂₂ O ₃₃ (Si-Al) Catalyst 조article

Tetraethyl orthosilicate (Si (OC ₂ H ₅ ) ₄ , SigmaAldrich), which is a silicon precursor, was mixed with tertiary distilled water, and a solution having a pH of 2.0 was prepared using nitric acid solution. In addition, an aluminum precursor (Al (NO ₃ ) ₃ 9H ₂ O, SigmaAldrich) and tertiary distilled water were mixed to prepare a solution. The two solutions were mixed and stirred at 40 ° C. for 1 hour. Ammonium hydroxide (NH ₄ OH) was added dropwise to the solution to adjust the pH to 8.5 and then aged at 40 ° C. for 1 hour. After filtering the solid product, the remaining ammonium nitrate was washed with tertiary distilled water. Washed once more with ethanol to form a solid with a pore structure. The filtered solid was dried at 80 ° C. for 10 hours and calcined at 550 ° C. for 3 hours to prepare a SiO ₂ -Al ₂ O ₃ (Si-Al) catalyst.

Experimental Example 1. Conversion rate of guaiacol and yield of cyclic hydrocarbon

Example 1 to 3, Comparative Examples 1 to 4, alumina catalyst (γ-Al ₂ O ₃ , Al) and CoMo catalyst were added to the solution in which 3 wt% of guai alcohol was added to a decane solvent. Each solution was prepared by adding g each to make a total volume of 50 mL. Each solution was filled with hydrogen gas at 300 ° C., and the reaction was carried out for 3 hours while maintaining a total pressure of 7 MPa to prepare cyclohexane from guoacol through hydrodeoxygenation and hydrogenation.

The conversion rate of guai acol was calculated | required from following formula (1), and the cyclohexane yield of guai acol was calculated | required from following formula (2).

[Equation 1]

[Equation 2]

The catalysts of Example 3 (Pd35WA) and Comparative Examples 2 (PdAl) to 3 (CoMo-S), which are the catalysts of the present invention, were converted to more than 90% of guaiacol to other materials. In addition, the catalyst (35WA), alumina catalyst (Al), and CoMo catalyst of Comparative Example 1 showed a conversion rate of 50% or more, and a conversion rate of less than 5% in the reaction without adding a catalyst.

However, conversion to cyclohexane, a cyclic hydrocarbon, was the highest at about 90% in Example 3 (Pd35WA), the catalyst of the present invention, and a low conversion of about 60% at the catalyst of Comparative Example 2 (PdAl). Seemed. In addition, other catalysts (Comparative Example 1, Comparative Example 3, Alumina catalyst and CoMo catalyst) did not show conversion to cyclohexane, and guiacol was converted to aromatic hydrocarbons such as catechol, anisol, phenol and cresol. It was confirmed that (Fig. 1).

In addition, in order to determine the production rate of the cyclic hydrocarbon converted from guaiacol according to the amount of tungsten included in the catalyst of the present invention, the catalysts of Comparative Examples 1 to 3 (Pd10WA, Pd20WA and Pd35WA) including tungsten Experiment was conducted using 2 (PdAl) and the catalyst of Comparative Example 4 (Si-Al).

In this experiment, it was confirmed that the guiacol is converted to 100%. Among them, the catalyst of Example 3 (Pd35WA) containing 35% by weight of tungsten produced the most cyclic hydrocarbon cyclohexane, and the catalysts of Examples 1 (Pd10WA) and 2 (Pd20WA) containing 10 and 20% by weight of tungsten. The yield was 60% or more. However, the catalyst of Comparative Example 4 (Si-Al) showed a lower yield of cyclohexane, and the catalyst of Comparative Example 2 (PdAl) not containing tungsten had a lower yield than the catalysts of Examples 1 to 3 of the present invention. (FIG. 2).

Experimental Example 2 Measurement of Durability of Catalysts for Forming Cyclic Hydrocarbons

Using the catalyst (Pd35WA) prepared in Example 3 to prepare a reaction solution in the same manner as in Experiment 1. In order to measure the durability of the catalyst of the present invention, the catalyst was reused 10 times to determine the yield of cyclohexane converted from guai alcohol.

Ten replicates showed a decrease in cyclohexane yield of less than about 5% (FIG. 3). Therefore, the durability of the catalyst for producing a cyclic hydrocarbon of the present invention was confirmed through experiments.

Experimental Example 3. Yield of cyclic hydrocarbons from various lignin conversions

The yield of cyclohexane, a cyclic hydrocarbon, was observed using anisole, catechol, and phenol, which are intermediate products of the decomposition of guiacol, in addition to guanin, which is a lignin converting material.

To prepare a solution in the same manner as in Experimental Example 1, the reaction material was anisol, catechol and phenol, the catalyst was prepared in each reaction solution using the catalyst (Pd35WA) of Example 3 of the present invention, The yield of cyclohexane was observed.

In the experiments with the anisol, the anisol was not 100% converted and the remaining substances were all 100% converted. In addition, it was confirmed that all four materials showed a high yield of 70% or more of cyclohexane (FIG. 4).

Therefore, it was found that the catalyst for producing a cyclic hydrocarbon of the present invention generates a cyclic hydrocarbon from a variety of lignin conversion materials in addition to gua alcohol in high yield.

Claims

A catalyst for producing a cyclic hydrocarbon represented by the following formula (1) or (2).

[Formula 1]

M / MoO x / γ-Al 2 O 3

[Formula 2]

M / WO x / γ-Al 2 O 3

M is Pd, Pt, Ru or Rh.
The catalyst of claim 1, wherein the molybdenum oxide (MoO x ) or tungsten oxide (WO x ) is included in an amount of 10 to 45 wt% based on the weight of the alumina carrier.
The catalyst for producing a cyclic hydrocarbon according to claim 1, wherein M is included in an amount of 1 to 5 wt% based on the weight of Formula 3 or Formula 4.

[Formula 3]

MoO x / γ-Al 2 O 3

[Formula 4]

WO x / γ-Al 2 O 3
The catalyst for producing a cyclic hydrocarbon according to claim 1, wherein the catalyst for producing a cyclic hydrocarbon is used as a reactant.
A method for producing a cyclic hydrocarbon from the lignin conversion material using the catalyst of claim 1.
The method of claim 5, wherein the cyclic hydrocarbon is produced by reacting for 1 to 3 hours at a reaction temperature of 200 to 400 ℃, a total pressure of 5 to 10 MPa for a method for producing a cyclic hydrocarbon from the lignin conversion material .