WO2009066925A2

WO2009066925A2 - Method of manufacturing glycerol ether

Info

Publication number: WO2009066925A2
Application number: PCT/KR2008/006803
Authority: WO
Inventors: Kwang Seop Jung; Jae Hyun Kim; Myung Goo Kang; Sang Chul Chung; Igor N. Filimonov
Original assignee: Gs Caltex Corporation
Priority date: 2007-11-19
Filing date: 2008-11-19
Publication date: 2009-05-28
Also published as: WO2009066925A3; KR20090051620A; KR100982632B1

Abstract

A method of manufacturing glycerol ether, and a fuel composition for an automobile including the glycerol ether are described. The method of manufacturing glycerol ether includes adding reactants including glycerol, a glycerol containing composition and iso-butene (i-butene) to a reaction container, and generating glycerol ether through a reaction of the reactants under a catalyst comprised of a metal containing ion-exchange resin.

Description

METHOD OF MANUFACTURING GLYCEROL ETHER

Technical Field

The present invention relates to a method of manufacturing glycerol ether, and a fuel composition for an automobile including the glycerol ether, and more particularly, to a method of manufacturing glycerol ether which may achieve excellent productivity and selectivity in synthesizing glycerol ether from glycerol, and a fuel composition for an automobile which may increase fuel efficiency of the automobile.

Background Art

Currently, studies for bio-diesel are actively made due to an increase in interests for environmental-friendly energy businesses. Accordingly, productivity of the bio- diesel may increase every year.

Along with an increase in the yield of the bio-diesel, supply quantities of byproducts generated due to production of the bio-diesel may be overly increased. As a representative example of the by-products of the bio-diesel, glycerol may be given.

It is possible for the glycerol to be transformed into various glycerol derivatives, for example, glycerol carbonate, epichlorohydrin, glycerol ether, 1,3-propane, and the like. In particular, the applicant has studied a method of selectively and effectively manufacturing a specific compound of the glycerol ether-based compounds while focusing on usefulness of glycerol ether of the glycerol derivatives.

Disclosure of Invention Technical Goals

An aspect of the present invention provides a method of effectively manufacturing a glycerol ether series compound from glycerol or a glycerol containing composition while focusing on usefulness of the glycerol ether.

Another aspect of the present invention provides a fuel composition for an automobile having high efficiency. Technical solutions

According to an aspect of the present invention, there is provided a method of manufacturing glycerol ether (GE), the method including: adding reactants including glycerol, a glycerol containing composition and iso-butene (i-butene) to a reaction container, and generating GE through a reaction of the reactants under a catalyst comprised of a metal containing ion-exchange resin. In this instance, dioxane acting as a co-solvent may be further added in the reaction container.

Also, the glycerol or glycerol containing composition may be acquired as a byproduct in a bio-diesel generation reaction.

Also, the generated GE may include di-glycerol tertiary butyl ether (di-GTBE), tri-glycerol tertiary butyl ether (tri-GTBE), or a mixture thereof.

Also, the metal containing ion-exchange resin may include metals such as Li, Na, Ba, Mg, Cs, Al, La, and Ag, and the metals may be included alone or any combination thereof.

Also, the metal may be included in the ion-exchange resin such that the metal is substituted for an acid point of about 25% to 75% within the metal containing ion- exchange resin.

Also, as the metal containing ion-exchange resin, a spherical shaped-porous polymer having a slufonic acid functional group may be used, and as the porous polymer, a polystyrene-divinylbenzene copolymer may be used. Also, the method may further include substituting hydrogen of a hydroxyl group within the glycerol with a methyl group through a reaction of the glycerol or the glycerol containing composition and methanol before adding the glycerol or the glycerol containing composition in the reaction container.

According to an aspect of the present invention, there is provided a fuel composition for an automobile, including: about 100 parts by weight of any one petroleum of a diesel and a gasoline; and about 1 to 10 parts by weight of at least one GE selected from a group consisting of di-GTBE and tri-GTBE.

In this instance, the fuel composition may further include about 1 to 10 parts by weight of Methyl-t-Butyl Glylcerol Ether (MBGE).

Brief Description of Drawings

FIG. 1 is a graph illustrating a change in a yield of di-glycerol tertiary butyl ether (di-GTBE) and tri-glycerol tertiary butyl ether (tri-GTBE) according to time and an amount of Ag;

FIG. 2 is a graph illustrating a conversion rate of glycerol when using dioxane as a co-solvent; and FIG. 3 is a graph illustrating a selectivity of di-GTBE (DTBE) and tri-GTBE

(TTBE) when using dioxane as a co-solvent.

Best Mode for Carrying Out the Invention

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. The embodiments are described below in order to explain the present invention by referring to the figures.

Manufacturing glycerol ether (GE) according to the present example embodiment may be performed such that a reactant solution is prepared by adding reactants including glycerol, a glycerol containing composition, and iso-butene (i- butene) to a reaction container, and GE is generated through a reaction of the prepared reactant solution under a catalyst comprised of a metal containing ion-exchange resin.

The reaction may be performed without a separate reaction solvent.

The glycerol may designate refined glycerol, and the glycerol containing composition may designate non-refined glycerol including ingredients other than the glycerol such as crude glycerol and the like. Also, the glycerol containing composition may be a comprehensive concept including a glycerol precursor and the like in which the glycerol is generated in a reaction.

According to example embodiments of the invention, as the glycerol or glycerol containing composition, commercial products may be used, however, glycerol generated as a byproduct in a bio-diesel manufacturing process may be preferably used in view of processing efficiency.

In general, glycerol or glycerin may be represented as

[Chemical formula 1]

According to example embodiments of the invention, the GE may be acquired through an etherification reaction of glycerol and i-butene or alcohols such as methanol ethanol, butanol, and the like.

According to example embodiments of the invention, when the glycerol is used as the reactant, various types of GE may be generated such that various alkyl groups of Table 1 below may be substituted in locations Of R₁, R₂, and R₃ of Chemical formula 2 below.

[Chemical formula 2]

[Table 1]

As shown in Table 1 , the generated GE may be classified into Mono-GTBE, di- GTBE, and tri-GTBE according to a number of substituted alkyl groups. Obviously, although not described, various isomers may exist in terms of a geometric structure or location.

According to example embodiments of the invention, di-GTBE and tri-GTBE of the GE may be effectively generated.

In a GE manufacturing reaction according to the present example embodiments, a solvent may be not used, however, dioxane acting as a co-solvent may be used.

The dioxane may be represented as

[Chemical formula 3]

When the dioxane is used as the co-solvent, a selectivity of di-GTBE and tri- GTBE may increase. Specifically, production of di-GTBE and tri-GTBE of the generated GE may increase. In addition, the dioxane may increase a conversion rate of glycerol.

Generation of the GE according to the present example embodiments may be represented as

[Equation 1]

According to the present example embodiments, as shown in Equation 1, glycerol and i-butene are added in the reaction container, and the GE may be acquired through a reaction of the glycerol and i-butene under a catalyst.

Even when a glycerol containing composition, which is different from refined glycerol, such as crude glycerol is used, only a glycerol ingredient may be selectively participated in the reaction of Equation 1.

Referring to Equation 1 , the generated GE may be Mono-GTBE, di-GTBE, and tri-GTBE.

However, selecting a desired one from among the above mentioned-three products is not easy. According to the present example embodiment of the invention, improving a selectivity and yield of di-GTBE and tri-GTBE may be a main technical solution.

As the catalyst, a metal containing ion-exchange resin may be used. The metal containing ion-exchange resin may be generated through a substitution reaction of a metal ion with an ion-exchange resin.

As the ion-exchange resin, a spherical shaped-porous polymer having a sulfonic acid functional group may be used. Also, as the porous polymer, a polystyrene- divinylbenzene copolymer may be used.

The ion-exchange resin may actually have a small bead shape and a size similar to hulled millet.

The metal may be substituted for a part of an acid point within the ion- exchange resin such that the metal included in the ion-exchange resin.

As the metal capable of being substituted within the ion-exchange resin, Li, Na, Ba, Mg, Cs, Al, La, and Ag may be used, and the above mentioned metals may be substituted alone or in any combination thereof.

Particularly, when the metal containing ion-exchange resin includes Ag, the Ag may be substituted for an acid point of about 25% to 75% of the sulfonic acid functional group within the ion-exchange resin.

When a substitution rate of the acid point within the metal containing ion- exchange resin is less than about 25%, the selectivity of di-GTBE and tri-GTBE may be reduced, and when the substitution rate thereof exceeds about 75%, a reaction speed may be reduced. Preferably, the substitution rate of the acid point within the metal containing ion-exchange resin of the Ag may be about 40% to 60%. The GE manufacturing reaction may be performed under conditions of a temperature of about 40 ^"C to 80 ^°C and a pressure of about 10 bar to 30 bar, which is effective in terms of reaction efficiency.

In addition, the ion-exchange resin acting as the catalyst may be powdered, thereby significantly increasing the reaction efficiency. The glycerol may be converted, through a prior reaction with methanol before participating in the reaction, into a type in which hydrogen of at least one hydroxyl group is substituted with a methyl group. A subsequent reaction of the glycerol in which the methyl group is substituted for the hydrogen thereof may be the same as described in Equation 1. Equation 2 below may show an example including a primary reaction A of the glycerol and methanol, and a secondary reaction B of the glycerol in which the methyl group is substituted for the hydrogen thereof and i-butene.

[Equation 2]

Referring to Equation 2, an intermediate is generated such that a single methyl group is replaced with the hydrogen of the hydroxyl group of the glycerol, whereby Methyl-t-Butyl Glylcerol Ether (MBGE) including the methyl group may be generated as a final product.

As a catalyst of the primary reaction (A) H₃PO₄ may be used. The GTBE and MBGE manufactured according to the present example embodiments of the invention may be mixed with a petroleum fuel to increase efficiency of a fuel for an automobile.

Specifically, a fuel composition for an automobile according to the present example embodiment of the invention may include the GTBE and MBGE or a combination thereof other than the petroleum fuel such as gasoline, diesel and the like. Particularly, di-GTBE or tri-GTBE may be used as the GTBE. The fuel composition for an automobile according to the present example embodiment of the invention may include about 100 parts by weight of the petroleum, and about 1 to 10 parts by weight of the di-GTBE and tri-GTBE or a combination thereof.

In the fuel composition for the automobile according to the present example embodiment of the invention, an octane number may increase, thereby achieving excellent fuel efficiency.

Also, the fuel composition for the automobile may further include about 1 to 10 parts by weight of the MBGE. When the MBGE is additionally included in the fuel composition, only the GTBE may be included in the fuel, whereby a problem of an increase in an end point may be alleviated.

[Examples]

[Examples 1 and 2 and Comparative Example 1]

As shown Table 2 below, glycerol, i-butene, and an ion-exchange resin catalyst (amberlyst-15) were reacted under reaction conditions as below, a production (R.Quan.) and yield of glycerol ether (GE) were measured.

Ion-exchange resin including Ag of about 50% was used as a catalyst in Example 1, and ion-exchange resin of a general commercial catalyst that was not modified into a metal was used as the catalyst in Comparative Example 1. Also, in Example 2, a catalyst obtained by powdering the catalyst of Example 1 may be used.

[Table 2]

Referring to Table 2, the Ag containing catalyst showed excellent yield and selectivity in comparison with the general commercial catalyst not including a metal. Also, using the powdered catalyst was more effective in terms of the reaction time.

Measurement of yield of Di-GTBE and Tri-GTBE depending on amount of Ag within ion-exchange resin and time An initial amount of glycerol acting as a reactant of the measurement was about

11.51 g (0.12 mol), and an initial amount of i-butene was about 28.05 g (0.50 mol). A reaction was performed under conditions of a temperature of about 60 ^°C and a pressure of about 20 bar.

As a metal containing ion-exchange resin, a catalyst obtained by substituting Ag of about 0%, 10%, 25%, 50%, and 75% for an ion-exchange resin catalyst (amberlyst-15) may be used.

A change in a yield of di-GTBE (DTBE) and tri-GTBE (TTBE) over time was measured.

FIG. 1 is a graph illustrating a change in a yield of di-glycerol tertiary butyl ether (di-GTBE) and tri-glycerol tertiary butyl ether (tri-GTBE) according to time and an amount of Ag.

Referring to FIG. 1 , when using a metal containing ion-exchange resin catalyst containing Ag at a substitution rate of about 50%, the yield was relatively excellent. Results of an early reaction time of the measurement may have errors due to the early reaction, and thus the meaning of the results was excluded in analyzing the graph.

Measurement of conversion rate of glycerol when using co-solvent

FIG. 2 is a graph illustrating a conversion rate of glycerol when using dioxane as a co-solvent. Referring to FIG. 2, a conversion rate of glycerol became significantly high in a short time when using dioxane as the co-solvent.

Measurement of selectivity of DTBE and TTBE when using co-solvent FIG. 3 is a graph illustrating a selectivity of di-GTBE (DTBE) and tri-GTBE (TTBE) when using dioxane as a co-solvent.

Referring to FIG. 3, a selectivity S of di-GTBE and tri-GTBE was relatively excellent when using dioxane as the co-solvent. According to the present example embodiments, di-GTBE and tri-GTBE may act as additives within the petroleum, so that improvement of the selectivity of di-GTBE and tri-GTBE is an important factor in terms of processing efficiency. Measurement of physical property of MBGE or GTBE containing gasoline Methyl-t-butyl glycerol ether (MGBE) or GTBE (glycerol t-butyl ether) were added in a gasoline as shown in Table 3, and various physical properties were measured.

The used GTBE was di-GTBE. [Table 3]

* The gasoline not including MTBE

As shown in Table 3, in a case of the gasoline with MBGE or GTBE, an octane number (RON) was relatively high, thereby achieving excellent fuel efficiency. Also, the gasoline with MBGE or GTBE exhibited decrease of a steam pressure. The gasoline with MBGE had a relatively low RON and end point in comparison with the gasoline with GTBE.

Accordingly, when the above-mentioned MBGE or GTBE containing gasoline is applied in an actual gasoline product, GTBE and MBGE are desirably mixed in their appropriate amounts.

Industrial Applicability

As described above, according to the present invention, a method of manufacturing glycerol ether (GE) may be expected to revitalize bio-diesel markets, and also expected to be utilized in the corresponding fields.

In particular, the method of manufacturing GE according to the present invention may replace MTBE included in existing petroleum products as well as having resource recycling effects while coinciding with a current nature-friendly trend.

Although a few embodiments of the present invention have been shown and described, the present invention is not limited to the described embodiments. Instead, it would be appreciated by those skilled in the art that changes may be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims

1. A method of manufacturing glycerol ether, the method comprising: adding reactants including glycerol, a glycerol containing composition and iso- butene (i-butene) to a reaction container, and generating glycerol ether through a reaction of the reactants under a catalyst comprised of a metal containing ion-exchange resin.

2. The method of claim 1, wherein the glycerol or glycerol containing composition is acquired as a byproduct in a bio-diesel generation reaction.

3. The method of claim 1, wherein the generated glycerol ether includes di- glycerol tertiary butyl ether (di-GTBE) and tri-glycerol tertiary butyl ether (tri-GTBE).

4. The method of claim 1, wherein the metal containing ion-exchange resin includes at least one metal selected from a group consisting of Li, Na, Ba, Mg, Cs, Al,

La, and Ag.

5. The method of claim 1, wherein the metal containing ion-exchange resin is a powder type.

6. The method of claim 1, wherein the metal containing ion-exchange resin is a spherical shaped-porous polymer having a sulfonic acid functional group.

7. The method of claim 6, wherein the porous polymer is a polystyrene- divinylbenzene copolymer.

8. The method of claim 1, wherein the metal containing ion-exchange resin includes Ag, and a substitution rate of Ag within the metal containing ion-exchange resin is about 25 % to 75%.

9. The method of claim 1, wherein dioxane acting as a co-solvent is further added in the reaction container.

10. The method of claim 1 , further comprising: substituting hydrogen of a hydroxy group within the glycerol with a methyl group through a reaction of the glycerol or the glycerol containing composition and methanol before adding the glycerol or the glycerol containing composition in the reaction container.

11. The method of claim 10, wherein the substitution is performed under a phosphoric acid catalyst.

12. A fuel composition for an automobile, comprising: about 100 parts by weight of any one petroleum of a diesel and a gasoline; and about 1 to 10 parts by weight of at least one glycerol ether selected from a group consisting of di-GTBE and tri-GTBE.

13. The fuel composition of claim 12, further comprising: about 1 to 10 parts by weight of Methyl-t-Butyl Glylcerol Ether (MBGE).