KR20090051620A - Method of manufacturing glycerol ether - Google Patents

Abstract

The present invention is to add a glycerol (Glycerol) or a glycerol-containing composition, and isobutene (iso-buten) in the reaction vessel, and reacted under a catalyst consisting of a metal-containing ion exchange resin to produce a glycerol ether (GE) It provides a method for producing a glycerol ether comprising a. The glycerol or glycerol containing composition can be obtained from by-products generated in the production of biodiesel.

Glycerol, biodiesel, glycerol ether, metal-containing ion exchange resin

Description

Method of manufacturing glycerol ether

The present invention relates to a method for preparing glycerol ether and a fuel composition for automobiles including the glycerol ether, and more particularly, to a method for producing glycerol ether which can secure excellent productivity and selectivity in synthesizing glycerol ether from glycerol. And a fuel composition for an automobile capable of increasing fuel efficiency of an automobile.

With the recent focus on environmentally friendly energy projects, research on biodiesel is expanding. Therefore, biodiesel production is expected to increase year by year.

As such, as biodiesel production increases, the supply of by-products generated by biodiesel production is also oversupply. Representative of the by-product of the biodiesel is glycerol.

The glycerol can be modified into various glycerol derivatives. For example, glycerol carbonate, glycerol ether, propylene glycerol, etc. are mentioned.

In particular, the inventors came to study a method for selectively and efficiently preparing specific compounds of the glycerol ether-based compounds for the purpose of usefulness of the glycerol ether in the glycerol derivatives.

It is an object of the present invention to provide a method for efficiently preparing a glycerol ether-based compound from glycerol or a glycerol-containing composition, in view of the usefulness of glycerol ether as described above.

It is another object of the present invention to provide a fuel composition for automobiles with high efficiency.

A method for producing a glycerol ether according to one aspect of the present invention is to add a glycerol (Glycerol) or a glycerol-containing composition, and isobutene (iso-buten) in the reaction vessel, the reaction under a catalyst consisting of a metal-containing ion exchange resin To produce glycerol ether (GE).

Dioxane may be further added to the reaction vessel as a cosolvent.

The glycerol or glycerol containing composition may be used that is obtained from the by-product of the biodiesel production reaction.

The resulting glycerol ether is di-glycerol tertiary butyl ether (di-GTBE), tri-glycerol tertiary butyl ether (tri-GTBE) or a mixture thereof Include.

The metal-containing ion exchange resin is a metal such as lithium (Li), sodium (Na), barium (Ba), magnesium (Mg), cesium (Cs), aluminum (Al), lanthanum (La), silver (Ag), and the like. It may contain, the metal may be contained alone or in combination of two or more.

The metal is preferably contained so that 25 to 75% of the acid point in the metal-containing ion exchange resin is substituted.

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

The preparation method may further include the step of replacing the hydrogen of the hydroxy group in the glycerol by a methyl group by reacting the glycerol or glycerol-containing composition with methanol before adding the glycerol or glycerol-containing composition to the reaction vessel.

Automotive fuel composition according to an aspect of the present invention is 100 parts by weight of petroleum fuel of diesel fuel or gasoline fuel, and di-glycerol tertiary butyl ether (Di-GTBE) and tri- 1 to 10 parts by weight of at least one glycerol ether selected from the group consisting of glycerol tertiary butyl ether (Tri-GTBE).

The fuel composition may further include 1 to 10 parts by weight of methyl-t-Butyl Glylcerol Ether (MBGE) in addition to the Di-GTBE and Tri-GTBE.

Hereinafter, the present invention will be described in detail.

In the preparation of glycerol ether (GE) according to the present invention, a reaction solution is prepared by adding glycerol (Glycerol) or a glycerol-containing composition and isobutene (iso-buten) in a reaction vessel, and preparing the reaction solution. Is reacted under a catalyst which is a metal-containing ion exchange resin.

The reaction can be carried out without a separate reaction solvent.

The glycerol refers to purified glycerol, and the glycerol-containing composition refers to glycerol which is not purified such as crude glycerol and also includes components other than glycerol. In addition, the glycerol-containing composition is a comprehensive concept including a glycerol precursor that can be produced glycerol during the reaction.

In the present invention, a commercially available product may be used as the glycerol or glycerol-containing composition, but it is remarkably advantageous in terms of process efficiency to use a glycerol component generated as a by-product in the process of producing biodiesel.

In general, glycerol or glycerin is represented by the following formula (1).

In the present invention, the glycerol ether as a product can be obtained by etherification of glycerol and isobutene or alcohols such as methanol, ethanol and butanol.

According to the present invention, glycerol ether which can be produced when using glycerol as a reactant is substituted with various alkyl groups of the following Table 1 in the positions of R ₁ , R ₂ , and R ₃ of Formula (2), thereby providing various forms Can have

As shown in Table 1, the resulting glycerol ether is mono-glycerol tertiary butyl ether (Mono-GTBE), di-glycerol tertiary butyl ether (Di-glycerol tertiary butyl ether) depending on the number of substituted ether, Di-GTBE) and mono-glycerol tertiary butyl ether (Tri-glycerol tertiary butyl ether, Tri-GTBE). Of course, although not mentioned, it is obvious that various isomers may exist in terms of geometry or position.

The present invention aims at the efficient production of, in particular, glycerol ethers, in particular Di-GTBE and Tri-GTBE.

Although no solvent is used in the reaction for preparing glycerol ether according to the present invention, dioxane may be used as an auxiliary solvent.

The dioxane is a compound represented by the following formula (3).

As a co-solvent, the use of the dioxane can increase the selectivity of Di-GTBE and Tri-GTBE. That is, the relative amount of Di-GTBE and Tri-GTBE in the resulting glycerol ether can be increased. On the other hand, the dioxane may increase the conversion rate of glycerol.

The production of glycerol ether according to the present invention can be represented by the following scheme (1).

According to the present invention, in order to produce glycerol ether, it can be obtained by adding glycerol and isobutene (iso-buten, i-buten) in the reaction vessel as shown in Scheme (1) and reacting under a catalyst.

Even without the use of purified glycerol, even when using a glycerol containing composition such as crude glycerol, only the glycerol component is selectively involved in the reaction according to the above reaction (1).

Referring back to Scheme (1), the glycerol ethers that can be produced are mono-glycerol tertiary butyl ether, di-glycerol tertiary butyl ether and tri- It is three kinds of glycerol tertiary butyl ether.

However, it is not easy to select the kind of the product as intended. In the present invention, improving the selectivity and yield of Di-GTBE and Tri-GTBE is one of important technical tasks.

As the catalyst, a metal-containing ion exchange resin is used. The metal-containing ion exchange resin may be formed by substitution reaction of metal ions with an ion exchange resin.

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

In practice, the ion exchange resin has a small bead shape of millet size.

The metal is contained in the ion exchange resin by being partially substituted at an acid point in the ion exchange resin.

Examples of the metal that may be substituted in the metal-containing ion exchange resin include lithium (Li), sodium (Na), barium (Ba), magnesium (Mg), cesium (Cs), aluminum (Al), lanthanum (La), Silver (Ag), and the like, and the metal may be substituted alone or in combination of two or more.

In particular, when the metal-containing ion exchange resin contains Ag, the Ag is replaced with 25 to 75% of the acid point of the sulfonic acid functional group in the ion exchange resin.

If the Ag substitution rate in the metal-containing ion exchange resin of Ag is less than 25% by weight, there is a problem that the selectivity decreases, whereas when the acid substitution rate exceeds 75%, the reaction rate is lowered. In particular, the acid substitution rate of the Ag in the metal-containing ion exchange resin is preferably 40 to 60%. The production reaction of the glycerol ether is advantageous in terms of reaction efficiency that is carried out under a temperature condition of 40 to 80 ℃, and a pressure condition of 10 to 30 bar.

On the other hand, by using powdered metal-containing ion exchange resin as the catalyst, the reaction efficiency can be further increased.

The glycerol may be converted into a form in which hydrogen of at least one hydroxy group is substituted with a methyl group by preferentially reacting with methanol prior to participating in the reaction. Subsequent reaction of the methyl group-substituted glycerol is as mentioned in Scheme (1) above.

Scheme (2) below shows an example including the first reaction (A) of glycerol and methanol and the second reaction (B) of glycerol and isobutene substituted with a methyl group.

Referring to Reaction Scheme (2), one methyl group is substituted with hydrogen of the hydroxy group of glycerol to produce an intermediate product. As a final product, methyl-t-Butyl Glylcerol contains a methyl group. Ether, MBGE) is created.

As the catalyst of the A reaction, phosphoric acid (H ₃ PO ₄ ) may be used.

In the present invention, GTBE and MBGE prepared above can be mixed with petroleum fuel to improve the efficiency of fuel for automobiles.

That is, the fuel composition for automobiles according to the present invention includes GTBE, MBGE, or a mixture thereof in addition to petroleum fuels such as gasoline and diesel.

In particular, as the GTBE, Di-GTBE (DGTBE) or Tri-GTBE (TGTBE) is used.

Automotive fuel composition according to an embodiment of the present invention includes 100 parts by weight of petroleum fuel, and 1 to 10 parts by weight of the Di-GTBE, Tri-GTBE or a mixture thereof.

The fuel composition for automobiles according to the exemplary embodiment is improved in octane number and excellent in fuel efficiency.

In addition, the automotive fuel composition may further include 1 to 10 parts by weight of MBGE. When MBGE is additionally included in the fuel composition for automobiles, only GTBE is included in the fuel, thereby alleviating the problem of increasing an end point.

EXAMPLE

[Examples 1 and 2 and Comparative Example 1]

As shown in Table 2 below, glycerol, isobutene, and ion exchange resin catalyst (Amberlyst-15) were used and reacted according to the following reaction conditions. Quan.) And yield were measured.

Example 1 used an ion exchange resin containing 50% Ag as a catalyst, and Comparative Example 1 used an ion exchange resin, which is a general commercial catalyst that is not modified with a metal, as a catalyst. As the catalyst, a catalyst powdered from the catalyst used in Example 1 was used.

Referring to Table 2, it can be seen that the catalyst containing Ag is better in yield and selectivity than in the case of using a commercial catalyst containing no metal. In addition, the powdered catalyst was found to be more efficient in terms of reaction time.

In ion exchange resin Ag  Content and time Di - GTBE  And Tri - GTBE Yield measurement

In this measurement, the initial amount of glycerol as a reactant was 11.51 g (0.12 mol), and the initial amount of isobutene was 28.05 g (0.50 mol). The reaction was carried out under a temperature of 60 ° C. and a pressure of 20 bar.

As the metal-containing ion exchange resin, a catalyst in which 0%, 10%, 25%, 50% and 75% of Ag was substituted in the ion exchange resin catalyst (Amberlyst-15) was used, respectively.

In addition, the change in yield of di-glycerol tertiary butyl ether (Di-GTBE, DTBE) and tri-glycerol tertiary butyl ether (Tri-GTBE, TTBE) with time was measured.

1 is a graph showing the yield change of di-glycerol tertiary butyl ether and tri-glycerol tertiary butyl ether with time and Ag substitution rate.

Referring to Figure 1, it was confirmed that the yield is relatively excellent when using a metal-containing ion exchange resin catalyst containing Ag at a substitution rate of 50%. In this measurement, the result value of the initial reaction time was an error due to the initial reaction, and its meaning was excluded in interpreting the graph.

Glycerol When Using Co-Solvent Conversion rate  Measure

2 is a graph showing the conversion rate of glycerol when dioxane is used as a cosolvent.

Referring to FIG. 2, the use of dioxane as a cosolvent showed very high glycerol conversion in a short time.

When using a co-solvent DTBE  And TTBED Selectivity measurement

3 is a graph showing selectivity of di-glycerol tertiary butyl ether (DTBE) and tri-glycerol tertiary butyl ether (TTBE) when dioxane is used as an auxiliary solvent.

Referring to FIG. 3, when dioxane was used as the cosolvent, it was found that the selectivity (S) of Di-GTBE and Tri-GTBE was relatively excellent.

Since the present inventors have in mind using Di-GTBE and Tri-GTBE as additives in petroleum fuel, the selectivity improvement of Di-GTBE and Tri-GTBE is an important factor in terms of process efficiency.

MBGE  or GTBE  Physical property evaluation of containing gasoline

Methyl-t-butyl glycerol ether (MBGE) or glycerol t-butyl ether (GTBE) was added to the gasoline and measured various physical properties as shown in Table 3 below. It was. The GTBE used was Di-GTBE.

* The gasoline does not contain MTBE (methyl-t-butyl ether)

As shown in Table 3, in the case of gasoline to which MBGE or GTBE was added, it was found that octane number (RON) was relatively high, which was excellent in terms of fuel efficiency. In addition, in the case of gasoline to which the MBGE or GTBE was added, there was an effect of reducing the vapor pressure. The octane number of the MBGE-added gasoline was relatively lower than that of the GTBE-added gasoline, but the end point was relatively low.

Therefore, when applied to an actual gasoline product, it would be desirable to use a suitable mixture of MBGE in addition to the GTBE.

The method for producing glycerol ether according to the present invention is very useful invention with the activation of the biodiesel market and is expected to be specifically implemented in the art.

In particular, it is believed that the present invention includes technology ideas that are able to replace the methyl tertiary-butyl ether (MTBE) contained in the existing petroleum fuel products as well as in terms of recycling of resources. .

As described above, the present invention has been described by way of a limited embodiment, but the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains may make various modifications and variations from this description. Do. Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be defined by the claims below and equivalents thereof.

1 is a graph showing the yield change of di-glycerol tertiary butyl ether and tri-glycerol tertiary butyl ether with time and Ag content.

2 is a graph showing the conversion rate of glycerol when dioxane is used as a cosolvent.

3 is a graph showing selectivity of di-glycerol tertiary butyl ether (DTBE) and tri-glycerol tertiary butyl ether (TTBE) when dioxane is used as an auxiliary solvent.

Claims (13)

Glycerol or a glycerol-containing composition, and isobutene, are added to the reaction vessel and reacted under a catalyst consisting of a metal-containing ion exchange resin to produce glycerol ether. Method for producing a glycerol ether. The method of claim 1, Wherein said glycerol or glycerol containing composition is obtained from a byproduct of a biodiesel production reaction. The method of claim 1, The resulting glycerol ether is characterized in that it contains di-glycerol tertiary butyl ether (di-GTBE) and tri-glycerol tertiary butyl ether (tri-GTBE) Method for producing glycerol ether. The method of claim 1, The metal-containing ion exchange resin is a group consisting of lithium (Li), sodium (Na), barium (Ba), magnesium (Mg), cesium (Cs), aluminum (Al), lanthanum (La) and silver (Ag). A method for producing glycerol ether, characterized in that it contains at least one metal selected from. The method of claim 1, The metal-containing ion exchange resin is a method for producing glycerol ether, characterized in that the powder form. The method of claim 1, The ion exchange resin is a method for producing glycerol ether, characterized in that the spherical porous polymer having a sulfonic acid functional group. The method of claim 6, The porous polymer is a method for producing glycerol ether, characterized in that the polystyrene divinylbenzene copolymer (Polystyrene-Divinylbenzene Copolymer). The method of claim 1, The metal-containing ion exchange resin comprises Ag, the method of producing a glycerol ether, characterized in that the substitution rate of Ag in the ion exchange resin is 25 to 75%. The method of claim 1, Dioxane (dioxane) is further added as an auxiliary solvent in the reaction vessel. The method of claim 1, Before adding the glycerol or glycerol containing composition to the reaction vessel, by reacting the glycerol or glycerol containing composition with methanol, further comprising the step of replacing the hydrogen of the hydroxy group in the glycerol with a methyl group Manufacturing method. The method of claim 10, Wherein said substitution is carried out under a phosphoric acid catalyst. 100 parts by weight of petroleum fuel of either diesel fuel or gasoline fuel; And For automobiles comprising 1 to 10 parts by weight of at least one glycerol ether selected from the group consisting of di-glycerol tertiary butyl ether and tri-glycerol tertiary butyl ether Fuel composition. The method of claim 12, Methyl tert-butyl glycerol ether (Methyl-t-Butyl Glylcerol Ether, MBGE) 1 to 10 parts by weight of a fuel composition for automobiles further comprising.

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