KR101104570B1 - Method of manufacturing glycerol mono-t-butyl ether - Google Patents

Abstract

Provided is a method for preparing mono-glycerol tertiary butyl ether by reacting a glycerol or a glycerol-containing composition under a hydrophobic solvent with a liquid isobutene using a catalyst for etherification reaction. The glycerol or glycerol containing composition can be obtained from by-products generated in the production of biodiesel.

Description

Method of manufacturing mono-glycerol tertiary butyl ether {Method of manufacturing glycerol mono-t-butyl ether}

The present invention relates to a method for preparing glycerol ether, and more particularly, to a method for effectively preparing mono-glycerol tertiary butyl ether to ensure high selectivity and high yield.

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, in view of the usefulness of the glycerol ether in the glycerol derivatives, the inventors have studied a method for producing mono-glycerol tertiary butyl ether as an example of the glycerol ether-based compounds in a selective and high efficiency.

One embodiment of the present invention in consideration of the usefulness of the glycerol ether as described above, efficiently preparing mono-glycerol tertiary butyl ether (mono-gylcerol tertiary butyl ether, mono-GTBE) from the glycerol or glycerol-containing composition Provide a way to.

Method for producing a mono-glycerol tertiary butyl ether according to an aspect of the present invention is to react a glycerol (glycerol) or glycerol-containing composition with a liquid isobutene (iso-butene) using a catalyst for the etherification reaction in a hydrophobic solvent Steps. As the hydrophobic solvent, an ether solvent may be used. For example, a short-chain ether compound may be used. Moreover, solvents, such as dioxane, can also be used.

As said glycerol or glycerol containing composition, what is obtained from the by-product of a biodiesel formation reaction can be used. On the other hand, the hydrophobic solvent may be used in a molar ratio of 1 to 5 moles with respect to 1 mole of glycerol or 1 mole of glycerol in the glycerol-containing composition.

The above-described reaction may be performed at a temperature of 50 to 150 ° C., and the isobutene may be used in a molar ratio of 1 to 5 moles with respect to 1 mole of glycerol or 1 mole of glycerol in the glycerol-containing composition. In addition, the reaction may be made in a batch reaction (batch reaction), for this purpose it can be used as a reactor having a stirrer to enable continuous stirring.

The catalyst for the etherification reaction may include Bronsted acid or Lewis acid, the catalyst for the etherification reaction, for example, lithium (Li), sodium (Na), barium (Ba), magnesium (Mg) And ion exchange resins containing cesium (Cs), aluminum (Al), lanthanum (La), silver (Ag), or mixtures thereof. Alternatively, as the catalyst for the etherification reaction, a heteropolyacid in which a metal is coordinated can be used.

According to the production method of mono-glycerol tertiary butyl ether according to the present invention, it is possible to synthesize mono-glycerol tertiary butyl ether with high selectivity from glycerol, and further excellent in process efficiency.

In addition, the yield of mono-glycerol tertiary butyl ether is maximized by maximizing the glycerol conversion of the mono-glycerol tertiary butyl ether synthesis reaction and the selectivity of mono-GTBE by appropriately adjusting the end time of the reaction. Can be optimized.

Hereinafter, the present invention will be described in detail.

According to one embodiment of the present invention, the mono-glycerol tertiary butyl ether is prepared by reacting glycerol or a glycerol-containing composition with a liquid isobutene in a hydrophobic solvent using an etherification catalyst. This can be done by.

The glycerol refers to purified glycerol, and the glycerol-containing composition refers to glycerol which is non-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 advantageous in terms of economics to use a glycerol component which is generated as a by-product in the production of biodiesel.

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

Glycerol ether as a reaction product can be obtained by etherification of glycerol and isobutene or alcohols such as methanol, ethanol and butanol.

The glycerol ether that can be produced when using glycerol as a reactant may have various forms by substituting various alkyl groups of the following Table 1 in the positions of R ₁ , R ₂ , and R ₃ of Formula (2).

As shown in Table 1, the glycerol ethers produced were mono-glycerol tertiary butyl ether (mono-GTBE) and di-glycerol tertiary butyl ether depending on the number of substitutions. ether, di-GTBE) and 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 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-butene, i-butene) 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).

The present invention provides a process for the efficient production of mono-GTBE in said glycerol ethers. That is, the present invention provides a method for increasing the selectivity and yield of the mono-GTBE.

According to one embodiment of the present invention, through the use of the hydrophobic solvent, it is possible to increase the selectivity of the mono-GTBE, it is possible to manufacture only mono-GTBE in high yield selectively. As the hydrophobic solvent, an ether solvent can be used, and preferably, a short chain or a low molecular weight ether compound can be used. Di-ethyl ether, methyl butyl ether, etc. are mentioned as an example of the said ether type compound. Dioxane or the like can also be used as the hydrophobic solvent. After completion of the reaction through the use of the hydrophobic solvent, phase separation of the product is induced to enable efficient separation of the active product. After the reaction, two phase separated liquid phases occur in the reactor, the upper layer separated mainly to contain the active product and the hydrophobic solvent, and the lower layer contains unreacted glycerol and catalyst. The active product includes mono-GTBE, di-GTBE and tri-GTBE.

The isobutene participates in the reaction in the liquid phase. Isobutene is usually present in the gas phase under atmospheric pressure, but in this reaction, it participates in the liquid phase by the pressure conditions in the reactor. Therefore, the reactor is preferably a reactor having a pressure control device, the pressure in the reactor can be adjusted by injecting nitrogen gas into the reactor. During the reaction, the pressure in the reactor is preferably adjusted to 300 to 400 psi. Furthermore, the reactor may comprise a continuously stirrable stirrer.

It is also desirable to control the quantitative relationship of the reactants participating in the reaction for efficient reaction. For example, the amount of the hydrophobic solvent is preferably adjusted to have a molar ratio of 1 to 5 moles per 1 mole of glycerol (or glycerol in the glycerol-containing composition). In addition, the amount of isobutene is preferably adjusted to have a molar ratio of 1 to 5 moles with respect to 1 mole of the glycerol (or glycerol in the glycerol-containing composition).

The reaction takes place under a temperature range of 50 to 150 ° C, preferably 50 to 90 ° C. When reacting under a temperature condition outside of the temperature range, the reaction may not occur or the selectivity of the mono-GTBE to be produced may be significantly reduced.

The reaction may be entirely in a batch reaction.

The catalyst for esterification reaction used in the ester production reaction may be a catalyst of Bronsted acid or Lewis acid, for example, heteropoly acid or heteropoly acid salt. Can be used. On the other hand, a metal-containing ion exchange resin may be used as the catalyst. 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. On the other hand, by using powdered metal-containing ion exchange resin as the catalyst, the reaction efficiency can be further increased.

In contrast, the reaction catalyst may be a metal-containing heteropolyacid, such as metal-containing phosphoric acid in the form of a metal and oxygen bonded like grapes, for example, may be used tungsostungic acid (phosphotungstic acid).

In the present invention, the mono-GTBE prepared above may 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 mono-GTBE generated and selected as described above in addition to petroleum fuels such as gasoline and diesel.

[Example]

Example 1

13.9 g of glycerol was added into 80 ml of a pressure etherification reactor pre-added with 0.8 g of phosphotungstic acid and 16 g of diethyl ether. 25.5 g of isobutene were added into the reactor and the pressure in the reactor was maintained at 350 psi using nitrogen. The reactants were reacted by heating the reactor to a temperature of 60 ° C. and agitating at a speed of 1200 rpm. After the reaction was completed, the products in the reactor were phase separated into two layers. The upper layer was separated from the two separated layers to volatilize the diethyl ether component included, and the product was analyzed. Based on the analysis results, the conversion rate (G) and selectivity (S) of glycerol were evaluated to calculate the yield (Y), and the results are shown in Table 2. In addition, Table 2 shows the change in data according to the reaction time, respectively.

time
(h) G, wt% MTBG, wt% DTBG, wt% TTBG, wt% DIB, wt% G conver-sion,% S MTBG,
% S DTBG,
% S TTBG,
% Y MTBG,
% Y DTBG,
% Y TTBG,
% 0.50 7.8% 79.6% 11.7% 0.0% 0.0% 0% 90% 10% 0% 0% 0% 0% 0.75 4.1% 83.4% 10.0% 0.0% 0.0% 3% 92% 8% 0% 3% 0% 0% 1.25 4.2% 83.8% 11.0% 0.0% 0.1% 4% 91% 9% 0% 4% 0% 0% 2.00 5.2% 76.5% 15.0% 0.0% 0.2% 11% 88% 12% 0% 10% One% 0% 3.00 6.2% 70.6% 19.6% 0.1% 0.5% 23% 83% 17% 0% 20% 3% 0% 5.92 9.8% 60.2% 26.0% 0.3% 1.6% 45% 76% 24% 0% 37% 7% 0% 8.75 9.9% 60.9% 26.3% 0.5% 1.2% 70% 76% 24% 0% 53% 17% 0% 22.08 2.6% 25.0% 54.7% 12.5% 3.9% 70% 35% 55% 10% 53% 17% 0%

G-glycerol; MTBG- mono-t-butyl ether of glycerol; DTBG-di-t-butyl ether of glycerol; TTBG- tri-t-butyl ether of glycerol; DIB-di-isobutene; S-selectivity; Y-yield

[Example 2]

15.9 g of glycerol was added into 80 ml of a pressure etherification reactor pre-added with 0.8 g of phosphotungstic acid and 18 g of diethyl ether. 21.3 g of isobutene was added into the reactor and the pressure in the reactor was maintained at 350 psi using nitrogen. The reactants were reacted by heating the reactor to a temperature of 60 ° C. and agitating at a speed of 1200 rpm. After the reaction was completed, the products in the reactor were phase separated into two layers. The upper layer was separated from the two separated layers to volatilize the diethyl ether component included, and the product was analyzed. Based on the analysis results, the conversion rate (G) and selectivity (S) of glycerol were evaluated to calculate the yield (Y), and the results are shown in Table 3. In addition, Table 3 shows the change in data according to the reaction time, respectively.

time
(h) G, wt% MTBG, wt% DTBG, wt% TTBG, wt% DIB, wt% G conver-sion,% S MTBG,
% S DTBG,
% S TTBG,
% Y MTBG,
% Y DTBG,
% Y TTBG,
% 0.50 6% 75% 17% One% 0% 3% 86% 14% One% 3% 0% 0% 1.50 4% 69% 19% 7% 0% 11% 80% 16% 5% 9% 2% One% 3.00 6% 73% 19% One% 0% 45% 84% 16% 0% 38% 7% 0% 4.33 7% 66% 23% 0% One% 73% 80% 20% 0% 58% 15% 0% 8.17 11% 61% 27% 0% 0% 68% 75% 25% 0% 51% 17% 0% 22.00 5% 33% 51% 9% One% 91% 44% 49% 7% 40% 45% 6%

G-glycerol; MTBG- mono-t-butyl ether of glycerol; DTBG-di-t-butyl ether of glycerol; TTBG- tri-t-butyl ether of glycerol; DIB-di-isobutene; S-selectivity; Y-yield

Comparative Example 1

14 g of glycerol were added into 80 ml of a pressure etherification reactor pre-added with 0.8 g of phosphotungstic acid. 25.5 g of isobutene were added into the reactor and the pressure in the reactor was maintained at 350 psi using nitrogen. The reactants were reacted by heating the reactor to a temperature of 60 ° C. and agitating at a speed of 1200 rpm. After the reaction was completed, the products in the reactor were phase separated into two layers. The upper layer was separated from the two separated layers to volatilize the diethyl ether component included, and the product was analyzed. Based on the analysis results, the conversion rate (G) and the selectivity (S) of glycerol were evaluated to calculate the yield (Y), and the results are shown in Table 4. In addition, Table 4 shows the change in data according to the reaction time, respectively.

time
(h) G, wt% MTBG, wt% DTBG, wt% TTBG, wt% DIB, wt% G conver-sion,% S MTBG,
% S DTBG,
% S TTBG,
% Y MTBG,
% Y DTBG,
% Y TTBG,
% 2 6% 98% One% 0% 0% One% 90% 0% 0% One% 0% 0% 6 7% 0% 6% 49% 7% 100% 10% 58% 32% 10% 57% 32% 21 11% 0% 10% 47% 17% 100% 18% 60% 22% 18% 60% 22% 31 5% 0% 12% 47% 19% 100% 21% 60% 19% 21% 60% 19%

G-glycerol; MTBG- mono-t-butyl ether of glycerol; DTBG-di-t-butyl ether of glycerol; TTBG- tri-t-butyl ether of glycerol; DIB-di-isobutene; S-selectivity; Y-yield

Comparative Example 2

14 g of glycerol was added into 80 ml of a pressure etherification reactor pre-added with 0.8 g of bead type reaction catalyst (product name: Amberlyst 15). 25.5 g of isobutene were added into the reactor and the pressure in the reactor was maintained at 350 psi using nitrogen. The reactants were reacted by heating the reactor to a temperature of 60 ° C. and agitating at a speed of 1200 rpm. After the reaction was completed, the products in the reactor were phase separated into two layers. The upper layer was separated from the two separated layers to volatilize the diethyl ether component included, and the product was analyzed. Based on the analysis results, the conversion rate (G) and the selectivity (S) of glycerol were evaluated to calculate the yield (Y) and the results are shown in Table 5. In addition, Table 5 shows the change in data according to the reaction time, respectively.

time
(h) G, wt% MTBG, wt% DTBG, wt% TTBG, wt% DIB, wt% G conver-sion,% S MTBG,
% S DTBG,
% S TTBG,
% Y MTBG,
% Y DTBG,
% Y TTBG,
% One 93% 6% One% 0% 0% 4% 93% 6% One% 4% 0% 0% 2 84% 16% 0% 0% 0% 11% 98% 2% 0% 11% 0% 0% 4.7 66% 29% 3% One% 2% 23% 92% 6% One% 21% One% 0% 8.0 5% 35% 45% 11% 4% 91% 48% 44% 8% 43% 40% 8% 12.5 One% 6% 44% 32% 16% 98% 14% 58% 32% 10% 57% 32% 21.0 One% 14% 46% 17% 17% 98% 24% 59% 17% 24% 58% 16%

G-glycerol; MTBG- mono-t-butyl ether of glycerol; DTBG-di-t-butyl ether of glycerol; TTBG- tri-t-butyl ether of glycerol; DIB-di-isobutene; S-selectivity; Y-yield

Glycerol Conversion rate  evaluation

Glycerol conversion was evaluated based on the results of Table 2, Table 3 and Table 4, which are the results of analyzing the active ingredients in the upper solution obtained in Examples 1, 2 and Comparative Example 1.

1 is a graph showing the glycerol conversion rate according to the time and the presence or absence of ether solvent, isobutene / glycerol content ratio. Referring to FIG. 1, it can be seen that in the case of the reaction according to Examples 1 and 2, the initial (within 5 hours) glycerol conversion rate is sharply increased compared to the reaction according to Comparative Example 1.

mono - GTBE  Selectivity evaluation

The selectivity of mono-glycerol tertiary butyl ether (mono-GTBE) was determined based on the results of Table 2, Table 3 and Table 4, which are the results of analyzing the active ingredients in the supernatant solutions obtained in Examples 1, 2 and Comparative Example 1. Evaluated.

Figure 2 is a graph showing the change in selectivity of mono-glycerol tertiary butyl ether with time, with or without ether solvent, isobutene / glycerol content ratio. Referring to FIG. 2, the reactions according to Examples 1 and 2 showed the first day and higher mono-GTBE (MTBG) selectivity compared to the reactions according to Comparative Example 1, in particular, initial (within 5 hours) mono- It can be seen that the GTBE selectivity is very high.

mono - GTBE  Yield evaluation

The yield of mono-glycerol tertiary butyl ether (mono-GTBE) was evaluated based on the results of Table 2, Table 3 and Table 4, which were the results of analyzing the active ingredients in the supernatant solutions obtained in Examples 1, 2 and Comparative Example 1. It was.

Figure 3 is a graph showing the change in yield of mono-glycerol tertiary butyl ether with time and the presence of ether solvent, isobutene / glycerol content ratio. Referring to FIG. 3, the reactions according to Examples 1 and 2 showed consistently higher mono-GTBE (MTBG) yields than the reactions according to Comparative Example 1, in particular, initial (within 5 hours) mono-GTBE. It can be seen that the yield is very high.

di - GTBE  And tri - GTBE Yield evaluation

Di-glycerol tertiary butyl ether (di-GTBE) and tri-glycerol based on the results of Table 2, Table 3 and Table 4 as a result of analyzing the active ingredients in the upper solution obtained in Examples 1, 2 and Comparative Example 1 The yield of tertiary butyl ether (tri-GTBE) was evaluated.

4 is a graph showing the yield change of di-glycerol tertiary butyl ether and tri-glycerol tertiary butyl ether according to the time and the presence or absence of ether solvent, isobutene / glycerol content ratio. Referring to FIG. 3, the yields of di-GTBE (FIG. 4A) and tri-GTBE (FIG. 4B) were consistently limited compared to the reactions according to Comparative Example 1 for the reactions according to Examples 1 and 2. In particular, the initial (within 10 hours) can be seen that the yield of the di-GTBE (DTBG) and tri-GTBE (TTBG) is significantly limited. Therefore, by properly adjusting the end time of the reaction, it can be seen that the selectivity and yield of mono-GTBE (MTBG) can be maximized.

1 is a graph showing the glycerol conversion rate according to the time and the presence or absence of ether solvent, isobutene / glycerol content ratio.

Figure 2 is a graph showing the change in selectivity of mono-glycerol tertiary butyl ether with time, with or without ether solvent, isobutene / glycerol content ratio.

Figure 3 is a graph showing the change in yield of mono-glycerol tertiary butyl ether with time and the presence of ether solvent, isobutene / glycerol content ratio.

4 is a graph showing the yield change of di-glycerol tertiary butyl ether and tri-glycerol tertiary butyl ether according to the time and the presence or absence of ether solvent, isobutene / glycerol content ratio.

Claims (14)

Reaction of glycerol or a glycerol-containing composition with liquid isobutene using a metal-containing heteropolyacid catalyst in the presence of at least one hydrophobic solvent selected from the group consisting of di-ethyl ether, methyl butyl ether and dioxane To prepare mono-glycerol tertiary butyl ether. delete delete delete The method of claim 1, Said glycerol or glycerol containing composition is obtained from a byproduct of a biodiesel production reaction. The method of claim 1, Wherein said hydrophobic solvent is used in a molar ratio of 1 to 5 moles per 1 mole of said glycerol. The method of claim 1, The reaction is carried out under a temperature of 50 to 150 ℃. The method of claim 1, Wherein the isobutene is used in a molar ratio of 1 to 5 moles per 1 mole of glycerol. The method of claim 1, Wherein said reaction consists of a batch reaction. The method of claim 1, The reactor in which the reaction takes place is characterized in that it comprises a stirrer capable of continuous stirring. delete delete delete The method of claim 1, Wherein said metal-containing heteropolyacid is tungstoic acid.

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