KR101804762B1 - Catalyst for preparing alkylene carbonate, method for preparing the catalyst, method and apparatus for preparing alkylene carbonate using the catalyst - Google Patents

Abstract

The present invention relates to a catalyst for preparing alkylene carbonate and, more specifically, to a catalyst for preparing alkylene carbonate which is a heterogeneous catalyst including an ester group (-COO-), a preparation method thereof, and a method and an apparatus for preparing alkylene carbonate by reacting alkylene oxide and carbon dioxide using the catalyst. The catalyst can react at low temperature and low pressure with respect to reaction conditions by an existing catalyst, can reduce reaction time and can obtain alkylene carbonate with high yield. Also, durability of the catalyst can be improved; the catalyst can be reused since separation with products is easy; and catalyst yield can be maintained even if the catalyst is repeatedly reused.

Description

TECHNICAL FIELD The present invention relates to a catalyst for preparing an alkylene carbonate, a method for preparing the same, and a method and an apparatus for producing an alkylene carbonate using the catalyst.

TECHNICAL FIELD The present invention relates to a catalyst for the production of an alkylene carbonate, a method for producing the same, and a method and apparatus for producing an alkylene carbonate using the catalyst.

BACKGROUND ART Alkylene carbonates such as ethylene carbonate and propylene carbonate are widely used as solvents and diluents in industrial processes, and are also used as cosmetic raw materials and secondary battery electrolytes. In addition, since alkylene glycol can be used as an intermediate in the preparation of an alkylene oxide, there is a growing interest in alkylene carbonates.

Conventionally, a method of reacting ethylene glycol with phosgene (COCl ₂ ) has been used for the production of alkylene carbonate. This reaction proceeds non-catalytic at normal temperature. However, due to the toxicity of the raw material phosphorane and the byproduct of hydrogen chloride, which is an environmental pollutant, recently, a process of mainly reacting alkylene oxide with carbon dioxide has been used.

However, since the reaction step of reacting an alkylene oxide with carbon dioxide to produce an alkylene carbonate requires a reaction under high temperature and high pressure, unlike a phosphine process which proceeds at room temperature without a catalyst, the alkylene oxide as a raw material is decomposed or There is a risk of explosion as well as a problem of mass production of by-products by polymerization.

In order to solve these problems, various catalysts have been developed and the reaction has been carried out at low temperature and low pressure.

For example, Japanese Patent Application Laid-Open No. 9-67365 discloses a method of using KI as a catalyst. In Japanese Patent Laid-open No. 59-13776, tributyl methylphosphonium iodide and tetraalkylphosphonium Describes a method using a tetraalkyl phosphonium halide.

Japanese Patent Application Laid-Open No. 9-235252 discloses a method using a polystyrene copolymer polymer having a quaternary phosphonium halide in the terminal group. In this document, it is described that when the reaction temperature is changed from 100 to 170 ° C for 1 to 5 hours, the yield reaches 50 to 95%.

However, these catalysts are expensive because they are ionic liquids. In the process using an actual commercialized homogeneous catalyst, an inorganic halide catalyst is used. The reaction temperature is 180 ° C., the pressure is 100 atm, the reaction time is 8 hours or more And the moisture content of carbon dioxide and alkylene oxide as raw materials must be controlled to several hundreds ppm or less.

In addition, since the inorganic halide material is a homogeneous catalyst that is dissolved in reactants and products, it is vacuum distilled to separate the product from the catalyst, and the separated catalyst is also discarded because it can not be recycled.

Japanese Patent Application Laid-Open No. 7-206846 discloses a method using a catalyst in which CsOH, RbOH and ammonium halide are substituted for an ion exchange resin by a method using an ion exchange resin.

U.S. Patent No. 4,233,221 describes a method of using ion exchange resins of the Dowex and Amberlite series. However, in this method, the yield of alkylene carbonate is only about 30 to 80%.

In addition to the catalysts described above, U.S. Patent No. 5,283,356 discloses that Co, Cr, Fe. (Rb) instead of a hydrogen ion of heteropoly acid is disclosed in JP-A-7-206547, and a method of using a phthalocyanine including Mn, Ni, Ti, V, Zr, Or a cesium (Cs) ion. However, in both cases, expensive catalysts are required, and the reaction temperature is in the mild condition of 120 to 180 캜, but the yield is insufficient at 30 to 90%.

As described above, in the method according to the prior art, in order to produce alkylene carbonate, the reaction conditions such as high temperature and pressure, long reaction time, moisture removal of raw materials, and the like are difficult, and selectivity and yield are low.

In addition, most of the catalysts of the prior art are poor in thermal stability, so that they are partially decomposed during a high-temperature reaction or distillation purification process to generate halide ions, and the generated halide ions react with alkylene oxides to generate halide- do.

On the other hand, a catalyst composed of manganese halide (MnX2, X = Cl, Br, I) and an alkali metal halide (U.S. Patent No. 6,160,130) and indium and lead halide as an improved catalyst for conducting the reaction under milder conditions, And halides (U.S. Patent No. 6,156,909). However, since these catalysts are homogeneous catalysts, there is a problem in recovering and reusing catalysts.

Patent Document 1: JP-A-9-67365 Patent Document 2: JP-A-59-13776 Patent Document 3: JP-A-9-235252 Patent Document 4: U.S. Patent No. 2,773,070 Patent Document 5: JP-A-7-206846 Patent Document 6: U.S. Patent No. 4,233,221 Patent Document 7: U.S. Patent No. 5,283,356 Patent Document 8: JP-A 7-206547 Patent Document 9: U.S. Patent No. 6,160,130 Patent Document 10: U.S. Patent No. 6,156,909

In an exemplary embodiment of the present invention, in one aspect, an alkylene carbonate capable of producing an alkylene carbonate in a high yield in a short time under mild reaction conditions at a low temperature and a low pressure by promoting a reaction between an alkylene oxide and carbon dioxide A method for producing the same, and a method and an apparatus for producing an alkylene carbonate using the catalyst.

In an exemplary embodiment of the present invention, there is provided a catalyst for producing alkylene carbonate, which is excellent in durability, advantageous in recovery and reuse of the catalyst, capable of maintaining the yield even when the catalyst is repeatedly used, And a method for producing an alkylene carbonate using the catalyst.

In exemplary embodiments of the present invention, as a catalyst for producing an alkylene carbonate, there is provided a catalyst for producing an alkylene carbonate containing an ester group (-COO-).

In an exemplary embodiment of the present invention, in another aspect, there is provided a process for preparing a catalyst for the production of an alkylene carbonate, comprising reacting a catalyst compound comprising at least one of a halide, an amine group and a hydroxyl group with an ester reaction precursor The present invention also provides a process for producing a catalyst for producing an alkylene carbonate.

Exemplary embodiments of the present invention also provide a method and apparatus for producing an alkylene carbonate by reacting an alkylene oxide with carbon dioxide in the presence of the catalyst for producing an alkylene carbonate.

According to the exemplary embodiments of the present invention, by promoting the carbon dioxide reaction with the alkylene oxide, it is possible to perform the reaction at a low temperature and a low pressure as compared with the reaction condition by the existing catalyst and to shorten the reaction time, Can be obtained.

In addition, the catalyst according to the exemplary embodiments of the present invention can be separated by simple precipitation and filtration by separating the product and the catalyst after the reaction with a heterogeneous catalyst which is not dissolved in reactants and products, Because it is also recyclable, it is also economically advantageous. Further, the durability of the catalyst is high and the catalyst yield can be maintained even when the catalyst is repeatedly used.

Figure 1 shows the FT-IR measurement results of the catalyst prepared in the example of the present invention.
Figure 2 is a GC / MS analysis result of four repeated experiments in an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail.

In the present specification, the alkyl group means straight chain or branched hydrocarbon, including, but not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.

As used herein, an aryl group may include both an aromatic group and a heteroaromatic group and a partially reduced derivative thereof. The arometical group is, for example, a simple or fused ring group of 5 to 15-ary, and the heteroaromatic group means an arometric group containing at least one hetero atom such as oxygen, sulfur or nitrogen.

Exemplary aryl groups include phenyl, benzyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, ), Oxazolyl, thiazolyl, tetrahydronaphthyl, and the like, but are not limited thereto.

The haloalkyl group as used herein refers to an alkyl group in which one or more of the hydrogens is substituted with a halogen, such as, but not limited to, trifluoromethyl, chloromethyl, and the like.

In exemplary embodiments of the present invention, as a catalyst for producing an alkylene carbonate, there is provided a catalyst comprising an ester group (-COO-). The catalyst also includes at least one of an amine group, a hydroxyl group (-OH), and a halide component. In this catalyst, the ester group serves to strengthen the bond of at least one of an amine group, a hydroxyl group, and a halide. In addition, this catalyst is a heterogeneous catalyst.

As described above, unlike the existing catalysts, the catalyst for preparing alkylene carbonates has an amine group, a hydroxy group, and a halide material immobilized by a chemical bond of an ester group in the catalyst, promoting carbon dioxide absorption, to cause a carbon dioxide addition reaction.

Further, since the ester group of the catalyst can strengthen the chemical bond of the amine group, the hydroxy group, and the halide, and can not be dissolved in reactants and products, the catalytic reactivity and durability can be improved.

In one exemplary embodiment, the catalyst is a catalyst represented by the following formula (1).

As shown in the above formula (1), the catalyst for producing an alkylene carbonate includes an ester group (-COO-), and also includes an amine group, a hydroxyl group (-OH), and a halide component.

Halide in Formula 1 is F, Cl, Br or I, and Br or I is preferable in view of the effect of the ring opening of O epoxide and the effect of carbon dioxide addition reaction.

In an exemplary embodiment of the present invention, in another aspect, there is provided a process for preparing a catalyst for the production of an alkylene carbonate, comprising reacting a catalyst compound comprising at least one of a halide, an amine group and a hydroxyl group with an ester reaction precursor The present invention also provides a process for producing a catalyst for producing an alkylene carbonate.

In an exemplary embodiment, the method comprises the steps of: generating a catalytic compound comprising an amine precursor, an aldehyde precursor, and an ammonium halide, wherein the catalyst compound comprises a halide, an amine group, and a hardoxy group; And reacting the catalyst compound with an ester reaction precursor to produce an ester group in the catalyst compound.

In one exemplary embodiment, the amine precursor is selected from the group consisting of urea, melamine, dicyandiamide, urea, melamine, cyanamide, guanidine, at least one substance including biguanidine, guarylurea, polycyclic guanidine and the like may be used.

In one exemplary embodiment, the aldehyde precursor may be one or more materials known as aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, glutaraldehyde, benzaldehyde, and the like.

In one exemplary embodiment, the ammonium halide may be at least one selected from, for example, NH ₄ I, NH ₄ Br, NH ₄ Cl, and the like.

In an exemplary embodiment, the ester reaction precursor may be selected from the group consisting of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, polyacrylic acid (PAA) , Graphene oxide, alginic acid, and the like, and a carboxyl group.

Exemplary embodiments of the present invention also provide a method of producing an alkylene carbonate by reacting an alkylene oxide with carbon dioxide under the catalyst for producing an alkylene carbonate.

Exemplary embodiments of the present invention also provide an apparatus for producing an alkylene carbonate wherein an alkylene oxide is reacted with carbon dioxide to produce an alkylene carbonate, wherein the apparatus comprises the catalyst.

In an exemplary embodiment, the alkylene oxide is represented by the following formula (2), and the alkylene carbonate may be a compound represented by the following formula (3).

In the above formulas 2 and 3, R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an aryl group, Can be formed.

In an exemplary embodiment, the alkylene oxide represented by Formula 2 includes, for example, ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, styrene oxide, cyclohexylene oxide, and the like. It is not.

In an exemplary embodiment, the amount of the catalyst to be used is preferably 0.0001-20 parts by weight, more preferably 0.1-5 parts by weight, based on 100 parts by weight of the alkylene oxide. When the amount is less than 0.0001 part by weight, the reaction rate may be too slow. When the amount is more than 20 parts by weight, the reaction rate and selectivity may not be further improved.

In an exemplary embodiment, the reaction temperature of the reaction may be 40-150 ° C or 80-150 ° C. If the reaction temperature is too low, the reaction rate may be slowed down. If the reaction temperature is too high, the alkylene oxide may cause self-polymerization and thus the reaction selectivity may be deteriorated.

In an exemplary embodiment, the reaction pressure of the reaction is 10 to 30 atm. When the reaction pressure is lower than 10 atm, the reaction rate may be slowed. If the reaction pressure is higher than 30 atm, the reaction rate is not improved but the apparatus cost may be excessively high.

In an exemplary embodiment, the yield of the reaction is 90-99%.

In an exemplary embodiment, the reaction time of the reaction is 3 to 5 hours.

In an exemplary embodiment, a reaction solvent is used in the reaction, and as the reaction solvent, the same alkylene carbonate as the product may be used. This is because the alkylene oxide, which is a reactant, has a high reactivity and is explosion dangerous. Therefore, it is possible to improve process safety by mixing stable alkylene carbonate as a product.

Hereinafter, specific embodiments according to embodiments of the present invention will be described in more detail. It should be understood, however, that the invention is not limited to the embodiments described below, but that various embodiments of the invention may be practiced within the scope of the appended claims, It will be understood that the invention is intended to facilitate the practice of the invention to those skilled in the art.

[ Example  One]

Of the new catalyst Manufacturing example  One

In a three-necked flask equipped with a thermometer, a reflux condenser and a dropping device, 5 g of biguanidine, 2.2 g of iodoammonium and 5.2 g of 35% formaldehyde were added and the mixture was stirred at a reaction temperature of 75 ° C and a pH of 3 for 1 hour. 5.2 g of 35% formaldehyde is further added via a dropping device, the pH is adjusted to 4.0 with a 20% hydrochloric acid solution, and the mixture is reacted for 12 hours.

1.5 g of the catalyst precursor synthesized by the above method, 50 g of distilled water and 0.5 g of polyacrylic acid were charged in a 100 mL two-necked flask equipped with a reflux condenser, and the reaction was carried out for 2 hours while stirring at 60 캜.

After the reaction, the water was removed under reduced pressure using a rotary evaporator, and a new catalyst powder containing an ester group was synthesized.

[ Example  2]

Of the new catalyst Manufacturing example  2

3.6 g of urea, 2.2 g of ammonium iodide, 5.0 g of 35% formaldehyde and 0.05 g of diethylenetriamine were placed in a three-necked flask equipped with a thermometer, a reflux condenser and a dropping device. After addition of 5.0 g of 35% formaldehyde through a dropping funnel, the mixture was adjusted to pH 4.0 with 20% hydrochloric acid solution and reacted for 12 hours.

1.5 g of the catalyst precursor synthesized by the above method, 50 g of distilled water and 0.5 g of graphene oxide were charged in a 100 mL two-necked flask equipped with a reflux condenser, and the reaction was carried out at 60 DEG C for 2 hours with stirring.

After the reaction, the water was removed under reduced pressure using a rotary evaporator, and a new catalyst powder containing an ester group was synthesized.

1 shows the FT-IR measurement results of the catalyst prepared in Example 1 of the present invention.

From the results of the FT-IR measurement of FIG. 1, it was confirmed that the produced catalyst had C≡N, C = N, -OH, and the like. In addition, the presence of an ester group was confirmed from C-O and C = O

Alkylene Of carbonate  Produce

Propylene oxide (PO, 10 g, 0.17 mol) and the new catalyst (0.2 g) obtained in Example 1 were charged in a 100-mL high-pressure reactor and then charged with carbon dioxide (CO ₂ ) to raise the temperature to 130 ° C.

Carbon dioxide was added again to bring the reactor pressure to 20 atm. After the reaction was carried out for 4 hours, the reactor was cooled to room temperature, and the catalyst was recovered. The catalyst was dried at 80 ° C for 12 hours, and the weight was measured and the catalyst was repeatedly used four times.

Figure 2 is a GC / MS analysis result of four repeated experiments in an embodiment of the present invention.

As can be seen from FIG. 2, the yield of propylene carbonate was 99.9% (PO → PC yield: 99.9%), and no halation impurities were produced. For reference, the yield is calculated by the following equation.

Yield (%) = (number of moles of alkylene carbonate / number of mols of raw alkylene oxide) x 100

As described above, when the catalyst of the exemplary embodiments of the present invention is used, the reaction can be performed at a low temperature and a low pressure as compared with the reaction conditions using existing catalysts, and the reaction time can be shortened and alkylene carbonate can be obtained in a high yield . Further, the durability of the catalyst can be improved, and a high catalyst yield can be maintained even after repeated use and reuse.

Claims (19)

As a catalyst for producing an alkylene carbonate,
Wherein the catalyst is a heterogeneous catalyst comprising both an ester group (-COO-), an amine group (-NH ₂ ), a hydroxyl group (-OH) and a halide.
delete The method according to claim 1,
Wherein the catalyst is represented by the following formula (1).
[Chemical Formula 1]

(Wherein n is a repeating unit)
The method according to claim 1,
Wherein the halide is Br or < RTI ID = 0.0 > I. < / RTI >
A process for producing a catalyst for the production of an alkylene carbonate according to any one of claims 1, 3 and 4,
Reacting a catalyst compound comprising all of a halide, an amine group, and a hydroxy group with an ester reaction precursor.
6. The method of claim 5,
The method includes the steps of: generating a catalyst compound comprising an amine precursor, an aldehyde precursor, and an ammonium halide, wherein the catalyst compound comprises a halide, an amine group, and a hydroxy group; And
And reacting the catalyst compound with an ester precursor to produce an ester group in the catalyst compound.
The method according to claim 6,
The amine precursor may be selected from the group consisting of urea, melamine, dicyandiamide, cyanamide, guanidine, biguanidine, guarylurea, polycyclic guanidine). < / RTI >
The method according to claim 6,
Wherein the aldehyde precursor is at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, glutaraldehyde and benzaldehyde.
The method according to claim 6,
Wherein the ammonium halide is at least one selected from NH ₄ I, NH ₄ Br and NH ₄ Cl.
The method according to claim 6,
The ester reaction precursor may be selected from the group consisting of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, polyacrylic acid (PAA), graphene oxide , And alginic acid. The method for producing a catalyst for producing an alkylene carbonate according to claim 1,
A process for producing an alkylene carbonate, which comprises reacting an alkylene oxide with carbon dioxide in the presence of a catalyst for the production of an alkylene carbonate according to any one of claims 1, 3 and 4 to produce an alkylene carbonate.
An apparatus for producing an alkylene carbonate by reacting an alkylene oxide with carbon dioxide to produce an alkylene carbonate,
The apparatus for producing an alkylene carbonate according to any one of claims 1, 3, and 4, comprising a catalyst for producing an alkylene carbonate.
13. The method of claim 12,
Wherein the alkylene oxide is represented by the following formula (1), and the alkylene carbonate is a compound represented by the following formula (2).
[Chemical Formula 1]

(2)

R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an aryl group, and may be bonded together with a carbon atom to form a hexagonal ring Can be formed.
13. The method of claim 12,
Wherein the catalyst is used in an amount of 0.0001 to 20 parts by weight per 100 parts by weight of the alkylene oxide.
13. The method of claim 12,
Wherein the reaction temperature of the reaction is in the range of 40 to 150 ° C.
13. The method of claim 12,
Wherein the reaction pressure of the reaction is 10 to 30 atm.
13. The method of claim 12,
Wherein the reaction time of the reaction is 3 to 5 hours.
13. The method of claim 12,
Wherein the yield of the reaction is 90 to 99%.
13. The method of claim 12,
Wherein a reaction solvent is used in the reaction, and the same alkylene carbonate as the product is used as the reaction solvent.

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