KR100870370B1 - Catalyst for manufacturing propanediol, method of manufacturing the same, and method of manufacturing propanediol using the same - Google Patents

Abstract

A catalyst for manufacturing propanediol is provided to have a high yield by making proper metal have an optimum of content and to heighten a profitability, safety and effectiveness of a propanediol-manufacturing process by progressing efficiently a reaction at a condition that a pressure and a temperature relatively are low in a case of manufacturing the propanediol from hydroxyacetone using the catalyst for manufacturing propanediol. A catalyst for manufacturing propanediol is manufactured by steps of: preparing a metal precursor solution by dissolving a metal precursor in a hydrophilic solvent; preparing a metal-containing support element in which a metal is dipped by mixing and agitating a metal oxide in the metal precursor solution; evaporating a hydrophilic solvent; drying and pulverizing the metal-containing support element; and plasticizing the metal-containing support element.

Description

Catalyst for propanediol production method, method for producing the same and method for producing propanediol using the same {Catalyst for manufacturing propanediol, method of manufacturing the same, and method of manufacturing propanediol using the same}

The present invention relates to a catalyst for producing propanediol, a method for producing the same, and a method for producing propanediol using the same, and more particularly, a catalyst for producing propanediol, which can produce propanediol in high yield at lower temperature and pressure conditions, and a production thereof It relates to a method and a method for producing propanediol using the same.

Since industrialization, the use of fossil fuels such as coal and oil as energy resources around the world has increased exponentially. All of the technologies and industries in use today have been built and developed on fossil fuels. However, the rapid increase in fossil fuel usage has caused many problems. One of the problems is the limit of reserves, and the amount of fossil fuel buried around the world is already showing its limits. In addition, the use of fossil fuels has caused many environmental pollution problems, such as the increase of carbon dioxide in the air. Due to this increase in environmental pollution, countries around the world are now making great efforts to reduce carbon dioxide emissions by signing the 1997 Kyoto Protocol. For these reasons, much resources and research are focused on the development of environmentally friendly energy sources that can replace fossil fuels.

Biodiesel has received a lot of attention as an alternative energy source. Biodiesel is a generic term for fuels with the same physical properties as diesel oil, which can be made from plant-derived resources such as rapeseed seeds, soybean oil, waste edibles, and vegetable oils such as brown rice oil. Because biodiesel has the same physical properties as diesel, it can be used directly in diesel engines that are currently being used. Due to the low emission of pollutants, countries are increasing mandatory use of biodiesel. Increasingly, biodiesel is being used.

Biodiesel is prepared through the synthesis of fatty acid methyl esters by transesterification from plant-derived resources. The economics of this biodiesel manufacturing process depend on the cost of the raw materials and the transesterification process. That is, the improved transesterification process may improve the yield of biodiesel or convert the by-products generated in the manufacturing process into other high value-added materials to improve economics.

Glycerol, which is a major by-product of the transesterification reaction, is used in the fields of beauty, pharmaceuticals, foods, etc., but the amount of glycerol supplied is excessive compared to industrial demand, and the value thereof eventually collapses. For this reason, the conversion of glycerol, a by-product of biodiesel, into other high value materials has already begun since the early 1990s, and is currently being converted by glycerol to 1,3-propanediol by DuPont, USA. Commercialization is being promoted. In addition, there is an increasing need for a process for efficiently producing high value-added 1,2-propanediol used as a synthetic material for pharmaceuticals, cosmetic intermediates, polyesters and unsaturated polyesters, and as a plasticizer for cellophane.

No process has been reported in Korea yet for the production of 1,2-propanediol from glycerol. The process may be accomplished by a biological method and a chemical method using a catalyst. US Patent Nos. 7,049,109 B2 and 6,727,088 B2, respectively, report a process for producing 1,2-propanediol by biological methods using microorganisms. However, in the case of biological processes, high selectivity can be obtained, but it can be seen through reports that the reaction time is long and there are many difficulties in maintaining the process. Many attempts have not yet been made in chemical processes using catalysts, and there has not yet been a systematic system for catalyst systems or reaction processes. In US Pat. No. 5,616,817, a catalyst of cobalt, copper, manganese, and molybdenum is prepared to convert glycerol to 1,2-propanediol. The reaction conditions presented are 100 to 700 atmospheres of high pressure and 180 to 270 ° C. It is a temperature condition, and preferable reaction conditions are 200-325 atmospheres and 200-270 degreeC temperature conditions are shown. However, this is a fairly harsh condition for the production of propanediol.

U.S. Patent Publication No. 2005/0244312 also discloses a two step reaction process for preparing 1,2-propanediol from glycerol. It is to produce 1,2-propanediol from glycerol through two stages: dehydration reaction to produce hydroxyacetone from glycerol and hydrogenation reaction to produce 1,2-propanediol from hydroxyacetone. However, the catalyst reported in the literature does not provide a description of the catalyst itself which can be used for the production of propanediol as a commercial catalyst, and the reaction can be performed only under severe conditions of high temperature and high pressure, thereby increasing the efficiency of the reaction conditions. There is a need for the development of a catalyst that can

The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing a catalyst that can be applied to a reaction step for producing propanediol from hydroxyacetone.

The present invention also aims to provide a catalyst for producing propanediol prepared by the above production method.

The present invention also aims to provide a process for producing propanediol in high yield at relatively low temperature and pressure conditions using the above catalyst.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

Method for preparing a catalyst for producing propanediol according to an aspect of the present invention comprises the steps of (A) dissolving a metal precursor in a hydrophilic solvent to prepare a metal precursor solution, (B) by mixing and stirring the metal oxide in the metal precursor solution, Preparing a metal-containing carrier in which the metal is supported on the metal oxide, (C) evaporating the hydrophilic solvent, (D) drying and pulverizing the metal-containing carrier, and (E) the metal-containing Firing the carrier. The catalyst for preparing propanediol may be used in a reaction process for converting hydroxyacetone into 1,2-propanediol (1,2-propanediol).

The method for preparing the catalyst for producing propanediol may further include reducing the catalyst (F) to increase the activity of the prepared catalyst.

In the present invention, a metal such as ruthenium (Ru), platinum (Pt), rhodium (Rh), palladium (Pd) may be used as the metal, and the precious metal may be used alone or in combination of two or more. As the hydrophilic solvent, at least one solvent selected from the group consisting of ethanol, butanol and water may be used. The metal oxide may be alumina, silica, titania, zirconia, and the metal oxide may be used alone or in combination of two or more. In particular, gamma alumina can be used as the metal oxide.

The metal has a content of 0.5 to 10% by weight, preferably 3 to 5% by weight relative to the total weight of the metal-containing support.

The firing step (E) takes place in an air atmosphere and in a temperature range of 300 to 1000 ° C.

The reduction step (F) is carried out in a hydrogen atmosphere and in the temperature range of 50 to 400 ℃.

The catalyst for producing propanediol according to an aspect of the present invention comprises 90 to 99.5 wt% of a metal oxide and 0.5 to 10 wt% of a noble metal supported on the metal oxide, and is used in a reaction process for converting hydroxyacetone to propanediol. do. The propanediol specifically includes 1,2-propanediol.

The precious metal is at least one precious metal selected from the group consisting of ruthenium (Ru), platinum (Pt), rhodium (Rh) and palladium (Pd). The metal oxide is characterized in that at least one selected from the group consisting of alumina, silica, titania and zirconia.

In the method for preparing propanediol according to an aspect of the present invention, a step of introducing hydroxyacetone and a catalyst for preparing propanediol into a reactor, agitation of the hydroxyacetone and the catalyst, and a purge for supplying hydrogen gas into the reactor ( purging) and a hydrogenation step of maintaining the inside of the reactor at a temperature of 80 to 200 ° C. and 10 to 100 atm to react the hydroxyacetone with hydrogen.

The catalyst in the reactor is characterized in that it comprises 0.1 to 10 parts by weight relative to 100 parts by weight of the hydroxyacetone. As the amount of the catalyst increases, the yield of propanediol may be increased. However, in consideration of economical efficiency, the amount of the catalyst is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight based on 100 parts by weight of hydroxyacetone.

The reactor uses a batch reactor (batch reactor).

The purge step is carried out for 10 to 60 minutes, preferably for about 30 minutes. In the case of hydroxyacetone, the reaction may proceed in a different route from the object of the present invention to produce propanediol in the air as a compound having good reactivity. Therefore, it is necessary to go through the above purge process. As the gas used in the purge process, nitrogen, argon, helium, or the like, which is not reactive, may be used, but it is preferable to use hydrogen, which is used as a reaction gas in a process for preparing propanediol, in the purge process. However, the present invention is not limited thereto, and in the purge process, not only hydrogen gas, but also nitrogen, argon, and helium gas may be used alone or in combination of two or more kinds thereof.

After the purge step is completed, the inside of the reactor is elevated and heated to a predetermined pressure and temperature range, and the hydrogenation reaction step is performed. When the reaction temperature is too low in the hydrogenation reaction, the production efficiency of propanediol is lowered, the reaction temperature is 80 to 200 ℃, preferably 140 to 180 ℃ is efficient. If the reaction temperature is lower than 80 ° C., the conversion of hydroxyacetone is lowered, and if it is higher than 200 ° C., the selectivity is lowered and is not preferable in terms of energy efficiency, so that the reaction temperature maintains a value in the range of 80 to 200 ° C. Description of the conversion rate and selectivity will be described later in Table 1 below.

For the same reason, the reaction pressure in the hydrogenation reaction is appropriately maintained at 10 to 150 atmospheres, preferably 30 to 80 atmospheres. The hydrogenation step is carried out for 6 to 48 hours, preferably 12 to 14 hours so that a sufficient conversion of hydroxyacetone to propanediol can occur. Propanediol, the final product prepared, can be identified through gas chromatography.

The catalyst for producing propanediol according to the present invention can produce a high yield of propanediol while having a small amount of precious metal content. In addition, when the propanediol is prepared by the hydrogenation reaction from hydroxyacetone using the catalyst for producing propanediol according to the present invention, the reaction can proceed efficiently under relatively low pressure and low temperature conditions, so the economic efficiency of the propanediol manufacturing process To increase safety, efficiency.

The present invention provides a catalyst for the hydrogenation of hydroxyacetone and a method for producing the same in the process of producing propanediol from hydroxyacetone. In particular, it provides a catalyst for producing propanediol, which can obtain a high yield even under low pressure and temperature conditions, and provides a method for producing propanediol using the same.

According to the method for producing a catalyst for producing propanediol of the present invention, a metal precursor solution is first prepared. The metal precursor solution is a compound in which a metal precursor is dissolved in a hydrophilic solvent, and the metal precursor is a compound that dissolves in the solution to provide metal ions. Precious metals such as ruthenium, platinum, rhodium and palladium are used as the metal, and ruthenium is most preferable in order to obtain high yield and high selectivity in the present invention.

A metal oxide is mixed and stirred in the metal precursor solution. Gamma alumina is used as the metal oxide. After the gamma alumina is added to the metal precursor solution, the mixture is vigorously stirred so that the metal is supported while being evenly dispersed in the gamma alumina to prepare a metal-containing support. The content of the supported metal is 0.5 to 10% by weight, preferably 3 to 5% by weight relative to the total weight of the metal-containing support.

Next, after evaporating the hydrophilic solvent, the metal-containing carrier is dried and pulverized to form a powder, and the powder-containing metal-containing carrier is calcined to prepare a catalyst for producing propanediol. The prepared catalyst may be reduced to increase the activity of the catalyst. The reduction step may be performed while supplying hydrogen gas at a predetermined rate, or may be performed while supplying a gas in which hydrogen gas and helium, argon, nitrogen gas, and the like are mixed.

The production process of propanediol using the catalyst for producing propanediol is as follows. The catalyst is added to the batch reactor together with hydroxyacetone and completely sealed. Next, the purge process is carried out for 10 to 60 minutes with vigorous stirring. After the purge process is completed, the temperature and pressure in the reactor are raised to proceed with the hydrogenation reaction, and when the hydrogenation reaction is performed, propanediol is prepared.

Hereinafter, the catalyst for producing propanediol and the method for preparing propanediol according to the present invention will be described in more detail with reference to the following examples, but the following examples are provided to illustrate the present invention in more detail. It is not limited to an Example.

Example 1

i) Preparation of Catalysts for Propanediol Preparation

RuCl ₃ · 3H ₂ O was used as the ruthenium precursor. 1.29 g of RuCl ₃ · 3H ₂ O was dissolved in 150 mL of ethanol to prepare a ruthenium precursor solution. 10 g of gamma alumina was added to the ruthenium precursor solution and stirred vigorously. The ruthenium precursor solution was placed in an evaporator and ethanol was evaporated while stirring was continued to obtain a ruthenium-containing carrier. Thereafter, the ruthenium-containing carrier was dried in a dryer, and then ground to have even particles. The pulverized particles were calcined at 500 ° C. for 6 hours under an air atmosphere.

After the calcination step, a catalyst carrying ruthenium was prepared as a catalyst for preparing propanediol. X-ray diffraction (XRD) results of the ruthenium-containing carrier before firing are shown in FIG. 1 (a), and X-ray diffraction (XRD) results of the catalyst prepared after firing are shown in FIG. Is shown. In FIG. 1, before the firing (a), the gamma alumina phase can be identified from the '▼' peak, and the ruthenium oxide (RuO ₂ ) phase can be identified from the '●' peak in (b).

ii) reduction of the catalyst for producing propanediol

1 g of the catalyst was charged into a tubular reactor, and the temperature was gradually raised while flowing 10 mL of H ₂ / N ₂ gas at 200 mL per minute. When the temperature reached 200 ° C., the temperature was kept constant for 4 hours. X-ray diffraction (XRD) results for the reduced catalyst are shown in FIG. In (c) of Figure 1 can be confirmed the ruthenium (Ru) phase from the '◆' peak. This means that ruthenium oxide contained in the catalyst prepared in ii) was reduced to ruthenium, and it can be seen that in this embodiment, a catalyst containing ruthenium in gamma alumina was prepared.

iii) preparation of propanediol

1 g of the catalyst activated by the above reduction process was added to a batch reactor together with 50 g of hydroxyacetone having a purity of 90% or more, and then the reactor was sealed. Next, 50 mL of hydrogen per minute was supplied for 30 minutes while stirring the inside of the reactor for the purge process. After the purge process was completed, the temperature of the reactor was increased to 100 ° C. while supplying hydrogen to raise the pressure inside the reactor to 80 atm. Thereafter, the pressure inside the reactor was 80 atm, the reaction temperature was maintained constant at 100 ℃ and vigorously stirred while the hydrogenation reaction proceeded for 12 hours. After the end of the hydrogenation reaction, the yield of the final product is summarized in Table 1 below.

Example 2

A catalyst was prepared in the same manner as in Example 1 i) and ii). Next, the final product was obtained in the same manner as in Example 1 except that the reaction temperature was changed to 120 ° C. in step iii). The yield of the final product is summarized in Table 1 below.

Example 3

A catalyst was prepared in the same manner as in Example 1 i) and ii). Next, the final product was obtained in the same manner as in Example 1 except that the reaction temperature was changed to 140 ° C. in step iii). The yield of the final product is summarized in Table 1 below.

Example 4

A catalyst was prepared in the same manner as in Example 1 i) and ii). Next, the final product was obtained in the same manner as in Example 1 except that the reaction temperature was changed to 180 ° C. in step iii). The yield of the final product is summarized in Table 1 below. In addition, the results of gas chromatography analysis of the final product prepared in Example 4 is shown in the graph of FIG. 2, it can be seen that 1,2-propanediol and byproducts were produced from hydroxyacetone.

% Conversion Selectivity (%) yield(%) Example 1 21.34 96.89 20.71 Example 2 50.70 94.95 48.14 Example 3 95.33 96.20 91.71 Example 4 99.0 99.0 98.0

In Table 1, the conversion rate represents the rate at which hydroxyacetone is converted to another compound by the hydrogenation reaction, and the selectivity indicates the ratio of propanediol to the converted compound. Yield represents the ratio converted from hydroxyacetone to propanediol and is the value corresponding to the product of the conversion and the selectivity.

As described above, although the present invention has been described with reference to limited embodiments and drawings, the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains various modifications and variations from such descriptions. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below but also by the equivalents of the claims.

The catalyst for preparing propanediol of the present invention can efficiently proceed the hydrogenation process of hydroxyacetone even with a small amount of precious metal, and can be utilized for mass production, and especially high yield of propanediol even at low pressure and temperature conditions compared to the conventional one. We can produce, and the utilization is expected.

FIG. 1 shows X-ray diffraction results of the ruthenium-containing carrier prepared in Example 1 (a), X-ray diffraction results of the catalyst prepared after firing (b), and X-ray diffraction results of the catalyst prepared after reduction It is a graph which shows (c).

FIG. 2 is a graph showing gas chromatography results for the final product after the conversion process from hydroxyacetone to 1,2-propanediol in Example 4. FIG.

Claims (17)

A process for preparing a catalyst added to a reaction process for producing propanediol from hydroxyacetone, (A) dissolving the metal precursor in a hydrophilic solvent to prepare a metal precursor solution; (B) mixing and stirring a metal oxide in the metal precursor solution to prepare a metal-containing support in which the metal is supported on the metal oxide; (C) evaporating the hydrophilic solvent; (D) drying and pulverizing the metal-containing support; And (E) calcining the metal-containing carrier; Method for producing a catalyst for producing propanediol comprising a. The method of claim 1, The production method of the catalyst for producing propanediol, In order to increase the activity of the prepared catalyst (F) reducing the catalyst; Method for producing a catalyst for producing propanediol further comprising a. The method of claim 1, The metal is a method for producing a catalyst for producing propanediol, characterized in that at least one precious metal selected from the group consisting of ruthenium (Ru), platinum (Pt), rhodium (Rh) and palladium (Pd). The method of claim 1, The hydrophilic solvent is at least one solvent selected from the group consisting of ethanol, butanol and water, the method for producing a catalyst for producing propanediol. The method of claim 1, The metal oxide is a method for producing a catalyst for producing propanediol, characterized in that at least one selected from the group consisting of alumina, silica, titania and zirconia. The method of claim 1, The metal is a method for producing a catalyst for producing propanediol, characterized in that the content of 0.5 to 10% by weight relative to the total weight of the metal-containing support. The method of claim 1, The firing step is a method for producing a catalyst for producing propanediol, characterized in that the air is made in a temperature range of 300 to 1000 ℃. The method of claim 2, The reduction step is a method of producing a catalyst for producing propanediol, characterized in that under a hydrogen atmosphere and in the temperature range of 50 to 400 ℃. 90 to 99.5 weight percent of metal oxides; And A catalyst for producing propanediol for converting hydroxyacetone into propanediol, comprising 0.5 to 10% by weight of a noble metal supported on the metal oxide. The method of claim 9, The precious metal is a catalyst for producing propanediol, characterized in that at least one precious metal selected from the group consisting of ruthenium (Ru), platinum (Pt), rhodium (Rh) and palladium (Pd). The method of claim 9, The metal oxide is a catalyst for producing propanediol, characterized in that at least one selected from the group consisting of alumina, silica, titania and zirconia. The method of claim 9, Propanediol is a catalyst for producing propanediol, characterized in that 1,2-propanediol. Introducing hydroxyacetone and the catalyst of claim 9 into the reactor; A purging step of supplying hydrogen gas into the reactor while stirring the hydroxyacetone and the catalyst; And A hydrogenation step of reacting the hydroxyacetone with hydrogen; Method for producing a propanediol comprising a. The method of claim 13, The catalyst is a method for producing propanediol, characterized in that 0.1 to 10 parts by weight based on 100 parts by weight of the hydroxyacetone. The method of claim 13, The purge step is a method for producing propanediol, characterized in that performed for 10 to 60 minutes. The method of claim 13, The hydrogenation step is a method for producing propanediol, characterized in that carried out by maintaining the inside of the reactor at a temperature of 80 to 200 ℃ and 10 to 100 atm. The method of claim 13, The hydrogenation step of producing a propanediol, characterized in that carried out for 6 to 48 hours.

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