Catalyst for producing propylene glycol by hydrocracking reaction of glycerol and method for producing same

Abstract

The present invention relates to: a nanocomposite catalyst and a method for producing same, wherein, in producing propylene glycol from glycerol through a hydrocracking reaction using a catalyst, the catalyst is K2O-CuO-SiO2 consisting of K oxide (K2O), Cu oxide (CuO), and silica (SiO2); and a method for producing propylene glycol from glycerol through a hydrocracking reaction using the catalyst.

Description

Catalyst for producing propylene glycol by hydrogenolysis of glycerol and method for producing the same

[0001] The present invention relates to a catalyst for producing propylene glycol by hydrogenolysis of glycerol and a method for producing the same, and more particularly, to a K2O-CuO-SiO2 nanocomposite catalyst having excellent glycerol conversion and propylene glycol selectivity in producing propylene glycol by hydrogenolysis of glycerol and a method for producing the same.

[0002]

[0003] The use of fossil fuels in modern society inevitably leads to climate and environmental problems, including global warming. Consequently, interest in and demand for carbon neutrality are steadily increasing. One example of such carbon neutrality measures is replacing some fossil fuels with biodiesel derived from biomass, which utilizes the abundant biomass in the biosphere and is being proposed as an environmentally friendly carbon neutrality strategy.

[0004] In the case of biodiesel produced by the transesterification reaction of triglyceride contained in the biomass, a huge amount of glycerol, a byproduct, is produced per ton of biodiesel produced, about 10 to 100 kg. Therefore, in order to process the glycerol, a use for the glycerol has been discovered, and in the 1990s, the demand in the cosmetics, pharmaceutical, and food industries was met by using the glycerol as a moisturizer, excipient, and additive. However, it eventually reached a state of oversupply, and other industrial uses such as high value-added chemical raw materials, polymer building blocks, and fuel additives must be sought.

[0005] Meanwhile, propylene glycol (also known as 1,2-propandiol) is an essential chemical with significant demand in the polyester resin, polyurethane, cosmetics, and deicing additive industries. However, conventionally, propylene glycol was typically manufactured via chlorohydrin or hydroperoxide routes based on petroleum-derived propylene oxide. However, this process involved the use of toxic oxidizing agents and the formation of chlorinated byproducts. Consequently, a method for producing propylene glycol through the hydrogenolysis of glycerol emerged.

[0006] Among these, propylene glycol, which is produced by the hydrogenation reaction of glycerol, is known as a high value-added material with various applications, such as an intermediate for pharmaceuticals and cosmetics, a synthetic raw material for polyester and unsaturated polyester, and a plasticizer for cellophane.

[0007] There has not been much research done on catalysts for the above reaction yet. Patent Publication No. 10-2011-0116480 A, when a precious metal catalyst supported on a similar hydrotalcite is used, has a problem in that the glycerol conversion rate is 58.5% and the propylene glycol selectivity is 85.5% under conditions of 180°C, 40 bar, and hydrogen flow, resulting in low glycerol conversion and propylene glycol selectivity. In addition, U.S. Patent Publication No. US 5616817 A manufactures a catalyst containing a mixture of cobalt, copper, manganese, and molybdenum to convert glycerol to propylene glycol, but presents high pressure of 100 to 700 bar and high temperature of up to 270°C as the reaction conditions, resulting in the problem that very harsh conditions are required.

[0008] In addition, a copper-chromium catalyst with a spinel structure has been reported as a recently developed catalyst, but this catalyst has the problem of being active under a high hydrogen pressure of 80 bar or more, and since such a high hydrogen pressure is a great burden in the chemical process, there has been difficulty in commercializing propylene glycol.

[0009] Meanwhile, in Patent Publication No. 10-2015-0125422 A, glycerol is converted into propylene glycol at a relatively low hydrogen pressure in a high yield using a NiO-CuO / SiO2 nanocomposite catalyst manufactured by a sol-gel method from a Ni precursor compound, a Cu precursor compound, and SiO2. However, the catalyst had a problem in that its long-term stability was somewhat poor.

[0010] Therefore, there is a need to develop a catalyst that has high glycerol conversion and propylene glycol selectivity even under low hydrogen pressure and temperature conditions, and also satisfies long-term stability.

[0011]

[0012] [Prior Art Literature]

[0013] [Patent Document]

[0014] (Patent Document 1) Korean Patent Publication No. 10-2011-0116480 (Published on October 26, 2011)

[0015] (Patent Document 2) U.S. Patent No. 5616817 (registration date: April 1, 1997)

[0016] (Patent Document 3) Korean Patent Publication No. 10-2015-0125422 (Published on November 9, 2015)

[0017]

[0018] The present invention was created to solve the above problem, and aims to provide a catalyst and a method for producing the same, which can stably produce propylene glycol for a long period of time even at a relatively low hydrogen pressure and low reaction temperature, in producing propylene glycol from glycerol through a hydrogenolysis reaction using a catalyst.

[0019] In addition, the present invention seeks to provide a method for producing propylene glycol from glycerol using the above catalyst.

[0020]

[0021] The present invention provides a catalyst for producing propylene glycol by hydrogenolysis of glycerol, characterized in that it comprises K oxide (K2O), Cu oxide (CuO), and silica (SiO2).

[0022] In the above catalyst, the total content of the K oxide (K2O) and Cu oxide (CuO) is 50 to 95 wt% with respect to the entire catalyst, the content of the K oxide (K2O) is 0.1 to 10.0 wt% with respect to the entire catalyst, and the particle size of the silica (SiO2) may be 5 nm to 10 ㎛.

[0023] In addition, the present invention provides a method for preparing a catalyst for producing propylene glycol by hydrogenolysis of glycerol, comprising the steps of: a) adding silica sol, K2O precursor, and CuO precursor to a solvent, mixing and reacting them to prepare a reaction mixture; b) adjusting the pH of the reaction mixture prepared in step a) to form a precipitate and maturing it; and c) washing, filtering, drying, and calcining the precipitate matured in step b) to prepare a K2O-CuO-SiO2 nanocomposite catalyst.

[0024] In one embodiment of the method of the present invention, the step a) may be characterized in that the silica sol, K2O precursor, and CuO precursor added to the solvent are added so that the SiO2 content is 5 to 50 wt%, the K2O content is 0.1 to 10 wt%, and the Cu / K molar ratio is 3 to 400 in the final manufactured K2O-CuO-SiO2 nanocomposite catalyst.

[0025] In addition, the present invention provides a method for producing propylene glycol by hydrogenolysis of glycerol, characterized in that it comprises the steps of: a) preparing an aqueous glycerol solution; b) filling a reactor with a catalyst according to the present invention; or a catalyst produced by a production method according to the present invention; and reducing the catalyst using hydrogen gas; and c) injecting the aqueous glycerol solution and hydrogen gas together into the reactor and causing a reaction to produce propylene glycol.

[0026] In the propylene glycol production method of the present invention, the molar ratio of hydrogen / glycerol supplied in step c) may be 2 to 200, the reaction temperature may be 180 to 260°C, the reaction pressure may be 15 to 45 bar, and the glycerol supply rate may be 0.05 to 3 g / h per 1 g of catalyst.

[0027]

[0028] When propylene glycol is produced by hydrogenolysis of glycerol using the K2O-CuO-SiO2 nanocomposite catalyst according to the present invention, not only can a high glycerol conversion rate and a high propylene glycol selectivity be achieved at a relatively low hydrogen pressure and low reaction temperature, but the K2O-CuO-SiO2 nanocomposite catalyst is stable in the long term, so that propylene glycol can be produced from glycerol in a high yield through hydrogenolysis for a long period of time.

[0029]

[0030] Hereinafter, with reference to the attached drawings, a catalyst for producing propylene glycol by hydrogenolysis of glycerol, a method for producing the same, and a method for producing propylene glycol using the catalyst will be described in detail so that a person having ordinary skill in the art to which the present invention pertains can easily practice the present invention.

[0031] When explaining in detail the principles of a preferred embodiment of the present invention, if it is determined that a specific description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof is omitted.

[0032] In addition, it should be understood that the embodiments described in this specification and the configurations illustrated in the drawings are only the most preferred embodiments of the present invention and do not represent all of the technical ideas of the present invention, and therefore, there may be various equivalents and modified examples that can replace them at the time of filing this application.

[0033]

[0034] The present invention relates to a K2O-CuO-SiO2 nanocomposite catalyst and a method for producing the same, which enable stable production of propylene glycol for a long period of time even at a relatively low hydrogen pressure and low reaction temperature in producing propylene glycol from glycerol through a hydrogenolysis reaction using a catalyst, and to a method for producing the same, and to producing propylene glycol by hydrogenolysis of glycerol using the K2O-CuO-SiO2 nanocomposite catalyst.

[0035] Hereinafter, a catalyst for producing propylene glycol by hydrogenation of glycerol according to the present invention and a method for producing the same will be described in detail.

[0036] A catalyst for producing propylene glycol by hydrogenation of glycerol according to one embodiment of the present invention is a nanocomposite catalyst composed of a K component, a Cu component, and silica, and can be expressed as K-Cu / SiO2, more specifically, K2O-CuO-SiO2.

[0037] The nanocomposite catalyst according to the present invention may exist in a form in which the K, Cu, and Si components are mixed as a composite oxide or a mixed oxide. For example, the K and Cu components may form a composite oxide represented by K2O-CuO and exist in a form supported on SiO2 particles or as separate particles. At this time, the SiO2 preferably has a particle size of 5 nm to 10 μm. When the particle size of the silica is within the above range, the conversion rate of glycerol and the selectivity of propylene glycol in the hydrogenolysis reaction of glycerol can be improved.

[0038] In the K2O-CuO-SiO2 nanocomposite catalyst according to the present invention, when the (K+Cu) component and the Si component are converted to the weight of each oxide, the (K+Cu) component is used in an amount of 50 to 95 wt%, preferably 60 to 90 wt%, and more preferably 70 to 80 wt%, with respect to the entire catalyst, and SiO2 may be included in an amount of 5 to 50 wt%, preferably 10 to 40 wt%, and more preferably 20 to 30 wt%.

[0039] In addition, in the K2O-CuO-SiO2 nanocomposite catalyst according to the present invention, the K component is used in a relatively small amount, and the K component may be included in an amount of 0.1 to 10 wt%, preferably 1 to 5 wt%, and more preferably 2.5 to 3.5 wt%, based on the weight of the oxide, relative to the entire catalyst.

[0040] In addition, in the present invention, the Cu / K molar ratio of the Cu component and the K component may be 3 to 400, preferably 5 to 40. If the value of Cu / K is less than 3, there is a problem of low glycerol conversion rate, and if it exceeds 400, there is a problem of catalyst stability.

[0041] As the K content increases to a more desirable range, the hydrogen adsorption capacity and hydrogen spillover effect by K increase, which in turn increases the glycerol conversion rate and propylene glycol selectivity.

[0042] In addition, the K2O-CuO-SiO2 nanocomposite catalyst according to the present invention can be processed to produce a catalyst molded body. At this time, there is no limitation on the form of the catalyst molded body, but it can be in the form of powder or pellets. Since the pellet form is preferable for application to a continuous process, it can be produced in the form of pellets and used according to a method commonly used in the art.

[0043] The K2O-CuO-SiO2 nanocomposite catalyst according to the present invention can be used by pretreatment under a hydrogen gas flow during the hydrogenation decomposition reaction of glycerol.

[0044] In addition, the K2O-CuO-SiO2 nanocomposite catalyst of the present invention is prepared by a co-precipitation method using a K2O precursor, a CuO precursor, and SiO2 particles.

[0045] More specifically, the method for preparing a K2O-CuO-SiO2 nanocomposite catalyst according to the present invention includes the steps of: a) adding a silica sol, a K2O precursor, and a CuO precursor to a solvent, mixing and reacting them to prepare a reaction mixture; b) adjusting the pH of the reaction mixture prepared in step a) to form a precipitate and maturing it; and c) washing, filtering, drying, and calcining the precipitate matured in step b) to prepare a catalyst powder. The catalyst powder (calcined precipitate) prepared through the steps described above can be molded by adding an organic or inorganic binder, kneading, and then extruding.

[0046] The solvent used in the above step a) is not particularly limited, but may be selected from polar or nonpolar solvents capable of dissolving the precursor, and for example, lower alcohols such as ethanol and butanol, water, or mixtures thereof may be used.

[0047] In addition, the K2O precursor and CuO precursor used in the above step a) are not particularly limited, but may be selected alone or in combination of two or more from the group consisting of carbides, oxides, chlorides, nitrides, sulfides, sulfates, nitrates, hydrates or anhydrides thereof.

[0048] In addition, in adding silica sol, K2O precursor, and CuO precursor to the solvent in step a), the silica sol added to the solvent is added so that SiO2 can be included in the final K2O-CuO-SiO2 nanocomposite catalyst in an amount of 5 to 50 wt%, preferably 10 to 40 wt%, and more preferably 20 to 30 wt%.

[0049] Additionally, the K2O precursor is added so that the amount of K2O in the final manufactured K2O-CuO-SiO2 nanocomposite catalyst is 0.1 to 10 wt%, preferably 1 to 5 wt%, and more preferably 2.5 to 3.5 wt%.

[0050] In addition, the CuO precursor is added so that the Cu / K molar ratio in the final manufactured K2O-CuO-SiO2 nanocomposite catalyst can be in the range of 3 to 400, preferably 5 to 40.

[0051] The method of controlling the pH of the reaction mixture in step b) can be performed by adding an alkaline carbonate or sodium hydroxide aqueous solution to the metal precursor solution. The specific pH value can vary within the range of 7 to 13 depending on the content of the metal component contained in the metal precursor solution.

[0052] In addition, in step b), the particle size, formation rate, etc. of the precipitate may vary depending on the concentration and addition rate of the alkaline carbonate or sodium hydroxide aqueous solution. For example, if the addition rate of the alkaline carbonate or sodium hydroxide aqueous solution is too fast or the concentration is too high, the particle size of the formed precipitate may become large, which may lower the activity of the catalyst. On the other hand, if the addition rate of the alkaline carbonate or sodium hydroxide aqueous solution is too slow or the concentration is too low, the efficiency of catalyst production may decrease. Therefore, in order to improve the catalytic activity and the efficiency of catalyst production, the concentration of the alkaline carbonate or sodium hydroxide aqueous solution is set within a range of 0.5 to 3 mol / L, and further, the alkaline carbonate or sodium hydroxide aqueous solution may be added to the metal precursor solution at a rate of 0.1 to 10 mL per minute.

[0053] In addition, step b) may mature the precipitate when the pH of the reaction mixture reaches a specific value within the range of 9 to 13. The maturation may be performed at 50 to 90°C for 2 to 12 hours so that the precipitation reaction can sufficiently occur. If the maturation temperature is too low or too high, it is difficult to form a precipitate having a particle size with high catalytic activity. Therefore, as described above, the maturation temperature may be set to 50 to 100°C, preferably 60 to 80°C.

[0054] The above step c) is a step of sufficiently washing with distilled water until the alkaline carbonate aqueous solution or sodium hydroxide aqueous solution remaining in the sediment is completely removed. After the washing, the washed sediment is filtered and dried. Drying is sufficiently performed at 80 to 200°C until the sediment is completely dry.

[0055] In addition, in the step c), the dried sediment is calcined to remove organic substances remaining in the sediment and form an appropriate alloy phase. The calcination can be performed within a temperature range of 400 to 700°C in an air atmosphere or an oxygen atmosphere, and preferably, when calcined at 500 to 600°C, an appropriate alloy phase can be formed. The specific calcination temperature can be determined as a temperature capable of forming an alloy phase exhibiting high catalytic activity, and may vary depending on the content of the metal component contained in the formed sediment.

[0056] In addition, an inorganic or organic binder may be added to the catalyst powder manufactured in step c), kneaded, and then extruded to manufacture a solid catalyst. The inorganic binder may be selected from other inorganic oxides, such as silica, zirconia, and titania, and the organic binder preferably includes at least one selected from organic binders for ceramics containing an ether bond. Examples of the organic binder include, but are not limited to, PMB-15U, PMB-40H, and MC-40H.

[0057] Catalyst powder with added binder is uniformly mixed using a mixer, then distilled water is added to create a dough for molding. This is then extruded through an extruder at an appropriate pressure and cut at regular intervals to create pellet-shaped catalysts. These pellet-shaped catalysts are then dried to remove moisture.

[0058] Meanwhile, when an organic binder is used for extrusion molding, the dried catalyst may be additionally calcined at high temperatures to remove organic binders that may interfere with catalyst activity and to increase catalyst strength. The calcination temperature is preferably approximately 550°C, and the calcination time is preferably 6 to 8 hours.

[0059]

[0060] In addition, a method for producing propylene glycol by hydrogenation of glycerol according to another embodiment of the present invention comprises the steps of: i) preparing an aqueous glycerol solution; ii) filling a reactor with a catalyst and reducing the catalyst using hydrogen gas; and iii) injecting the aqueous glycerol solution and hydrogen gas together into the reactor and reacting them to produce propylene glycol.

[0061] In the above step i), if the glycerol aqueous solution contains nonvolatile impurities such as salts generated during the biodiesel synthesis process, it is preferable to first separate the glycerol using an evaporator and then supply it to the catalytic reactor in terms of catalyst deactivation. However, in the case of impurities having a lower boiling point than glycerol (such as methanol and water), they may be supplied to the catalytic reactor together with glycerol. The concentration of glycerol ultimately fed into the catalytic reactor may generally be selected from 10 to 98%, preferably 20 to 95%, and more preferably 30 to 90%.

[0062] In addition, the step ⅱ) reduces the catalyst at a temperature range of 250 to 350°C, preferably 270 to 330°C, during catalyst reduction.

[0063] In addition, in the step ⅲ), the molar ratio of hydrogen / glycerol is in the range of 2 to 200, preferably 3 to 100, more preferably 4 to 30, and even more preferably 5 to 25.

[0064] In addition, in the step ⅲ), the reaction temperature is 180 to 260°C, preferably 200 to 240°C, more preferably 210 to 230°C, and the reaction pressure is 15 to 45 bar, preferably 20 to 40 bar.

[0065] In addition, in the step ⅲ), the glycerol supply rate is 0.05 to 10 g / h per 1 g of catalyst, preferably 0.1 to 8 g / h, and more preferably 0.2 to 5 g / h.

[0066] Meanwhile, a method for producing propylene glycol by hydrogenation of glycerol according to one embodiment of the present invention may further include a step of separating propylene glycol from glycerol and water in the reaction result of step ⅲ) through a method such as distillation or extraction.

[0067] At this time, if the catalyst of the present invention is formed into a certain shape such as a pellet and used, it can be helpful in continuously performing the above manufacturing method.

[0068] One of the features of the present invention is that the temperature and pressure of the hydrogenation reaction can be appropriately controlled to maintain glycerol in a liquid phase and bring it into contact with a catalyst and hydrogen to perform the catalytic hydrogenation reaction in a liquid phase, thereby preventing not only disadvantages or problems associated with a gas phase reaction, but also having the advantage of significantly preventing problems such as coking that inevitably accompany gas phase catalytic reactions.

[0069]

[0070] Hereinafter, the effectiveness of the catalyst for producing propylene glycol according to the present invention in producing propylene glycol through the hydrogenolysis of glycerol using a catalyst will be examined through examples. It should be noted that the following examples are provided to illustrate one or more preferred embodiments of the present invention, but the present invention is not limited to these embodiments. Numerous modifications may be made to the following examples within the scope of the present invention.

[0071]

[0072] <Example 1: Glycerol hydrogenation reaction using K2O(3)-CuO(77)-SiO2 nanocomposite catalyst>

[0073] To 500 ml of distilled water, 3.56 g of colloidal silica sol (Ludox SM-30, 30 wt%), 12.50 g of Cu(NO3)2·3H2O, and 0.23 g of KNO3·H2O were added simultaneously at a rate of 1 to 6 cc / min while stirring at 600 rpm and maintaining the temperature at 5 ℃. Then, 1 M NaOH was slowly added while stirring until the pH of the reaction mixture became 9.2, and the mixture was reacted at room temperature with stirring for 18 hours, and aged at 70 ℃ for 3 hours to form a precipitate.

[0074] The reaction mixture was cooled to room temperature and filtered to recover the precipitate, which was washed with 1000 ml of distilled water until no Na ions were detected, and dried at 100°C for 12 hours to obtain the precipitate in powder form.

[0075] The obtained powder was calcined at 550°C in an air atmosphere for 6 hours to prepare a K2O(3)-CuO(77)-SiO2 nanocomposite catalyst.

[0076] 1.0 g of the K2O(3)-CuO(77)-SiO2 nanocomposite catalyst prepared in the above step was placed in a fixed bed reactor, and treated at 290°C for 5 hours using 10% H2 gas, followed by 0.5 h -1 An 80 wt% aqueous glycerol solution was supplied at a flow rate of WHSV, and hydrogen was supplied at a flow rate of 48 cc / min. At this time, the temperature of the reactor was maintained at 220°C and the pressure at 30 bar. After the reaction was carried out for 342 hours under the above conditions, the product was analyzed by gas chromatography. The results are shown in Table 1 below.

[0077]

[0078] <Example 2: Glycerol hydrogenation reaction using K2O(1)-CuO(79)-SiO2 nanocomposite catalyst>

[0079] A nanocomposite catalyst was prepared in the same manner as in Example 1, except that 3.56 g of silica sol (Ludox SM-30, 30 wt%), 12.50 g of Cu(NO3)2·3H2O, and 0.07 g of KNO3·H2O were added.

[0080] Hydrogenolysis of glycerol was performed under the same method and conditions as in Example 1, and the product was analyzed by gas chromatography. The results are shown in Table 1 below.

[0081]

[0082] <Example 3: Glycerol hydrogenation reaction using K2O(5)-CuO(75)-SiO2 nanocomposite catalyst>

[0083] A nanocomposite catalyst was prepared in the same manner as in Example 1, except that 3.56 g of silica sol (Ludox SM-30, 30 wt%), 12.50 g of Cu(NOS)2·3H2O, and 0.41 g of KNO3·H2O were added.

[0084] Hydrogenolysis of glycerol was performed under the same method and conditions as in Example 1, and the product was analyzed by gas chromatography. The results are shown in Table 1 below.

[0085]

[0086] <Comparative Example 1: Glycerol hydrogenation reaction using CuO(10)-SiO2 nanocomposite catalyst>

[0087] A nanocomposite catalyst was prepared in the same manner as in Example 1, except that the K precursor was not used and 1.56 g of Cu(NO3)2·3H2O and 3.43 g of colloidal silica were used.

[0088] Hydrogenolysis of glycerol was performed under the same method and conditions as in Example 1, and the product was analyzed by gas chromatography. The results are shown in Table 1 below.

[0089]

[0090] <Comparative Example 2: Glycerol hydrogenation reaction using CuO(80)-SiO2 nanocomposite catalyst>

[0091] A nanocomposite catalyst was prepared in the same manner as in Example 1, except that no K precursor was used and 12.50 g of Cu(NO3)2·3H2O and 3.43 g of colloidal silica were used.

[0092] Hydrogenolysis of glycerol was performed under the same method and conditions as in Example 1, and the product was analyzed by gas chromatography. The results are shown in Table 1 below.

[0093] Example Catalytic reaction time 0~26 h 374~398 h Glycerol conversion (%) PG selectivity (%) Glycerol conversion (%) PG selectivity (%) Example 1 K2O(3)-CuO(77)-SiO2 99.90 93.09 97.80 97.65 Example 2 K2O(1)-CuO(79)-SiO2 99.99 2.03 49.25 96.32 Example 3 K2O(5)-CuO(75)-SiO2 99.5 94.4 5 6 9.17 96.80 Comparative example 1 CuO(10)-SiO2 61.25 71.56 41.21 68.12 Comparative example 2 CuO(80)-SiO2 95.5 96.4 2 42.36 71.47

[0094]

[0095] In the above Table 1, it can be confirmed that Examples 1 to 3 containing more K have excellent conversion and selectivity of glycerol, and that the conversion and selectivity of glycerol are maintained without decreasing even during long-term reaction.

[0096]

[0097] While the present invention has been described above with reference to the embodiments described herein and illustrated in the accompanying drawings, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent embodiments are possible. Accordingly, the technical protection scope of the present invention should be defined by the following claims.

[0098]

[0099] When propylene glycol is produced by the hydrogenolysis reaction of glycerol using the K2O-CuO-SiO2 nanocomposite catalyst according to the present invention, not only can a high glycerol conversion rate and a high propylene glycol selectivity be achieved under conditions of relatively low hydrogen pressure and low reaction temperature, but the K2O-CuO-SiO2 nanocomposite catalyst has very high catalytic stability, so that propylene glycol can be produced from glycerol in a high yield through the hydrogenolysis reaction for a long period of time, and thus can be widely used in industrial fields requiring demand for propylene glycol, such as polyester resins, polyurethanes, cosmetics, and deicing additives.

Claims

1. In a catalyst for producing propylene glycol by hydrogenolysis of glycerol, A catalyst for producing propylene glycol by hydrogenolysis of glycerol, characterized in that the catalyst is composed of K oxide (K2O), Cu oxide (CuO) and silica (SiO2).

2. In claim 1, A catalyst for producing propylene glycol by hydrogenolysis of glycerol, characterized in that the total content of K oxide (K2O) and Cu oxide (CuO) is 50 to 95 wt% with respect to the entire catalyst.

3. In claim 2, A catalyst for producing propylene glycol by hydrogenolysis of glycerol, characterized in that the content of the above K oxide (K2O) is 0.1 to 10.0 wt% with respect to the entire catalyst.

4. In claim 1, A catalyst for producing propylene glycol by hydrogenolysis of glycerol, characterized in that the particle size of the silica (SiO2) is 5 nm to 10 ㎛.

5. In a method for producing a catalyst for producing propylene glycol by hydrogenolysis of glycerol, a) A step of preparing a reaction mixture by adding silica sol, K2O precursor and CuO precursor to a solvent, mixing and reacting them; b) a step of forming and maturing a precipitate by adjusting the pH of the reaction mixture prepared in step a); and c) A method for producing a catalyst for producing propylene glycol by hydrogenolysis of glycerol, characterized by comprising a step of washing, filtering, drying and calcining the matured precipitate in step b) to produce a K2O-CuO-SiO2 nanocomposite catalyst.

6. In paragraph 5, Step a) above, A method for producing a catalyst for producing propylene glycol by hydrogenolysis of glycerol, characterized in that the silica sol, K2O precursor and CuO precursor added to the solvent are added so that the final K2O-CuO-SiO2 nanocomposite catalyst has 5 to 50 wt% of SiO2, 0.1 to 10 wt% of K2O and a Cu / K molar ratio of 3 to 400.

7. A method for producing propylene glycol by hydrogenolysis of glycerol using a catalyst according to any one of claims 1 to 4 or a catalyst manufactured according to any one of claims 5 to 6, a) Step of preparing a glycerol aqueous solution; b) a step of reducing the catalyst using hydrogen gas after filling the catalyst into the reactor; and c) A method for producing propylene glycol by hydrogenolysis of glycerol, characterized by including a step of injecting the glycerol aqueous solution and hydrogen gas together into a reactor and causing a reaction to produce propylene glycol.

8. In paragraph 7, A method for producing propylene glycol by hydrogenation of glycerol, wherein in step c), the molar ratio of hydrogen / glycerol supplied is 2 to 200.

9. In paragraph 7, A method for producing propylene glycol by hydrogenation of glycerol, characterized in that in the above step c), the reaction temperature is 180 to 260 ℃ and the reaction pressure is 15 to 45 bar.

10. In paragraph 7, A method for producing propylene glycol by hydrogenation of glycerol, characterized in that the glycerol supply rate in the above step c) is 0.05 to 3 g / h per 1 g of catalyst.