KR20100079570A - Method of manufacturing catalyst for propanediol, and method of manufacturing propanediol using the same - Google Patents

Abstract

PURPOSE: A manufacturing method of a catalyst for manufacturing propanediol and a manufacturing method of propanediol using the same are provided to produce propanediol from glycerol with high yield at a low temperature and pressure condition. CONSTITUTION: A manufacturing method of a catalyst for manufacturing propanediol includes the following steps: preparing a metal precursor solution by dissolving a metal precursor compound in a solvent; forming precipitate by adjusting pH of the metal precursor solution; aging the precipitate; drying the aged precipitate after filtering; and calcinating the dried precipitate. The method further includes a step for reducing the catalyst to increase activity of the catalyst. The metal precursor compound is chrome, copper, nickel, zinc and manganese.

Description

Method for producing propanediol catalyst and method for producing propanediol using the same {METHOD OF MANUFACTURING CATALYST FOR PROPANEDIOL, AND METHOD OF MANUFACTURING PROPANEDIOL USING THE SAME}

The present invention relates to a method for producing a catalyst for producing propanediol and a method for producing propanediol using the same.

Since industrialization, the use of fossil fuels such as coal and petroleum as energy resources around the world has increased exponentially. All of the technologies and industries currently in use have been developed based 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 have made great efforts to reduce carbon dioxide emissions by signing the 1997 Kyoto Protocol. For these reasons, much research has been focused on developing environmentally friendly energy sources that can replace fossil fuels.

Recently, biodiesel has received much attention as an alternative energy source for fossil fuels. The biodiesel collectively refers to fuels having the same physical properties as diesel oil (diesel), which can be made by processing plant-derived resources such as vegetable oils such as rapeseed seed, soybean oil, waste edible oil, and brown rice oil. Since the biodiesel has the same physical properties as those of general diesel fuel, the biodiesel can be used directly in a diesel engine currently used, and has a merit of low emission of pollutants.

The biodiesel is prepared through the synthesis of fatty acid methyl esters by transesterification from plant-derived resources. On the other hand, glycerol generated as a main by-product from the transesterification reaction is used in the fields of beauty, pharmaceuticals, foods, etc., but the amount of glycerol supplied is excessively large compared to industrial demand, and eventually its value has plunged. For this reason, the conversion of glycerol, which is a by-product of biodiesel, into other high value materials has already begun since the early 1990s, and is currently being used by DuPont of the United States for the conversion of glycerol from 1,3-propanediol. 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 of pharmaceuticals, cosmetic intermediates, polyesters, unsaturated polyesters, and plasticizers of cellophane.

The process for producing 1,2-propanediol from the glycerol has not been reported in Korea yet. The process can be divided into biological methods and chemical methods 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 methods using such catalysts. This is because the system for the catalyst system or the reaction process has not yet been established. 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. In addition, US Patent Publication No. 2005/0244312 discloses a two-step reaction process for preparing 1,2-propanediol from glycerol. In other words, 1,2-propanediol is produced from glycerol through two steps: a dehydration reaction to produce hydroxyacetone from glycerol and a 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 that 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 improving the efficiency of the reaction conditions. There is a demand for development of a catalyst that can be further enhanced.

The present invention provides a process for preparing a catalyst that can be applied to a single reaction process for producing propanediol from glycerol.

The present invention provides a catalyst for producing propanediol prepared by the above production method.

The present invention provides a process for producing propanediol in high yield at relatively low temperature and pressure conditions using the 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.

According to an aspect of the present invention, a method for preparing a catalyst for producing propanediol is a method for preparing a catalyst added in a single reaction process for producing propanediol from glycerol, and preparing a metal precursor solution by dissolving at least one metal precursor compound in a solvent. step; Adjusting the pH of the metal precursor solution to form a precipitate; Aging the precipitate; Filtering and drying the aged precipitate; And calcining the dried precipitate.

On the other hand, a method for producing propanediol according to an aspect of the present invention comprises the steps of adding a glycerol and a catalyst prepared according to the above in the reactor; Supplying hydrogen gas into the reactor while stirring the glycerol and the catalyst; And reacting the glycerol and the hydrogen.

According to the present invention, propanediol can be prepared directly from glycerol in high yield using a catalyst having an optimum amount of suitable metal. In addition, when preparing a propanediol directly from the glycerol through a hydrogenation reaction, the reaction can be efficiently carried out even under relatively low pressure and low temperature conditions can increase the economics, safety, efficiency and the like of the propanediol manufacturing process.

According to the present invention, in the production of a catalyst for producing propanediol, it is possible to efficiently prepare the catalyst by finding a suitable ratio between a metal component having a high activity and the metal components, and in particular, the production cost using a low-cost raw material It can be lowered and practically applied to the process.

In particular, according to the method for preparing propanediol according to the present invention, it is possible to efficiently produce propanediol at a relatively low pressure and low temperature even when a large amount of catalyst is not used, compared to the conventional method, and thus can be utilized for mass production.

Hereinafter, a method for preparing a catalyst for producing propanediol and a method for producing propanediol using the same according to an aspect of the present invention will be described in detail.

The catalyst for producing propanediol according to one aspect of the present invention is added to a single reaction process for producing propanediol from glycerol. That is, propanediol can be produced directly from glycerol through the single reaction process. Therefore, when preparing a propanediol from glycerol using the catalyst according to an aspect of the present invention, it is possible to further improve the economics, safety, efficiency and the like of the process.

Method for preparing a catalyst for producing propanediol according to an aspect of the present invention is to prepare a metal precursor solution by dissolving at least one kind of metal precursor compound in a solvent, forming a precipitate by adjusting the pH of the metal precursor solution, the precipitate Aging step, filtering and drying the aged precipitate, and calcining the dried precipitate. In addition, the method for preparing a catalyst for producing propanediol according to an aspect of the present invention may further include reducing the catalyst to increase the activity of the catalyst prepared by the calcination. Hereinafter, it will be described in detail for each step.

The process for preparing a catalyst for producing propanediol according to one aspect of the present invention starts with preparing a metal precursor compound and a solvent. After preparing the metal precursor compound and the solvent, respectively, the metal precursor compound may be dissolved in the solvent to prepare a metal precursor solution.

Although it does not specifically limit as said metal precursor compound, For example, the thing containing the metal which has high activity can be used. For example, as the metal precursor compound, a chromium precursor compound, a copper precursor compound, a nickel precursor, each containing a non-noble metal such as chromium (Cr), copper (Cu), nickel (Ni), zinc (Zn), and manganese (Mn) A compound, a zinc precursor compound, a manganese precursor compound, etc. can be used individually or in combination of 2 or more types. Among them, in order to obtain high yield and high selectivity, a copper precursor compound and a chromium precursor compound may be used simultaneously as the metal precursor compound, and the ratio of the total number of chromium atoms to the total number of copper atoms in the metal precursor compounds used at this time It may be 2: 1. Alternatively, the amount of the metal precursor compound may be adjusted so that the metal precursor solution includes 40 to 90 atom% of chromium atoms and 10 to 60 atom% of copper atoms relative to the total number of atoms of the metal components in the metal precursor solution. In addition, various combinations may be possible in the type and amount of the metal precursor compound used. The metal precursor compound may be, for example, a metal salt such as nitrate, acetate, carbonate, acetate, halogen salt or the like; Halides; oxide; It may be a compound such as sulfide, but the present invention is not limited thereto. The metal salts, halides, oxides, sulfides and the like may be used alone or in combination of two or more, and they may be in the form of hydrates or anhydrides.

The solvent may be either a polar or nonpolar solvent. Since the said metal precursor should just be able to melt | dissolve as said solvent, it is not specifically limited, For example, ethanol, butanol, distilled water, etc. can be used individually or in combination of 2 or more types. In addition, lower alcohols can also be introduced as a solvent.

Next, the pH of the metal precursor solution is adjusted to form a precipitate. The precipitate is a compound containing a metal element of the metal precursor compound, it may be formed within a specific pH range. The pH adjustment may vary depending on the type of metal precursor compound, but may be performed, for example, by adding an alkali carbonate or sodium hydroxide aqueous solution to the metal precursor solution. The alkali carbonate or sodium hydroxide aqueous solution may be added to the metal precursor solution so that the pH may be 7 to 13, and the specific pH value is in the range according to the type and content of the metal component contained in the metal precursor solution. Can vary within.

The particle size, the formation rate, etc. of the precipitate may vary depending on the concentration and the addition rate of the alkali carbonate or the aqueous sodium hydroxide solution. For example, if the addition rate of the alkali carbonate or sodium hydroxide aqueous solution is too fast or the concentration is too high, there is a problem in that the activity of the catalyst is lowered due to the increase in the size of the precipitate formed particles. On the other hand, if the addition rate of the alkali carbonate or sodium hydroxide aqueous solution is too slow or the concentration is too low, the efficiency of the catalyst production may be reduced. Therefore, in order to effectively suppress the problems, the concentration of the alkali carbonate or sodium hydroxide aqueous solution is set within the range of 0.5 to 3 mol / L, and the alkali carbonate or sodium hydroxide aqueous solution is added at a rate of 0.1 to 10 mL per minute. It can be added to the metal precursor solution.

Next, when the pH of the metal precursor solution reaches a specific value within the range of 9 to 13, the precipitate may be aged. The aging may be carried out for 2 to 12 hours at 50 to 90 ℃ so that the precipitation reaction occurs sufficiently. If the aging temperature is too low or too high, it is difficult to form a precipitate having a high particle size of catalytic activity, and as described above, the aging temperature can be set at 50 to 90 ° C, preferably 60 to 80 ° C.

Next, the solution is sufficiently washed with distilled water until the alkali carbonate aqueous solution or the sodium hydroxide aqueous solution remaining in the precipitate is completely removed. The washed precipitate is then filtered and dried. The drying is carried out sufficiently at 80 to 200 ° C. until the precipitate is completely dried.

Next, the dried precipitate may be calcined to remove organic matter remaining in the precipitate and to form an appropriate alloy phase. The calcination may be performed in a temperature range of 400 to 700 ° C. under an air atmosphere or an oxygen atmosphere. The specific calcination temperature may be set to a temperature capable of forming an alloy phase exhibiting high catalytic activity and may vary depending on the type and content of the metal component contained in the formed precipitate. For example, metal components such as copper, chromium, nickel, etc. may form an appropriate alloy phase when calcined at 400 to 700 ° C, preferably 500 to 600 ° C.

The catalyst produced after the calcination process may have various structures. For example, it may have a structure containing a chromium and copper at the same time, for example, CuCr ₂ O ₄ . Such structures may be determined by the type and amount of the metal precursor compound to be added when preparing the metal precursor solution. For example, the catalyst may contain 40 to 90 atom% of chromium atoms and 10 to 60 atom% of copper atoms relative to the total number of atoms of the metal components of the catalyst. In the case of a catalyst having a structure of CuCr ₂ O ₄ , that is, a ratio of the total number of chromium atoms to the total number of copper atoms of 2: 1, the catalytic activity may exhibit the best characteristics. This will be described later in more detail in the Examples.

Next, the catalyst can be reduced if necessary to increase the activity of the catalyst. The reduction may be carried out at 200 to 500 ℃, preferably at 300 to 400 ℃ while supplying hydrogen gas at a predetermined rate. A reduction temperature range of 200 to 500 ° C. is a temperature at which the metal can be selectively reduced to provide optimum catalytic activity. Meanwhile, the reduction may be performed while additionally supplying nitrogen, helium or argon gas in addition to hydrogen gas. The nitrogen, helium, or argon gas may be supplied alone or in combination of two or more, respectively, and may be supplied in the form of a mixed gas mixed with the hydrogen gas. The volume ratio of hydrogen gas in the mixed gas may be 10 to 20%. For example, the volume ratio of the mixed gas supplied in the reduction step may be 10% hydrogen gas, 90% nitrogen gas (ie, 10% H ₂ / N ₂ ).

According to the above, in the preparation of a catalyst for producing propanediol, it is possible to find a suitable ratio between a metal component having a high activity and the metal components. In addition, low-cost metal precursor compounds can be used to lower the production cost of catalyst production and can be practically applied to mass production.

On the other hand, the method for producing propanediol according to an aspect of the present invention is a step of introducing a glycerol and the catalyst prepared according to the above, the reactor while stirring the glycerol and the catalyst, supplying hydrogen gas into the reactor, And reacting the glycerol and the hydrogen. Hereinafter will be described in detail for each step.

The process for producing propanediol according to one aspect of the present invention begins with preparing glycerol and the catalyst, respectively, and then introducing the glycerol and the catalyst into the reactor. The glycerol may be a byproduct generated in the production of biodiesel, but the present invention is not limited thereto. For example, the glycerol may be synthesized through various routes or produced as a by-product of various synthesis reactions. In addition to these, commercially available ones may be used as the glycerol. If the amount of the catalyst is insufficient, the activity may not appear sufficiently in the reaction process, the higher the amount of the catalyst can be obtained a higher yield of propanediol, but considering the economical content of the catalyst is 1 to 100 parts by weight of glycerol 10 parts by weight, more preferably 2 to 5 parts by weight. As the reactor, for example, a batch reactor can be used.

Next, after the reactor is completely sealed, hydrogen gas is supplied into the reactor, for example, for 30 to 60 minutes while stirring the glycerol and the catalyst so that the inside of the reactor is formed in a hydrogen gas atmosphere. In addition, the mixed gas which mixed hydrogen gas, helium, argon, nitrogen gas, etc. may be supplied in the said reactor.

Next, the inside of the reactor is elevated and heated to a predetermined pressure and temperature range to react the glycerol and the hydrogen. In the reaction, if the reaction temperature is too low, the production efficiency of propanediol is low, the reaction temperature is 150 to 300 ℃, preferably 210 to 280 ℃, more preferably 220 to 260 ℃ is effective. When the reaction temperature is lower than 150 ° C, the conversion rate of glaserol is lowered, and when the reaction temperature is higher than 300 ° C, the selectivity is lowered and is not preferable in terms of energy efficiency. In the reaction, for the same reason, the reaction pressure is appropriately maintained at 20 to 100 atmospheres, preferably 60 to 90 atmospheres. The reaction can be carried out, for example, for 0.5 to 48 hours, preferably for 5 to 15 hours, so that a sufficient conversion from glycerol to propanediol can occur. The propanediol may be 1,2-propanediol and / or 1,3-propanediol.

According to the above, propanediol can be prepared directly from glycerol in high yield using a catalyst having an appropriate amount of a suitable metal. The production of such propanediol can be carried out at relatively low pressure and low temperature conditions, thereby improving the economics, safety, efficiency and the like of the propanediol manufacturing process.

Hereinafter, the catalyst for producing propanediol and the method for preparing propanediol according to an aspect of the present invention will be described in more detail with reference to Examples, but the following Examples are exemplary for explaining the present invention in more detail. Is not limited to the following examples.

EXAMPLE

Example 1

i) Preparation of Catalysts for Propanediol Preparation

400 mL of distilled water of 7.32 g of copper nitrate (Cu (NO ₃ ) ₂ · 2H ₂ O) and 26 g of chromium nitrate (Cr (NO ₃ ) ₂ · 9H ₂ O) so that the ratio of the number of copper atoms: chromium atoms is 1: 2. It was dissolved in to prepare a metal precursor solution, and then an aqueous sodium hydroxide solution having a concentration of 3 mol / L was added until the pH of the metal precursor solution reached 12 to form a precipitate.

Next, the precipitate was aged while maintaining the temperature of the metal precursor solution in which the precipitate was formed at 60 ° C. and stirring for 6 hours. The precipitate was washed with distilled water and then dried at 80 ° C. for 24 hours, after which the dried precipitate was ground to uniform particles. Next, it was calcined for 6 hours at a temperature of 550 ° C and an air atmosphere. The results of analyzing the calcined catalyst oxide by X-ray diffraction analysis (XRD) are shown in FIG. 1. 1 is the diffraction angle (2 theta), and the vertical axis represents the diffraction intensity. The result for the catalyst prepared in this example is (c), the third graph from above. In (c) of FIG. 1, the CuCr ₂ O ₄ phase was identified from the '◆' peak.

ii) reduction of the catalyst for producing propanediol

1.5 g of the catalyst was charged into a tubular reactor, and the temperature was gradually increased while flowing 10% H ₂ / N ₂ mixed gas at 200 mL per minute. After the temperature reached 320 ° C., the temperature was kept constant for 2 hours to reduce the catalyst. X-ray diffraction (XRD) results for the reduced catalysts are shown in FIG. In (c) of FIG. 2, the reduced CuCr ₂ O ₄ phase was identified from the '◆' peak.

iii) preparation of propanediol

1 g of the catalyst activated by the reduction process was introduced into a batch reactor together with 50 g of glycerol having a purity of 90% or more, and then the reactor was sealed. Next, 50 mL of hydrogen per minute was fed into the reactor for 30 minutes while stirring the inside of the reactor. Next, while supplying hydrogen at a high pressure into the reactor, the temperature inside the reactor was raised to 240 ° C. while raising the pressure inside the reactor to 80 atm. Subsequently, 1,2-propanediol was prepared by reacting the glycerol and the hydrogen for 12 hours while maintaining a constant reaction temperature at 240 ° C. and stirring vigorously at 80 atm. The conversion of the glycerol, the yield of 1,2-propanediol and the selectivity of 1,2-propanediol are shown in Table 1. Here, the conversion rate represents the ratio of glycerol converted to another compound by the reaction of the glycerol and the hydrogen, the selectivity represents the proportion of propanediol in the converted compound. The yield represents the ratio converted from glycerol to propanediol and is a value corresponding to the product of the conversion and the selectivity.

Examples 2 to 5

The metal precursor solution so that the ratio of the number of copper atoms to the number of chromium atoms is 1: 0 (Example 2), 1: 1 (Example 3), 1: 3 (Example 4), and 0: 1 (Example 5), respectively. Was prepared. The remaining steps i), ii) and iii) were carried out in the same manner as in Example 1 to prepare a catalyst and 1,2-propanediol. The conversion of glycerol, the yield of 1,2-propanediol and the selectivity of 1,2-propanediol for Examples 2-5 are shown in Table 1. In addition, the results of X-ray diffraction analysis for the catalyst before reduction and the catalyst after reduction prepared in Examples 2 to 5 are shown in FIGS. 1 and 2.

Metal ratio Conversion rate
(mol%) Selectivity
(mol%) yield
(mol%) Example 1 Cu: Cr = 1: 2 80.3 83.9 67.4 Example 2 Cu: Cr = 1: 0 42 63.8 26.8 Example 3 Cu: Cr = 1: 1 63 74.6 47 Example 4 Cu: Cr = 1: 3 62 81.3 50.4 Example 5 Cu: Cr = 0: 1 9 0 0

1 is a graph showing the results of X-ray diffraction analysis for the catalyst prepared by the process i) in Examples 1 to 5, wherein the catalyst is not reduced. (A) Example 2, (b) Example 3, (c) Example 1, (d) Example 4, (e) results for the catalyst prepared by Example 5 to be.

Referring to FIG. 1, (a) is a case where the ratio of the number of copper atoms to the number of chromium atoms is 1: 0, and it was found that a copper oxide (CuO) phase was formed from the '□' peak. As shown in (b), (c), (d) and (e) in FIG. 1, the proportion of chromium gradually increases. As the ratio of chromium increases, the intensity of the '□' peak representing the copper oxide phase decreases, and as can be seen from (c), it can be seen from the '◆' peak that a CuCr ₂ O ₄ phase is formed. As in Example 5, when the ratio of the number of copper atoms to the number of chromium atoms is 1: 3, it can be seen from the '▲' peak that a chromium oxide (Cr ₂ O ₃ ) phase is formed. The catalyst of Example 5 was not excellent in crystallinity, and as can be seen from the results of Table 1, it was found that the yield shows almost no catalytic activity.

Figure 2 is a graph showing the results of X-ray diffraction analysis for the catalyst prepared by the process i) and ii) in Examples 1 to 5, wherein the catalyst is reduced. (A) of Example 2, (b) of Example 3, (c) of Example 1, (d) of Example 4, and (e) of the catalyst prepared by Example 5 to be.

As in the case of FIG. 1, the ratio of chromium gradually increases as it goes up to (a), (b), (c), (d) and (e) of FIG. As the amount of chromium added increases, the copper phase decreases and the reduced CuCr ₂ O ₄ phase develops little by little. In particular, in the case of a catalyst in which the ratio of the number of copper atoms to the number of chromium atoms is mixed with 1: 2 (Example 1, FIG. 2 (c)), the copper phase or the chromium oxide phase does not exist, and all metals contain CuCr ₂ O ₄ . It can be seen that it forms a reduced phase.

Examples 6-37

i) and ii) the same process as in Example 1 to prepare a catalyst. iii) In the preparation of propanediol, the addition amount of the catalyst relative to the total weight of glycerol, the reaction pressure, the reaction temperature and the reaction time during the reaction of the glycerol and the hydrogen were set as shown in Table 2 below In the same manner as in iii) of Example 1, a catalyst and 1,2-propanediol were prepared. The conversion of the glycerol, the yield of 1,2-propanediol and the selectivity of 1,2-propanediol are shown in Table 2.

pressure
(bar) Temperature
(℃) Catalytic amount
(wt%) time
(hr) Conversion rate
(mol%) Selectivity
(mol%) yield
(mol%) Example 6 20 180 2 12 10 94 10 Example 7 20 200 2 12 26 90 24 Example 8 20 220 2 12 59 87 51 Example 9 20 240 2 12 75 24 18 Example 10 20 260 2 12 83 6 5 Example 11 40 180 2 12 21 48 10 Example 12 40 200 2 12 23 99 24 Example 13 40 220 2 12 47 94 44 Example 14 40 240 2 12 86 78 67 Example 15 40 260 2 12 97 52 50 Example 16 60 180 2 12 10 89 9 Example 17 60 200 2 12 30 95 28 Example 18 60 220 2 12 60 93 56 Example 19 60 240 2 12 92 86 79 Example 20 60 260 2 12 98 78 76 Example 21 80 180 2 12 12 97 12 Example 22 80 200 2 12 37 72 26 Example 23 80 220 2 12 63 82 51 Example 24 80 240 2 12 95 91 87 Example 25 80 260 2 12 99 85 84 Example 26 80 240 0.5 12 59 47 27 Example 27 80 240 One 12 76 74 56 Example 28 80 240 5 12 99 88 87 Example 29 80 240 2 One 41 30 13 Example 30 80 240 2 2 55 77 43 Example 31 80 240 2 3 65 86 55 Example 32 80 240 2 4 77 60 46 Example 33 80 240 2 5 80 89 71 Example 34 80 240 2 6 79 85 68 Example 35 80 240 2 9 86 89 77 Example 36 80 240 2 18 75 50 38 Example 37 80 240 2 24 71 39 28

Referring to Examples 6 to 25 of Table 2, when the reaction pressure, the amount of catalyst, and the reaction time are the same, the yield increases as the reaction temperature increases, but it can be seen that the yield decreases beyond a certain reaction temperature. there was. In the above embodiment, it can be seen that the yield is maximum when the reaction temperature is 240 ?. In addition, when the reaction temperature, the amount of catalyst and the reaction time are the same, as the reaction pressure increases, the yield did not show a big difference, but it was found that the yield increases at the high reaction temperature. In the above embodiment, when the reaction pressure is 80 atm, it can be seen that the yield is the maximum.

Referring to Examples 25 to 28, it was found that the conversion, selectivity, and yield increased as the amount of the catalyst added increased, but the conversion, selectivity, and yield did not increase significantly beyond a certain range. In this embodiment, the conversion, selectivity and yield do not increase significantly when the amount of catalyst added exceeds 2 wt%.

Referring to Examples 25, 29 to 37, when the reaction pressure, the reaction temperature, the amount of the catalyst is constant, as the reaction time increases, the conversion rate, selectivity and yield tends to increase but exceeds the predetermined reaction time It was found that the selectivity and yield decreased. In this embodiment, when the reaction time is 12 hours, it has the maximum yield.

As described above, the present invention has been described by way of limited embodiments and drawings, but 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.

1 is a graph showing the results of X-ray diffraction analysis for the catalysts prepared in Examples 1 to 5. (A) Example 2, (b) Example 3, (c) Example 1, (d) Example 4, (e) results for the catalyst prepared by Example 5 As such, the catalyst is not reduced.

2 is a graph showing the results of X-ray diffraction analysis for the catalysts prepared in Examples 1 to 5. (A) of Example 2, (b) of Example 3, (c) of Example 1, (d) of Example 4, and (e) of the catalyst prepared by Example 5 The catalyst is reduced.

Claims (19)

A process for preparing a catalyst added to a single reaction process for producing propanediol from glycerol, Dissolving at least one kind of metal precursor compound in a solvent to prepare a metal precursor solution; Adjusting the pH of the metal precursor solution to form a precipitate; Aging the precipitate; Filtering and drying the aged precipitate; And Calcining the dried precipitate Method for producing a catalyst for producing propanediol comprising a. The method of claim 1, Reducing the catalyst to increase the activity of the catalyst produced by the calcination Method for producing a catalyst for producing propanediol further comprising. The method of claim 1, And a metal of the metal precursor compound is at least one selected from the group consisting of chromium (Cr), copper (Cu), nickel (Ni), zinc (Zn) and manganese (Mn). The method of claim 1, A method for producing a catalyst for producing propanediol, wherein a ratio of total chromium atoms to total copper atoms in the metal precursor compounds used is 2: 1, using a copper precursor compound and a chromium precursor compound simultaneously as the metal precursor compound. The method of claim 1, Wherein the metal precursor solution comprises 40 to 90 atom% of chromium atoms and 10 to 60 atom% of copper atoms relative to the total number of atoms of the metal components. The method of claim 1, PH control of the metal precursor solution is a method for producing a catalyst for producing propanediol is carried out by adding an alkali carbonate or sodium hydroxide aqueous solution to the metal precursor solution. The method of claim 6, A method for producing a catalyst for producing propanediol, wherein the concentration of the alkali carbonate or sodium hydroxide aqueous solution is 0.5 to 3 mol / L. The method of claim 6, The alkali carbonate or sodium hydroxide aqueous solution is added to the metal precursor solution at a rate of 0.1 to 10 mL per minute to prepare a catalyst for producing propanediol. The method of claim 1, Method of producing a catalyst for producing propanediol is adjusted to pH 7 to 13 by adjusting the pH of the metal precursor solution. The method of claim 1, The aging process of the catalyst for producing propanediol is carried out for 2 to 12 hours at 50 to 90 ℃. The method of claim 1, Process for producing a catalyst for producing propanediol wherein the drying is carried out at 80 to 200 ℃. The method of claim 1, The calcination is carried out at 400 to 700 ℃ a method for producing a catalyst for producing propanediol. The method of claim 2, A method for producing a catalyst for producing propanediol, wherein the reduction is performed under a gas atmosphere containing hydrogen gas and at 200 to 500 ° C. The method of claim 13, The method of producing a catalyst for producing propanediol, wherein the gas atmosphere further comprises at least one gas selected from the group consisting of nitrogen, helium and argon. Injecting glycerol and the catalyst prepared by claim 1 into the reactor; Supplying hydrogen gas into the reactor while stirring the glycerol and the catalyst; And Reacting the glycerol and the hydrogen Method for producing a propanediol comprising a. The method of claim 15, Method for producing propanediol is the content of the catalyst is 1 to 10 parts by weight relative to 100 parts by weight of the glycerol. The method of claim 15, Process for producing propanediol wherein the supply of hydrogen gas is carried out for 30 to 60 minutes. The method of claim 15, The reaction method of the said glycerol and the said hydrogen is carried out on the conditions of 150-300 *, and 20-100 atmospheres. The method of claim 15, The reaction method of the glycerol and the hydrogen is carried out for 0.5 to 30 hours.

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