KR100881344B1 - Method of preparing dichloropropanol from glycerol using heteropolyacid catalysts - Google Patents

Abstract

A method of preparing dichloropropanol is provided to reduce the manufacturing costs by simplifying a process and to have no separation problem of an azeotropic mixture of catalyst and reaction product. A method of preparing dichloropropanol by reacting glycerol and chlorinating agent uses a heteropolyacid catalyst. The heteropolyacid catalyst is selected from a Keggin type heteropoly acid having the atomic ratio of pivotal element: coordinate element of 1:12, and a Wells-Dawson type heteropoly acid having the atomic ratio of pivotal element: coordinate element of 2:18. The reaction is the homogenous or heterogeneous catalyst reaction. The chlorinating agent is the hydrochloride aqueous solution or hydrogen chloride gas. The chlorination is carried out at a temperature of 50~200 °C under the pressure of 1~50 bar.

Description

Method of preparing dichloropropanol from glycerol using heteropolyacid catalysts

The present invention relates to a process for preparing dichloropropanol from glycerol using a catalyst, and more particularly to a process for preparing dichloropropanol from glycerol using a heteropolyacid catalyst.

Currently bio-diesel is developed and produced competitively all over the world, and has already begun production in Korea and is marketed as an additive material of diesel oil.

In the production of such biodiesel, a huge amount of glycerol, which is about 10% of the biodiesel production, is produced. However, since such glycerol is excessively supplied due to excessive supply compared to demand, it is desirable to achieve high value of glycerol by converting it to dichloropropanol having high added value.

Meanwhile, dichloropropanol is a raw material for producing epichlorohydrin, and most of the dichloropropanol currently supplied to the market is made from propylene. Specifically, the method for producing dichloropropanol is the step of preparing allyl chloride by high temperature chlorination of propylene and reacting allyl chloride and chlorine again using excess industrial water to produce dichloropropanol. It consists of steps. However, the production method of dichloropropanol using propylene has problems such as supply and demand instability due to the rising price of propylene, generation of a large amount of wastewater and waste, excessive initial investment costs due to the two-step manufacturing method, and difficulty in new expansion of the manufacturing method. Has

Accordingly, the process of directly preparing dichloropropanol by a one-step preparation method in which glycerol is reacted with hydrochloric acid in the presence of a catalyst has secured economic feasibility. This one-step manufacturing method using glycerol can reduce the raw material cost by using inexpensive glycerol as a reactant, and can also significantly reduce the amount of wastewater and wastes by not using industrial water during the process. In addition, the process and environment-related investment costs are reduced, the initial investment costs are low. In addition, the production method using glycerol, unlike the conventional method for preparing dichloropropanol through a two-step process from propylene, there is an environmentally friendly advantage by directly preparing dichloropropanol from glycerol as a biodiesel by-product.

In addition, by directly producing dichloropropanol by reacting glycerol and hydrochloric acid using a catalyst, it is possible to reduce costs and save energy through efficient catalyst development. Therefore, when developing an excellent catalytic process for producing dichloropropanol directly using glycerol, it is possible to preempt the environmental, economic and investment costs in the production of dichloropropanol and to secure technological competitiveness.

Currently, the main producers of epichlorohydrin, the final product from glycerol, are Dow Chemical of the United States and Solvay of Germany, which use a carboxylic acid-based homogeneous catalyst and a continuous process using hydrogen chloride gas as a chlorinating agent. Dichloropropanol is produced from glycerol by the process (WO2006 / 020234, WO2005 / 054167, WO2005 / 021476).

Patents on catalytic processes for the direct preparation of dichloropropanol from glycerol have been rarely reported except for some of the patents mentioned above.

It is an object of the present invention to provide a process which allows the production of dichloropropanol from glycerol in high yield using a heteropolyacid catalyst.

Another object of the present invention is to provide a method for preparing dichloropropanol which can simplify the process and reduce the production cost.

It is still another object of the present invention to provide a method for preparing dichloropropanol, which is free from azeotropic mixtures of catalysts and reaction products, facilitates catalyst recovery, and enables catalyst regeneration.

Still another object of the present invention is to provide a method for preparing dichloropropanol, which can efficiently treat glycerol generated in a biodiesel manufacturing process and achieve high value of glycerol.

The present invention to solve the above problems,

In the method for producing dichloropropanol by reacting glycerol with a chlorinating agent, a method for producing dichloropropanol, characterized in that a heteropolyacid catalyst is used.

According to one embodiment of the present invention, the heteropolyacid catalyst is selected from Keggin-type heteropolyacids having an atomic ratio of central element: isotope of 1:12 and Wells-Dawson type heteropolyacids having an atomic ratio of core element: isotope of 2:18.

According to another embodiment of the present invention, the Keggin-type heteropolyacid catalyst, _12- molybdo tungstophosphoric acid (H ₃ PMo _12-X W _X O ₄₀ ), 12- molybdo tungstosilonic acid (H ₄ SiMo _12-X W _X O ₄₀ ), _12- Tungsutobanadophosphate (H _{3 + X} PW _12-X V _X O ₄₀ ), _12- molybdovanadophosphate (H _{3 + X} PMo _12-X V _X O ₄₀ ), 12-tungstoniobium phosphate (H _{3 + X} PW _12-X Nb _X O ₄₀ ), And among these, all or part of the hydrogen atom is selected from the group consisting of a heteropoly acid substituted with a metal,

In the above formulas, X = 0-12.

According to another embodiment of the present invention, the Wells-Dawson-type heteropolyacid catalyst is, 18-molybdobanadophosphoric acid (H _{6 + X} P ₂ Mo _18-X V _X O ₆₂ ), 18- tungsutobanado Phosphoric acid (H _{6 + X} P ₂ W _18-X V _X O ₆₂ ), 18-molybdoungstosphosphoric acid (H ₆ P ₂ Mo _18-X W _X O ₆₂ ), 18-tungsteniodium phosphate (H _{6 + X} P ₂ W _18-X Nb _X O ₆₂ ), 18-molybdo tungstosilonic acid (H ₇ Si ₂ Mo _18-X W _X O ₆₂ ), and all or part of hydrogen atoms in these are metal It is selected from the group consisting of heteropoly acid substituted by

In the formulas is X = 0-18.

According to another embodiment of the invention, the reaction is a homogeneous or heterogeneous catalysis.

According to another embodiment of the present invention, water is used as the reaction medium in the catalysis.

According to another embodiment of the invention, the heteropolyacid catalyst is recovered after the reaction and reused.

According to another embodiment of the invention, the chlorinating agent is an aqueous hydrogen chloride solution or hydrogen chloride gas.

According to another embodiment of the present invention, the chlorination reaction is carried out at a temperature of 50 ~ 200 ℃.

According to another embodiment of the invention, the chlorination reaction is carried out at a pressure of 1 ~ 50bar.

According to another embodiment of the present invention, the chlorination reaction is performed for 10 minutes to 50 hours.

In addition, the present invention to solve the above problems,

In the method for producing epichlorohydrin (ECH) by reacting glycerol with a chlorinating agent to produce dichloropropanol,

It provides a method for producing epichlorohydrin comprising a method for producing dichloropropanol according to any one of the above embodiments, or using dichloropropanol prepared by the method.

According to the present invention, there can be provided a process for producing dichloropropanol in high yield from glycerol using a heteropolyacid catalyst.

In addition, according to the present invention, there can be provided a method for producing dichloropropanol that can reduce the manufacturing cost by simplifying the process.

In addition, according to the present invention, there is no problem of separation of the azeotrope mixture of the catalyst and the reaction product, the catalyst recovery is easy, and a method for preparing dichloropropanol capable of regenerating the catalyst can be provided.

According to the present invention, there can be provided a method for producing dichloropropanol, which can efficiently treat glycerol generated in the biodiesel manufacturing process and achieve high value-adding of glycerol.

Next, a method for preparing dichloropropanol according to a preferred embodiment of the present invention will be described in detail.

The method for producing dichloropropanol according to the present invention includes a chlorinated reaction of glycerol and uses a heteropolyacid catalyst. That is, the method is a method for producing dichloropropanol by chlorination of glycerol using a heteropolyacid catalyst.

The heteropolyacid catalyst includes at least one of a Keggin-type heteropolyacid having an atomic ratio of a central element: isotope 1:12 and a Wells-Dawson type heteropolyacid having an atomic ratio of a central element: isotope 2: 2.

The Keggin-type heteropolyacid catalyst, _12- molybdo tungstophosphoric acid (H ₃ PMo _12-X W _X O ₄₀ ), 12- molybdo tungstosilonic acid (H ₄ SiMo _12-X W _X O ₄₀ ), 12-Tungsutobanadophosphate (H _{3 + X} PW _12-X V _X O ₄₀ ), _12- molybdobanadophosphoric acid (H _{3 + X} PMo _12-X V _X O ₄₀ ), _12- tungstonio Empty phosphoric acid (H _{3 + X} PW _12-X Nb _X O ₄₀ ), All or part of these hydrogen atoms include a heteropoly acid substituted with a metal, or a mixture thereof, and is a number of X = 0 to 12 in the above formulas. The metal may include cesium (Cs) or silver (Ag).

The Wells-Dawson type heteropolyacid catalyst is, 18-molybdovanadoic acid (H _{6 + X} P ₂ Mo _18-X V _X O ₆₂ ), 18- tungsutobanado phosphoric acid (H _{6 + X} P ₂ W _{18 -X} V _X O ₆₂ ), 18-molybdo tungstophosphoric acid (H ₆ P ₂ Mo _18-X W _X O ₆₂ ), 18-tungsteniodium phosphoric acid (H _{6 + X} P ₂ W _18-X Nb _X O ₆₂ ), _18- molybdo tungstosilonic acid (H ₇ Si ₂ Mo _18-X W _X O ₆₂ ), and a heteropoly acid in which all or part of hydrogen atoms thereof are substituted with a metal, In the case of X = 0-18. The metal may include cesium (Cs) or silver (Ag).

As described above, the heteropolyacid catalyst substituted with a metal such as cesium or silver forms a three-dimensional structure which is insoluble in water and has a surface area of 40 m ² / g or more. As such, when an insoluble heteropolyacid catalyst forming a three-dimensional structure is used, the reaction can be performed in a heterogeneous process.

The heteropolyacid catalyst is used for homogeneous or heterogeneous catalysis, and in this case, water is preferably used as the reaction medium. This is because the solubility of glycerol in water is particularly excellent. However, the present invention is not limited thereto, and various organic solvents may also be used.

In addition, the heteropolyacid catalyst may be recovered after the reaction and reused. In other words, the solid product can be recovered by evaporating the liquid product after the reaction, and it can be reused by feeding it into the reactor. The reason why the heteropolyacid catalyst can be recovered and reused after the reaction is that the mixed solution containing the heteropolyacid catalyst and the reaction product after the reaction does not form an azeotrope. When the mixed solution forms an azeotrope as in the case of using a conventional carboxylic acid-based catalyst, the liquid phase and the gas phase are in equilibrium, and the component ratio is constant and the boiling point does not change. There is a problem that is difficult to separate the catalyst from.

In addition, the chlorination agent used in the chlorination reaction may be used aqueous hydrogen chloride or hydrogen chloride gas, but the present invention is not limited thereto.

In addition, as a reactor, a batch reactor including an internal component formed of or coated with a material resistant to the chlorinating agent may be used. Materials that are resistant to chlorinating agents include Hastelloy C or Teflon.

The purified heteropolyacid catalyst is present in the reactor in a dissolved or dispersed state in the reaction medium. The addition of catalyst in a batch reactor can proceed in a discontinuous manner. In this embodiment, the chlorination reaction is generally carried out at a temperature of 50 to 200 ℃. If the reaction temperature is less than 50 ℃ is not preferable in terms of the reaction rate, if it exceeds 200 ℃ is not preferable in terms of energy loss. In addition, the chlorination reaction is generally carried out in a pressure range of 1 bar or more, in particular 1 to 50 bar. The higher the reaction pressure, the better the activity, but when the predetermined pressure (50 bar) or more does not show a large difference in the reaction activity. The reaction pressure is controlled using an inert gas, for example nitrogen. The reaction time is generally 10 minutes to 50 hours. If the reaction time is less than 10 minutes, the conversion rate of glycerol is not low, it is not preferable, and if it exceeds 50 hours, the reaction is almost completed, there is no change in conversion or selectivity. In the present invention, "dichloropropanol" means a mixture of isomers consisting of 1,3-dichloropropan-2-ol and 1,2-dichloropropan-3-ol. In the method for preparing dichloropropanol according to the present embodiment, 1,3-dichloropropan-2ol is mainly produced, which material is particularly suitable as a reactant for epichlorohydrin preparation.

In the reaction for producing dichloropropanol directly from glycerol using a heteropolyacid catalyst, the conversion rate of glycerol and the selectivity of dichloropropanol are calculated by the following equations (1) and (2), respectively.

% Conversion of glycerol = (moles of glycerol reacted / moles of glycerol supplied) × 100

Selectivity (%) of dichloropropanol = (moles of dichloropropanol produced / moles of glycerol reacted) × 100

Selectivity of dichloropropanol is calculated based on a mixture of isomers consisting of 1,3-dichloropropan-2-ol and 1,2-dichloropropan-3-ol.

On the other hand, it may also be provided a method for producing epichlorohydrin comprising a method for producing dichloropropanol having the above configuration or using a dichloropropanol prepared by the above method. Specifically, a method for preparing epichlorohydrin from glycerol using a heteropolyacid catalyst may be represented by the following Chemical Formula 1.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example

(Preparation of Dichloropropanol from Glycerol Under Heteropoly Acid Catalyst)

Example 1 Use of Keggin-type heteropolyacid catalyst in which the central element is phosphorus (P) and molybdenum (Mo) and tungsten (W) are bonded to the isotope (uniform liquid phase reaction)

Dichloropropanol was prepared from glycerol using a total of five catalysts in the form of H ₃ PMo _12-X W _X O ₄₀ (X = 0, 3, 6, 9, 12) as the heteropolyacid catalyst. Catalysis was achieved in the liquid phase in a batch reactor with a volume of 200 ml. The internal components of the batch reactor were formed from Hastelloy C and Teflon, materials that are resistant to chlorinating agents. For accurate quantification, the heteropolyacid catalyst was heat treated at 300 ° C. for 2 hours to remove crystal water contained therein. 12.6 g of glycerol, 20 g of water, 79 g of aqueous hydrogen chloride solution at a concentration of 37 wt%, and 15 g of anhydrous heteropolyacid catalyst were charged to a batch reactor. Thereafter, the reaction temperature was fixed at 110 ° C., and the reaction was performed for 20 hours while maintaining the reaction pressure at 10 bar under stirring. At this time, the reaction pressure was adjusted using nitrogen which is an inert gas. After completion of the reaction, the temperature of the reactor was cooled to room temperature, and then the product was analyzed using gas chromatography. In addition, the conversion rate of glycerol and the selectivity of dichloropropanol were respectively calculated by Equation 1 and Equation 2, and the results are shown in Table 1 below. As used in Table 1 below, "MCPD" and "DCP" mean monochloropropanediol and dichloropropanol, respectively. Representative by-products of the reaction (Acrolein), 1,2-dichloropropane (1,2-Dichloropropane), 1,2-dichloroethane (1,2-Dichloroethane), acetol (Acetol) Etc.

Referring to Table 1, the selectivity of DCP increased as the number of substitutions of tungsten as an isotope increased.

catalyst % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₃ PMo ₁₂ O ₄₀ 100 12.0 81.5 6.5 H ₃ PMo ₉ W ₃ O ₄₀ 100 27.0 64.7 8.3 H ₃ PMo ₆ W ₆ O ₄₀ 100 41.3 43.9 14.8 H ₃ PMo ₃ W ₉ O ₄₀ 100 52.9 31.6 15.5 H ₃ PW ₁₂ O ₄₀ 100 59.2 7.9 32.9

Example  2: the central element is silicon ( Si ) And molybdenum ( Mo ) And tungsten (W) In place of Combined Keggin brother Heteropolyacid  Using catalyst ( Homogeneity  Liquid phase reaction)

Dichloropropanol was prepared from glycerol using a total of five catalysts in the form of H ₄ SiMo _12-X W _X O ₄₀ (X = 0, 3, 6, 9, 12) as the heteropolyacid catalyst. Reaction conditions and analysis conditions were the same as in Example 1. Conversion of glycerol and selectivity for dichloropropanol were calculated, respectively, and the results are shown in Table 2 below.

Referring to Table 2, the selectivity of DCP increased as the number of substitutions of tungsten as an isotope increased.

catalyst % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₄ SiMo ₁₂ O ₄₀ 100 38.0 55.7 6.3 H ₄ SiMo ₉ W ₃ O ₄₀ 100 43.0 43.6 13.4 H ₄ SiMo ₆ W ₆ O ₄₀ 100 60.9 25.1 14.0 H ₄ SiMo ₃ W ₉ O ₄₀ 100 60.3 24.6 15.1 H ₄ SiW ₁₂ O ₄₀ 100 61.3 23.1 15.6

Example  3: The central element is phosphorus (P) and tungsten (W) and vanadium (V) In place of Combined Keggin brother Heteropolyacid  Using catalyst ( Homogeneity  Liquid phase reaction)

Dichloropropanol was prepared from glycerol using a total of four catalysts in the form H _{3 + X} PW _{12 - X} V _X O ₄₀ (X = 0, 1, 2, 3) as heteropolyacid catalysts. Reaction conditions and analysis conditions were the same as in Example 1. Conversion of glycerol and selectivity for dichloropropanol were calculated, respectively, and the results are shown in Table 3 below. Referring to Table 3, the selectivity of DCP decreased as the number of substitution of vanadium as an isotope increased.

catalyst % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₃ PW ₁₂ O ₄₀ 100 59.2 7.9 32.9 H ₄ PW ₁₁ VO ₄₀ 100 57.6 27.5 14.9 H ₅ PW ₁₀ V ₂ O ₄₀ 100 52.8 35.6 11.6 H ₆ PW ₉ V ₃ O ₄₀ 100 71.4 17.2 11.4

Example  4: The central element is phosphorus (P) and molybdenum ( Mo ) And vanadium (V) In place of Combined Keggin brother Heteropolyacid  Using catalyst ( Homogeneity  Liquid phase reaction)

Dichloropropanol was prepared from glycerol using a total of four catalysts in the form of H _{3 + X} PMo _12-X V _X O ₄₀ (X = 0, 1, 2, 3) as a heteropolyacid catalyst. Reaction conditions and analysis conditions were the same as in Example 1. Conversion of glycerol and selectivity of dichloropropanol were calculated, respectively, and the results are shown in Table 4 below. Referring to Table 4, the selectivity of DCP decreased as the number of substitution of vanadium as an isotope increased.

catalyst % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₃ PMo ₁₂ O ₄₀ 100 12.0 81.5 6.5 H ₄ PMo ₁₁ VO ₄₀ 100 22.4 71.4 6.2 H ₅ PMo ₁₀ V ₂ O ₄₀ 100 11.3 83.8 4.9 H ₆ PMo ₉ V ₃ O ₄₀ 100 27.6 68.2 4.2

Example  5: Heteropolyacid Hydrogen atom  Partially substituted with metal Keggin brother Heteropolyacid  Using catalyst ( Heterogeneity  reaction)

From glycerol using two catalysts, a 12- tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) catalyst and a catalyst in the form of Cs _2.5 H _0.5 PW ₁₂ O ₄₀ prepared by substituting cesium for some of its hydrogen atoms. Dichloropropanol was prepared. Reaction conditions and analysis conditions were the same as in Example 1. Conversion of glycerol and selectivity for dichloropropanol were calculated, respectively, and the results are shown in Table 5 below. Referring to Table 5, the selectivity of DCP by the catalyst in which some of the hydrogen atoms were substituted with cesium was lower than that of the mother catalyst unsubstituted with cesium.

catalyst % Conversion of glycerol % Selectivity of product MCPD by-product DCP _{Cs 2 .5 H 0 .5 PW 12} O 40 100 48.0 34.4 17.6 H ₃ PW ₁₂ O ₄₀ 100 59.2 7.9 32.9

Example  6: Keggin brother Heteropoly acid  12- Tungstoic acid  Change in the amount of catalyst used

Dichloropropanol was prepared from glycerol by varying the amount of Keggin type heteropolyacid 12-tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ). Reaction conditions and analysis conditions were the same as in Example 1. However, the reaction experiment was carried out while varying the amount of the catalyst to 15g, 30g, 40g, 47.96g, respectively. Conversion of glycerol and selectivity of dichloropropanol were respectively calculated and the results are shown in Table 6 below. Referring to Table 6, it was found that the selectivity of DCP increased as the amount of the catalyst used increased.

catalyst Usage of catalyst (g) % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₃ PW ₁₂ O ₄₀ 15 100 59.2 7.9 32.9 30 100 40.8 20.6 38.6 40 100 46.4 12.3 41.3 47.96 100 41.4 16.3 42.3

Example  7: Keggin brother Heteropoly acid  12- Tungstoic acid  Using a catalyst (change in reaction time)

Dichloropropanol was prepared from glycerol with varying reaction times using a ₁₂ -tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) catalyst, a Keggin type heteropolyacid. Reaction conditions and analysis conditions were the same as in Example 1. However, the reaction experiment was carried out while changing the reaction time to 5 hours, 10 hours, 20 hours, 30 hours. Conversion of glycerol and selectivity of dichloropropanol were respectively calculated, and the results are shown in Table 7 below. Referring to Table 7, the selectivity of DCP increased as the reaction time increased.

catalyst Reaction time (hr) % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₃ PW ₁₂ O ₄₀ 5 100 24.0 66.8 9.2 10 100 46.5 42.3 11.2 20 100 59.2 7.9 32.9 30 100 45.6 14.2 40.2

Example  8: Keggin brother Heteropoly acid  12- Tungstoic acid  Using catalyst (reaction pressure change)

Dichloropropanol was prepared from glycerol using a ₁₂ -tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) catalyst, a Keggin-type heteropolyacid, with varying reaction pressure. Reaction conditions and analysis conditions were the same as in Example 1. However, the reaction experiment was performed while changing the reaction pressure to 1bar, 5bar, 10bar, 15bar, 20bar, 25bar. Conversion of glycerol and selectivity for dichloropropanol were calculated, respectively, and the results are shown in Table 8 below. Referring to Table 8, as the reaction pressure increases, the DCP selectivity increases and shows the highest DCP selectivity at 10 bar, but there is no significant difference in DCP selectivity at pressures above 10 bar.

catalyst Reaction pressure (bar) % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₃ PW ₁₂ O ₄₀ One 100 33.1 59.2 7.7 5 100 37.0 48.8 14.2 10 100 59.2 7.9 32.9 15 100 20.5 47.8 31.7 20 100 24.4 45.7 29.9 25 100 23.2 46.2 30.6

Example  9: Keggin brother Heteropoly acid  12- Tungstoic acid  Using catalyst (reaction temperature change)

Dichloropropanol was prepared from glycerol using a ₁₂ -tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) catalyst, a Keggin type heteropolyacid, with varying reaction temperatures. Reaction conditions and analysis conditions were the same as in Example 1. However, the reaction experiment was performed while changing the reaction temperature to 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃. Conversion of glycerol and selectivity for dichloropropanol were calculated, respectively, and the results are shown in Table 9 below. Referring to Table 9, as the reaction temperature increases, the DCP selectivity increases and shows the highest DCP selectivity at 130 ° C, but no significant difference in DCP selectivity is shown at temperatures above 130 ° C.

catalyst Reaction temperature (℃) % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₃ PW ₁₂ O ₄₀ 100 100 50.4 46.5 3.1 110 100 59.2 7.9 32.9 120 100 31.3 28.6 40.1 130 100 6.4 15.6 78.0 140 100 5.8 18.2 76.0 150 100 1.1 22.1 76.8

Example  10: Keggin brother Heteropoly acid  12- Tungstoic acid  Use catalyst (with or without heat treatment)

Dichloropropanol was prepared from glycerol using ₁₂ -tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀ ) catalyst, a Keggin type heteropolyacid, which was heat treated or not. Reaction conditions and analysis conditions were the same as in Example 1. However, in the case of using the catalyst without heat treatment, the process of removing the crystal water by heating the solid heteropolyacid catalyst at 300 ° C. for 2 hours was omitted. In addition, in this embodiment, the reaction temperature was maintained at 130 ℃, the reaction pressure to 10bar, the reaction proceeded for 20 hours. Conversion of glycerol and selectivity of dichloropropanol were respectively calculated, and the results are shown in Table 10 below. Referring to Table 10, the heat treated catalyst showed slightly higher DCP selectivity than the unheated catalyst, but the difference was not large.

catalyst % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₃ PW ₁₂ O ₄₀ Heat treatment 100 1.9 25.4 72.7 Heat treatment oil 100 0 25.2 74.8

Example  11: The central element is phosphorus (P) and molybdenum ( Mo ) And vanadium (V) In place of  Combined Wells - Dawson brother Heteropolyacid  Use catalyst

Dichloropropanol was prepared from glycerol using a total of four catalysts in the form of H _{6 + X} P ₂ Mo _18-X V _X O ₆₂ (X = 0, 1, 2, 3) as a heteropolyacid catalyst. Reaction conditions and analysis conditions were the same as in Example 1. Conversion of glycerol and selectivity of dichloropropanol were calculated, respectively, and the results are shown in Table 11 below. Referring to Table 11, it was found that the selectivity of DCP generally decreased as the number of substitution of vanadium as an isotope increased.

catalyst % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₆ P ₂ Mo ₁₈ O ₆₂ 100 11.6 84.8 3.6 H ₇ P ₂ Mo ₁₇ VO ₆₂ 100 0 95.5 4.5 H ₈ P ₂ Mo ₁₆ V ₂ O ₆₂ 100 0 96.3 3.7 H ₉ P ₂ Mo ₁₅ V ₃ O ₆₂ 100 4.8 92.7 2.5

Example  12: The central element is phosphorus (P) and molybdenum ( Mo ) And tungsten (W) In place of  Combined Wells - Dawson brother Heteropolyacid  Use catalyst

Dichloropropanol was prepared from glycerol using a total of six catalysts in the form of H ₆ P ₂ Mo _18-X W _X O ₆₂ (X = 0, 3, 6, 9, 15, 18) as heteropolyacid catalysts. Reaction conditions and analysis conditions were the same as in Example 1. Conversion of glycerol and selectivity of dichloropropanol were calculated, respectively, and the results are shown in Table 12 below. Referring to Table 12, the selectivity of DCP increased as the number of substitutions of tungsten as an isotope increased.

catalyst % Conversion of glycerol % Selectivity of product MCPD by-product DCP H ₆ P ₂ Mo ₁₈ O ₆₂ 100 11.6 84.8 3.6 H ₆ P ₂ Mo ₁₅ W ₃ O ₆₂ 100 17.9 72.9 9.2 H ₆ P ₂ Mo ₉ W ₉ O ₆₂ 100 42.4 39.8 17.6 H ₆ P ₂ Mo ₃ W ₁₅ O ₆₂ 100 60.9 17.9 21.2 H ₆ P ₂ W ₁₈ O ₆₂ 100 17.0 52.8 30.2

Evaluation example

Evaluation Example 1: Change of DCP selectivity according to change of central atom (heteroatom) in Keggin type heteropolyacid catalyst coordinated with molybdenum (Mo) and / or tungsten (W) (Example 1 and Example 2)

In each case where dichloropropanol was prepared from glycerol using the heteropolyacid catalysts of Examples 1 and 2, the selectivity (%) of dichloropropanol was shown graphically in FIG. 1.

Referring to FIG. 1, it was confirmed that DCP selectivity is better when a heteropolyacid catalyst having a phosphorus (P) element is used than a heteropolyacid catalyst having a silicon element (Si). In addition, in this evaluation example, the most preferred catalyst in terms of DCP selectivity was found to be 12- tungstophosphoric acid.

Evaluation Example 2 In the two Keggin-type heteropolyacid catalysts in which the central element is phosphorus (P) and tungsten (W) or molybdenum (Mo) are basically coordinated, respectively, a part of the isotope is substituted with vanadium (V). Change in DCP Selectivity According to the Number of Substitutions (Examples 3 and 4)

In each case where dichloropropanol was prepared from glycerol using the heteropolyacid catalysts of Examples 3 and 4, the selectivity (%) of dichloropropanol is shown graphically in FIG. 2.

Referring to FIG. 2, when the same number of vanadium (V) is coordinated, the use of a catalyst coordinated with tungsten (W) has better DCP selectivity than the case of using a catalyst coordinated with molybdenum (Mo). Appeared. In addition, in this evaluation example, the most preferred catalyst in terms of DCP selectivity was found to be 12- tungstophosphoric acid.

Evaluation Example 3 Substituents of vanadium when a part of the isotope is substituted with vanadium (V) in the Keggin type heteropolyacid catalyst and the Wells-Dawson type heteropolyacid catalyst in which the central element is phosphorus (P) and molybdenum (Mo) are basically coordinated Of DCP selectivity according to (Example 4 and Example 11)

In each case where dichloropropanol was prepared from glycerol using the heteropolyacid catalysts of Examples 4 and 11, the selectivity (%) of dichloropropanol is shown graphically in FIG. 3.

Referring to FIG. 3, when the same number of vanadium (V) is coordinated, the use of the Keggin type heteropolyacid catalyst is superior to the case of using the Wells-Dawson type heteropolyacid catalyst. In addition, in this evaluation example, the most preferred catalyst in terms of DCP selectivity was found to be 12- tungstophosphoric acid.

Evaluation Example 4 When a part or all of the isotopes are replaced by tungsten (W) in the Keggin type heteropolyacid catalyst and the Wells-Dawson type heteropolyacid catalyst in which the central element is phosphorus (P) and molybdenum (Mo) is basically coordinated Changes in DCP Selectivity According to the Number of Substitutions (Examples 1 and 12)

In each case where dichloropropanol was prepared from glycerol using the heteropolyacid catalysts of Examples 1 and 12, the selectivity (%) of dichloropropanol is shown graphically in FIG. 4.

Referring to FIG. 4, the case where the Wells-Dawson type heteropolyacid catalyst is used in the catalyst in which molybdenum (Mo) is basically coordinated and part or all of it is substituted with tungsten (W) is compared with the case of using the Keggin type heteropolyacid catalyst. DCP selectivity was found to be good. As a result, however, the most preferred catalyst in terms of DCP selectivity was 12-tungstoic acid, a Keggin type heteropolyacid catalyst.

The method for preparing dichloropropanol according to the present invention having the above structure can directly prepare dichloropropanol from glycerol by using a heteropolyacid catalyst, and solves the existing problems such as catalyst recovery and separation of the catalyst and the reaction product azeotrope. It can be overcome. In addition, it is easy to recover and regenerate the catalyst, which not only simplifies the process, but also can produce expensive dichloropropanol from low-cost glycerol in high yield.

Although preferred embodiments of the present invention have been described above with reference to the drawings and embodiments, these are merely exemplary, and various modifications and equivalent other embodiments are possible to those skilled in the art. You will understand. Therefore, the protection scope of the present invention should be defined by the appended claims.

1 is a graph showing the change of DCP selectivity according to the change of central atom (heteroatom) in a Keggin type heteropolyacid catalyst coordinated with molybdenum (Mo) and / or tungsten (W) (execution) Example 1 and Example 2).

FIG. 2 shows the substitution of vanadium when a part of the isotope is substituted with vanadium (V) in two Keggin-type heteropolyacid catalysts in which the central element is phosphorus (P) and the tungsten (W) or molybdenum (Mo) is basically coordinated respectively. It is a graph which shows the change of DCP selectivity with a number (Example 3 and Example 4).

FIG. 3 shows the substitution number of vanadium when a part of the isotope is substituted with vanadium (V) in the Keggin type heteropolyacid catalyst and the Wells-Dawson type heteropolyacid catalyst in which the central element is phosphorus (P) and molybdenum (Mo) is basically coordinated. It is a graph which shows the change of DCP selectivity according to (Example 4 and Example 11).

4 shows the substitution of tungsten when a part or all of the isotopes are substituted with tungsten (W) in the Keggin type heteropolyacid catalyst and the Wells-Dawson type heteropolyacid catalyst in which the central element is phosphorus (P) and molybdenum (Mo) is basically coordinated It is a graph which shows the change of DCP selectivity with a number (Example 1 and Example 12).

Claims (12)

A method for producing dichloropropanol by reacting glycerol with a chlorinating agent, wherein a heteropolyacid catalyst is used. The method of claim 1, The heteropolyacid catalyst is a method for producing dichloropropanol, characterized in that it is selected from Keggin-type heteropolyacid having an atomic ratio of central element: isotope of 1:12 and Wells-Dawson type heteropolyacid having an atomic ratio of central element: isotope of 2:18. The method of claim 2, The Keggin-type heteropolyacid catalyst, _12- molybdo tungstophosphoric acid (H ₃ PMo _12-X W _X O ₄₀ ), 12- molybdo tungstosilonic acid (H ₄ SiMo _12-X W _X O ₄₀ ), 12-Tungsutobanadophosphate (H _{3 + X} PW _12-X V _X O ₄₀ ), _12- molybdobanadophosphoric acid (H _{3 + X} PMo _12-X V _X O ₄₀ ), _12- tungstonio Empty phosphoric acid (H _{3 + X} PW _12-X Nb _X O ₄₀ ), And among these, all or part of the hydrogen atom is selected from the group consisting of a heteropoly acid substituted with a metal, Method of producing dichloropropanol, characterized in that the number of X = 0 ~ 12 in the formula. The method of claim 2, The Wells-Dawson type heteropolyacid catalyst is, 18-molybdobanadophosphoric acid (H _{6 + X} P ₂ Mo _18-X V _X O ₆₂ ), 18- tungstobanadophosphoric acid (H _{6 + X} P ₂ W _{18 - X V X O 62),} 18- molybdate FIG tungstophosphoric acid _{(H 6 P 2 Mo 18-} X W X O 62), 18- O tongue Stony emptying acid (H ₆ P ₂ W _{18 + X - X} Nb _X O ₆₂ ), _18- molybdo tungstosilonic acid (H ₇ Si ₂ Mo _18-X W _X O ₆₂ ), and a heteropoly acid in which all or part of hydrogen atoms are substituted with metals , Method of producing dichloropropanol, characterized in that the number of X = 0 ~ 18 in the formula. The method of claim 1, The reaction is a method for producing dichloropropanol, characterized in that the homogeneous or heterogeneous catalysis. The method of claim 5, Process for producing dichloropropanol, characterized in that water is used as the reaction medium. The method of claim 5, The heteropolyacid catalyst is a method for producing dichloropropanol, characterized in that recovered after the reaction is reused. The method of claim 1, The chlorinating agent is a method for producing dichloropropanol, characterized in that the aqueous hydrogen chloride or hydrogen chloride gas. The method of claim 1, Method for producing a dichloropropanol, characterized in that the chlorination reaction proceeds at a temperature of 50 ~ 200 ℃. The method of claim 1, Method for producing dichloropropanol, characterized in that the chlorination reaction proceeds at a pressure of 1 ~ 50bar. The method of claim 1, Method for producing dichloropropanol, characterized in that the chlorination reaction proceeds for 10 minutes to 50 hours. In the method for producing epichlorohydrin (ECH) by reacting glycerol with a chlorinating agent to produce dichloropropanol, A method for producing epichlorohydrin, comprising the process for producing dichloropropanol according to any one of claims 1 to 11.

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