JP2010047492A - Method for producing dichloropropanol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing dichloropropanol by which water-containing glycerol can efficiently be chlorinated by the reaction with hydrogen chloride gas in the presence of a chlorination catalyst having high activity without using a special reaction apparatus in the production of the dichloropropanol. <P>SOLUTION: The method for producing dichloropropanol includes chlorinating the hydroxy groups of the glycerol and/or a glycerol derivative in the presence of the hydrogen chloride gas by using a metal chloride and/or a mixed catalyst of a metal oxide and a ≥9C aliphatic carboxylic acid and/or a derivative of the aliphatic carboxylic acid. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing dichloropropanol by chlorinating glycerin.

  Dichloropropanol is used as a raw material such as epichlorohydrin and epoxy resin or as an intermediate for organic synthesis.

  Generally, as a method for producing dichloropropanol from glycerin, a chlorination method using hydrogen chloride gas or a hydrogen chloride aqueous solution is known. For example, a method of performing chlorination while blowing hydrogen chloride gas with various carboxylic acids as catalysts (see, for example, Patent Document 1) is known. Is obtained at a rate. It is also known that the reaction proceeds efficiently when by-product water is continuously removed from the reaction system in the same reaction system in the presence of various carboxylic acids (for example, Patent Document 2 and Patent Document 3). reference). The reaction proceeds sequentially, and when hydrogen chloride gas is passed, monochloropropanol is first produced, and then dichloropropanol is obtained in a high yield when hydrogen chloride gas is continuously supplied up to 2 mol (see, for example, Patent Document 2). ). In that case, the produced | generated dichloropropanol is shown to be a mixture of 1, 3- dichloro- 2-propanol and 2, 3- dichloro- 1-propanol (for example, refer patent document 3). In addition, acidic water and dichloropropanol are distilled off in an azeotropic form while continuously supplying an aqueous hydrogen chloride solution in the presence of various carboxylic acids including dicarboxylic acids such as adipic acid and / or derivatives thereof. In addition, a method for stably isolating and producing the dichloropropanol is disclosed. However, when the water content of the raw material glycerin is high, these methods generally tend to increase the reaction time. In order to promote chlorination, it is necessary to increase the concentration of hydrogen chloride in the reaction system, and as a stepwise dehydration method therefor, a reaction using a plurality of reactors has been proposed (for example, see Patent Document 4). ).

  On the other hand, as a one-step efficient chlorination method, a pressure reaction with hydrogen chloride gas in the presence of various carboxylic acids and / or derivatives thereof has been proposed (see, for example, Patent Document 5). However, the pressure reactor at that time requires a corrosion-resistant material.

  In the chlorination reaction of glycerin, the process in which the alcohol moiety forms an ester by dehydration reaction with carboxylic acid is important for promoting the reaction, and it is estimated that the dichloronation reaction is slower than the monochlorination reaction from glycerin. Have been reported (for example, see Non-Patent Document 1). Accordingly, there is a need for a catalyst that promotes the reaction from monochloropropanediol to dichloropropanol.

  However, as disclosed in the above prior literatures, the reaction catalysts for producing dichloropropanol by chlorination of glycerin so far are mainly carboxylic acids and / or derivatives thereof, such as zinc chloride There have been few reports on reactions using metal chlorides or metal oxides as catalysts.

  On the other hand, examples of synthesizing various alkyl chlorides using zinc chloride as a catalyst in a general alcohol chlorination reaction are known (see, for example, Non-Patent Document 2). In addition, a method of chlorinating a compound having oxymethyl with hydrogen chloride gas in the presence of a metal chloride and a carboxylic acid has been reported. As the carboxylic acid, a lower aliphatic carboxylic acid having 2 to 8 carbon atoms is reported. It has been shown that acids are effective (see, for example, Patent Document 6).

German Patent No. 197308 US Patent No. 2,198,600 Special table 2007-504101 Special table 2007-515183 gazette WO2006 / 20234 pamphlet JP 2002-20333 A Industrial & Engineering Chemistry Research 46 (20), 6456 (2007) Organic Synthesis Coll. Vol. I 142 (1941)

  At present, it is required to use a dedicated device for the production of dichloropropanol.

  The present invention has been made in view of the above-described background art, and its object is to use hydrogen chloride gas in the presence of a chlorination catalyst having high activity in the production of dichloropropanol without using a special reaction apparatus. It is an object of the present invention to provide a process for producing dichloropropanol capable of efficiently chlorinating hydrous glycerin.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a metal chloride and / or a metal oxide and an aliphatic carboxylic acid having 9 or more carbon atoms and / or the aliphatic carboxylic acid derivative. It has been found that when a mixed catalyst is used, the hydroxyl group of glycerin and / or a glycerin derivative can be efficiently chlorinated in high yield in the presence of hydrogen chloride gas, and the present invention has been completed.

  That is, the present invention uses a mixed catalyst of a metal chloride and / or metal oxide and an aliphatic carboxylic acid having 9 or more carbon atoms and / or the aliphatic carboxylic acid derivative in the presence of hydrogen chloride gas. The present invention relates to a process for producing dichloropropanol characterized by chlorinating hydroxyl groups of glycerin and / or glycerin derivatives.

  Hereinafter, the present invention will be described in detail.

  Examples of the aliphatic carboxylic acid having 9 or more carbon atoms and / or the aliphatic carboxylic acid derivative as the catalyst component used in the present invention include azelaic acid, decanoic acid, sebacic acid, undecanedioic acid, lauric acid, and dodecanedioic acid. , Tridecanedioic acid, tetradecanoic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, azelaic anhydride, decanoic anhydride, sebacic anhydride, undecanedioic anhydride, lauric anhydride, dodecanedioic anhydride , Tridecanedioic anhydride, tetradecanoic anhydride, tetradecanedioic anhydride, pentadecanedioic anhydride, hexadecanedioic anhydride, azelaic acid chlorinated product, decanoic acid chlorinated product, sebacic acid chlorinated product, undecanedioic acid chlorine , Chlorinated lauric acid, Chlorinated dodecanedioic acid, Chlorinated tridecanedioic acid, Tetradecanoic acid Chloride, tetradecanedioic acid chloride, pentadecanedioic acid chloride, hexadecanedioic acid chloride, azelate, decanoate, sebacate, undecanoate, laurate, dodecanedioate, tridecanedioic acid Salt, tetradecanoate, tetradecanedioate, pentadecanedioate, hexadecanedioate, azelaic acid ester, decanoic acid ester, sebacic acid ester, undecanedioic acid ester, lauric acid ester, dodecanedioic acid ester, tridecanedioic acid Examples include esters, tetradecanoic acid esters, tetradecanedioic acid esters, pentadecanedioic acid esters, and hexadecanedioic acid esters. Among these, diacids or diacid derivatives of each acid are preferable, and are easily available and industrial. Sebacic acid is particularly preferred from the viewpoint of ease of handling. The amount of the aliphatic carboxylic acid having 9 or more carbon atoms and / or the aliphatic carboxylic acid derivative is preferably 0.01 to 0.5 mol per 1.0 mol of glycerin and / or glycerin derivative. If the amount is less than 0.01 mol, a sufficient reaction rate cannot be obtained. If the amount exceeds 0.5 mol, no improvement in the reaction rate is observed, and conversely, the product of chlorinated ester increases.

  Examples of the metal chloride and / or metal oxide that are catalyst components used in the present invention include zinc chloride, ferrous chloride, ferric chloride, copper chloride, magnesium chloride, calcium chloride, zinc oxide, ferrous oxide, Ferric oxide, copper oxide, magnesium oxide, and calcium oxide are preferred. The amount of the metal chloride and / or metal oxide used is preferably 0.01 to 0.5 mol per 1.0 mol of glycerin and / or glycerin derivative, and is sufficient to be less than 0.01 mol. The reaction rate cannot be obtained, and if it exceeds 0.5 mol, the reaction rate is not improved and the by-products are increased. In the present invention, the metal chloride may be supplied in the form of a metal hydroxide or the like, and it is considered that the metal hydroxide becomes a metal chloride and reacts with the supplied hydrogen chloride gas.

  Examples of glycerol and / or glycerol derivatives used in the present invention include synthetic glycerol, crude glycerol from biodiesel, purified glycerol, 3-chloro-1,2-propanediol, diglycerol, diglycerol monochlorohydrin, and diglycerol. Dichlorohydrin, glycerol carboxylic acid ester, glycerol monochlorohydrin carboxylic acid ester, diglycerol monochlorohydrin carboxylic acid ester, glycerol dicarboxylic acid diester, glycerol monochlorohydrin dicarboxylic acid diester, diglycerol monochlorohydrin dicarboxylic acid diester, glycerol dicarboxylic acid Acid monoester, glycerol monochlorohydrin dicarboxylic acid monoester, and diglycerol monochlorohydrin dica Such Bonsan monoester and the like, may be used in combination singly or with any solvent.

  There is no problem if the water content of the glycerin and / or glycerin derivative as a raw material is 50% or less by weight with respect to the weight of the glycerin and / or glycerin derivative. In consideration of water removal, it is preferably 30% or less, which is a range in which azeotropic dehydration is possible during the reaction.

  The amount of hydrogen chloride (gas) used in the present invention is not limited at all in terms of supply rate and supply amount because unreacted hydrochloric acid can be reused, but per 1.0 mol of glycerol and / or glycerol derivative. The amount is preferably 2.0 to 10.0 mol, and if it is less than 2.0 mol, the reaction is not completed, and if it exceeds 10.0 mol, it is necessary to increase the by-products and recover excess hydrogen chloride. Occurs.

  The temperature range suitable as the reaction temperature is 50 to 250 ° C., but it is particularly desirable that the water used for the reaction and the reaction product water can be distilled off, preferably 100 to 200 ° C. When the temperature is lower than 50 ° C., a sufficient reaction rate cannot be obtained, and when the temperature exceeds 250 ° C., polymer by-products increase and the target product is likely to be decomposed.

  Examples of the purification method include a method in which a dichloropropanol solution obtained after chlorination is distilled together with acidic water under reduced pressure or atmospheric pressure, and after neutralization, dichloropropanol is isolated and purified by distillation.

  According to the method for producing dichloropropanol of the present invention, hydrous glycerin and / or glycerin derivatives can be efficiently chlorinated in high yield.

  Hereinafter, the details of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The yield of the product in this example was confirmed by gas chromatography.

  Gas chromatography: (GC-17A manufactured by Shimadzu Corporation, measurement condition capillary column (DB-5 manufactured by J & WS Science), temperature rise, detector FID).

  First, the chlorination reaction of 3-chloro-1,2-propanediol, which is presumed to be the rate-limiting reaction, will be described.

Example 1
A 200 ml round bottom four-necked flask equipped with a stirrer and a blowing tube, and further equipped with a distillation column and a distillation distiller, 36.8 g of 3-chloro-1,2-propanediol containing 17% by weight of water (0.33 mol), 1.35 g (6.7 mmol) of sebacic acid and 3.86 g (28.3 mmol) of zinc chloride were added and stirred while supplying hydrogen chloride gas into the reactor at 0.06 mol / hour. The temperature was raised to 120 ° C., and the reaction was continued under the same conditions for 25 hours. As a result of conducting gas chromatographic analysis (internal standard method) on the distillate and reaction liquid obtained after completion of the reaction, the peak of 3-chloro-1,2-propanediol disappeared and 1,3-dichloro-2 It was confirmed that 87.2% of propanol and 7.6% of 2,3-dichloro-1-propanol were obtained.

  At that time, as a result of performing gas chromatography analysis (area% method) equipped with a capillary column on the reaction solution after 12 hours in the middle, the conversion of 3-chloro-1,2-propanediol was 95.4%. It was. The conversion results are shown in Table 1.

  Next, in order to compare the effect of the reaction catalyst, the conversion rate after 12 hours was measured for the chlorination reaction with other catalysts including various carboxylic acids.

Example 2
The reaction was conducted in the same manner as in Example 1 except that instead of using 3.86 g (28.3 mmol) of zinc chloride in Example 1, 7.72 g (56.7 mmol) of zinc chloride was used.
Table 1 shows the conversion rate after 12 hours of Example 2 together with other examples.

Example 3
The reaction was carried out in the same manner as in Example 1 except that 2.30 g (28.3 mmol) of zinc oxide was used instead of 3.86 g (28.3 mmol) of zinc chloride.
Table 1 shows the conversion rate of Example 3 after 12 hours together with other examples.

Example 4
The reaction was conducted in the same manner as in Example 1 except that 1.35 g (6.7 mmol) of sebacic acid was used in Example 1, and 1.34 g (6.7 mmol) of lauric acid was used. Table 1 shows the conversion rate of Example 4 after 12 hours together with other examples.

Example 5
The reaction was conducted in the same manner as in Example 1 except that 1.54 g (6.7 mmol) of dodecanedioic acid was used instead of 1.35 g (6.7 mmol) of sebacic acid in Example 1. Table 1 shows the conversion rate of Example 5 after 12 hours together with other examples.

Example 6
The reaction was conducted in the same manner as in Example 1 except that 1.91 g (6.7 mmol) of hexadecanedioic acid was used instead of 1.35 g (6.7 mmol) of sebacic acid in Example 1. Table 1 shows the conversion rate of Example 6 after 12 hours together with other examples.

Comparative Example 1
The reaction was conducted in the same manner as in Example 1 except that 3.86 g (28.3 mmol) of zinc chloride used in Example 1 was not used. Table 1 shows the conversion rate of Comparative Example 1 after 12 hours together with other examples.

Comparative Example 2
The reaction was conducted in the same manner as in Example 1 except that 0.40 g (6.7 mmol) of acetic acid was used instead of 1.35 g (6.7 mmol) of sebacic acid in Example 1. Table 1 shows the conversion rate of Comparative Example 2 after 12 hours together with other examples.

Comparative Example 3
The reaction was performed in the same manner as in Example 1 except that 0.79 g (6.7 mmol) of succinic acid was used instead of 1.35 g (6.7 mmol) of sebacic acid in Example 1. Table 1 shows the conversion rate of Comparative Example 3 after 12 hours together with other examples.

Comparative Example 4
The reaction was carried out in the same manner as in Example 1 except that 0.88 g (6.7 mmol) of glutaric acid was used instead of 1.35 g (6.7 mmol) of sebacic acid in Example 1. Table 1 shows the conversion rate of Comparative Example 4 after 12 hours together with other examples.

以上の検討結果から、表１に示されるように、３−クロロ−１，２−プロパンジオールの塩素化反応において、本発明による混合触媒を用いた場合には、１２時間後の転化率が高いことが分かった。従って、金属塩化物及び／又は金属酸化物と炭素数が９個以上の脂肪族カルボン酸及び／又は当該脂肪族カルボン酸誘導体との混合触媒は、明らかに有効であることが判明した。

From the above examination results, as shown in Table 1, in the chlorination reaction of 3-chloro-1,2-propanediol, when the mixed catalyst according to the present invention is used, the conversion rate after 12 hours is high. I understood that. Accordingly, it has been found that a mixed catalyst of a metal chloride and / or metal oxide and an aliphatic carboxylic acid having 9 or more carbon atoms and / or the aliphatic carboxylic acid derivative is clearly effective.

  Subsequently, it shows below about the chlorination reaction of glycerol.

Example 7
In the same manner as in Example 1, a 200 ml round bottom four-necked flask equipped with a stirrer and a blowing tube, and further equipped with a distillation column and a distillation distiller, was charged with 42.8 g (0 .33 mol), 1.35 g (6.7 mmol) of sebacic acid and 3.86 g (28.3 mmol) of zinc chloride, and while stirring, while supplying hydrogen chloride gas into the reactor at 0.06 mol / hour, The temperature was raised to 120 ° C. The reaction was continued for 15 hours under the same conditions. As a result of performing gas chromatography analysis (area% method) equipped with a capillary column on the reaction solution after 15 hours, the residual ratio of 3-chloro-1,2-propanediol was 10.7%. Further, the reaction was continued for 25 hours, and as a result of conducting gas chromatography analysis (internal standard method) on the distillate and the reaction solution obtained after the completion of the reaction, 17.6% of 1,3-dichloro-2-propanol was obtained. It was confirmed that 3.7% of 2,3-dichloro-1-propanol was obtained. The results of Example 7 are shown in Table 2.

Comparative Example 5
The reaction was conducted in the same manner as in Example 7 except that 3.86 g (28.3 mmol) of zinc chloride used in Example 7 was not used. As a result of performing gas chromatography analysis (area% method) equipped with a capillary column on the reaction solution after 15 hours, the residual ratio of 3-chloro-1,2-propanediol was 20.7%, and the reaction was slow. . Therefore, the temperature was further raised to 150 ° C., and the reaction was carried out for 10 hours under the same conditions. As a result of conducting gas chromatography analysis (internal standard method) on the distillate and the reaction solution obtained after completion of the reaction, 72.7% of 1,3-dichloro-2-propanol and 2,3-dichloro-1- It was confirmed that 11.5% of propanol was obtained. The results of Comparative Example 5 are shown in Table 2.

Comparative Example 6
In Comparative Example 5, the reaction was carried out in the same manner as Comparative Example 5 except that 4.04 g (20.0 mmol) of sebacic acid was used instead of 1.35 g (6.7 mmol) of sebacic acid. The results of Comparative Example 6 are shown in Table 2.

Comparative Example 7
In Comparative Example 5, the reaction was performed in the same manner as Comparative Example 5 except that 5.72 g (28.3 mmol) of sebacic acid was used instead of 1.35 g (6.7 mmol) of sebacic acid. The results of Comparative Example 7 are shown in Table 2.

以上の検討結果から、表２に示されるように、グリセリンの塩素化反応において、本発明による混合触媒を用いた場合には、１５時間後の３−クロロ−１，２−プロパンジオールの残存率は低く、また、反応終了後のジクロロプロパノールの収率も高いため、金属塩化物及び／又は金属酸化物と炭素数が９個以上の脂肪族カルボン酸及び／又は当該脂肪族カルボン酸誘導体との混合触媒は、明らかに有効であることが判明した。

From the above examination results, as shown in Table 2, when the mixed catalyst according to the present invention was used in the glycerol chlorination reaction, the residual rate of 3-chloro-1,2-propanediol after 15 hours. And the yield of dichloropropanol after completion of the reaction is high, so that the metal chloride and / or metal oxide and the aliphatic carboxylic acid having 9 or more carbon atoms and / or the aliphatic carboxylic acid derivative Mixed catalysts have been found to be clearly effective.

Claims (12)

Glycerin and / or glycerin derivatives in the presence of hydrogen chloride gas using a mixed catalyst of a metal chloride and / or metal oxide and an aliphatic carboxylic acid having 9 or more carbon atoms and / or the aliphatic carboxylic acid derivative A process for producing dichloropropanol, characterized by chlorinating the hydroxyl group. Glycerin derivatives are 3-chloro-1,2-propanediol, diglycerol, diglycerol monochlorohydrin, diglycerol dichlorohydrin, glycerol carboxylate, glycerol monochlorohydrin carboxylate, diglycerol monochlorohydrin carboxylic acid Ester, glycerol dicarboxylic acid diester, glycerol monochlorohydrin dicarboxylic acid diester, diglycerol monochlorohydrin dicarboxylic acid diester, glycerol dicarboxylic acid monoester, glycerol monochlorohydrin dicarboxylic acid monoester, and diglycerol monochlorohydrin dicarboxylic acid monoester The dichloropropano according to claim 1, which is at least one selected from the group consisting of The method of production. The metal chloride is at least one selected from the group consisting of zinc chloride, ferrous chloride, ferric chloride, copper chloride, magnesium chloride, and calcium chloride. A method for producing dichloropropanol. The metal oxide is at least one selected from the group consisting of zinc oxide, ferrous oxide, ferric oxide, copper oxide, magnesium oxide, and calcium oxide. A method for producing dichloropropanol. The aliphatic carboxylic acid is selected from the group consisting of azelaic acid, decanoic acid, sebacic acid, undecanedioic acid, lauric acid, dodecanedioic acid, tridecanedioic acid, tetradecanoic acid, tetradecanedioic acid, pentadecanedioic acid, and hexadecanedioic acid. The method for producing dichloropropanol according to claim 1, wherein the method is at least one kind. The aliphatic carboxylic acid derivative is azelaic anhydride, decanoic anhydride, sebacic anhydride, undecanedioic anhydride, lauric anhydride, dodecanedioic anhydride, tridecanedioic anhydride, tetradecanoic anhydride, Tetradecanedioic anhydride, pentadecanedioic anhydride, hexadecanedioic anhydride, azelaic acid chlorinated product, decanoic acid chlorinated product, sebacic acid chlorinated product, undecanedioic acid chlorinated product, lauric acid chlorinated product, dodecanedioic acid chlorinated product, Tridecanedioic acid chloride, tetradecanoic acid chloride, tetradecanedioic acid chloride, pentadecanedioic acid chloride, hexadecanedioic acid chloride, azelate, decanoate, sebacate, undecanoate, laurate, Dodecanedioate, tridecanedioate, tetradecanoate, tetradecanedioate, pentadecane Acid salt, hexadecanedioic acid salt, azelaic acid ester, decanoic acid ester, sebacic acid ester, undecanoic acid ester, lauric acid ester, dodecanedioic acid ester, tridecanedioic acid ester, tetradecanoic acid ester, tetradecanedioic acid ester, pentadecane diacid It is at least 1 type chosen from the group which consists of an acid ester and hexadecanedioic acid ester, The manufacturing method of the dichloropropanol of Claims 1-4 characterized by the above-mentioned. The amount of the aliphatic carboxylic acid and / or the aliphatic carboxylic acid derivative used is 0.01 to 0.5 mol per 1.0 mol of glycerin and / or glycerin derivative. The manufacturing method of the dichloropropanol of description. The dichloropropanol according to claim 1, wherein the metal chloride and / or metal oxide is used in an amount of 0.01 to 0.5 mol per 1.0 mol of glycerin and / or glycerin derivative. Manufacturing method. The method for producing dichloropropanol according to claim 1, wherein the glycerin and / or the glycerin derivative contains 50% or less of water by weight. The method for producing dichloropropanol according to claim 1, wherein the amount of hydrogen chloride gas used is 2.0 to 10.0 mol per 1.0 mol of glycerin and / or glycerin derivative. The method for producing dichloropropanol according to claim 1, wherein chlorination is carried out in a temperature range of 50 to 250 ° C. The method for producing dichloropropanol according to any one of claims 1 to 11, wherein the dichloropropanol solution obtained after chlorination is distilled together with acidic water, and after neutralization, the dichloropropanol is isolated and purified by distillation.