KR101128861B1 - Method of preparing chlorohydrins by reaction of polyhydroxy aliphatic hydrocarbon with chlorination agent - Google Patents

Abstract

A method for producing chlorohydrins from polycarboxylic acid aliphatic hydrocarbons, including glycerol, is disclosed. The method for producing the disclosed chlorohydrins includes irradiating ultrasonic waves to the reaction mixture during the reaction.

Description

Method of preparing chlorohydrins by reaction of polyhydroxy aliphatic hydrocarbon with chlorination agent

Disclosed is a method for producing chlorohydrins by reaction of a polyacid aliphatic hydrocarbon with a chlorinating agent. More specifically, a method for producing chlorohydrin by reacting a multi-acid aliphatic hydrocarbon with a chlorinating agent, comprising irradiating ultrasonic waves to a reaction mixture during the reaction is disclosed.

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 glycerol has an excessive supply compared to demand and its value is continuously decreasing, it is desirable to achieve high value of glycerol by converting it into chlorohydrins such as high value-added dichloropropanol.

Meanwhile, chlorohydrins are raw materials for producing epichlorohydrin, and most of the chlorohydrins currently supplied to the market are made from propylene. Specifically, the method for producing chlorohydrins is a step of preparing allyl chloride by high temperature chlorination of propylene and using the excess industrial water to react the allyl chloride again with a chlorinating agent to give chlorohydrins. It consists of two steps of preparing a step. However, the production method of chlorohydrin using propylene is unstable due to rising price of propylene, generation of a large amount of wastewater and waste, excessive initial investment by the two-step manufacturing method, and difficulty in new expansion of the manufacturing method. Has the problem.

Accordingly, the process of directly producing chlorohydrins by the one-step preparation method of reacting a multi-acid aliphatic hydrocarbon including glycerol with a chlorinating agent in the presence of a catalyst has secured economic feasibility. The production method of this one-stage chlorohydrin using polycarboxylic acid aliphatic hydrocarbons, including glycerol, as a raw material can not only reduce raw material costs by using inexpensive polyhydric aliphatic hydrocarbons, but also does not use industrial water during the process. And it is possible to drastically reduce the amount of waste generated is environmentally advantageous, the process and environmental investment costs are reduced, the initial investment costs are low. In addition, unlike the conventional method for preparing chlorohydrin through a two-step process from propylene, the chlorohydrin is prepared by directly chlorohydrin from a polycarboxylic acid aliphatic hydrocarbon including glycerol, which is a by-product of biodiesel. There is an environmentally friendly advantage to manufacturing.

However, the production method of the chlorohydrin using a polycarboxylic acid aliphatic hydrocarbon, including glycerol as a reaction raw material produces water as a by-product, the reaction proceeds by inhibiting the chlorination reaction of the polycarboxylic acid aliphatic hydrocarbon There is a problem that the reaction time is gradually slowed as the reaction time is longer.

One embodiment of the present invention provides a method for producing chlorohydrin by the reaction of a multi-acid aliphatic hydrocarbon and a chlorinating agent comprising the step of irradiating the reaction mixture with ultrasonic waves during the reaction.

One aspect of the invention,

A method for producing chlorohydrins by reaction of a multi-acid aliphatic hydrocarbon and a chlorinating agent, the method of producing chlorohydrins comprising the step of irradiating the reaction mixture in the ultrasonic wave during the reaction.

The polycarboxylic acid aliphatic hydrocarbon may be a compound having 2 to 20 carbon atoms, in which two or more hydroxyl groups are bonded to different carbon atoms.

The polycarboxylic acid aliphatic hydrocarbon is 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, glycerol At least one compound selected from the group consisting of 1,2,4-butanetriol, 1,4-butanediol and esters of the above compounds.

The chlorinating agent may comprise hydrogen chloride gas or hydrochloric acid.

The chlorohydrin may be a compound in which at least one hydroxyl group and at least one chlorine atom are bonded to different carbon atoms.

The chlorohydrins are composed of 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, 1,3-dichloropropane-2-ol and 2,3-dichloro propane-1-ol. At least one compound selected from the group.

The frequency band of the ultrasonic wave may be 20 kHz to 100 kHz.

The reaction can proceed without catalyst or in the presence of a catalyst.

The catalyst may include at least one selected from the group consisting of an organic acid catalyst, a carboxylic acid catalyst, a nitrile catalyst and a solid catalyst.

The reaction proceeds in at least one of a batch reactor, a semi-batch reactor, a continuous stir tank reactor (CSTR) and a plug flow reactor, and at least one of the reactors. The reactor may be equipped with an ultrasonic generator.

The reaction may be carried out at a temperature of 50 ~ 300 ℃.

The reaction can be carried out at a pressure of 0.1 ~ 30bar.

The reaction may proceed for 10 minutes to 50 hours.

Another aspect of the invention,

As a method of producing epichlorohydrin (ECH) from chlorohydrins produced by the reaction of a polyacid aliphatic hydrocarbon and a chlorinating agent,

It provides a method for producing epichlorohydrin including the method for producing the chlorohydrins.

According to one embodiment of the present invention, by providing an ultrasonic wave to the reaction mixture during the reaction, there is provided a method for producing chlorohydrin by the reaction of a polycarboxylic acid aliphatic hydrocarbon and chlorinating agent, the reaction time is shortened Can be.

Next, the method for producing chlorohydrins according to one embodiment of the present invention will be described in detail.

Method for producing chlorohydrin according to an embodiment of the present invention is a method for producing chlorohydrin by the reaction of a polycarboxylic acid aliphatic hydrocarbon and a chlorinating agent, comprising the step of irradiating ultrasonic waves to the reaction mixture during the reaction. . In this way, the ultrasonic wave is irradiated to generate a shock wave by cavitation in the reaction mixture to maximize the mixing effect, thereby increasing the reaction frequency and increasing the reaction time by increasing the collision frequency of the polycarboxylic acid aliphatic hydrocarbon and the chlorinating agent as a reaction material. It can be shortened. In the present specification, 'cavitation' means that when a low pressure occurs in the liquid, the gas contained in the liquid escapes and collects at a low pressure, thereby creating a void space without liquid.

The polycarboxylic acid aliphatic hydrocarbon may be a compound having 2 to 20 carbon atoms, in which two or more hydroxyl groups are bonded to different carbon atoms. Specifically, the polycarboxylic acid aliphatic hydrocarbon is 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propane Diol, glycerol, 1,2,4-butanetriol, 1,4-butanediol and at least one compound selected from the group consisting of esters of the above compounds.

The chlorinating agent may be hydrogen chloride gas or hydrochloric acid. Specifically, the chlorinating agent may be a hydrochloric acid or hydrogen chloride solution dissolved in a solvent such as hydrogen chloride gas or water diluted by mixing with an inert gas. In addition, hydrogen chloride gas may be directly dissolved in a multi-acid aliphatic hydrocarbon at normal pressure or under pressure.

The chlorohydrin may be a compound in which at least one hydroxyl group and at least one chlorine atom are bonded to different carbon atoms. Specifically, the chlorohydrins are 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, 1,3-dichloropropane-2-ol and 2,3-dichloropropane-1 And at least one compound selected from the group consisting of -ols.

As used herein, the term "reaction mixture" refers to a mixture comprising at least one compound of glycerol and a chlorinating agent as a reaction material, and dichloropropanol as a reaction product.

Irradiation of the ultrasonic wave may be performed while the reaction mixture is stirred, or may be performed in an unstirred state.

The frequency band of the ultrasonic wave irradiated to the reaction mixture may be 20kHz to 100kHz. If the frequency band of the ultrasonic wave is less than 20 kHz, the mixing effect of the reaction mixture is not sufficient, and if it exceeds 100 kHz, the shock wave due to cavitation does not occur and the mixing effect is not preferable.

The reaction may proceed in the absence of a catalyst or in the presence of a catalyst. The catalyst may be an organic acid catalyst, a carboxylic acid catalyst, a nitrile catalyst, a solid catalyst and a mixture of two or more thereof.

The organic acid catalyst is, for example, at least one member selected from the group consisting of monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, malonic acid, levulinic acid, citric acid, succinic acid, propionic acid and derivatives of the organic acids described above. It may be a compound of.

The carboxylic acid catalyst is, for example, monocarboxylic acid ester, polycarboxylic acid ester, monocarboxylic acid anhydride, polycarboxylic acid anhydride, monocarboxylic acid chloride, polycarboxylic acid chloride, monocarboxylic It may be at least one compound selected from the group consisting of acid salts, polycarboxylic acid salts and derivatives of the respective carboxylic acid compounds.

The nitrile-based catalysts are acetonitrile, propionitrile, acrylonitrile, valeronitrile, isobutyronitrile, hydroxyacetonitrile, chloroacetonitrile, succinonitrile, glutaronitrile, adiponitrile and phenylacetonitrile. At least one compound selected from the group consisting of:

The solid catalyst may be, for example, an inorganic oxide, an inorganic halide, a strongly acidic organic compound, and a mixture of two or more thereof.

The inorganic oxide may include at least one compound selected from the group consisting of metal oxides, complex oxides, oxyacids and oxyacid salts. The metal oxide may be, for example, SiO ₂ , Al ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , ZrO ₂ , SnO ₂ , CeO ₂ , Ga ₂ O ₃ , La ₂ O ₃ . The complex oxide may be, for example, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , TiO ₂ -ZrO ₂ , SiO ₂ -ZrO ₂ , MoO ₃ -ZrO ₂ , zeolites, heteropolyacids (ie, P, Mo Polyacids containing elements such as, V, W, Si, and the like) and heteropolyacids. The oxy acid and oxy acid salt may be, for example, BPO ₄ , AlPO ₄ , polyphosphoric acid, acidic phosphate, H ₃ BO ₃ , acidic borate, niobic acid.

The inorganic halide may be, for example, a Group 3A element on the periodic table such as scandium, yttrium, lanthanum, actinium; Group 4A elements on the periodic table, such as titanium, zirconium and hafnium; Elements of Group 5A on the periodic table such as vanadium, niobium, and tantalum; Group 8 elements on the periodic table, such as iron, cobalt, nickel, palladium, and platinum; Group 2B elements on the periodic table such as zinc; Group 3B elements on the periodic table such as aluminum and gallium; Metal halides such as metal fluorides, chlorides, bromide and iodides of Group 4B elements on the periodic table such as germanium and tin.

The strongly acidic organic compound may be, for example, an organic sulfonic acid compound such as a sulfonic acid group-containing ion exchange resin and a sulfonic acid compound including a condensed carbon ring.

In addition, the reactors used in the reaction may include, for example, batch reactors and semi-batch reactors comprising internal components formed of or coated with a material resistant to chlorinating agents. Materials that are resistant to chlorinating agents include Hastelloy C or Teflon.

In addition, the reaction may be carried out at a temperature of 50 to 300 ℃, for example, 100 to 200 ℃. If the reaction temperature is less than 50 ℃ is not preferable in terms of reaction rate, if it exceeds 300 ℃ is not preferable in terms of energy loss. In addition, the reaction can be carried out in the pressure range of 0.1 to 30 bar, for example, 6 to 7 bar. If the reaction pressure is less than 0.1 bar, the reaction activity is too low, and if it exceeds 30 bar, the effect of increasing the reaction activity with increasing pressure is insignificant. The reaction pressure can be adjusted using an inert gas, for example nitrogen. The reaction time is generally 10 minutes to 50 hours, such as 10 minutes to 100 minutes. If the reaction time is less than 10 minutes, the conversion rate of the polycarboxylic acid aliphatic hydrocarbon as a reaction raw material is too low, and if it exceeds 50 hours, the reaction is almost completed and there is no change in conversion or selectivity.

One example of the reaction is a chlorination reaction of glycerol represented by the following Scheme 1.

In the method for preparing chlorohydrins according to one embodiment of the present invention, glycerol may be used as a reaction raw material. In this case, 1,3-dichloropropan-2-ol is mainly produced, and monochloropropanediol and trichloro are used as by-products. Rolopane and water are produced. 1,3-dichloropropan-2-ol is particularly suitable as a reaction raw material for the production of epichlorohydrin.

In this specification, a mixture of isomers consisting of 1,3-dichloropropan-2-ol (hereinafter 1,3-DCP) and 1,2-dichloropropan-3-ol (hereinafter 1,2-DCP) is referred to as " Dichloropropanol (DCP) ".

Scheme 1

The selectivity of monochloropropanediol (MCP) and the selectivity of dichloropropanol (DCP) in the reaction can be calculated by the following equations (1) and (2), respectively.

[Equation 1]

Selectivity (wt%) of monochloropropanediol (MCP) = (mass of monochloropropanediol produced) / (total mass of reaction product) × 100

[Equation 2]

Selectivity (wt%) of dichloropropanol (DCP) = (mass of dichloropropanol produced) / (total mass of reaction product) × 100

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

The chlorination reaction of Scheme 1 is carried out in at least one of a batch reactor, a semi-batch reactor, a continuous stirring tank reactor (CSTR) and a plug flow reactor, the reactor At least one of these reactors may be equipped with an ultrasonic generator.

The method for producing chlorohydrins having the above structure can increase the reaction rate and shorten the reaction time by increasing the reactivity to the chlorination reaction of carboxylic acid, such as glycerol and the multi-acid aliphatic hydrocarbon by ultrasonic irradiation.

Meanwhile, epichlorohydrin (ECH) may be prepared by reacting dichloropropanol prepared by the method for preparing chlorohydrins with an alkali such as sodium hydroxide.

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

Example

Example 1 Preparation of Dichloropropanol from Glycerol by Ultrasonic Irradiation in the Presence of Acetic Acid Catalyst

The reaction of dichloropropanol, a raw material of epichlorohydrin, was carried out in a semi-batch reactor equipped with an ultrasonic generator (frequency: 20 kHz, output: 600 W) with a volume of 500 liters. The internal components of the semi-batch reactor were formed of Hastelloy C, a material that is resistant to chlorinating agents. First, 300 g of glycerol and 15 g of anhydrous acetic acid were added to the semi-batch reactor. Thereafter, the reaction temperature was fixed at 130 ° C., and 99.7 vol.% Of hydrogen chloride gas, which is a chlorinating agent, was continuously introduced into the semi- batch reactor at a constant pressure of 6 bar in an unstirred state, and at the same time, ultrasonic waves (frequency: 40 kHz) were added to the reaction mixture. , Power: 600 W) while proceeding the reaction. During the course of the reaction, the reaction mixture was collected at 5 minute intervals, and then analyzed by gas chromatography to analyze the contents of reactants (glycerol) and products (MCP + DCP + water, etc.) in the reaction mixture. Record the temperature of the reactor to room temperature, analyze the composition of the reaction mixture using gas chromatography, and selectivity of monochloropropanediol and selectivity of dichloropropanol by Equation 1 and Equation 2 above. Each calculation was performed and the results are shown in Table 1 together with the reaction termination time. Here, the 'end time of reaction' refers to the time taken from the start of the reaction until the time when the weight change of the product according to the reaction time is '0'.

As used in Table 1 below, "MCP" and "DCP" mean monochloropropanediol and dichloropropanol, respectively.

Example 2 Preparation of Dichloropropanol from Glycerol by Ultrasonic Irradiation

Dichloropropanol was prepared from glycerol in the same manner as in Example 1, except that the reaction temperature and the introduction pressure of the hydrogen chloride gas were changed to 160 ° C. and 7 bar, respectively, without using an acetic acid catalyst. After completion of the reaction, the reaction termination time, the selectivity of monochloropropanediol and the selectivity of dichloropropanol were measured and / or calculated, and the results are shown in Table 1 below.

Comparative Example 1: Dichloropropanol was prepared from glycerol without ultrasonication in the presence of an acetic acid catalyst.

Dichloropropanol was prepared from glycerol in the same manner as in Example 1, except that the reaction mixture was not irradiated with ultrasonic waves while the reaction was in progress, and the reaction mixture was stirred at a speed of 300 rpm instead. After completion of the reaction, the reaction termination time, the selectivity of monochloropropanediol and the selectivity of dichloropropanol were measured and / or calculated, and the results are shown in Table 1 below.

Comparative Example 2: Dichloropropanol was prepared from glycerol without ultrasonication in a non-catalyst state

Without using an acetic acid catalyst, the reaction temperature and the introduction pressure of hydrogen chloride gas were changed to 160 ° C. and 7 bar, respectively, and the reaction mixture was stirred at a speed of 300 rpm without irradiating ultrasonic waves to the reaction mixture during the reaction. Except that, dichloropropanol was prepared from glycerol in the same manner as in Example 1. After completion of the reaction, the reaction termination time, the selectivity of monochloropropanediol and the selectivity of dichloropropanol were measured and / or calculated, and the results are shown in Table 1 below.

 [Table 1]

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Reaction termination time
(Hour: minute: second) 0:41:00 0:52:00 1:07:30 1:32:00 Product
Selectivity (wt%)
DCP 83 60 83 60 MCP 9 33 9 33

Referring to Table 1, Examples 1 and 2 were no difference in DCP selectivity and MCP selectivity compared to Comparative Examples 1 and 2, it was found that the reaction termination time is shortened.

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

Claims (14)

A method for producing chlorohydrins by reaction of a polyacid aliphatic hydrocarbon with a chlorinating agent, the method comprising irradiating ultrasonic waves to a reaction mixture during the reaction, The polycarboxylic acid aliphatic hydrocarbon is a compound having 2 to 20 carbon atoms, two or more hydroxyl groups are bonded to different carbon atoms, The chlorohydrin is a method of producing chlorohydrin is a compound in which at least one hydroxyl group and at least one chlorine atom is combined with different carbon atoms. delete The method of claim 1, The polycarboxylic acid aliphatic hydrocarbon is 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, glycerol And 1,2,4-butanetriol, 1,4-butanediol and a method for producing chlorohydrin comprising at least one compound selected from the group consisting of esters of the above compounds. The method of claim 1, The chlorinating agent is a method for producing chlorohydrin containing hydrogen chloride gas or hydrochloric acid. delete The method of claim 1, The chlorohydrins are composed of 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, 1,3-dichloropropane-2-ol and 2,3-dichloro propane-1-ol. A method for producing chlorohydrins comprising at least one compound selected from the group. The method of claim 1, The frequency band of the ultrasonic wave is a method for producing chlorohydrins of 20kHz to 100kHz. The method of claim 1, The reaction is a process for producing chlorohydrins in the absence of a catalyst or in the presence of a catalyst. The method of claim 8, The catalyst is a method for producing chlorohydrin comprising at least one selected from the group consisting of an organic acid catalyst, a carboxylic acid catalyst, a nitrile catalyst and a solid catalyst. The method of claim 1, The reaction proceeds in at least one of a batch reactor, a semi-batch reactor, a continuous stir tank reactor (CSTR) and a plug flow reactor, and at least one of the reactors. The reactor of the manufacturing method of chlorohydrin equipped with an ultrasonic generator. The method of claim 1, The reaction is a method for producing chlorohydrin proceeds at a temperature of 50 ~ 300 ℃. The method of claim 1, The reaction is a method for producing chlorohydrin proceeds at a pressure of 0.1 ~ 30bar. The method of claim 1, The reaction is a method for producing chlorohydrin for 10 minutes to 50 hours. As a method of producing epichlorohydrin (ECH) from chlorohydrins produced by the reaction of a polyacid aliphatic hydrocarbon and a chlorinating agent, 14. A process for producing epichlorohydrin comprising the process for producing chlorohydrins according to any one of claims 1, 3, 4 and 6 to 13.