JP2013014527A - Production method of olefin chlorohydrin-based compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of an olefin chlorohydrin-based compound, by which an olefin chlorohydrin-based compound can be more efficiently produced while making use of a byproduct hydrogen chloride in the production process without wasting it.SOLUTION: The production method of an olefin chlorohydrin-based compound comprises allowing hypochlorous acid obtained by dissolving chlorine in water to react with an olefin-based compound. In the production method of an olefin chlorohydrin-based compound, hydrogen chloride as a byproduct in the production of the hypochlorous acid is made to react with an olefin oxide-based compound to obtain an olefin chlorohydrin-based compound.

Description

  The present invention relates to a method for producing an olefin chlorohydrin compound.

A method for producing olefin chlorohydrin by reacting chlorine, water, and alkene is conventionally known (Non-patent Document 1). This reaction consists of (1) formation of hypochlorous acid (HOCl) and hydrogen chloride (HCl) by reaction of chlorine and water, and (2) formation of olefin chlorohydrin by reaction of olefin and hypochlorous acid. It is believed to proceed in the two stages shown.
Since the reaction (1) is an equilibrium reaction, it usually does not proceed when a certain ratio is reached. However, hypochlorous acid generated by the reaction is added to the double bond of the olefin by the reaction (2), and the olefin chloro By being consumed as hydrin, the equilibrium of (1) further tilts to the right, and chlorine reacts with water.

However, hydrogen chloride which is by-produced simultaneously with hypochlorous acid in the reaction of (1) is not consumed and remains in the system as hydrochloric acid, so this reaction eventually reaches equilibrium, and chlorine does not react with water. As a result, there was a problem that chlorine was dissolved in water as it was, and the dissolved chlorine was added to the double bond of olefin, whereby olefin dichloride was by-produced.
Therefore, a method has been studied in which by-products of olefin dichloride are suppressed by adding an alkali metal salt or an alkaline earth metal salt to the reaction system and neutralizing hydrochloric acid (Patent Document 1).
However, in such a method, by-produced hydrochloric acid, alkali metal salt or alkaline earth metal salt for neutralizing it has nothing to do with the production of olefin chlorohydrin. Salt and the like must be treated as mere waste in the production process.

J. Am. Chem. Soc., 41, p1419 (1919)

JP-A-6-25037

  The present invention has been made in view of the above problems, and by consuming hydrogen chloride produced as a by-product, the production of olefin chlorohydrin compounds can be promoted, and the produced hydrogen chloride can be used without wasting it. Then, it aims at providing the manufacturing method of the olefin chlorohydrin type compound which can manufacture an olefin chlorohydrin type compound more efficiently using a production process.

The method for producing an olefin chlorohydrin compound of the present invention is a method for producing an olefin chlorohydrin compound by reacting hypochlorous acid obtained by dissolving chlorine in water with an olefin compound. Then, an olefin oxide compound is reacted with hydrogen chloride produced as a by-product during the production of hypochlorous acid to obtain an olefin chlorohydrin compound.
In this method, the olefinic compound is preferably at least one selected from the group consisting of ethylene, propylene and allyl chloride.
The olefin oxide compound is preferably a corresponding oxide of the olefin compound.

  According to the present invention, the production of an olefin chlorohydrin compound can be promoted by consuming by-produced hydrogen chloride. Furthermore, it becomes possible to produce the olefin chlorohydrin compound more efficiently by using the hydrogen chloride produced as a by-product without wasting it and making use of it in the production process.

In the method for producing an olefin chlorohydrin compound of the present invention,
(1) A step of dissolving hypochlorous acid by dissolving chlorine in water,
(2) a step of producing hydrogen chloride as a by-product when chlorine is dissolved in water to produce hypochlorous acid;
(3) reacting the obtained hypochlorous acid with an olefinic compound to produce an olefin chlorohydrin compound,
(4) A step of reacting the obtained hydrogen chloride with an olefin oxide compound to produce an olefin chlorohydrin compound is included.
In step (2), when hypochlorous acid is produced, hydrogen chloride is by-produced, and this hydrogen chloride quickly dissolves in water to form hydrochloric acid (hereinafter referred to in this specification). Then, hydrogen chloride including hydrogen chloride dissociated as hydrochloric acid is called hydrogen chloride).
Therefore, the method for producing an olefin chlorohydrin compound of the present invention is mainly composed of a series of three reaction steps.
Usually, the step (1) and the step (2), the step (3), and the step (4) are sequentially performed.

Step (1) and (2)
Chlorine is usually supplied as a gas. For example, it is suitable to supply at a supply rate of about 10 to 50 sccm with respect to 100 g of water. In this case, the supply time is not particularly limited, but when the reaction between chlorine and water reaches equilibrium, chlorine will not dissolve, so chlorine may be dissolved in water as it is, in order to avoid this The supply time is preferably about 100 minutes or less with respect to 100 g of water.
The concentration of hypochlorous acid produced by the reaction between chlorine and water is not particularly limited. However, since the stability deteriorates as the concentration increases, it is suitable that the concentration is about 20 wt% or less in the reaction solution.

Process (3)
The olefin compound to be reacted with hypochlorous acid is an unsaturated hydrocarbon compound having one double bond in the molecule, and any known in the art may be used. Although the carbon number is not specifically limited, For example, it is suitable that it is about 8 or less, and about 2-4 are preferable. Examples of the olefin compound include olefin, olefin alcohol, olefin chloride, olefin aldehyde, olefin carboxylic acid, and olefin ketone. Among these, olefins and olefin chlorides are preferable, and ethylene, propylene, butene, ethylene chloride, allyl chloride, methylallyl chloride, and the like are more preferable, and ethylene, propylene, allyl chloride, and the like are more preferable. Is mentioned.

  At this time, the olefinic compound may be supplied simultaneously with chlorine from the viewpoint of safety. Similarly, from the viewpoint of safety, the olefinic compound is preferably the same amount (same rate) or more than the supply amount (or supply rate) of chlorine.

Process (4)
The olefin oxide compound to be reacted with hydrogen chloride as a by-product may be any olefin compound as long as it is an oxide of the olefin compound described above, but preferably the olefin compound used in step (3). It is an oxide of a compound. Therefore, for example, when ethylene is used as the olefin compound in step (3), ethylene oxide is used, when propylene is used in step (3), propylene oxide is used, and when allyl chloride is used in step (3). Is preferably epichlorohydrin. Thereby, the same kind of olefin chlorohydrin compound can be obtained by steps (3) and (4), and a higher concentration olefin chlorohydrin compound can be produced.

  The olefin oxide compound may be supplied as it is into the reaction solution without separating the by-produced hydrogen chloride. In this case, it is suitable to supply the olefin oxide compound together with the supply of the olefin compound described above.

In addition, when there is too much quantity of hydrogen chloride which exists in a reaction solution, olefin dichloride may be by-produced by supply of an olefin oxide type compound. On the other hand, if the amount of hydrogen chloride in the reaction solution is too small, olefin diol may be produced as a by-product due to the supply of the olefin oxide compound. Therefore, it is preferable to appropriately adjust the concentration of hydrogen chloride in the reaction solution at the time of supplying the olefin oxide compound, or to appropriately adjust the timing of supplying the olefin oxide compound to the reaction system.
It is suitable to set the supply amount of the olefin oxide compound depending on the mol concentration of hydrogen chloride or the like. For example, when the obtained olefin chlorohydrin compound and hydrogen chloride mixed solution contains 1 mol of olefin chlorohydrin compound and about 1 mol of hydrogen chloride, the supply amount of the olefin oxide compound is 1 mol or less in total. Is suitable. Further, the supply rate is suitably about the same as the supply rate of chlorine (for example, about 10 to 50 sccm for 100 g of water).

  As described above, when olefin dichloride is by-produced, the pH of the reaction system is maintained at about 0.5 to 6, more preferably about 3 to 5. On the other hand, when olefin diol is by-produced, it is preferable to separate and concentrate hydrogen chloride to adjust the amount of hydrogen chloride.

In the reactions (1) to (4) described above, the reaction for generating hypochlorous acid and the reaction between hypochlorous acid and the olefinic compound proceed sufficiently even at room temperature, and thus there is no need for heating. However, in order to further promote the reaction between chlorine and water, a range of about 0 ° C. to room temperature is preferable.
These reactions can be performed using conventional reactors. For example, any of a batch type reactor or a continuous type reactor can be used.

The olefin chlorohydrin compound obtained by the reaction can be separated and recovered by a method known in the art. Further, it may be further purified.
Separation / recovery and / or purification methods can be performed by methods known in the art. For example, simple distillation, precision distillation, azeotropic distillation, membrane separation, extraction and the like may be performed alone, or may be performed repeatedly, or two or more may be performed in combination.
When extracting, since it is necessary to use a large amount of solvent, it is preferable to carry out simple distillation as an industrially simple method.
In the case of membrane separation, it is preferable to use a membrane that is resistant to hydrogen chloride.

Usually, in the production of an olefin chlorohydrin compound, the reaction proceeds so as to obtain a solution of about 5 to 7.5% by weight of the olefin chlorohydrin compound in order to suppress by-products of olefin dichloride.
However, as in the present invention, in the production of hypochlorous acid and by-product reaction of hydrogen chloride, hydrogen chloride is effectively consumed by reacting hydrogen chloride in the reaction system with an olefin oxide compound. Can do. Thereby, the byproduct of an olefin dichloride can be suppressed effectively. Furthermore, by using an olefin oxide compound, the equilibrium reaction between chlorine and water can be further promoted, and a higher concentration olefin chlorohydrin compound solution can be obtained.

  On the other hand, after separating by-product hydrogen chloride from this reaction system as hydrochloric acid, when hydrogen chloride contained in hydrochloric acid is reacted with an olefin oxide compound, it is not an equilibrium reaction between chlorine and water. The reaction can proceed depending on the concentration of hydrogen chloride, and a high-concentration olefin chlorohydrin compound solution can be obtained.

Below, the manufacturing method of the olefin chlorohydrin type compound of this invention is demonstrated in detail.
First, the reactor and measurement method used in the examples are shown.
The reaction of the olefin chlorohydrin compound was carried out using a glass reaction vessel having a capacity of 500 ml. By blowing chlorine gas into water and simultaneously injecting the olefin compound, an olefin chlorohydrin compound and a hydrogen chloride aqueous solution are obtained. When the hydrogen chloride concentration reached about pH 3, an olefin oxide compound was blown into this aqueous solution to obtain olefin chlorohydrin.

The reaction solution is gas chromatograph (manufactured by Shimadzu Corporation, trade name GC-2010), capillary column (manufactured by Agilent J & W, trade name DB-1, 30 m × 0.25 mm (inner diameter), film thickness 1.0 μm), hydrogen flame ionization detection. Quantification was performed using a vessel (FID).
Each product (mol%) = each product amount (mol) / total product amount (mol) × 100

Example 1
500 mL of water is put into a glass reaction vessel, and chlorine (70 sccm) and ethylene gas (110 sccm) are blown. When pH 3 is passed, ethylene oxide is blown at a feed rate of 70 sccm for 3 hours, and a 12.8 wt% ethylene chlorohydrin aqueous solution. Got.

Comparative Example 1
500 mL of water was put into a glass reaction vessel, and chlorine (70 sccm) and ethylene gas (110 sccm) were blown in for 3 hours to obtain 7.0 wt% of ethylene chlorohydrin.

Example 2
Water (500 mL) was put into a glass reaction vessel, and chlorine (70 sccm) and ethylene gas (110 sccm) were blown into it to obtain an aqueous solution of 7.4 wt% ethylene chlorohydrin and 3.8 wt% hydrogen chloride.
Thereafter, the internal pressure was adjusted to 5 kPa, vacuum simple distillation was performed at 65 ° C. for 2 hours, and the mixture was separated into a 21 wt% ethylene chlorohydrin solution and a 7.3 wt% hydrogen chloride solution.
Subsequently, ethylene oxide was blown into the 7.3 wt% hydrogen chloride solution at a supply rate of 50 sccm for 4 hours to obtain a 13.2 wt% ethylene chlorohydrin aqueous solution.

Example 3
Water (500 mL) was put into a glass reaction vessel, and chlorine (70 sccm) and ethylene gas (110 sccm) were blown into it to obtain an aqueous solution of ethylene chlorohydrin 7.3 wt% and hydrogen chloride 3.6 wt%.
Thereafter, ethylene oxide was blown into the obtained ethylene chlorohydrin solution at a supply rate of 50 sccm for 2 hours to obtain a 9.8 wt% ethylene chlorohydrin aqueous solution.

Example 4
While putting 500 mL of water into a glass reaction vessel and blowing at a supply rate of 35 sccm of chlorine, 10.0 g of allyl chloride was dropped over 90 minutes to obtain an aqueous solution of 2.3 wt% dichloropropanol and 0.8 wt% hydrogen chloride. .
Thereafter, 12.5 g of epichlorohydrin was dropped into the obtained dichloropropanol aqueous solution over 1 hour to obtain a 4.6 wt% dichloropropanol aqueous solution.

  According to the present invention, production of an olefin chlorohydrin compound capable of producing an olefin chlorohydrin compound more efficiently by using by-produced hydrogen chloride without wasting it and making use of it in the production process. A method can be provided.

Claims (3)

A step of dissolving chlorine in water to obtain hypochlorous acid and obtaining hydrogen chloride as a by-product,
Reacting the hypochlorous acid with an olefin compound to obtain an olefin chlorohydrin compound,
A process for producing an olefin chlorohydrin compound comprising the step of reacting the hydrogen chloride with an olefin oxide compound to obtain an olefin chlorohydrin compound.   The method for producing an olefin chlorohydrin compound according to claim 1, wherein the olefin compound is at least one selected from the group consisting of ethylene, propylene, and allyl chloride.   The method for producing an olefin chlorohydrin compound according to claim 2, wherein the olefin oxide compound is a corresponding oxide of the olefin compound.