JPS6039051B2 - Method for producing halohydrin and glycol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing halohydrins and glycols by oxidizing olefins with an oxygen-containing gas in an aqueous solution containing halogen ions.

Conventionally, methods for producing halohydrins, such as chlorohydrin, using olefins as starting materials include reacting olefins with molecular chlorine in an aqueous solution.
known and practiced industrially.

However, in the above method for producing chlorohydrin, the molecular chlorine required as a raw material is usually produced by electrolysis of sodium chloride, and its production consumes a lot of electricity, so it is quite expensive.

That is, this method has the disadvantage that molecular chlorine used as a raw material is expensive. On the other hand, as a method for producing glycol, a method of hydrolyzing an epoxy compound is carried out industrially. Epoxy compounds can generally be obtained by epoxidizing an olefin using chlorohydrin, a peracid such as peracetic acid, or a hydroperoxide such as ethylbenzene hydroperoxide as an oxidizing agent. However, these methods all have drawbacks such as consuming expensive by-products and problems in the disposal of by-products. In order to compensate for these drawbacks, an olefin and an oxygen-containing gas are reacted in acetic acid in the presence of a catalyst such as a tellurium compound.
A method has been proposed in which glycol is converted into acetate ester and then hydrolyzed to produce glycol, but since the method involves acetate ester, the reaction equipment is complicated and the reaction operations are complicated. . It is an object of the present invention to provide a process for the production of halohydrins and glycols which does not have the disadvantages mentioned above.

As a result of detailed research on the reaction between olefins and oxygen-containing gases in aqueous solutions, the present inventors have discovered that in the presence of halogen ions and compounds or ions of elements selected from the group consisting of tin, tellurium, indium, and titanium. In addition, the inventors discovered that halohydrins and glycols can be produced directly from olefins in a single reaction when olefins are oxidized with an oxygen-containing gas, leading to the completion of the present invention.

That is, the method of the present invention directly reacts olefin with an oxygen-containing gas in an aqueous solution containing halogen ions in the presence of a compound or ion of an element selected from the group consisting of tin, tellurium, indium, and titanium. This is a method for producing halohydrins and glycols. According to the method of the present invention, halohydrins and glycols can be produced by simplifying the production process without using expensive molecular halogens.

In the method of the present invention, the olefin used is an aliphatic hydrocarbon having 2 to 8 carbon atoms, such as ethylene, propylene, isoptene, cyclohexene, or octene. The halogen species is chlorine, bromine, or iodine, and chlorine is usually used frequently. As the halogen ion, hydrogen halide, such as hydrogen chloride, is usually preferred. Water is used as the reaction solvent, and the concentration of halogen ions in the aqueous solution is between 0.5 and 2.
A range of 0% by weight is used, but typically 1-4% by weight.
is the preferred range. The catalyst used in the method of the invention is a compound or ion of an element selected from the group consisting of tin, tellurium, indium, and titanium.

Compounds include oxides, hydroxides, halides, oxyacids, or salts, such as stannous/stannic oxide, tellurium oxide, telluric acid, tellurium oxysulfide, tellurium hydroxide, and indium oxide. , indium nitrate, titanium halide, titanic acid, or titanium oxide are often used. The amount of catalyst used is 0.1% of the aqueous solution used for the reaction.
A range of ˜1% by weight is suitable. The catalyst species may be a homogeneous phase dissolved in water or a heterogeneous phase insoluble in water, and in either case, it can be similarly subjected to the reaction. The amount of olefin used relative to the water solvent is preferably in the range of 5 to 20% by weight. The oxygen-containing gas is usually air or oxygen, or may be a mixed gas of oxygen and an inert gas.

There is no particular restriction on the ratio of olefin to oxygen-containing gas as long as it is outside the explosive range. Reaction temperature is 50-200q
o, and at this temperature, the reaction solvent and olefin are reacted under pressure higher than the pressure necessary to maintain the liquid phase.

The time required for the reaction is typically 1 to 5 hours, taking a batch-type reaction as an example.

The present invention will be explained below with reference to Examples.

Example 1 In a Hastelloy microautoclave with an internal volume of 50', a 3% by weight hydrochloric acid aqueous solution of 20% and stannic chloride (S to 14%) was added.
・Group 20) o. After charging the reactor for 7 days and purging the system with nitrogen gas, 1.7 days of ethylene (50k9/kg) and 15k9/kg of oxygen were injected.

Insert the autoclave into an oil bath and heat at 140℃ for 3
I made her react while worshiping her for hours.

The pressure during the reaction reached a maximum of 140k9/s. After cooling the autoclave, the reaction liquid inside was analyzed, and ethylene chlorohydrin was produced in 1.05 hours and ethylene glycol was produced in 0.506 hours.

The production of acetaldehyde and dichloroethane was in trace amounts. Example 2 Using the same reactor and reaction method as in Example 1, 20 parts of a 3% by weight aqueous hydrochloric acid solution and 0.54 parts of tellurium tetrachloride were charged into an autoclave, and 2.8 parts of propylene and 15 parts of oxygen were charged.
K9/Na was injected and reacted at 100 oo for 4 hours.

When the reaction solution was collected and analyzed, 1.00 hours of propylene chlorohydrin and 0.210 hours of propylene were produced.
Examples 3 to 6 Reactions were carried out in the same manner as in Example 1, using various catalysts and olefins.

HC1, HBr and HI are all 3% by weight aqueous solutions. The results obtained are shown in the table.

Claims (1)

[Claims] 1 An aliphatic olefin having 2 to 8 carbon atoms, tin,
A method for producing halohydrins and glycols, which comprises reacting with an oxygen-containing gas in an aqueous solution containing halogen ions in the presence of a compound or ion of an element selected from the group consisting of tellurium, indium, and titanium.