JPS6039330B2 - Method for hydration of olefin and etherification of glycol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for hydrating iso-olefin and etherifying glycol, in which the iso-olefin is hydrated in the coexistence of glycol.

The iso-olefin is hydrated in the presence of a strongly acidic cation exchange resin catalyst and converted to the corresponding tertiary alcohol.
The method is “INDUSTRIAL ANDENGINEE”
RINGCHEMISTRY” magazine, volume 53, page 209 (
(1961) and others. However, in this hydration reaction, the utilization efficiency (conversion rate) of isolefins is low, and in the current situation where petroleum resources are in short supply, it is desired to increase the utilization efficiency of isolefins. JP-A-46-5618 also describes a method for hydrating isobutylene similar to the above, and in Example 1, it is stated that isobutylene was completely converted to tertiary butyl alcohol. However, when the method of Example 1 was repeated, the conversion rate of isobutylene was actually very low. US Patent No. 3,285,977, British Patent No. 1,311,172,
JP-A-50-32116, JP-A No. 50-126603,
No. 50-1137906 describes a method of conducting the hydration reaction in the presence of a solvent such as acetic acid, alcohol, ketone, dioxane, glycol, or glycol ether as a method for increasing the reaction rate during hydration of iso-olefins. Disclosed.

However, even in these methods, the utilization efficiency of isoolefins is not sufficient. For example, U.S. Patent No. 32859
According to No. 77, when no solvent is used, the conversion rate of isobutylene is 32.0%, but when inpropyl alcohol is used as a solvent, the conversion rate of isobutylene is 47.0%.
It is stated that the improvement is 2%. However, this level of improvement is not sufficient. Furthermore, when glycol monoether is used as a solvent, it reacts with isoolefins and becomes glycol diether with little utility value, which is not preferable. When glycol ether is used as a solvent, the isoolefin conversion rate is not sufficiently improved. U.S. Patent No. 4,096,194 uses a large amount of solvent (for example, using 6 times the amount of water to the iso-olefin, A method is disclosed in which the hydration reaction of isoolefins is carried out in such a way that the water and the hydrocarbon finally form a homogeneous phase by using twice the weight of the solvent. However, this method requires too much solvent and is not practical as an industrial method. If it is possible,
It is desired to increase the utilization efficiency of iso-olefins with a small amount of solvent used. In addition, in all of the above methods, a larger number of moles of water than the iso-olefin is used, but if a large amount of water is used, the alcohol produced will be obtained as a dilute aqueous solution, and separation of the alcohol will be expensive. This is not satisfactory as an industrial method.

U.S. Pat. No. 4,087,471 uses a small amount of water with a water:isoptylene molar ratio of 0.06:1 to 0.24:1;
A method is disclosed for hydrating isoptylene while controlling the reaction temperature by cooling and recycling a portion of the reaction product. However, with this method, increasing the conversion rate of isobutylene leads to isobutylene oligomers having low utility value.
is produced in large amounts, and if the production of isobutylene oligomers is suppressed, the conversion rate of isobutylene becomes low, which is not satisfactory as an industrial method. As a result of various studies on the hydration reaction of iso-olefins, the present inventors found that when iso-olefins were hydrated using glycol as a solvent and a smaller number of moles of water than the iso-olefins, the amount of solvent used was The present invention was completed based on the discovery that at least the conversion rate of isoolefins can be increased and the production of undesirable by-products such as isoolefin oligomers can be suppressed. In order to increase the utilization efficiency of iso-olefin, it is common knowledge to increase the molar ratio of water: iso-olefin, and most conventional methods also require a molar ratio of water: iso-olefin of 1 or more: 1. However, in the method of the present invention, unlike such conventional methods, it has been found that when the reaction is carried out in the coexistence of glycol, the utilization efficiency of the iso-olefin is increased when a smaller number of moles of water than the iso-olefin is used. Further, at this time, the glycol added to the reaction system reacts with the isoolefin and is etherified to become glycol ether. Therefore, the gist of the present invention is to react an iso-olefin having 4 to 6 carbon atoms with water in the presence of a strongly acidic enteric ion exchange resin catalyst and glycol and at a molar ratio of water to iso-olefin of 0.
The present invention relates to a method for hydrating iso-olefins and etherifying glycol, which is carried out under conditions of 8 or less: 1 to produce a corresponding tertiary alcohol and glycol ether.

In the process of the present invention, the isolefin is brought into contact with water and glycol, and hydration of the isolefin and etherification of the glycol occur simultaneously, and the corresponding tertiary alcohol and glycol ether (glycol monotertiary alkyl ethers and glycol di-tertiary alkyl ethers).

Even if the iso-olefin having 4 to 6 carbon atoms as a reaction raw material is a pure product,
It may be a mixture of two or more iso-olefins or a fraction containing iso-olefins.

Economically, C4, C5, and C6 fractions obtained from petroleum refining equipment or hydrocarbon cracking equipment, such as thermal cracking of naphtha or fluid catalytic cracking of kerosene and gas oil fractions, are preferable because they contain iso-olefins. It is something. Examples of such isoolefin-containing fractions include n-butane, i-butane, butene-1, butene-2, a C4 fraction containing isobutylene as a main component, n-pentane, i-pentane, pentene-1, bentene-2, C5 fraction mainly composed of isoamylenes, 2,3-dimethyl-1-butene, 2,3-
Dimethyl-2-butene, 2-methyl-1-bentene, 2
-Methyl-2-bentene, 3-methyl-2-bentene,
There are C6 hydrocarbons containing iso-olefins having 6 carbon atoms such as 2-ethyl-1-butene and 1-methyl-cyclobentene. Only the isoolefin in the crab meat reacts almost selectively. Glycols include diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, neobentyl glycol, hexamethylene glycol, 2-methyl-1,3-butanediol, and glycerin-1 methyl. Examples include ether, glycerin monoalkyl ether such as glycerin-2-methyl ether, glycerin-1-ethyl ether, and glycerin-2-ethyl ether.

Examples of strong acid type intestinal ion exchange resins used as catalysts include styrene sulfonic acid type ion exchange resins (sulfonated copolymers of styrene and polyunsaturated compounds such as divinylbenzene), and phenolsulfonic acid type ion exchange resins. General strong acid type cation exchange resins that have strong acidity and have sulfonic acid groups such as ion exchange resin (condensation of phenol sulfonic acid with formaldehyde), sulfonated coal, sulfonated asphalt, etc. be.

Furthermore, the physical structure of these ion exchange preformed resins can be either a gel type or a giant network structure. The reaction method of the present invention is preferably a continuous reaction method.

For example, a method in which raw materials of isoolefin, water, and glycol are flowed in parallel flow to a catalyst bed, a method in which a mixed raw material of water and glycol and isoolefin are flowed in the same flow to a catalyst bed, a method in which glycol or water is flowed in parallel flow with isolefin to a catalyst bed. Possible methods include a method in which water or glycol is injected from the middle of the reaction tower, a method in which raw materials are continuously supplied to a complete mixing type reaction vessel, mixed with a catalyst, and a product is continuously extracted. The molar ratio of water to isoolefin fed to the reactor must be under conditions of 0.8:1 or less, preferably 0.04:1 to 0.7:1. If the molar ratio of water:isoolefin exceeds 0.8:1, the conversion rate and reaction rate of isoolefin will rapidly decrease, resulting in a rapid decrease in the utilization efficiency of isoolefin. The molar ratio of glycol to isoolefin is preferably about 0.2:1 to 20:1, particularly preferably about 0.5:1 to 10:1. If the molar ratio of glycol:isoolefin is too large, the equipment capacity will be excessive and processing costs will increase, and if this molar ratio is too small, the creation of isoolefin oligomers will increase and the utilization rate of isoolefin will be low. So I don't like it. The production ratio of tertiary alcohol and glycol ether changes depending on the ratio of water and glycol used, and the water:glycol molar ratio is set so that the production ratio of alcohol and ether becomes a desired value. The molar ratio of water to glycol is usually less than about 4:1, particularly preferably from about 0.002:1 to 3.5:1. If the molar ratio of water to glycol is too large, the conversion of iso-olefin will decrease and the production of ino-olefin oligomers will increase, and if this molar ratio is too low, the capacity of the apparatus will become excessive. Glycol dissolves hydrocarbons well, and in the present invention, it usually has two phases: an aqueous phase and an oil phase.
The reaction takes place in this phase. The amount of glycol used to form the two phases is about 1 to 400% by weight, based on the isoolefin-containing hydrocarbon.

The reaction temperature is preferably about 40 to 120 qo, particularly about 50 qo.
~9000 is preferred.

If the reaction temperature is too low, the reaction rate will be slow, and if the reaction temperature is too high, the life of the catalyst will be shortened. The reaction pressure is preferably a pressure necessary to maintain the iso-olefin in a liquid state in the catalyst bed, but is not limited to this, and a pressure such that a part of the iso-olefin is in a gaseous state is preferably adopted. can also be implemented. The reaction pressure usually employed is about 4-40k9/c, especially about 5-255k9/c.
C is preferable. In addition, the liquid space velocity of all raw materials is approximately 0.1~
1 Mr-1, especially about 0.2 to sphere r-1 is preferred. For the separation and purification of the reaction product mixture thus obtained, conventional distillation methods, extraction methods, extractive distillation methods, etc. can be used as appropriate. According to the invention, the iso-olefin reacts with water and glycol,
Moreover, the reaction rate is fast, and the conversion rate and utilization efficiency of iso-olefin are high.

In the method of the present invention, the iso-olefin conversion rate is high, but the by-product of iso-olefin oligomers is small. Furthermore, although glycol is converted into glycol ether, most of it is glycol monoether, and the by-product of glycol dieter is small. Glycol ether has low utility value, but glycol monoether has high utility value as a water-soluble solvent, etc., and the production of glycol monoether is rather preferable. The amount of water used for the reaction is small, the water content in the product mixture is low, and the product mixture can be easily separated and purified. Next, the present invention will be explained with reference to examples.

Example 1 A stainless steel reaction tube with an inner diameter of 12 ◇ and a length of 4 skins was filled with particles with a particle size of 0.3 to 1. Overhead, 9 equivalents of exchange capacity 4.9/ter dry resin, porosity 30-35%, average pore size 200-600
Amberlyst 15, a strong acid type cation exchange resin having a large network structure and having sulfonic acid groups, was filled.

The upper part 50c of the resin layer was filled with glass beads having the same particle size to improve the dispersion of the two liquid phases. In this reaction tube, an isobutylene-containing C4 fraction having the composition shown in Table 1, water,
and ethylene glycol at the feedstock ratios (molar ratios) shown in the upper row of Table 2, with a liquid hourly space velocity of 0. Shoes R-1, temperature 60qC, pressure 20k9/me passed. The analysis results in steady state were as shown in Table 2. Table 1 Comparative Example 1 A reaction was carried out in the same manner as in Example 1, except that ethylene glycol was not used, the amount of water used was increased, and the molar ratio of water:isobutylene was set to 4.00:1.

The results are shown in Table 2. Comparative Example 2 The amount of water used was increased, and the molar ratio of water:isobutylene was set to 4.
The reaction was carried out in the same manner as in Example 1 except that the ratio was changed to 00:1.

The results are shown in Table 2. Table 2 Dm Ethylene glycol ditertiary butyl ether t21 Ethylene glycol ditertiary butyl ether comparison Example 1 is “ INDUST
RIAL ANDENGINEERING CHEMIS
TRY” magazine, Vol. 53, p. 209 (1961), and Comparative Example 2 is based on U.S. Patent No. 3285977.
Example 1 is based on the method of the present invention.

Comparative Example 1 uses only water and isobutylene as reaction raw materials, and the isobutylene conversion rate is 35.0%, and when the reaction is carried out in the presence of ethylene glycol, the isobutylene conversion rate is 49%, as shown in Comparative Example 2. .4%. In order to significantly increase the isobutylene conversion above 49.4%, according to the method of U.S. Pat. No. 4,096,194, the amount of solvent added must be further increased to create a homogeneous phase of water and hydrocarbons. . However, according to the present invention, Example 1
As shown in Figure 2, even if the amount of solvent is not increased, the isobutylene conversion rate can be significantly improved by reducing the amount of water used. Moreover, even if the amount of water used is reduced, almost no isobutylene oligomer is produced. Furthermore, compared to Comparative Examples 1 and 2, there was almost no formation in Example 1. Also, comparative example 1
, 2, the water content in the product mixture of Example 1 is very low. Example 2 A reaction was carried out in the same manner as in Example 1, except that 50 to 100 mesh gel-type strong acid type cation exchange resin Derwex 50W 1 x 8 was used instead of Amberlyst 15 as a catalyst.

The results were almost the same as in Example 1. Example 3 A reaction was carried out in the same manner as in Example 1, except that the reaction temperature was changed and the liquid hourly space velocity of the raw material was set to 3.0 hr-1.

The isobutylene conversion rate is shown in Table 3, and the selectivity of the reaction product was the same as in Example 1, with no significant difference. Table 3 Example 4 The reaction was carried out in the same manner as in Example 1 except that the reaction pressure was varied between 7 and 40 k9/kg.

The conversion rate of isoptylene was 70 to 73%, and almost no difference was observed due to pressure. Example 5 Instead of C4 fraction, isoamylenes 21. The reaction was carried out in the same manner as in Example 1, except that the C5 hydrocarbon fraction containing 1% by weight was used so that the isoamylene was the same mole as the isobutylene in Example 1.

As a result, the conversion rate of isoamylene was 69.0%,
The selectivity of the reaction product is 37.1 for tertiary amyl alcohol.
Mol%, ethylene glycol mono and di tertiary
The amount of amyl ether was 62.9 mol%. *Example
6 Instead of C4 crab, 17 isoolefins with 6 carbon atoms
The reaction was carried out in the same manner as in Example 1 except that the C6 hydrocarbon fraction containing % male by weight was used so that the isoolefins were in the same molar amount as the isobutylene in Example 1.

The conversion rate of iso-olefins having 6 carbon atoms was 64.0%, and the selectivity of the reaction product was 64.0%.
) 41.1% by mole, and 58.9% of mono- and di-tertiary alkyl ethers of ethylene glycol. Examples 7 to 11 Reactions were carried out in the same manner as in Example 1, except that the same moles of various glycols were used instead of ethylene glycol.

The results are shown in Table 4. Table 4 Example 12 Isobutylene, water and ethylene glycol were reacted in the same manner as in Example 1 except that the molar ratio of water:isobutylene was changed.

The results are shown in Table 5. Example 13 Isobutylene, water and ethylene glycol were reacted in the same manner as in Example 1 except that the molar ratio of ethylene glycol:isobutylene and the molar ratio of water:isobutylene were changed.

The results are shown in Table 5. Table 5

Claims (1)

[Claims] 1. When reacting an isoolefin having 4 to 6 carbon atoms with water, the reaction is carried out in the presence of a strong acid type cation exchange resin catalyst and glycol, and the molar ratio of water to isoolefin is 0.
．． A method for etherifying glycol for the hydration of isoolefins, which is carried out under conditions of 8 or less: 1 to produce a corresponding tertiary alcohol and glycol ether. 2 The molar ratio of water:isoolefin is 0.04:1 to 0.
The method according to claim 1, wherein the reaction is carried out under conditions of 7:1. 3. The method according to claim 1, wherein the reaction is carried out in the presence of glycol in an amount to form two phases, an aqueous phase and an oil phase.