JPS6334134B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for simultaneously producing alkylene glycol mono s-butyl ether (ASB) and s-butyl alcohol (SBA), and more specifically, in the presence of a strong acid type cation exchange catalyst, n-
The present invention relates to a method for simultaneously producing ASB and SBA by contacting a mixture containing butene or n-butene with alkylene glycol (AG) in the presence of water. According to the method of the present invention, the production of by-products is small and the target products, ASB and SBA, can be obtained with high selectivity and high yield. A method for producing glycol monoalkyl ether from olefin and glycol using a strong acid type cation exchanger as a catalyst is known from U.S. Pat. No. 2,480,940 and others. It is also well known that ethylene glycol-t-butyl ether is produced in high yield. However, compared to isoolefins, n-olefins have low reactivity and are difficult to react with, so not many studies have been reported on this type of reaction. Regarding the reaction between AG and n-olefin,
A sufficient conversion rate cannot be obtained at a similar low temperature reduction, and in order to increase the conversion rate, it is necessary to raise the temperature to 120°C or higher.
In that case, the amount of dialkylene glycol (DAG) produced by dehydration condensation of AG, oligomers produced by polymerization of olefin, or polymers obtained by converting them increases, which causes problems such as deterioration of the catalyst. For example, according to Japanese Patent Publication No. 57-35687, butene-1 and ethylene glycol (EG) were reacted at 90°C for 20 hours in the presence of an ion exchange resin, with a conversion rate of 69.5% and a selectivity of 83.4% (secondary It is said that ethylene glycol mono-s-butyl ether (ESB) was obtained as a product (diether 16.6%).
This result is far from practical in terms of reaction rate, and it is clear that when a mixture of butanes and n-butene is used, the conversion rate will be much lower than this due to a decrease in concentration. Therefore, a method of increasing the reaction temperature is considered, but a large amount of diether is already produced as a by-product even under the above conditions, and it is clear that increasing the temperature further will accelerate the formation of polymers and reduce the selectivity. Therefore, increasing the reaction temperature poses a considerable problem in practice. On the other hand, as a method for producing SBA, a method of synthesizing SBA from n-butene using sulfuric acid as a reaction medium (catalyst) is generally well known. but,
This method has many problems, such as causing corrosion of the equipment materials, requiring a large amount of thermal energy to separate the product from the catalyst, and causing environmental pollution. Further, even if phosphoric acid, heteropolyacid, and water-soluble metal salts thereof are used as catalysts, they cannot escape from the same problems as sulfuric acid in that they are water-soluble catalysts. In this regard, if a solid catalyst is used, the reaction product and the aqueous phase can be easily separated, and the used catalyst can be easily recovered. For these reasons,
Many methods using solid catalysts have also been proposed.
However, when using these catalysts, sufficient n
- Requires relatively high temperatures and pressures or large amounts of water to achieve butene conversion. Although the equilibrium in this hydration reaction favors the production of alcohol at low temperature and high pressure, even if the reaction is carried out at the above-mentioned relatively low temperature and high pressure, the alcohol concentration in the distillate is at most 2% or less. This is only possible and requires a fairly large capacity reactor. Furthermore, since a large amount of water is circulated, it is extremely disadvantageous in terms of thermal energy. Styrene-divinylbenzene copolymers with sulfonic acid groups are said to have relatively high catalytic activity for hydration even at relatively low temperatures of 100 to 130°C, but they still require large amounts of water. The thermal energy required for this is enormous. n-
In the hydration of butenes, recycling the SBA-containing aqueous product without thorough stripping is not a desirable method due to the unfavorable effects on the reaction equilibrium. If you try to raise the reaction temperature to a higher temperature in order to obtain an industrially sufficient reaction rate in the first stage, there is a disadvantage that the sulfonic acid group in the catalyst will gradually be removed and deactivated. This is disadvantageous in terms of equilibrium. The use of solvents has been proposed as a way to increase the reaction rate at low temperatures, but this has not yet been effective enough to compensate for the disadvantages of using solvents in terms of separation process and thermal energy. . As a result of intensive research to solve these various problems described above, the present inventors have found that n- By reacting mixtures containing butene or n-butene, the formation of dialkylene glycol (DAG) and polymers can be suppressed, ASB can be obtained in high yield, and the molar ratio of water and n-butene can be reduced to a normal level. We have found that SBA can be simultaneously produced in comparable high yields at values much lower (e.g., 3:1 or less) than those used in hydration (20:1 to 500:1),
The invention has been completed. That is, the gist of the present invention is to add n- to alkylene glycol and 2 to 100 wt% water based on the alkylene glycol using a strong acid type cation exchanger as a catalyst.
Mixtures containing butene or n-butene from 80 to
The present invention resides in a method for simultaneously producing alkylene glycol mono-s-butyl ether and s-butyl alcohol, which comprises bringing them into contact at a temperature of 180°C. In the method of the present invention, n-butene is added to water and
When brought into contact with AG, hydration of n-butene, etherification of AG and hydrolysis of the ether occur simultaneously, and alkylene glycol mono-s-butyl ether (ASB) corresponding to SBA is co-produced. In the present invention, examples of strong acid type cation exchangers that can be used as catalysts include styrene sulfonic acid type cation exchange resins (sulfonated crosslinked copolymers of styrene and polyunsaturated compounds such as divinylbenzene). , phenolsulfonic acid type cation exchange resin (phenolsulfonic acid condensed with formaldehyde), sulfonated coal,
There are those having sulfonic acid groups, such as sulfonated asphalt and sulfonic acid type cation exchange resins in which sulfonic acid groups are bonded to fluororesins (for example, Naphion manufactured by DuPont). Macroporous strong acid cation exchange resins, such as Amberlyst
15, Amberlite 200, etc. are examples of preferred catalysts. Next, n-butene, which is a raw material, may be used alone or as a mixture with butanes. If it contains isobutene, alkylene glycol monot-butyl ether (ATB) and t-butyl alcohol (TBA) are simultaneously produced. Although the separation process becomes a little complicated, it is also possible to react in one step. However, when containing a large amount of isobutene, first react most of the isobutene under low temperature conditions, separate unreacted butenes by liquid-liquid separation, etc., and then react the unreacted butenes under predetermined temperature conditions. It is more preferable to do this. As a mixture containing n-butene, a mixture obtained by extracting and removing butadiene from a _C4 fraction obtained by steam, thermal or catalytic cracking of petroleum, or a mixture containing i-butene is industrially used. Usually used. In addition, as alkylene glycol as a raw material, ethylene glycol (EG), propylene glycol (1,2-, 1,3-) or butylene glycol (1,3-, 1,4-, 2,3-1,2
-) is used. Pentylene glycol, hexylene glycol, etc. also react, but are not practical. Most preferred is the use of ethylene glycol.
There is no need to particularly increase the purity of EG; for example, if it contains a certain amount of products from which unreacted butenes and butanes have been separated by liquid-to-liquid separation or simple distillation after reaction, or if SBA is azeotroped with water, The separated product can be used as a raw material as it is. In that case, ethylene glycol monos
- The effect of improving reactivity due to the solvent effect of butyl ether (ESB) and promoting the production of SBA by hydrolysis of ESB can also be obtained. The main reactions in the method of the present invention are shown below using a chemical formula for 1-butene. Ether reaction CH ₂ =CHCH ₂ CH ₃ +HO-A-OH →C ₂ H ₅ CH(CH ₃ )-O-A-OH (1) Hydration of n-butene CH ₂ =CHCH ₂ CH ₃ +H ₂ O → C ₂ H ₅ CH(OH)CH ₃ (2) Hydrolysis of ether C ₂ H ₅ CH(CH ₃ )-O-A-OH+H ₂ O →C ₂ H ₅ CH(OH)CH ₃ +HO-A-OH (3) However, in the above formula, A is a C ₂ to C ₄ alkylene group. Reaction methods include fixed bed distribution method, fluidized bed method, stirring batch method, stirring continuous method, etc., and raw material supply methods include ascending parallel flow,
Any commonly used method can be used, such as descending parallel flow or countercurrent flow. Water is generally supplied to the reaction system in a mixture with alkylene glycol, but of course it can also be supplied separately. The ratio of water and alkylene glycol to be supplied to the reaction system is water:AG = 2:100 to 100:100 (weight ratio),
Preferably it is 3:100 to 30:100, and if the ratio is expressed as a molar ratio with alkylene glycol as ethylene glycol, water:EG = 6:100 to
The molar ratio is 350:100, preferably 10:100 to 100:100. The molar ratio of glycol:n-butene is approximately 0.5:1
~10:1 is preferred, particularly about 1:1 to 5:1. If the molar ratio of glycol:n-butene is too large, the equipment capacity will be excessive and processing costs will increase; if this molar ratio is too small, the by-product of n-butene oligomers will increase, and the utilization rate of n-butene will decrease. This is not preferable as it also lowers the value. The reaction temperature is about 80-180℃, and 90-150℃
The temperature is preferably 100 to 140°C. 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, and the production of oligomers will increase, which is undesirable. In addition, it is desirable that the reaction pressure be such that the corresponding n-butene can maintain a liquid phase, and generally 10 to 100 kg/
cm ² , preferably 30 to 50 Kg/cm ² . The amount of catalyst to be used relative to all reaction raw materials can be selected within a wide range, but if AG and water are in excess, the concentration of the product in the distillate will be low, which will be disadvantageous in terms of separation and heat costs. In the case of the flow method, the liquid time space velocity (SV) of butenes
is 0.05 to 10 hr ^-1 , preferably 0.1 to 1.0 hr ^-1 ,
The combined SV of AG and water is 0.05 to 20 hr ^-1 , preferably 0.2 to 1.0 hr ^-1 . In the case of batch type, the ratio of catalyst to total raw materials is 5
~30vol%. In the present invention, the volume of the catalyst is shown in the state in which it is swollen to the state of use. The reaction can be carried out in both heterogeneous and homogeneous systems. Since ethylene glycol has low compatibility with hydrocarbons, one method to carry out the reaction in a homogeneous system is to recycle the reaction product containing glycol ethers. 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 present invention, n-butene reacts with water and glycol, and the reaction rate is fast, and the conversion rate and utilization rate of n-butene are high. In the method of the present invention, n-
Although the conversion rate of butene is high, the by-product of n-butene oligomer is small. In addition, glycol is converted into glycol ether, but most of it is glycol monoether, with little glycol diether being produced as a by-product. Glycol monoether has high utility value as a water-soluble solvent. 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. The method of the present invention will be explained in more detail below with reference to Examples and Comparative Examples. Example 1 Put 25 g of Our Burst 15 in a dry state swollen with EG into a 500 ml autoclave.
85 g of the butene fraction listed in Table 1, 167 g of EG,
50 g of water (30 wt% based on EG) was reacted at 130° C. and 60 Kg/cm ² with stirring (500 rpm) for 3 hours. The conversion rate of 1-butene at that time was 43%, and the composition of the reaction product liquid obtained after removing the unreacted butene fraction is shown in Table 2.
Butyl ether (DBE), diethylene glycol (DEG), n-butene dimer (DNB), etc. were not observed.

【table】

[Table] Comparative Example 1 Reaction was carried out under the same conditions as in Example 1 except that EG was 0% without adding water. The 1-butene conversion rate was 52%, but as shown in Table 3, DEG,
DNB was a byproduct.

[Table] Example 2 Amberlyst 15 swollen with water as a catalyst was placed in a stainless steel reaction tube with an inner diameter of 28 mm and a length of 700 mm.
Filled with 350 c.c., and the butene fraction shown in Table 4 was measured at the SV value.
0.12/hr, and a mixture of EG and 22.9wt% water based on EG was supplied from above at an SV value of 0.18/hr, and 130
The reaction was carried out at 50 Kg/cm ² at ℃. At this time, the conversion rate of n-butene (1-butene and 2-butenes) was 53.6%, and the ESB selectivity was
The SBA selectivity was 78.1 mol% and 21.9 mol%.
The composition of the distillate excluding the unreacted butene fraction is shown in Table 5.

【table】

[Table] * Ethylene glycol mono-
t-Butyl ether Example 3 The reaction was carried out under the same conditions as in Example 2, except that the SV value of the mixture of EG and 22.9 wt% water based on EG was set to 0.47/hr. The n-butene conversion rate was 64.5%, with ESB and
The selectivity of SBA was 74.3 and 25.7 mol%, respectively. Example 4 Amberlite 200 was used as a catalyst, the amount of water supplied was 3.9 wt% based on EG, the SV value of the mixed solution of it and EG was 0.27/hr, and the SV value of the butene fraction was
The reaction was carried out under the same conditions as in Example 2 except that the reaction rate was 0.18/hr. The n-butene conversion rate at this time was 53.9%,
The selection rates for ESB and SBA were 87.4 and 87.4, respectively.
It was 11.4 mol%. The composition of the distillate excluding the unreacted butene fraction is shown in Table 6.

[Table] Comparative Example 2 The reaction was carried out under the same conditions as in Example 4, except that the amount of water supplied was 0.2 wt% based on EG. The n-butene conversion rate at this time was 69.1%,
The selectivity of ESB and SBA is 95.3 and 3.8 mol%, respectively.
It was hot. Table 7 shows the composition of the distillate excluding the unreacted butene fraction.

[Table] Comparative Example 3 A reaction with a butene fraction was carried out under the same conditions as in Example 4 except that only water was supplied in the absence of EG. The molar ratio of water to n-butene in the feedstock is
Although the n-butene conversion rate was as high as 12.8%, the conversion rate of n-butene at this time was 11.7%, and as shown in Table 8, the amount of SBA produced in the distillate was 2.7% by weight.

[Table] Example 5 The reaction was carried out under the same conditions as in Example 1 except that 1,2-propylene glycol (PG) was used instead of ethylene glycol (the amount of water supplied was 30 wt% based on PG). The conversion rate of 1-butene was 36%, and Table 9 shows the composition of the reaction product liquid obtained after removing the unreacted butene fraction.

[Table] Example 6 The reaction was carried out under the same conditions as in Example 1 (the amount of water supplied was 30 wt% based on PG) except that 1,3-butylene glycol (BG) was used instead of ethylene glycol. The conversion rate of 1-butene was 28%, and Table 10 shows the composition of the reaction product liquid obtained after removing the unreacted butene fraction.

[Table] Example 7 Put 50 c.c. of Awabarite 200 swollen with water into a 200 ml autoclave, add 25 g of the butene fraction listed in Table 11, 83 g of 1,2-propylene glycol (PG), and water. 88 20g (24wt% based on PG standard)
The reaction was allowed to proceed for 5 hours at 25 Kg/cm ² with stirring (500 rpm). Butene (isobutene, 1-
The conversion rate of (butene and 2-butenes) was 41%, and the composition ratio of the reaction product excluding unreacted butene fraction, water and PG is shown in Table 12. No duplexes of butenes were observed.

【table】

【table】

Claims (1)

[Claims] 1 Based on alkylene glycol and alkylene glycol using a strong acid type cation exchanger as a catalyst
A method for simultaneously producing alkylene glycol mono-s-butyl ether and s-butyl alcohol, which comprises contacting n-butene or a mixture containing n-butene with ~100 wt% water at a temperature of 80 to 180°C.