JPH06102632B2 - Method for producing 1,4-butanediol - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing 1,4-butanediol. 1,4-Butanediol is an important chemical raw material, generally polybutylene terephthalate
(PBT), polyurethane (PU), tetrahydrofuran
(THF), γ-butyrolactone, and other high value-added polymers or chemical products. Conventionally, 1,4-butanediol was produced by the Reppe process using acetylene and formaldehyde as starting materials. However, since acetylene as a raw material is limited in terms of supply and is expensive, this method may rapidly become uneconomical in the future. Therefore, a production method that does not use acetylene as a raw material has been expected.

[0002]

2. Description of the Related Art Of the various methods for producing 1,4-butanediol that does not use acetylene, the method using allyl alcohol as a raw material is said to have the most potential.
The production method is to obtain 1,4-butanediol by hydrogenating an intermediate product 4-hydroxybutyraldehyde obtained by hydroformylation of allyl alcohol in the presence of carbon monoxide and hydrogen in the presence of hydrogen. is there. The chemical reaction formula is as follows.

[Chemical 1]

[Chemical 2]

The study of the hydroformylation reaction of allyl alcohol was first published in 1948.
Adkins and Gee. Research paper by Kuresec [Journal of the American Chemical Society. 7
Volume 8, 388- (1948) and Volume 79, 3051-
(1949)]. The study uses tetracarbonylhydrocobalt [HCo (CO) 4] as a catalyst for the hydroformylation reaction, but it has low catalytic activity and requires reaction at high temperature and high pressure. The 4-hydroxybutyraldehyde yield and selectivity were very low. Then C. Kay, Brown. Gee. Wilkinson [Tetrahedron Letters, 22nd
, 1725 (1969) and Journal of the Chemical Society (A), 2753- (1970)
Year)] and Be Fel. M. Barr [Hemiker Zaiting, Vol. 101, pp. 343- (1977)], etc., is a rhodium compound whose main component is hydrocarbonyltris (triphenylphosphine) rhodium in the production method of H. Adkins and G. Cresek. And a tri-substituted phosphine ligand (ligand) are used as a catalyst system to increase the reaction speed 100 to 1000 times,
The yield and selectivity of hydroxybutyraldehyde were greatly improved, and it was put into practical use.

Since allyl alcohol as a raw material is not a compound produced in a large amount, whether the production method itself is competitive in order to enable commercialization of the method for producing 1,4-butanediol. In addition to the above problem, it becomes a problem regarding whether or not the supply amount and supply price of allyl alcohol can be commercialized. Conventionally, allyl alcohol has been produced by one of the following three methods. 1. Isomerization of propylene oxide

[Chemical 3] 2. Hydroxylation reaction of allyl chloride

[Chemical 4] 3. Acrolein hydrogenation reaction

[Chemical 5] However, all of the above-mentioned three methods are not suitable for the production of 1,4-butanediol because the production cost of allyl alcohol is very high.

Therefore, a new method for producing allyl alcohol was developed, which reduced the production cost and enabled mass production. Therefore, from allyl alcohol 1,4-
The manufacturing method for producing butanediol has become more competitive. In this novel production method, allyl acetate and water are produced by acetic acid reaction of propylene, acetic acid and oxygen, and allyl acetate is hydrolyzed to obtain allyl alcohol. The chemical reaction formula is as follows.

[Chemical 6]

[Chemical 7]

The allyl alcohol obtained by this method contains about 30% water and a small amount of allyl acetate, and its composition is close to the azeotropic composition of allyl alcohol and water.
It is difficult to separate allyl alcohol. Therefore, refining this azeotrope increases the production cost, and once pure allyl alcohol is obtained and 1,4-butanediol is produced from this, the cost is increased and the competitiveness is reduced. .

Japanese Patent Publication Sho 51-Kuraray Co., Ltd.
In 29412 (1976), a method for producing 1,4-butanediol from pure allyl alcohol was published. The method is a method for producing 1,4-butanediol by hydroformylation of pure allyl alcohol, carbon monoxide and hydrogen in an organic solvent of a carbonyl complex compound catalyst containing rhodium. Then, the reaction mixture is extracted with water and the organic phase containing the catalyst and the aqueous phase containing the aldehyde are separated. Then, the organic phase is recycled in the hydroformylation system, and the aqueous phase is added with hydrogen to produce 1,4-butanediol.

This production method is characterized in that after the hydroformylation reaction, the hydroformylation product can be extracted to separate the hydroformylation catalyst. The separation of the hydroformylation product and the hydroformylation catalyst has conventionally been carried out by a distillation method (J. Farbe, Ed., New Synthesis with Carbon Monooxide, Springer Burlag 1980, p.171-). However, since distillation needs to be operated at higher temperatures, aldehydes tend to be high boiling products, which can accumulate in the reaction system, degrading catalyst activity. In this respect, the method of Kuraray Co., Ltd. does not have the above-mentioned drawbacks.

The method of Kuraray Co., Ltd. does not have the above-mentioned drawbacks, but this method is particularly suitable only for a system using purified allyl alcohol as a raw material. The production cost is high when a highly pure allyl alcohol is produced from this and used as a raw material. Further, when allyl alcohol containing allyl acetate and water is used as the first raw material, there is a drawback that the activity of the catalyst of the hydroformylation reaction system is lowered (see JP-A-50-30809 and JP-B-5725018). Kuraray Co., Ltd. has proposed the method of Japanese Examined Patent Publication No. 57-25018 as a manufacturing method using allyl alcohol containing this allyl acetate as the first raw material.

The method is such that after the hydroformylation product is extracted with water, a part of the hydroformylation catalyst solution is taken out and brought into contact with an alkaline aqueous solution, and the hydroformylation catalyst solution is recovered and used in the hydroformylation system. Is. While this method stabilizes the activity of the hydroformylation catalyst, it only solves some of the problems, and many problems remain in the process, as also discussed below. Thus, the method of stabilizing the activity of the hydroformylation catalyst of Kuraray Co., Ltd. is not the best method.

[0011]

DISCLOSURE OF THE INVENTION The present inventors have studied for many years and found that the activity of hydroformylation catalysts in a process for producing 1,4-butanediol using allyl alcohol containing allyl acetate and water as a starting material. The cause of the decrease was found. That is, it was clarified that the acidic substance obtained by the hydrolysis of allyl acetate is one of the causes of the decrease in the activity of the hydroformylation catalyst. The method of Japanese Examined Patent Publication (Kokoku) No. 57-25018 solves the problem that the activity of the hydroformylation catalyst is lowered, but after the hydroformylation reaction, the hydroformylation catalyst requires a two-step treatment of extraction with water and an alkaline aqueous solution. And in the second stage, when extracting with an alkaline aqueous solution, wastewater is produced. Since the acetic acid is contained in the water phase during the extraction with water in the first step, adverse effects such as impurities and high boiling point products gradually appear in the subsequent hydrogenation reaction. And that method also needs to be improved.

The method for producing 1,4-butanediol of the present invention is intended to solve the drawbacks of the conventional method for producing 1,4-butanediol using allyl alcohol containing allyl acetate and water as a starting material. After the hydroformylation reaction, the hydroformylation product is extracted with an alkaline aqueous solution in the presence of one or both of carbon monoxide and hydrogen, and the rhodium-containing complex compound solution remaining after the extraction is recovered, and the next hydroformylation product is recovered. Used for chemical reaction. Then, a hydrogenation catalyst was added to the extract and hydrogenation was performed in the presence of hydrogen to obtain 1,4
To produce butanediol. This method not only solves the problem existing in the Kuraray Co., Ltd. manufacturing method,
The processing method has also become easier.

[0013]

Therefore, according to the present invention,
An improved method for producing 4-butanediol, in which allyl alcohol containing allyl acetate and water obtained from allyl acetate, an organic solvent, a rhodium complex compound catalyst, and a tri-substituted phosphine in the presence of carbon monoxide and hydrogen, A hydroformylation reaction is carried out, the hydroformylation product is then extracted with an alkaline aqueous solution, and the extraction residual liquid of the rhodium-containing complex compound is recovered and used for the next hydroformylation reaction. Then, a hydrogenation catalyst is added to the extract, and hydrogenation is performed in the presence of hydrogen to produce 1,4-butanediol. This manufacturing method of the present invention eliminates the drawbacks of the method of Japanese Patent Publication No. 57-25018, and the processing procedure is simpler.

The catalyst used in the hydroformylation reaction in the present invention comprises a rhodium complex compound and a phosphine compound ligand. Rhodium complex compounds include hydrocarbonyl tris (triphenylphosphine) rhodium, chlorocarbonylbis [triphenylphosphine] rhodium, acetylacetonatocarbonyl (triphenylphosphine).
Rhodium is used. The activity of such rhodium complex compounds is so high that they catalyze at low temperatures, low pressures and low concentrations. During the progress of the hydroformylation reaction, 4
-With the production of hydroxybutyraldehyde,
2-Methyl-3-hydroxypropyl aldehyde is produced. It is necessary to add a tri-substituted phosphine ligand into the catalyst to reduce the production of its isomers and to stabilize the hydroformylation catalyst. This tri-substituted phosphine compound is, for example, triphenylphosphine, para-bromophenyldiphenylphosphine, butoxydiphenylphosphine, n-butyldiphenylphosphine, t-butyldiphenylphosphine, cyclohexyldiphenylphosphine, di-n- Butylphenylphosphine, ethyldiphenylphosphine, heptyldiphenylphosphine, hexyldiphenylphosphine, methyldiphenylphosphine, isopropyldiphenylphosphine, O-
Trilyldiphenylphosphine, p-tolyldiphenylphosphine, triisobutylphosphine, tri-n-butylphosphine and the like are 1,4-bis (diphenylphosphino) butane as bistri-substituted phosphine compounds,
1,3-bis (diphenylphosphino) propane, 1,2-
Bis (diphenylphosphino) ethane, 2,3-O-isopropylidene group-2,3-dihydroxy-1,4-bis
(Diphenylphosphino) butane, trans-1,2-
There are bis (diphenylphosphinomethyl) cyclobutane and the like, and examples of the ferrocene compound include 1,1-bis (diphenylphosphino). When rhodium is used as the complex compound catalyst in the present invention, the concentration of rhodium is about 0.5 to 20 mM, preferably 1 to 10 mM. The molar ratio of the tri-substituted phosphine compound to rhodium is about (3 to 1000): 1 and (30 to 35).
0): 1 is preferred.

The organic solvent used for the hydroformylation reaction is an organic solvent in which the hydroformylation catalyst is easily dissolved and has poor mutual solubility with water, and among them, aromatic compounds are particularly suitable, for example, benzene / toluene / xylene /
Most suitable are mesitylene, chlorobenzene, promobenzene, dichlorobenzene, chloromethylbenzene, and bromomethylbenzene. The amount of the organic solvent used is 1 to 15 times the weight of the allyl alcohol raw material.

In the present invention, since the extraction method is different from the conventional method,
As the first raw material of allyl alcohol used in the hydroformylation reaction, since the crude allyl alcohol containing allyl acetate and water obtained from allyl acetate can be used as it is, the treatment cost of the crude allyl alcohol is not necessary, and The production cost of 1,4-butanediol can be reduced and competitiveness can be enhanced.

Since the pressure and temperature of the hydroformylation reaction and the molar ratio of hydrogen to carbon monoxide affect the reaction rate and selectivity, the operating pressure is usually -100 kg / cm ² G, preferably 3-15 kg / cm ² G. Is. Operating temperature is 0 ℃ ~ 150
The temperature is 50 ° C, but preferably 50 to 100 ° C. The molar ratio of hydrogen to carbon monoxide is 0.1 to 10, preferably 0.5 to 3.

After completion of the hydroformylation reaction of the production method of the present invention, the hydroformylation product is treated with an alkaline aqueous solution.
It is possible to reduce the amount of acidic substances in the hydroformylation catalyst solution at the same time as the extraction with the (extractant). In this case, regarding the hydrogenation reaction after extraction, when considering high boiling point compounds and impurities that are difficult to separate, the pH of the extraction liquid (aqueous phase)
It is necessary to adjust the pH of the alkaline aqueous solution so that the pH becomes 5.0 to 9.0. The alkaline aqueous solution is prepared by mixing a compound such as a hydroxide compound or a carbon salt or an acetate salt with pure water. It is also necessary to consider the amount of extractant used. If the amount of the extractant used is too small, the extraction efficiency will be low. Since the temperature of the hydroformylation product in the extract is high, the amount of by-products produced increases and the yield of 1,4-butanediol decreases as the hydrogenation reaction proceeds. Therefore, it is not preferable that the amount of the extractant used is too small. However, if the amount of the extractant used is too large, the extraction efficiency will be high, but the concentration of the hydroformylation product will be low, and therefore the reaction rate will be slow when the hydrogenation reaction proceeds. Therefore, it is necessary to increase the volume of the hydrogenation reactor. The amount of the extractant used (and hence the dose of the extract) is preferably about 1 to 20 times the weight of the raw material allyl alcohol.

As the hydrogenation catalyst used in the hydrogenation reaction of the present invention, a catalyst supported on a metal carrier such as palladium, rhodium, nickel, ruthenium, cobalt or platinum, an acid compound catalyst such as rhenium oxide or copper chromium oxide, and Raney nickel and the like are preferable, and nickel, a catalyst supported on a ruthenium metal carrier, copper chromium oxide, and Raney nickel are particularly preferable. The amount of hydrogenation catalyst used is preferably 5 to 40% by weight of allyl alcohol.

The hydrogenation pressure is 10 to 100 kg / cm ² G
Therefore, 20 to 60 kg / cm ² G is preferable. Reaction temperature is 50
The temperature is preferably 70 to 130 ° C. Examples of the present invention will be shown below, but this does not limit the scope of the present invention.

Example 1 Hydrocarbonyl tris (triphenylphosphine) rhodium 0.184 g, triphenylphosphine 7.711 g,
21.250 g of allyl alcohol, 2.360 g of water and 1,
86.370 g of 3,5-trimethylbenzene (meditylene)
Was placed in a stainless sleeve type stirred reactor (referred to as a hydroformylation reactor), and the pressure inside the reactor was adjusted with hydrogen and carbon monoxide (molar ratio 1.2) while maintaining the temperature of the reactor at 68 ° C. The hydroformylation reaction was carried out for 3.5 hours, maintaining the pressure at 4.4 kg / cm ² G. The conversion rate of allyl alcohol was 99%.

Next, the reaction solution was extracted with 93.4 ml of water in the presence of hydrogen and carbon monoxide (molar ratio 1), and the upper layer 1,3,5-trimethylbenzene solution containing the hydroformylation catalyst was extracted. A lower layer aqueous solution containing the hydroformylation product was obtained. This upper layer liquid was further put in the above-mentioned hydroformylation reactor and the above-mentioned reaction was repeated, and the lower layer liquid was a separate stainless sleeve type agitator (referred to as hydrogenation reactor).
5,000 g of hydrogenation catalyst (Ni-3266P, manufactured by Hershaw / Filtrol Co., USA) was added to
At a temperature of 86 ° C, the pressure in the reactor was adjusted to 80 kg / with hydrogen.
The hydrogenation reaction was carried out for 8 hours while maintaining cm ² G. As a result, 24.006 g of 1,4-butanediol, 6.398 g of 2-methyl-propanediol, and 0.3 of propanol.
721 g were obtained.

21.250 g of allyl alcohol, 2.360 g of water and 0.333 g of allyl acetate were added to the solution of the hydroformylation catalyst returned to the above hydroformylation reactor.
And hydrogen and carbon monoxide at a temperature of 68 ° C.
The hydroformylation reaction was carried out for 3.5 hours while maintaining the internal pressure of the reactor at 4.4 kg / cm ² G (molar ratio 1.2). The conversion of allyl alcohol was only 42%.

Next, the reaction solution was treated with hydrogen hydroxide and carbon monoxide (molar ratio 1) in the presence of sodium hydroxide aqueous solution (pH 12.
5) Extraction was performed with 93.4 ml to obtain a layered solution of an upper layer 1,3,5-trimethylbenzene solution containing a hydroformylation catalyst and a lower layer aqueous solution containing a hydroformylation product. Of lower layer liquid
The pH value was 8.6. The upper layer liquid thus obtained was returned to the above-mentioned hydroformylation reactor and the reaction was repeated.

To the solution returned to the hydroformylation reactor described above, 21.250 g of allyl alcohol, and 2.3 of water.
The hydroformylation reaction was carried out by adding 60 g. As in the above case, at a temperature of 68 ° C., hydrogen and carbon monoxide (molar ratio 1.2) were used to increase the pressure in the reactor to 4.4 kg / cm ^2.
Maintained at G and reacted for 3.5 hours. As a result, the conversion rate of allyl alcohol was 99%.

Next, the reaction solution was extracted with 93.4 ml of water in the presence of hydrogen and carbon monoxide (molar ratio 1), and the separated lower layer solution was put into a hydrogenation reactor to carry out hydrogenation. Catalyst 5.032g
Was added, and the reaction was carried out for 8 hours at a temperature of 86 ° C. while maintaining the pressure in the reaction solution with hydrogen at 80 kg / cm ² G. As a result, 23.764 g of 1,4-butanediol, 6.270 g of 2-methyl-1,3-propanediol and 0.731 g of propanol were obtained.

Comparative Example 1 As in Example 1, except that in the reaction process of Example 1, the hydroformylation reaction, which was carried out by extraction with an aqueous sodium hydroxide solution having a pH value of 12.5, was carried out in air. The raw materials were fed under the same conditions to carry out the reaction. The catalyst solution obtained by this reaction was returned to the hydroformylation reactor again, and the reaction was carried out for 3.5 hours. As a result, the conversion rate of allyl alcohol was only 9%.

Example 2 In the reaction process of Example 1, the same conditions as in Example 1 were used except that the hydroformylation reaction carried out by extraction with an aqueous sodium hydroxide solution having a pH of 12.5 was carried out in hydrogen. The raw materials were supplied to carry out the reaction. The catalyst solution obtained in this reaction was returned to the hydroformylation reactor again,
The reaction was carried out for 3.5 hours. As a result, the conversion rate of allyl alcohol was 99%.

Example 3 Hydrocarbonyl tris (triphenylphosphine) rhodium 0.514 g, triphenylphosphine 1.322 g,
2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino) butane 1.255
g, 21.250 g of allyl alcohol, 2.500 g of water, 0.184 g of allyl acetate and 87.800 g of benzene were placed in a stainless sleeve type stirring reactor (hydroformylation reactor), and the temperature inside the reactor was kept at 70 ° C. , Hydrogen and carbon monoxide (molar ratio of 1.5) were used to carry out the reaction for 3.5 hours while maintaining the pressure in the reactor at 5 kg / cm ² G. The conversion rate of the obtained allyl alcohol was only 64%.

Next, the reaction solution was treated with hydrogen and carbon monoxide (molar ratio 1) in the presence of an aqueous solution of potassium hydroxide (pH 12.
3) Extraction was performed with 110 ml to obtain a separated layer liquid of an upper layer benzene solution containing a hydroformylation catalyst and a lower layer aqueous solution containing a hydroformylation product. The pH of the lower layer aqueous solution was 7.7. The upper layer liquid was returned to the above hydroformylation reactor.

In the hydroformylation reactor in which the above hydroformylation catalyst was returned, allyl alcohol 21.25 was added.
0 g and 2.500 g of water were added, and the hydroformylation reaction was further carried out. In this reaction, hydrogen and carbon monoxide (molar ratio of 1.5) were used at a temperature of 70 ° C. and a pressure of 5 k in the reactor.
It was carried out for 3.5 hours while maintaining g / cm ² G, and as a result, the conversion rate of allyl alcohol was 99%.

Then, the reaction solution is treated with hydrogen and carbon monoxide.
In the presence of (molar ratio 1), extracted with 110 ml of water, the separated lower layer liquid was put into a hydrogenation reactor, and the hydrogenation catalyst was added thereto.
(Hoechst RCH Nickel 152/35) 5.621g
Was added, and the hydrogenation reaction was carried out for 8 hours while maintaining the pressure in the reactor at 80 kg / cm ² G with hydrogen at a temperature of 85 ° C. And 25.512 g of 1,4-butanediol,
There were obtained 3.071 g of 2-methyl-1,3-propanediol and 1.792 g of propanol.

Example 4 A continuous hydroformylation reaction and an extract were carried out. A stainless sleeve type stirred reactor was used for the hydroformyl reaction, and a packed bed tower type extraction tower was used for the extraction. The hydroformylation reaction is carried out using hydrocarbonyl tris (triphenylsulfosphine) rhodium (concentration 2 mmo
le / l), triphenylphosphine 320 mmole / l, catalyst solution average residence time 3.5 hours, allyl alcohol supply
(Containing 10% wt of water and 0.004% wt of allyl acetate) 52.2g
/ Hr, reaction temperature 65 ° C., reaction pressure 4.2 kg / cm ² G, and the molar ratio of hydrogen to carbon monoxide was 1; The extraction was carried out under the conditions that the injection amount of water was 486 ml / hr and the amount of the hydroformyl reaction solution introduced was 310 ml / hr; with the extraction tower filled with hydrogen and carbon monoxide.

The average allyl alcohol conversion rate for 5 days after the start of the reaction was 92%. The extract (aqueous phase) was hydrogenated in a hydrogenation reactor using a Hershaw / Phytolol Ni-3266p hydrogenation catalyst, resulting in 1,4-
The butanediol selection rate was 66.1%, the 2-methyl-propanediol selection rate was 30.2%, and the propanol selection rate was 2.2%.

The continuous hydroformylation reaction and the operation of the extraction system were continued for 25 days, resulting in a conversion of allyl alcohol of 67%. Next, the hydroformylation product was extracted using an aqueous sodium hydroxide solution instead of water as an extractant for the extraction tower. The injection amount of this extractant is 3
It was kept constant at 10 ml / hr. However, the pH of the extractant was finely adjusted so that it was between 9.5 and 11.5, and the pH value of the extract was adjusted to be between 5 and 9. After continuing the operation for another 5 days, the conversion rate of allyl alcohol became 93%, and the selection rate after hydrogenation of the extract (aqueous phase) was 66.6% for 1,4-butanediol and 2-methyl 1,3-propanediol was 30.8% and propanol was 2.2%.

Example 5 A continuous hydroformylation reaction and extraction were carried out.
A stainless sleeve type stirring reactor was used for the hydroformylation reaction, and a packed bed tower type extraction tower was used for the extraction. In the hydroformylation reaction, hydrocarbonyl tris (triphenylphosphine) rhodium was used at 2 mmole / l and triphenylphosphine at 320 mmole / l, the average residence time of the catalyst solution was 3.5 hours, the amount of allyl alcohol supplied (water 11% wt, acetic acid (Including allyl 0.009% wt) 52.6 g /
hr, the reaction temperature was 65 ° C., the reaction pressure was 4.2 kg / cm ² G, and the molar ratio of hydrogen to carbon monoxide was 1; The extraction was carried out by injecting the extractant at a rate of 465 ml / hr, and introducing the hydroformylation reaction solution at a rate of 312 ml / hr; using an aqueous sodium hydroxide solution as the extractant, the pH value of which was 9-11. PH value of the extract is 5
I made it between ~ 9.

Extraction was carried out with hydrogen and carbon monoxide enclosed in the extraction tower. The average propanol conversion rate for 5 days after the start of the reaction was 93%. And extract
After hydrogenation of (aqueous phase), the selection rate of 1,4-butanediol was 66.6%, the selection rate of 2-methyl-propanediol was 30.8%, and the selection rate of allyl alcohol was 2.2%. there were. The conversion rate of allyl alcohol after continuously operating the hydroformylation reaction and the extraction system for 25 days was 93%, and the selection rate after hydrogenation of the extract (aqueous phase) was 5 days. Was the same as

Claims (3)

[Claims] 1. A hydroformylation reaction of allyl acetate obtained by hydrolyzing allyl acetate and allyl alcohol containing water, an organic solvent, a rhodium complex compound catalyst and a tri-substituted phosphine compound in the presence of carbon monoxide and hydrogen. Then, the hydroformylation product is extracted with an alkaline aqueous solution, the extraction residual liquid of the rhodium-containing complex compound is recovered and subjected to the next hydroformylation reaction, and a hydrogenation catalyst is added to the extraction liquid to remove hydrogen. A method for producing 1,4-butanediol, which comprises hydrogenating in the presence. 2. The method for producing 1,4-butanediol according to claim 1, wherein the dose of the extract is 1 to 20 times the weight of allyl alcohol. 3. The method for producing 1,4-butanediol according to claim 1, wherein the pH of the extract is adjusted to 5-9.