JPS635043A - Production of 2c alcohol - Google Patents

Abstract

PURPOSE:To produce a 2C alcohol such as ethylene glycol, ethanol, etc., from carbon monoxide and hydrogen in liquid phase in high efficiency, by carrying out the reaction in the presence of a rhodium-based catalyst and a pyrrolidine compound in the reaction system. CONSTITUTION:Carbon monoxide is made to react with hydrogen in the presence of a rhodium-containing catalyst (rhodium compound or rhodium metal may be used as the catalyst) to obtain a 2C alcohol such as ethylene glycol, ethanol, etc. The alcohol can be produced in high efficiency and exceptionally high catalytic activity and selectivity by carrying out the reaction in the presence of a pyrrolidine compound of formula (R is alkyl or hydroxyalkyl; R' is H, alkyl or hydroxyalkyl) (e.g. N-methyl-pyrrolidine) in the reaction system. The pyrrolidine compound may be used as a reaction solvent and the amount of the pyrrolidine compound is preferably >=3wt% of the whole solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for efficiently producing alcohols such as ethylene glycol and ethanol from -oxidized carbon and hydrogen by liquid phase reaction.

Ethylene glycol is used as a raw material for polyester, a freezing agent, etc., and ethanol is used for solvents, additives, antifreeze agents, and various chemical raw materials.It is also possible to use it as a raw material for ethylene, both of which are industrially useful. It is an important basic chemical product.

[Conventional technology]

Conventionally, these alcohols with 2 carbon atoms (C2 allure)
C2 was mainly produced using petroleum as a raw material, but in recent years, with the aim of diversifying chemical raw materials, such C2 Section J where the development of technology to manufacture Allure is important
Befriend giants.

A method using a rhodium catalyst has also been proposed. Many proposals have already been made regarding methods using upper rhodium catalysts, and quaternary ammonium salts (Japanese Unexamined Patent Application Publication No. 1973
1-32506), AL-42809, and Japanese Unexamined Patent Publication No. 52-42810. Further, JP-A No. 55-9065 describes a method in which phosphine oxyto is coexisting with an acid. Further, JP-A-60-136524 and JP-A-60-149537 describe a method using trialkylylphosphine. [Problem to be solved by the invention] However, in the above method, the production activity of C2 alcohol per catalyst metal (number of turnovers: number of moles of acid/(
In addition to the problem of low carbon catalytic metal (catalyst metal) and reaction time, it also reduces by-products of methanol and formic acid, and reduces C2
There is a practical need to improve alcohol selectivity.

[Means for solving problems]

As a result of extensive research in order to overcome the above problems, the present inventors have discovered that by using a rhodium-containing catalyst and allowing collidines to exist in the reaction system when reacting carbon oxide and hydrogen, The present invention was based on the discovery that uniquely high catalytic activity and speed could be obtained from the results of a method that could not be predicted. That is, the present invention provides a method for producing ethylene glycol and ethanol, which is characterized by using a rhodium-containing catalyst and allowing birolines to be present in the reaction system when reacting -carbon and hydrogen. It is something that

According to the present invention, C2 alcohols such as ethylene glycol and ethanol can be produced with high selectivity from synthesis gas by liquid phase reaction, so the present invention has great significance.

The present invention will be explained in detail below.

The PIOIJ resin used in the present invention is represented by formula (1).

It is a hydroquine alkyl group in which a group or a part of the alkyl group is substituted with an OH group. Further, R' is H, an alkyl group or a hydroxyalkyl group.

The molar ratio of carbon monoxide and hydrogen used in the present invention is usually C
o:H2=1:10 to 5:1, preferably 1:4 to 2:1. The pressure of this mixed gas (synthesis gas) is 250kg/12~3000kg/CIr
L2 preferably 300kg/cIrL2~2000kg
/CTL2 range. The pyrrolidines of the present invention can be used as reaction solvents. It can also be used after being diluted with a suitable diluent. As the diluent, those commonly used in this type of reaction can be used, but preferred diluents include hydrocarbons such as tocite, toluene, xylene, therine, hexane, and peptane, and N-thylpyrrolidone and N-ethylpyrrolidone. Pyrrolidones, N N
The '-dimethylimidazolidino diluents can be used alone or in mixtures.

Although any ratio of pyrrolidines to diluent can be used, the ratio of pyrrolidines to the total solvent is usually l wt
% or more, preferably 3 wt% or more.

In the present invention, any rhodium compound or rhodium metal can be used as a catalyst as long as it can produce soluble active species under the reaction conditions.

Examples of the rhodium compound include tetrarhodium dodecacarbonyl, tris(acetylacetone)rhodium, acetylacetonatodicarbonylrhodium, and acid rhodium.

The catalyst concentration in the reaction solvent is usually 0.0IX109-atom to 5p-a in terms of metal rhodium.
tom range, preferably 0. lX10 p-
The range is from atom to 1,9-atom. Although the reaction temperature is in the range of 150 to 350°C, it can be easily carried out by a more preferred known method.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 A tetrarhodium dodecacarbonyl reaction was carried out with 7 ml of N-methylpyrrolidine in a 20-liter autoclave (manufactured by Inconel Steel) that was purged with nitrogen. After the reaction,
The autoclave was cooled and the product was analyzed by gas chromatography, which revealed 22.05 mmol of ethylene glycol, 10.02 mmol of ethanol, and 1.1 mmol of methanol.
3 mmol and 0.18 mmol of methyl formate were obtained.

The turnover number of ethylene glycol and ethanol is different.The selectivity is expressed as carbon efficiency as shown in the following formula.

MeOH: Number of moles of methanol produced, MF: Number of moles of methyl formate produced, EtOH: Number of moles of ethanol produced, E
G: Number of moles of ethylene glycol produced Comparative Example I When the reaction was carried out under the same conditions as in Example 1 except that 1-(3-methylbutyryl)pyrrolidine was used instead of N-methylpyrrolidine, 0.45 mmol of ethylene glycol, Only 0.20 mmol of ethanol and 0.14 mmol of methanol were obtained.

Comparative Example 2 A reaction was carried out under the same conditions as in Example 1 except that pyrrolidine was used instead of N-methylbiclizine and the reaction temperature was 230°C. As a result, 4.96 mmol of ethylene glycol,
0.27 mmol of ethanol, 212 mmol of methanol and 0.9 mmol of methyl formate were obtained. The turnover numbers of ethylene glycol and ethanol are 198 mol/C9-atOm Rh) h and l, respectively.
Q, 3m01/ (,9atom Rh) h and ivy. The selectivity of C2 alcohol was 82.6%.

Comparative Example 3 N-methyl biO instead of 7 ml of N-methylpyrrolidine
When the reaction was carried out under the same conditions as in Example 2 except that 7 ml of lydone was used, 0.69 mmol of ethylene glycol and 0.14 mmol of methanol were obtained. Turnover number of ethylene glycol: d27.5 mol
/ (g-atom Rh) hte was there.

Example 3 Ethylene glycol 5.80 mmol, ethanol 04
3 mmol, methanol 11.46 mmol and methyl formate 1.51 mmol were obtained. The ter7 over number of ethylene glycol is 58.011101/ (g-at
om Rh) hteatsuta.

Comparative Example 4 The same conditions as in Example 3 were used except that 7 mi of toluene was used instead of 2 ml of l-(2-hydroxyethyl)pyrrolidine and 5 ml of toluene. As a result, 0.14 mmol of ethylene glycol, 7.55 mmol of methanol 315 mmol of methyl formate were obtained.

No ethanol production was observed. Ethylene glycol turnover aU1.4m○l/U-atom
Rh) It was h.

Example 4 Same as Example 1 except that the reaction temperature was 250°C.
Rh) It was h. Additionally, 147 mmol of methanol and 0.24 mmol of methyl formate were obtained.

Example 5 1-Methyl-2-pyrrolidineethanol 7 as a solvent
Anti-Gt was conducted under the same conditions as in Example 4 except that ml was used. In this case, the amount of ethylene glycol produced was 869 mmol, and the amount of ethanol produced was 1.78 mmol. Additionally, 2.94 mmol of methanol and 0.14 mlJ mole of methyl formate were obtained.

The turnover number of ethylene glycol was 6t348.

Comparative Example 5 N-)Tylpyrrolidine 7 Instead of rnlO, 2 ml of N-methylpyrrolidine and 5 triphthylphosphine oxides
The reaction was carried out under the same conditions as in Example 1 except that 0.30 mmol of ethylene glycol and 1 to 2 ml of ethane were used.
The reaction was carried out under the same conditions as in Comparative Example 5 except that 2 ml of -hydroquinethyl)pyrrolidine and 5 ml of N-ethylpyrrolidone were used. 600 mmol of ethylene glycol, 3.8 mmol of ethanol, 171 mmol of methanol, and 11 mmol of methyl formate O. I got it.

Example 7 7 ml of N-methylpyrrolidiy and 0.025 mmol of tetrarhodium dodecacarbonyl were charged into an autoclave, and the amount was 1800 kg/crn in the same manner as in Example 1.
.

When the reaction was carried out at 230°C for 1 hour, 6.69 mmol of ethylene glycol, 046 mmol of ethanol,
606 mmol of methanol and 0.35 mmol of Qb chill were obtained. The turnover number of ethylene glycol is 66
．． g mol /Qq -atom Rh) h Tatsuta.

Example 8 0.57 mmol of givamethyl was obtained. The turnover number of ethylene glycol was 927. Compared to Example 7, the amount of C2 alcohol produced increased.

Example 9 A reaction was carried out in the same manner as in Example 7 except that 5 ml of N-methylpyrrolidine was coexisting with 1 ml of N,N'-dimethylimidazolidinone, and 9.69 mmol of ethylene glycol,
2.10 mmol of ethanol, 12.45 mmol of methanol, and 0.69 mmol of methyl formate were obtained. Example 7
The amount of C2 alcohol produced increased compared to the above.

Example 1O N-methylpyrrolidine 2ml, tetrahydrofuran 5v
The reaction was carried out under the same conditions as in Example 3 except that rlk was used, and 9.90 mmol of ethylene glycol, 92 mmol of ethanol Q, 15.07 mmol of methanol, and 0.95 mmol of methyl formate were obtained. When the reaction was carried out under the same conditions as in Example 10, except that 7 rnl of tetrahydrofuran was used instead, 1.54 mmol of ethylene glycol, 10.33 mmol of methanol, and 2.36 mmol of methyl Gibin were obtained. The turnover number of ethylene glycol is 15.4rnol/
(g-atom Rh) h.

Implementation 82 Li 11 An autoclave (manufactured by Steloy C) equipped with a magnetic induction stirring device with an internal volume of 40 m1 was replaced with nitrogen gas, and acetylacetonate (biscarbonyl) rhodium 0.1 mmol and triinpropylphosphine 0.5 mmol,
2 ml of N-methylpyrrolidine, 3 ml of tetraglyme
was charged and replaced with a mixed gas of CO:H2=1:1.

Next, the autoclave was filled with a mixed gas of the same composition at 360 kg/ctrt2 at room temperature, and when the temperature of the reaction system reached 230'C, 10% ethylene glycol, 3.46 mmol ethylene glycol, and 0.16 mmol ethanol were added. 4.62 mmol of methanol, 0.14 mmol of methyl formate, trace amounts of 1,2 propanediol, glycerin, and trace amounts of methane and CO2 as gas products were detected.

Ethylene glycol turnover PH34,5mo
l / (g-atom Rh) h teatsu7'(.

Example 12 Under the conditions of Example 11, the pressure of the mixed gas was 490 kg at room temperature.
The reaction was carried out under the same conditions except that /C7n2 was used. The maximum pressure when the reaction temperature is reached is approximately 685
' was 9/crn2.

Gas chromatographic analysis of the reaction products revealed 51 mmol of ethylene glycol, 0.20 mmol of ethanol, 3.88 mmol of methanol, and 0.1 mmol of methyl formate.
Example 13 A reaction was carried out for 2 hours under the conditions of Example 11, except that N n-octylpyrrolidine was used in place of N-methylpyrrolidine.

The analysis results of the reaction product by gas chromatography showed that ethylene glycol 5. loa mmol, ethanol 0.1
3 mmol of methanol, 4.31 mmol of methanol, 7' o pandiol, glycerin, methane, CO2, etc. were produced. At this time, the turnover number of ethylene glycol is 28.3 mol / (,9-atom Rh)
It was h.

Example 17 The inside of a 200 ml autoclave (manufactured by Steloy C) equipped with a magnetic induction stirring device was thoroughly replaced with nitrogen gas, and 1.4 mmol of rhodium acetylacetonato(biscarbonyl) and triisopropylene were added under constant pressure. , 240
'C for 1 hour.

After the reaction was completed, the autoclave was cooled, and the reaction products were taken out and analyzed by gas chromatography. As a result, 5450 mmol of ethylene glycol, 4.55 mmol of ethanol, 64.30 mmol of methanol, and 78 mmol of methyl formate were found.
mil J mole, plus a trace amount of 1,2 propanediol,
Glycerin, methane, CO2, etc. were obtained. At this time, the turnover number of ethylene glycol is 3 B, g
It was 2 mol/(gatom Rh) h.

Example 18 Under the conditions of Example 13, N -n-octylpyrrolidine 0.
The reaction was carried out using 048 ml and 5.0 ml of tetraglyme.

As a result of gas chromatographic analysis of the reaction products, the turnover number of ethylene glycol was 2.41 mmol and ethanoethylene glycol was 12.1 mol/(g
-atom Rh) h There was.

Example 19 Under the conditions of Example 13, N -n-octylpyrrolidine 0.
The reaction was carried out using 12 ml and 5.0 ml of tetraglyme.

As a result of gas chromatographic analysis of the reaction product, 3.13 mmol of ethylene glycol and 0.01 mmol of ethanol were found.
mmol, methanol 5.82 mmol, methyl formate 0
939 mmol, and trace amounts of other products such as 1,2 propanediol, glycerin, methane, and CO2 were detected.

Ethylene glycol turnover acid 15.7mo
i / (g-atom Rh) h There was.

〔effect〕

Claims (1)

[Claims] When carbon monoxide and hydrogen are reacted using a rhodium-containing catalyst, the reaction system is expressed by the following formula (1) (wherein R is an alkyl group or a part of the alkyl group is OH). A method for producing ethylene glycol and ethanol, which comprises the presence of a pyrrolidine represented by (1) a hydroxyalkyl group substituted with R, (2) H, an alkyl group or a hydroxyalkyl group. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼