JPH0669974B2 - Method for producing alcohol for plasticizer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an alcohol for a plasticizer. More specifically, the present invention relates to a method for producing an alcohol for a plasticizer having 9 carbon atoms, which is excellent in the color tone of a plasticizer ester as a product when used as a raw material for a plasticizer.

[Conventional technology]

Conventionally, a hydroformylation reaction of an olefin having 8 carbon atoms, which is obtained by dimerizing a 4 carbon fraction (hereinafter referred to as BB fraction), which is obtained in large amounts from the thermal cracking of naphtha or the catalytic cracking of heavy oil, is carried out. An aldehyde having 9 carbon atoms is produced, hydrogenated to produce an alcohol having 9 carbon atoms, and the alcohol having 9 carbon atoms obtained by purification is preferably used as a raw material of a plasticizer for vinyl chloride resin. It is well known (British Patent No. 789,777, Japanese Patent Publication No. 61-15849).
Etc.).

The above-mentioned alcohol having 9 carbon atoms contains many isomers and trace impurities because the olefin having 8 carbon atoms obtained by dimerization in the raw BB fraction is a mixture of many isomers. There is.

[Problems to be solved by the invention]

However, even when a trace amount of impurities contained by distilling the above-mentioned alcohol having 9 carbon atoms is removed to such an extent that there is no problem in terms of product purity and purified, and used as the alcohol for the plasticizer, It has been found that there are many cases where the agent performance fails, particularly in the color tone of the ester product. Here, the color tone of the ester is determined by the sulfuric acid coloring test method. Therefore, in this case, a product that passes the sulfuric acid coloring test cannot be obtained unless the alcohol obtained by the hydrogenation reaction is subjected to any treatment other than distillation purification.

[Means for solving problems]

As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems in the production of the alcohol having 9 carbon atoms, the olefin having 12 carbon atoms in the alcohol having 9 carbon atoms significantly deteriorates the sulfuric acid coloring test results. It has been found. As a result of investigating a specific solution based on this finding, the present inventors have adjusted the content of the olefin having 12 carbon atoms in the olefin having 8 carbon atoms as a raw material, and have performed the hydroformylation reaction and the hydrogenation reaction. The present invention has been completed by discovering that the results of the sulfuric acid coloring test of product alcohols are remarkably improved by carrying out the above under specific conditions.

That is, the gist of the present invention is to produce an alcohol having 9 carbon atoms by a hydroformylation reaction and a hydrogenation reaction using an olefin having 8 carbon atoms obtained by dimerizing a butene fraction as a raw material. 12 carbons as raw material
With an olefin content of 0.1% by weight or less,
The conversion ratio of the olefin having 8 carbon atoms in the hydroformylation reaction is in the range of 40 to 99%, and the conversion ratio of the aldehyde having 9 carbon atoms in the hydrogenation reaction is in the range of 80 to 99.99%. The method for producing an alcohol for a plasticizer.

Hereinafter, the present invention will be described in detail.

The butene fraction that is a raw material of the method of the present invention is a BB fraction having butenes as a main component, and a BB fraction obtained by the thermal cracking of naphtha or a BB fraction obtained by the catalytic cracking of heavy and light oils. Either can be used.

It is also possible to dimerize the BB fraction obtained by thermal decomposition of naphtha as it is, but so-called Spent BB fraction after extracting and separating butadiene from the BB fraction, and further isobutene was further separated from the Spent BB fraction. The later so-called spent spent BB fraction can also be preferably used.

The BB fraction obtained by catalytic cracking of heavy and light oils is mainly a mixture of butene and butane, and it is also possible to dimerize it as it is, but after isobutene is separated from the BB fraction by distillation or the like. BB fractions can also be used suitably.

The BB fraction as described above can be dimerized by a usual dimerization reaction method. That is, nickel salt and aluminum
There are a method using a so-called Ziegler-type catalyst using an alkyl halide as a catalyst, a method using an acid catalyst using solid phosphoric acid as a catalyst, and either method can be used.

In the method of the present invention, a dimerization reaction product obtained by dimerizing the above BB fraction, that is, an isomer mixture of an olefin having 8 carbon atoms is distilled to obtain a olefin having 12 carbon atoms.
A fraction (hereinafter referred to as an octene fraction) consisting of 0.1% by weight or less, preferably 0.05% by weight or less, of an olefin isomer mixture having 8 carbon atoms is obtained and used as a raw material in the method of the present invention.

Distillation of the dimerization reaction product may vary depending on the isomer composition distribution of the olefin having 8 carbon atoms, but usually, simple distillation or a top pressure of a distillation column having 1 to 100 theoretical plates is used. It is carried out by distillation under the conditions of 10 mmHg to atmospheric pressure and the column top temperature of 10 to 130 ° C. to obtain an octene fraction having a C12 olefin content in the above range.

When the octene fraction containing more than 12 carbon atoms in the above olefin content is used as the olefin raw material, the sulfuric acid coloring test results are good even if the obtained alcohol having 9 carbon atoms is purified by distillation. It is difficult to get good alcohol.

In the method of the present invention, first, the octene fraction obtained above is subjected to a hydroformylation reaction with carbon monoxide and hydrogen to produce an aldehyde having 9 carbon atoms.

The hydroformylation reaction can be carried out by a usual method. As the catalyst, any ordinary catalyst system such as a rhodium-based catalyst or a Colvalt-based catalyst used in an industrial hydroformylation reaction can be used.

In the case of a cobalt-catalyzed hydroformylation reaction,
Usually, the cobalt concentration is 0.05 to 50 wt% (Co atom), the temperature is
The reaction is carried out at a temperature of 80 to 180 ° C., a pressure of 50 to 300 kg / cm ² G, and a hydrogen / carbon monoxide (volume ratio) of 0.5 to 10. Further, the cobalt catalyst may be modified with a ligand such as triarylphosphine (eg triphenylphosphine) and used. A solvent is not usually used, but an organic solvent inert to the reaction can also be used.

In the case of the rhodium-catalyzed hydroformylation reaction,
Usually, the rhodium concentration is 0.1-1000ppm (Rh atom), the temperature is
The reaction is carried out at a temperature of 80 to 200 ° C., a normal pressure to 500 kg / cm ² G, and a hydrogen / carbon monoxide (volume ratio) of 0.5 to 10. Further, the rhodium catalyst can be used after being modified with a ligand such as triarylphosphine (eg triphenylphosphine). A solvent is not usually used, but an organic solvent inert to the reaction can also be used.

A preferred hydroformylation method using the rhodium catalyst is a method using a catalyst system containing rhodium and an oxide of a trivalent organic phosphorus compound. In this case, the oxide of the trivalent organic phosphorus compound is usually added in an amount of 10 per mol of rhodium.
The octene fraction is subjected to hydroformylation reaction with carbon monoxide and hydrogen under the reaction conditions described above to produce an aldehyde having 9 carbon atoms.

Examples of the trivalent organic phosphorus compound oxide include arylphosphine oxides such as tolphenylphosphine oxide, tritolylphosphine oxide, and trianisylphosphine oxide; alkyl phosphine oxides of tributylphosphine oxide and trioctylphosphine oxide; and alkyl groups. Alkylaryl phosphine oxide having an aryl group combined therewith; aryl phosphite oxide such as triphenyl phosphite oxide (ie triphenyl phosphate), tritolyl phosphite oxide; triethyl phosphite oxide, tripropyl phosphite oxide, tributyl phosphite Alkyl phosphite oxides such as oxides; alkyl aryl phosphite oxides having both an alkyl group and an aryl group; and the like. It is.

In the method of the present invention, the conversion rate of the olefin having 8 carbon atoms in the hydroformylation reaction is set in the range of 40 to 99%. If the conversion rate is less than 40%, there are many unreacted substances and the amount of recycle increases, which is not economically advantageous. In addition, the conversion rate
If it exceeds 99%, it has the effect of reducing the residual amount of the olefin having 12 carbon atoms, which is a harmful component, as described above, but on the other hand, it is necessary to increase the reaction temperature, reaction time, catalyst amount, etc. In addition, it also leads to an increase in undesirable side reaction products and the like, which is not preferable.

In the above hydroformylation reaction, a part of the olefin having 12 carbon atoms is also converted into the corresponding aldehyde or paraffin. The conversion rate is related to the conversion rate of C8 olefins, and although there are some differences depending on the catalyst and reaction conditions, the conversion rate of C8 olefins is 40%.
When the conversion rate is about 5%, the conversion rate is about 5%, and when the conversion rate of the olefin having 8 carbon atoms is about 99%, the conversion rate is about 5%.
40%. The C12 olefin is also a mixture of many isomers, and their boiling points are widely distributed from the boiling range of C9 aldehyde to the boiling range of C9 alcohol. However, it is difficult to separate and remove by distillation in the subsequent step.

An aldehyde or a mixture of an aldehyde and an alcohol obtained by subjecting the octene fraction to a hydroformylation reaction by the above-described method is then subjected to a water addition reaction to obtain an alcohol having 9 carbon atoms.

The hydrogenation reaction can be carried out by a usual method. As the catalyst, nickel, chromium, using an ordinary hydrogenation catalyst such as copper, the pressure is usually atmospheric pressure or higher, preferably 30 to 300 atm,
The reaction is usually performed at room temperature or higher, preferably 100 to 200 ° C.

In the method of the present invention, the conversion rate of the aldehyde having 9 carbon atoms in the hydrogenation reaction is set in the range of 80 to 99.99%. If the conversion rate is less than 80%, there are many unreacted substances and the amount of recycle increases, which is not economically advantageous. Further, when the conversion rate exceeds 99.99%, there is an effect of reducing the residual amount of the olefin having 12 carbon atoms which is a harmful component, but on the other hand, it is necessary to increase the reaction temperature, the reaction time, the catalyst amount, etc. However, it is not preferable because it causes an increase in undesirable side reaction products and the like.

Also in the hydrogenation reaction, part of the olefin having 12 carbon atoms is converted to the corresponding paraffin. The conversion rate is related to the conversion rate of the C9 aldehyde and may vary depending on the catalyst and the reaction conditions. However, when the conversion rate of the C9 aldehyde is about 80%, the above conversion rate is about
15%, conversion rate of C9 aldehyde is 99.99%
In this case, the conversion rate is about 60%.

The crude alcohol thus obtained is purified by distillation in a rectification column. Distillation and purification of crude alcohol usually requires 3 theoretical plates.
~ 100-stage distillation column using a top pressure of several mmHg ~ 760mmHg,
It is carried out under the condition that the overhead temperature is 50 to 220 ° C.

The purified C9 alcohol thus obtained is
It is esterified with an acid such as phthalic anhydride or adipic acid by a usual method to give a plasticizer ester. The color tone is of particular importance in the quality of the ester and is measured by the sulfuric acid coloring test method.

The sulfuric acid coloring test method includes Monsanto method, Eastman method,
There are Sekisui method and the like, but the main operations are the same except for the fine conditions, and the Monsanto method is generally widely used. The Monsanto method was also adopted in the examples described later, and the measuring method is shown below.

100 ml of sample in a washed and dried 300 ml flat bottom flask with stopper
Put in. 98wt% at room temperature below 30 ℃ while stirring the sample
Add 8 ml of concentrated sulfuric acid in a 25 ml buret at a rate of 2 ml / min. The flask is stoppered and immersed in a water bath at 98 ± 2 ° C for 2 hours. Then, after cooling with water to room temperature,
Transfer 100 ml to a flat-bottom glass colorimetric tube with a height of 25 mm and a height of 270 mm,
Visually compare the same amount of APHA-type standard solution with the same colorimetric tube, and use the APHA value of the same color as the measured value.

The composition of the APHA stock solution is as follows.

Put potassium chloroplatinic acid (K ₂ PtCl ₆₎ 1.245g of cobalt chloride _{(CoCl 2 · 6H 2 O)} 1.000g 98% or more concentrated sulfuric acid 100ml to 1000ml ml volumetric flask, and dissolved by adding distilled water, with distilled water Make exactly 1000 ml. This solution is APHA50
It is 0, and thereafter, it is proportionally diluted with distilled water to obtain a low APHA color standard solution.

〔Example〕

Next, specific embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples without departing from the gist thereof.

Example-1 (1) Synthesis of olefin having 8 carbon atoms C ₄ fraction after removal of butadiene and isobutene from BB fraction obtained from naphtha cracker (composition: 6% by weight of isobutene, 43% by weight of 1-butene) , 2-butene 25% by weight, butanes 25% by weight, other 1% by weight) were dehydrated with a molecular sieve 13X. Then, in a 10-volume SUS induction stirring autoclave, under a nitrogen atmosphere, 4 kg of the C ₄ fraction after dehydration described above, 5.5 g of nickel octanoate n-hexane solution (Ni content 6 wt%) and ethylaluminum dichloride. 11.3 g was charged and the dimerization reaction was carried out at 40 ° C. for 7 hours.

After the reaction, 640 g of a 5 wt% H ₂ SO ₄ aqueous solution was added to deactivate the catalyst and then separated into liquids, and then purified by distillation by a 15-stage distillation column to obtain an octene fraction. The distillation in this case was carried out in a batch system, the reflux ratio was 3.0, and the yield of the octene fraction obtained by the distillation was 95%. The concentration of olefin having 12 carbon atoms in this octene fraction was measured by gas chromatography and found to be 0.06 wt%.

The above operation was repeated 3 times.

(2) Synthesis of alcohol having 6 carbon atoms Under a nitrogen atmosphere in a SUS autoclave with a volume of 10, 2.0 kg of the octene fraction obtained in (1) above, 0.3 g of an aqueous rhodium acetate solution (containing 10% as Rh metal) and triethyl ether. Phenylphosphine oxide (1.63 g) was added, the total pressure was maintained at 160 kg / cm ² G with oxo gas having H ₂ / CO = 1, and the hydroformylation reaction was carried out at a reaction temperature of 130 ° C. After 5 hours, since the absorption of gas was stopped, the reactor was cooled, the pressure of oxo gas was released, the whole amount of the reaction liquid was taken out, and then aldehyde and alcohol were obtained by simple distillation under a reduced pressure of 5 to 10 mmHg. The conversion of the octene fraction in the hydroformylation reaction was 95%, the total yield of aldehyde and alcohol was 93%, and the remaining 2% was mainly high boiling by-products. The total yield of aldehyde and alcohol in simple distillation was about 97%.

Next, in a 10-volume autoclave made of SUS, under nitrogen atmosphere, the total amount of the liquid obtained from the above simple distillation and the nickel-supported solid catalyst were collected.
Charge 160 g and maintain the total pressure at 90 kg / cm ² G with hydrogen gas.
Hydrogenation reaction was carried out at a reaction temperature of 30 ° C.

After 5 hours, gas absorption was completed, so quenching was performed, hydrogen gas was depressurized, the entire amount of the reaction solution was taken out, and the solid catalyst was removed to remove it, followed by refining in an Olderyo distillation column with an inner diameter of 35 mm x 20 plates. I stayed. The reflux ratio was 10, the pressure was 10 mmHg, and the alcohol was separated from the unreacted aldehyde and the high-boiling by-product. The conversion rate of aldehyde in the hydrogenation reaction was 99.9%.

The alcohol yield in the hydrogenation reaction was 97%, and about 2.9% was mainly high boiling by-products. The alcohol yield in the rectification was about 98%.

(3) Sulfuric acid coloring test of the alcohol The purified alcohol obtained in (2) above was subjected to a sulfuric acid coloring test by the Monsanto method. The results are shown in Table-1.

Example-2 A hydroformylation reaction and subsequent simple distillation were carried out by the same operation as in (2) of Example-1 except that the reaction temperature was 115 ° C. The conversion of the octene fraction in the hydroformylation reaction was 53%, the total yield of aldehyde and alcohol was 52.5%, and there was 0.5% mainly high boiling by-product formation. The total yield of aldehyde and alcohol in simple distillation was about 98%.

Next, the hydrogenation reaction and the subsequent rectification were carried out by the same operation as in (2) of Example-1 except that the reaction temperature was 100 ° C. The conversion rate of aldehyde in the hydrogenation reaction was 83%.

The alcohol yield in the hydrogenation reaction was 82.1%, and 0.9% was mainly high-boiling products. The alcohol yield in the rectification was about 97%.

The results of the sulfuric acid coloring test of the obtained purified alcohol are shown in Table-1.
Shown in.

Example-3 A hydroformylation reaction and subsequent simple distillation were performed in substantially the same manner as (2) of Example-1 except that a Co-based catalyst was used.

That is, 2.0 kg of the octene fraction obtained in (1) of Example-1 and 20 g of dicobalt octacarbonyl were added to a SUS autoclave having a volume of 10 under a nitrogen atmosphere, and the total pressure was adjusted with oxo gas of H ₂ / CO = 1. Was maintained at 160 kg / cm ² G and the hydroformylation reaction was carried out at 120 to 130 ° C. After 2 hours, gas absorption stopped, so the reactor was rapidly cooled, and a 3% Na aqueous solution was injected under pressure.
After deactivating the cobalt catalyst, the mixture was further cooled, the pressure of the oxo gas was released, and then the entire amount of the reaction liquid was taken out and separated into liquids to obtain an organic phase. Then, aldehyde and alcohol were obtained by simple distillation under reduced pressure of 10 mmHg. The conversion of the octene fraction in the hydroformylation reaction was 90%, and the total yield of aldehyde and alcohol was 82%. There was predominantly high boiling by-product formation of 8%.

The total yield of aldehyde and alcohol in simple distillation was 95%.

Next, the hydrogenation reaction and the subsequent rectification were carried out in the same manner as in (2) of Example-1. The addition rate of aldehyde in the hydrogenation reaction was 99.8%. The alcohol yield in the hydrogenation reaction was 96%, and about 2.8% was mainly high boiling by-products.
The alcohol yield in the rectification was about 98%.

The results of the sulfuric acid coloring test of the obtained purified alcohol are shown in Table-1.
Shown in.

Example-4 (1) Synthesis of olefin having 8 carbon atoms The same procedure as in (-1) of Example-1 was carried out except that the reflux ratio was 30. Number of carbon atoms in the obtained octene fraction
The concentration of 12 olefins was 0.02 wt%.

(2) Synthesis of alcohol having 9 carbon atoms The hydroformylation reaction and simple distillation were performed in exactly the same manner as in (2) of Example-1 except that the octene fraction obtained in (1) above was used. The conversion of the octene fraction in the hydroformylation reaction was 95%, the total yield of aldehyde and alcohol was 93.5%, and the production of mainly high boiling by-products was 1.5%.

The hydrogenation reaction and rectification were also carried out in the same manner as in Example 1 (2). The results were almost the same.

The results of the sulfuric acid coloring test of the obtained purified alcohol are shown in Table-1.
Shown in.

Comparative Example-1 (1) Synthesis of olefin having 8 carbon atoms Except that the distillation was carried out at a reflux ratio of 0.5 and the distillation yield of the octene fraction was 98%, exactly the same as in Example-1 (1). I did. The concentration of olefin having 12 carbon atoms in the obtained octene fraction was 0.16 wt%.

(2) Synthesis of alcohol having 9 carbon atoms Except that the octene fraction obtained in (1) above was used, the same procedure as in (2) of Example-1 was carried out, and almost the same results were obtained.

The results of the sulfuric acid coloring test of the obtained purified alcohol are shown in Table-1.
Shown in.

Comparative Example-2 A hydroformylation reaction was carried out in the same manner as in (2) of Example-1 except that the octene fraction obtained in Comparative Example-1 (1) was used and the reaction temperature of the hydroformylation reaction was 150 ° C. Simple distillation was performed. The conversion of the octene fraction in the hydroformylation reaction was 99.5%. The total yield of aldehyde and alcohol was 88%, with 11.5% predominantly high boiling by-products. The yield of aldehyde and alcohol in simple distillation is
It was 94%.

Next, (2) of Example-1 except that the reaction temperature was 170 ° C.
The hydrogenation reaction and the subsequent rectification were carried out in exactly the same manner as in. Aldehyde conversion in the hydrogenation reaction was almost 100%. The production rate of mainly high boiling by-products was 14.5%. The alcohol yield in the rectification was about 95%.

The results of the sulfuric acid coloring test of the obtained purified alcohol are shown in Table-1.
Shown in.

[Effects of the Invention] By the method of the present invention, it is possible to produce an alcohol for a plasticizer having 9 carbon atoms, in which the results of the sulfuric acid coloring test are significantly improved.

Claims (1)

[Claims] 1. A carbon number of 8 obtained by dimerizing a butene fraction.
In producing an alcohol having 9 carbon atoms by a hydroformylation reaction and a hydrogenation reaction using the olefin of
The C8 olefin raw material having a C12 olefin content of 0.1% by weight or less is used, and the conversion of the C8 olefin in the hydroformylation reaction is in the range of 40 to 99%. A method for producing an alcohol for a plasticizer, characterized in that a conversion rate of an aldehyde having 9 carbon atoms in a hydrogenation reaction is set in a range of 80 to 99.99%.