JPS62164645A - Production of carboxylic acid - Google Patents

Abstract

PURPOSE:To suppress the formation of sulfuric acid compounds as a by-product and obtain a carboxylic acid without coloring or bad smell in high yield, by using a catalyst consisting of sulfuric acid and phosphoric acid and further a metallic compound in reacting an olefin or alcohol with carbon monoxide and water. CONSTITUTION:An olefin or alcohol is reacted with carbon monoxide and water in the presence of a catalyst containing (A) preferably 30-90wt%, particularly 40-80wt% sulfuric acid, (B) 5-70wt%, preferably 15-55wt% phosphoric acid or further (C) 0.1-4wt%, preferably 0.2-2wt%, based on the mixture of the components (A) with (B), metallic compound, preferably metallic oxide (for cuprous oxide) at -10-+80 deg.C, preferably 0-30 deg.C to reduce the content of sulfur compounds in the resultant product without adopting purifying operation using an oxidizing agent and afford the aimed carboxylic acid in a yield as high as in a well-known method using sulfuric acid catalyst.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing tM of carboxylic acid, and more specifically, the so-called Kotsuho reaction in which an olefin or alcohol is reacted with water in the presence of a sulfuric acid catalyst. The present invention relates to a method for producing carboxylic acid that can reduce impurities such as sulfur compounds and the like in the method for producing carboxylic acid.

[Prior art and its problems 1 The Kotsuho reaction, in which an olefin or alcohol is reacted with carbon monoxide and water in the presence of a sulfuric acid catalyst, is well known. The resulting carboxylic acid has a bad odor because it contains sulfur compounds such as esters.

It has drawbacks such as coloring.

In order to overcome this drawback, a purification operation has been proposed in which the crude fat obtained by separating the sulfuric acid catalyst from the Kotsujo reaction product is brought into contact with an oxidizing agent prior to distillation (
For example, see Japanese Patent Application Laid-open No. 18897/1983).

However, as an industrial production method, it is preferable not to add new components such as oxidizing agents during purification operations, so if you want to omit purification operations such as adding oxidizing agents as a post-treatment step, sulfuric acid catalyst It is necessary to reduce the concentration of sulfur compounds in the carboxylic acid to reduce the number of places where the sulfur compounds mixed in the carboxylic acid are produced, and thereby the production of the carboxylic acid is also suppressed.

[Purpose of the invention] This invention has been made based on the above circumstances.

The purpose of this invention is to reduce the amount of sulfur compounds mixed in the produced carboxylic acid without adopting a purification operation using an oxidizing agent, and to achieve the same yield of carboxylic acid as when using a sulfuric acid catalyst. An object of the present invention is to provide a method for producing a carboxylic acid using the Kotsuho reaction, which has a high yield.

[Means for achieving the above-mentioned object 1] The gist of the present invention for achieving the above-mentioned object is to prepare an olefin or an alcohol in the presence of a catalyst consisting of sulfuric acid and phosphoric acid or a catalyst consisting of sulfuric acid, phosphoric acid and a metal compound. , a method for producing a carboxylic acid, which is characterized by reacting carbon monoxide with water.

As the olefin used in the method of this invention, all known raw materials that can be used in the so-called Kotzho reaction can be used. For example, ethylene, propylene, n
-butylene, isobutylene diisobutylene, 1-hexene, 2-hexene, 3-hexene, 1-hepteno, 2-
Olefins with linear or branched chains such as heptene, 3-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1-nonene, 2-nonene, 3-nonene, 4-nonene and hexadecene , cyclohexene, and cycloolefins such as cyclohexene substituted with an alkyl group such as a methyl group or an ethyl group, or a vinyl group. Furthermore, diolefins such as butadiene, halogenated olefins such as acryl chloride, methacryl chloride, etc. can also be used. In the present invention, one type of the various olefins described above may be selected, or a mixture of two or more types or a mixture of isomers may be used.

However, among the various types of resins mentioned above, carbon atoms of 4 to
Olefins having 15 linear or branched chains are preferred, and diisobutylene is particularly preferred.

Further, as the alcohol, for example, ethanol,
Aliphatic alcohols such as n-propatool, impropatool, n-butanol, imbutanol, tert-butanol; n-hexanol, 5ea-hexanol, tert-hexanol.

Higher alcohols such as heptatool, octatool, and mixtures thereof can be used. moreover,
Layered alcohols such as cyclopentanol and cyclohexanol can also be used. Further, halohydrins such as 2-monochloromethyl-2-propatol and 2-monochloromethyl-2-butamer can also be used as raw materials. Aliphatic alcohols having 4 or more carbon atoms are preferred.

- Carbon oxide is most preferably pure, but carbon monoxide-containing gases obtained from water gas, generator gas, coke oven gas, etc. can also be used.

Pure wood is most preferable, and distilled water, ionized water, etc. can be used.

The catalyst used in this invention consists of sulfuric acid and phosphoric acid or sulfuric acid, phosphoric acid and a metal compound.

Using a catalyst made of sulfuric acid and phosphoric acid can reduce the content of fE yellow compounds in the product, and a catalyst made by adding a metal compound to sulfuric acid and phosphoric acid can reduce the content of &tM compounds in the product. In addition to the effect of reducing the content of 111, it is possible to improve the yield of the produced carboxylic acid.

The concentration of the sulfuric acid in the catalyst is generally preferably 30 to 9%, particularly preferably 40 to 80%.

Further, the concentration of the phosphoric acid in the catalyst is usually 5 to 5.
70% by weight, preferably 15 to 55% by weight.

%.

There are no particular restrictions on the method for preparing the catalyst.

for example! A catalyst liquid containing sulfuric acid and phosphoric acid is prepared by mixing acid and phosphoric acid in advance by a normal mixing operation, and when using the catalyst, this catalyst liquid is used as it is or diluted, and further, The metal compound may be added to and mixed with the catalyst liquid, and then the catalyst liquid containing the metal compound may be added to the reaction system.

Alternatively, sulfuric acid, phosphoric acid, and a metal compound may be mixed and prepared in advance, and this metal compound-containing catalyst liquid may be used as described above.

Furthermore, the raw material olefin or alcohol,
Sulfuric acid and phosphoric acid may be added to the mixture of carbon monoxide and water at the same time or sequentially, if necessary. Note that when they are added sequentially, there is no restriction on the order in which the catalyst components are added.

Alternatively, the catalyst component may be added to one reaction vessel, and the raw materials may be added thereto.

In any case, when olefins or alcohols, carbon monoxide, and water react, a catalyst consisting of sulfuric acid and phosphoric acid or a catalyst consisting of sulfuric acid, phosphoric acid, and a metal compound must be present. Good.

As the metal compound, for example, in addition to cuprous oxide, silver oxide, silver sulfate, gold oxide, etc., metal copper, a mixture of a divalent copper compound and metal copper, etc. can be used, but preferred are They are cuprous oxide and silver oxide.

When the metal compound, especially cuprous oxide, is used as a component of the catalyst, the amount of this metal used is usually 0.1 to 4% by weight, based on the weight of the mixture of sulfuric acid and phosphoric acid. , preferably 0.62 to 2% by weight.

The amount of the catalyst used may be 75 ml or more per 0.3 mol of the olefin or alcohol supplied.

In the presence of said catalyst. The reaction between these olefins or alcohols, carbon monoxide, and water can be carried out in a batch, semi-batch, or continuous manner using one reaction system at a predetermined reaction temperature.
One reaction can be carried out under a given reaction pressure.

The reaction temperature is usually -1θ to 80°C, preferably 0
If the 0 reaction temperature, which is 30°C, is lower than -10°C, the 1 reaction rate will decrease, which is not preferable, and if it is higher than 80°C, sulfuric acid sludge, sulfuric ester, etc. may increase, which is not preferable.

The reaction pressure is usually sufficient from 0 to 100 Kg/ctn'G, preferably from 1G to 15K g/c
There is ny'te. This is because by setting the reaction pressure to 10 to 15 Kg/Cm'', it is possible to prevent a decrease in the yield of carboxylic acid due to the use of the low concentration sulfuric acid.

A reaction time of 10 to 120 minutes is usually sufficient.

In the method of this invention, the target product carboxylic acid and byproducts such as olefin polymers are produced by the Kotsuto reaction. For example, when diisobutylene is used as a raw material, 2,2,4,4-tetramethyl Pentanoic acid, 2
, 2,3.4-tetramethylpentanoic acid, 2-ethyl-
2,3,3-trimethylbutanoic acid, 2,5.5-trimethyl-hexanoic acid, 2-ethyl-4,4-dimethyl-
A carboxylic acid mixture whose main component is a carboxylic acid having an Rg number of 9, which is a mixture of pentanoic acid, 2-isopropyl-3,3-dimethylbutanoic acid, etc., is obtained as the desired product.

After the reaction is completed, for example, n-' is extracted from the reaction product liquid obtained.
The desired carboxylic acid can be obtained by extracting with an organic solvent such as xane, washing with water, and removing the extraction solvent.

In the method of this invention, one reaction product liquid contains one catalyst &
The production of sulfur compounds derived from sulfuric acid, which is a component, is reduced, and therefore, the amount of sulfur compounds mixed into the carboxylic acid is also reduced, making it possible to obtain a carboxylic acid without coloration or bad odor.

The detailed reason why the use of the catalyst can suppress the production of sulfur compounds is unknown.

However, even though the mechanism for suppressing the production of sulfur compounds has not been theoretically elucidated, the method of this invention suppresses the production of sulfur compounds and produces products without foul odor or coloring.
Moreover, since carboxylic acid can be produced in high yield, the method of the present invention can be said to be an industrially advantageous method for producing carboxylic acid.

[Effect of the invention 1] According to this invention, (1) the amount of sulfur compound produced as a side reaction product is small, and carboxylic acid with less coloring and bad odor can be produced; (2) a sulfuric acid catalyst is used. It is possible to provide a method for producing a carboxylic acid that has excellent advantages such as being able to produce a carboxylic acid in a high yield similar to the case where the carboxylic acid is produced.

[Examples] Next, the present invention will be explained in further detail by showing examples and comparative examples of the present invention.

(Examples 1 to 5, Comparative Examples 1 to 3) An aqueous solution of sulfuric acid and phosphoric acid (no phosphoric acid was used in the comparative examples) at the concentrations shown in Table 1 and an oxidized No. 1 solution shown in Table 1.
A catalyst consisting of copper and the amount of catalyst shown in Table 1 was charged into a reaction vessel, the interior of the reaction vessel was sufficiently replaced with carbon monoxide, and the mixture was stirred until it became saturated. While maintaining the carbon monoxide pressure in the reaction vessel at 15 K g/crn', diisobutylene and carbon monoxide were added to the reaction vessel under the reaction conditions shown in Table 1. reacted. In addition, the carbon monoxide that was consumed and decreased during one reaction was replenished in the same amount.

After the reaction time of 1.5 hours had elapsed, the supply of diynbutylene was stopped, and the mixture was stirred for an additional hour.

Then an equal amount of water was added.

The reaction mixture thus obtained was directly used without diluting with water for Example 1.2 and Comparative Example 1.2.
Examples 3 to 5 and Comparative Example 3 were diluted three times with water, and then extracted three times with 200 mjl of n-hexane.

A small amount of sulfuric acid mixed in the extract was removed by washing with water, and
-Hexane was removed by distillation to obtain a carboxylic acid mixture having the composition shown in Table 1.

The results are shown in Table 1.

The sulfur content in the produced carboxylic acid mixture was measured using a trace sulfur analyzer [manufactured by Mitsubishi Ka IO & Co., Ltd.], and the phosphorus content was measured by incinerating the produced carboxylic acid mixture in an electric furnace, After collection, the determination was made by adding an indicator and measuring the absorbance due to color development.

(Example 6) The same procedure as in Example 4 was carried out except that 1-octatool was used instead of diisobutylene.

The yield of the carboxylic acid mixture was 55.6%, and the composition of the carboxylic acid mixture was: trimethyl acetic acid at 20.3 tons, CS carboxylic acid at 10.7 tons, C-licarponic acid at 40.8 tons. % by weight, other carboxylic acids 27.6
Tundu:%, and the f2 yellow content in the carboxylic acid mixture is (1,033%), and the phosphorus content is 10p
It was below pm.

Patent applicant: Idemitsu Petrochemical Co., Ltd. Continuation of amendment, 1
February 2611, 1986 To the Commissioner of the Patent Office, 5
11 Indication of East case Patent Application No. 5748 of 1985 2 Name of IJI Process for manufacturing carboxylic acid 3 Person making amendment Relationship with IS case Patent applicant address 11-1 Marunouchi Pressure RL, Chiyo January-ku, Tokyo
1) Name: Idemitsu Petrochemical Co., Ltd. Representative: Takeshi Yamato 4 Agent address: 2nd floor 6, Karakawa Building, 3-2 Nishi-Shinjuku 6-chome, Shinjuku-ku, Tokyo Number of inventions to be increased by the amendment 07 Subject of the amendment ``Specification-1'' Column 8 of “+iT Detailed Description of the Invention”
Contents of amendment (1) Details -: 3 lines from the bottom of page 4 [Replace "acrylic chloride" described in 1 with "allyl chloride",
Correct "methacrylic chloride" to "methacrylic chloride".

(2) Details! ; written on page 6, line 10 of “
``Sulfur compound'' will be replaced with ``Sulfur compound.''

(3) "Silver oxide" described in the 5th line of page 8 of Akira, It, ■H was replaced with "silver oxide" and "PI#kakin" was replaced with "silver oxide".
Corrected to "ferrous oxide".

(4) "Silver resistant" written on page 8, line 8 of the specification is corrected to "silver oxide."

(5) In the second line from page F of page 14 of the specification, "is the main component" is corrected to "is the main component, etc."

Claims (4)

[Claims] (1) Production of a carboxylic acid characterized by reacting an olefin or alcohol, carbon monoxide, and water in the presence of a catalyst consisting of sulfuric acid and phosphoric acid or a catalyst consisting of sulfuric acid, phosphoric acid, and a metal compound. Method. (2) The method for producing a carboxylic acid according to claim 1, wherein the metal compound is a metal oxide. (3) The method for producing a carboxylic acid according to claim 2, wherein the metal oxide is cuprous oxide. (4) The method for producing a carboxylic acid according to any one of claims 1 to 3, wherein the reaction is carried out at -10 to 80°C.