KR20150123039A - Preparation method of benzoic acid - Google Patents
Preparation method of benzoic acid Download PDFInfo
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- KR20150123039A KR20150123039A KR1020140049374A KR20140049374A KR20150123039A KR 20150123039 A KR20150123039 A KR 20150123039A KR 1020140049374 A KR1020140049374 A KR 1020140049374A KR 20140049374 A KR20140049374 A KR 20140049374A KR 20150123039 A KR20150123039 A KR 20150123039A
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- zirconium
- cobalt
- ethylbenzene
- manganese
- ppmw
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/04—Monocyclic monocarboxylic acids
- C07C63/06—Benzoic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
The present invention relates to a process for producing benzoic acid, and more particularly, to a process for producing benzoic acid of high purity at a high yield through an environmentally friendly and economical oxidation process.
Benzoic acid is used in the production of preservatives or caffeine, and is also used as a raw material for medicines such as expectorants and antipyretics. In addition, salts of benzoic acid and benzoic acid esters are important raw materials used to synthesize many organic materials such as plasticizers, resins, fragrances or solvents.
A method of synthesizing benzoic acid using phthalic anhydride or benzotrichloride as a starting material or a method of synthesizing benzoic acid by oxidizing toluene with dichromate or sulfuric acid has been known. Also, there is a method of producing benzoic acid through a cannizzaro reaction by reacting benzaldehyde with a base. However, according to this method, it is known that the yield of benzyl alcohol is equivalent to that of benzoic acid as a reaction by-product and the reaction yield is considerably low.
On the other hand, US Patent Publication No. 2013-0144084 discloses a method for synthesizing benzoic acid in ethyl benzene using Perovskite catalyst. Although the selectivity of benzoic acid can be secured up to 60% in the above process, the reaction product is evaporated and dried during the production of the catalyst, and the reaction product is calcined at a temperature of 1000 ° C or more for 12 hours, and then a nitrogen atmosphere is formed at 500 ° C for 6 hours The manufacturing steps thereof are very complicated and considerable time is required. In addition, about 30% of N-hydroxyphthalimide used as a cocatalyst is added in an amount of about 30% based on the weight of ethylbenzene, oxygen gas is required to be 20 bar or more in the reaction, and stirring is performed at 1500 rpm or more. .
Also, U.S. Patent Publication No. 2004-0015009 discloses a method of oxidizing an aromatic compound using a methanesulfonate-based catalyst. However, according to this method, benzoic acid can be obtained by the oxidation reaction, but the reaction time is about 48 hours and the methane sulfonate catalyst used for the reaction is added at a ratio of about 1: 1 relative to the weight of ethylbenzene, Is about 20%, indicating a very low selectivity.
The present invention is to provide a production method capable of providing high purity benzoic acid in high yield through an environmentally friendly and economical oxidation process.
The present invention includes a step of oxidizing ethylbenzene in an organic solvent containing an organic acid in the presence of a complex catalyst containing cobalt, manganese, and bromine and a zirconium compound, wherein the organic solvent and ethylbenzene And a content of zirconium in the zirconium compound relative to the total amount is 40 ppmw to 400 ppmw.
Hereinafter, a method for producing benzoic acid according to a specific embodiment of the present invention will be described in detail.
According to an embodiment of the present invention, there is provided a process for producing a zirconium compound, which comprises oxidizing ethylbenzene in an organic solvent containing an organic acid in the presence of a complex catalyst comprising cobalt, manganese, and bromine and a zirconium compound, And a content of zirconium in the zirconium compound relative to the total amount of ethylbenzene is 40 ppmw to 400 ppmw.
In the process of oxidizing ethylbenzene, when the reaction temperature is low, there is a problem that the production time is prolonged and exposed to heat for a long time to lower the reaction yield, etc. When the reaction temperature is high, a large amount of byproducts are generated due to high temperature, There was a problem that was difficult to obtain at high selection.
On the other hand, in the process for producing benzoic acid of the above embodiment, the complex catalyst and the zirconium compound are used to selectively oxidize under relatively mild conditions to prevent corrosion of the reactor, while converting the ethylbenzene as a reactant into high efficiency, Can be synthesized.
Specifically, since the above-mentioned specific amount of zirconium compound is used together with the complex catalyst in the step of oxidizing ethylbenzene, the reaction yield can be secured to a high level without raising the reaction temperature, Benzoic acid can be obtained with high purity.
The zirconium compound plays a role of improving the activity of the metal component in the complex catalyst used as the main catalyst of the oxidation reaction even in a low temperature range and promotes the oxidation reaction of ethylbenzene, , The selectivity of benzoic acid can be increased in the course of synthesis, and the purity of benzoic acid finally produced can be further increased.
The zirconium compound means an organic compound or an inorganic compound containing zirconium. Examples of the zirconium compound include zirconium, zirconium organic acid salts, zirconium inorganic acid salts, and mixtures of two or more thereof. Specifically, the zirconium compound may include at least one compound selected from the group consisting of zirconium acetate, zirconium sulfate, and zirconium nitrate.
As described above, the content of zirconium in the zirconium compound may be 40 ppm to 400 ppmw, 50 ppmw to 250 ppmw, or 70 ppmw to 200 ppmw, based on the total amount of the organic solvent and ethylbenzene.
If the content or amount of zirconium contained in the zirconium compound is too small relative to the total amount of the organic solvent and ethylbenzene, the effect of increasing the conversion of ethylbenzene and increasing the selectivity of the benzoic acid finally produced may not be sufficiently exhibited. If the content or amount of zirconium contained in the zirconium compound is too large as compared with the total amount of the organic solvent and ethylbenzene, side reactions may be promoted and the selectivity of benzoic acid in final products may also be lowered.
On the other hand, the composite catalyst may contain cobalt, manganese, and bromine as active components.
Among the complex catalysts, cobalt and manganese can act as a major active component in the step of oxidizing ethylbenzene, and bromine in the complex catalyst converts ethylbenzene to radical or peroxide form It seems to play a role in regulating or accelerating the oxidation reaction or in controlling the rate of the total oxidation reaction.
The composite catalyst may comprise cobalt, manganese, and bromine in a weight ratio of 1: 1 to 3: 2 to 4.
Also, the composite catalyst may include 10 to 300 ppmw of cobalt, 20 to 600 ppmw of manganese, and 25 to 750 ppmw of bromine based on the total amount of the organic solvent and ethylbenzene.
If the content of the cobalt in the composite catalyst is too small, the oxidation reaction rate may be lowered and the reaction time may become longer, unreacted ethylbenzene may remain in excess, the efficiency of the oxidation reaction of ethylbenzene may be lowered, Can be reduced. If the content of the cobalt in the composite catalyst is too large, the side reaction may be promoted or the purity of the finally produced benzoic acid may be lowered
If the content of manganese in the composite catalyst is too small, the activity of the complex catalyst may be lowered to inhibit the oxidation reaction, the efficiency of the oxidation reaction of ethylbenzene may be lowered, or the purity of the benzoic acid have. Also, if the content of manganese in the composite catalyst is too large, the oxidation reaction of the manganese catalyst itself may proceed and a large amount of unreacted ethylbenzene may remain and the purity of benzoic acid may be lowered.
In addition, if the content of bromine in the composite catalyst is too small, the initiation of the ethylbenzene oxidation reaction is not successful and the conversion of the reactant may be lowered. If the content of bromine in the complex catalyst is too high, radical generation of hydrocarbons other than ethylbenzene may be promoted in the reaction system, excess side reaction may proceed, and the selectivity of benzoic acid finally produced may be lowered.
The cobalt, manganese, and bromine contained in the composite catalyst may be contained in the metal itself, or may be in the form of an organic compound or an inorganic compound containing the metal.
In addition, the composite catalyst may contain a compound having at least two of cobalt compound, manganese compound and bromine compound bonded thereto, and may also include a mixture of cobalt compound, manganese compound and bromine compound.
Specifically, the composite catalyst may include at least one cobalt compound selected from the group consisting of cobalt, cobalt nitrate, cobalt sulfate, cobalt hydrochloride, cobalt carboxylate of 2 to 20 carbon atoms, and hydrates thereof.
Also, the complex catalyst may include at least one bromine compound selected from the group consisting of bromine, hydrogen bromide, cobalt bromide, manganese bromide, bromacetic acid, ammonium bromide, potassium bromide, sodium bromide and bromoanthracene.
In addition, the composite catalyst may include at least one manganese compound selected from the group consisting of manganese, manganese halide, cobalt carboxylate of 2 to 20 carbon atoms, sulfate, nitrate, and hydrates thereof.
Even when cobalt, manganese, and bromine are contained in the composite catalyst in the form of an organic compound or an inorganic compound of the metal, the composite catalyst may contain 10 to 300 ppmw of cobalt, 20 to 600 ppmw of manganese, And 25 to 750 ppmw of bromine. The above-mentioned contents are based on the metal atoms of cobalt, manganese and bromine contained in the composite catalyst.
Meanwhile, the step of oxidizing ethylbenzene may be carried out using an organic solvent containing an organic acid, or may be carried out in the organic solvent.
The organic solvent may contain at least 10 wt% or at least 50 wt% of an organic acid, and only organic acids may be used as the organic solvent.
The organic acid included in the organic solvent may be a carboxylic acid having 2 to 20 carbon atoms. The carboxylic acid having 2 to 20 carbon atoms may be an aliphatic carboxylic acid having 2 to 20 carbon atoms or an aromatic carboxylic acid having 6 to 20 carbon atoms. More specific examples thereof include acetic acid, butyric acid, palmitic acid, oxalic acid, propionic acid, .
In the step of oxidizing the ethylbenzene, the organic solvent containing the organic acid may be used in an amount of 50 to 5,000 parts by weight based on 100 parts by weight of the ethylbenzene.
Meanwhile, the step of oxidizing ethylbenzene may include water in the reaction medium in addition to the organic solvent containing the organic acid. The water may be added to an organic solvent or the like to be present in the reaction medium, or may be present in the reaction medium as the complex catalyst is used in an aqueous solution state. Water may be present in the reaction medium in an amount of 0.5 wt% to 2.0 wt%.
The oxidation reaction may include contacting the gas containing oxygen with the ethylbenzene. The gas containing oxygen may contain 10 vol% or more, 20 vol%, or 50 vol% or more of oxygen, and may contain other inert gases as the remainder, and may contain only oxygen.
As the ethylbenzene present in the organic solvent containing the organic acid is brought into contact with the gas containing oxygen in the presence of the above-mentioned complex catalyst, the oxidation reaction proceeds so that benzoic acid can be prepared from ethylbenzene.
The oxidation reaction may be carried out at a pressure of 5 bar to 75 bar, or a pressure of 10 bar to 50 bar. If the pressure of the oxidation reaction is too low, the oxidation reaction does not sufficiently take place and the efficiency of the production process of benzoic acid may be lowered. In addition, if the pressure of the oxidation reaction is too high, a large amount of energy is consumed in the manufacturing process, and the production cost may be greatly increased, and the by-product may be excessively included in the finally produced benzoic acid.
Further, the oxidation reaction may be carried out at a temperature of 50 to 250 ° C, or a temperature of 70 to 220 ° C, a temperature of 100 to 200 ° C, or a temperature of 110 to 150 ° C. If the temperature at which the oxidation reaction is performed is low, the reaction rate may be insufficient or the yield of the production reaction may be lowered. In addition, if the temperature at which the oxidation reaction is performed is high, ethylbenzene as a reactant may be exposed to a high temperature and an excess of an adduct may be generated, so that the selectivity and purity of benzoic acid may be lowered.
The time during which the oxidation reaction is performed is not limited to a great extent, and can be performed, for example, from 30 minutes to 10 hours, or from 1 hour to 8 hours. If the oxidation reaction time is too short, the oxidation reaction is not sufficiently performed, and the final reaction yield and the like may be greatly lowered. If the oxidation reaction time is too long, the reaction time may be prolonged and the formation of side reaction products may be promoted.
Meanwhile, in the method for producing benzoic acid of the embodiment, the oxidation reaction may further include stirring the reaction product containing ethylbenzene at a rate of 10 to 1,000 rpm. As the reactant containing ethylbenzene is stirred, a uniform oxidation reaction proceeds throughout the reactants to increase the conversion of ethylbenzene and the reaction yield.
According to the present invention, it is possible to provide a production method capable of providing high purity benzoic acid with high yield through an environmentally friendly and economical oxidation method.
According to the above-described production method, it is possible to provide benzoic acid, which is useful as an intermediate of medicine, agricultural chemicals and various chemical products, in a high purity and a high yield by conducting a selective oxidation reaction in an environmentally friendly manner without using environmental pollutants. Also, according to the above production method, corrosion of the reactor performed in the oxidation reaction process can be prevented, and the economical efficiency can be greatly improved.
The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
[ Example And Comparative Example : Preparation of benzoic acid]
Example 1
Ethylbenzene and acetic acid were fed into a 500 mL high-pressure reactor equipped with a stirrer at a weight ratio of 1:19. Cobalt acetate, manganese acetate and hydrogen bromide were fed at 80 ppm and 160 ppm, respectively, based on the total weight of ethylbenzene and acetic acid, 200 ppm (based on the core metal content) and 50 ppmw zirconium acetate (based on Zr).
The inside of the high-pressure reactor was replaced with nitrogen atmosphere, and the inside of the reactor was maintained at a pressure of 30 bar by supplying air, and then the temperature of the reactor was raised to 130 ° C to carry out the oxidation reaction. At this time, the stirring was carried out at a stirring speed of 400 rpm in the oxidation reaction and the reaction was continued until there was no change in pressure.
After completion of the oxidation reaction, the temperature inside the reactor is cooled to room temperature and the reaction product is collected. Then, the reaction product was analyzed using a gas chromatograph equipped with a flame ionization detector. Based on the results, the conversion of ethylbenzene (= [content of ethylbenzene initially added - content of ethylbenzene contained in the product] / [content of ethylbenzene initially added] * 100) and selectivity of benzoic acid The percentage of the benzoic acid in the composition is calculated, and the results are shown in Table 1 below.
Example 2 to 4
A product containing benzoic acid was obtained in the same manner as in Example 1 except that zirconium acetate was added in the amounts shown in Table 1 below. The conversion of ethylbenzene and the selectivity of benzoic acid are shown in Table 1 below.
Comparative Example 1 To 3
A product containing benzoic acid was obtained in the same manner as in Example 1 except that zirconium acetate was added in the amounts shown in Table 1 below. The conversion of ethylbenzene and the selectivity of benzoic acid are shown in Table 1 below.
The results of the synthesis of Example 3 and Comparative Example are shown in Table 1 below.
division
[Cobalt / manganese / bromine] (ppmw)
(ppmw)
(%)
(° C)
(bar)
As shown in Table 1, it was confirmed that the synthesis results of Examples 1 to 4 can achieve higher reactant (ethylbenzene) conversion and benzoic acid selectivity than Comparative Examples 1 to 4. Especially, in Examples 1 to 3 using zirconium of 50 ppm, 100 ppm and 200 ppm, respectively, it was confirmed that the selectivity of benzoic acid was over 90% and the conversion of ethylbenzene as a reactant was also ensured to be 99% or more.
Claims (16)
Wherein the content of zirconium in the zirconium compound with respect to the total amount of the organic solvent and ethylbenzene is 40 ppmw to 400 ppmw.
Wherein the content of zirconium in the zirconium compound relative to the total amount of the organic solvent and ethylbenzene is from 50 ppm to 250 ppmw.
Wherein the zirconium compound comprises at least one member selected from the group consisting of zirconium, zirconium organic acid salts and zirconium inorganic acid salts.
Wherein the zirconium compound comprises at least one compound selected from the group consisting of zirconium acetate, zirconium sulfate and zirconium nitrate.
Wherein the composite catalyst comprises cobalt, manganese, and bromine in a weight ratio of 1: 1 to 3: 2 to 4.
Wherein the composite catalyst comprises 10 to 300 ppmw of cobalt, 20 to 600 ppmw of manganese and 25 to 750 ppmw of bromine, based on the total amount of the organic solvent and ethylbenzene.
Wherein the composite catalyst comprises at least one cobalt compound selected from the group consisting of cobalt, cobalt nitrate, cobalt sulfate, cobalt hydrochloride, cobalt carboxylate of 2 to 20 carbon atoms, and hydrates thereof.
Wherein the complex catalyst comprises at least one bromine compound selected from the group consisting of bromine, hydrogen bromide, cobalt bromide, manganese bromide, bromoacetic acid, ammonium bromide, potassium bromide, sodium bromide and bromoanthracene.
Wherein the composite catalyst comprises at least one manganese compound selected from the group consisting of manganese, manganese halide, cobalt, and a carboxylic acid salt, a sulfate, a nitrate, and a hydrate thereof having 2 to 20 carbon atoms.
Wherein the organic acid contained in the organic solvent comprises a carboxylic acid having 2 to 20 carbon atoms.
Wherein the organic solvent is used in an amount of 50 to 5,000 parts by weight based on 100 parts by weight of the ethylbenzene.
Wherein the oxidation reaction comprises contacting the gas containing oxygen with the ethylbenzene.
Wherein the oxidation reaction is carried out under a pressure of from 5 bar to 75 bar.
Wherein the oxidation reaction is carried out at a temperature of from 50 캜 to 250 캜.
Wherein the oxidation reaction is carried out for 30 minutes to 10 hours.
Wherein the oxidation reaction further comprises stirring the reaction product containing ethylbenzene at a rate of 10 to 1,000 rpm.
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