KR101707036B1 - Production Method of Dicarboxylic Acid from Castor Oil - Google Patents

Abstract

The present invention relates to a method for producing a dicarboxylic acid from a castor oil, and more particularly, to a method for producing a dicarboxylic acid from a castor oil by mixing castor oil and NaOH with zinc oxide (ZnO) Cooling the reaction product to remove octanol, and adding sulfuric acid to the remaining solution to adjust the pH; Separating the oil component from the reactant and further adding sulfuric acid thereto to lower the pH; And separating the dicarboxylic acid from the reactant. The present invention also relates to a method for producing a dicarboxylic acid from a castor oil. The production method according to the present invention improves the yield of dicarboxylic acid production by reducing the production amount of by-products such as fatty acid and reducing the loss during the process, as compared with the conventional production method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dicarboxylic acid,

The present invention relates to a method for producing a dicarboxylic acid from a castor oil, and more particularly, to a method for producing a dicarboxylic acid from a castor oil using zinc oxide as a catalyst.

It is no exaggeration to say that there are no chemical materials that have not been used in our lives. As such, all of our resources use chemical materials produced from petroleum as raw materials and commercialize them. Particularly, according to the development of technology, polymers using petroleum resources are used in various fields such as general shoes, clothes, furniture, automobiles, and household appliances. Polymers produced from petroleum can be improved in convenience because of their good physical properties. Therefore, the polymer market is continuously increasing. However, since polymers are produced using petroleum as a raw material, they are not environmentally friendly and contain many harmful components, which causes various diseases including atopy in the human body.

In addition, since petroleum resources are limited, there is a growing need for materials to replace polymers using petroleum resources. Currently, studies on environmentally friendly biopolymers that can replace polymers made from petroleum have been proceeding very rapidly.

However, such a biopolymer is a raw material produced in nature, and has disadvantages of not having physical properties as much as petroleum resources, and a production yield is low, thereby increasing the production cost of the final biopolymer.

As a basic material used as a raw material for biopolymers, a lot of researches are currently being conducted using starch, protein, and fat, and research is proceeding in a wide variety of ways.

On the other hand, castor oil is a petroleum-like oil and has a -OH group, which is suitable for the production of dicarboxylic acid, and is a raw material for biopolymers that can have water resistance, chemical resistance, heat resistance and thixotropy It can be said that it is appropriate.

In the conventional method for producing dicarboxylic acid from castor oil, dicarboxylic acid is produced by reacting castor oil with an alkali catalyst at a high temperature of 200 ° C or higher for 5 hours or more. At this time, octanol, glycerin and fatty acid are produced as by-products.

The dicarboxylic acid prepared from castor oil is sebacic acid. For the production of sebacic acid, a method using a microwave or a method using an adipic acid other than caterpile Lt; / RTI >

Sebacic Acid is a dicarboxylic acid and a derivative of castor oil as white flakes or powder crystals. It is soluble in ethanol, ether and slightly soluble in water. Sebacic acid is derived from the Latin sebaceus (resin candle) or sebum (resin) based on what is used in the manufacture of candles. Their derivatives such as sebacic acid and azelaic acid have a variety of industrial uses such as plasticizers, lubricants, hydraulic oils, cosmetics, candles, and the like. It is used in the synthesis of polyamides and alkyd resins. It is also used as an intermediate for fragrances, preservatives and phaeaceous materials.

The chemical, physical properties and specifications of sebacic acid are shown in Table 1 below.

Chemical name Decanedioic acid
1,8-octanedicarboxylic acid
Dicarboxylic acid C10 The C10H18O4 CAS number 111-20-6 Physical condition and appearance White pieces or powder crystals in pure state Molecular Weight 202.24 g / mole Color Colorless to light yellow incense The fragrant aroma of fatty acids Boiling point decomposition Melting point 132 DEG C (269.6 DEG F) importance 1.207 (water = 1) Density at 25 ° C 1.209 g per cubic centimeter Dispersion characteristic Soluble in water, methanol, diethyl ether, acetone

There are two basic methods for the preparation of sebacic acid. The traditional method is to use castor oil as a starting material and the new method uses adipic acid as a starting point. Although sebacic acid can be synthesized from phenol and cresol, castor oil oxidation is considered to be a more eco-friendly method. Sebacic acid is produced by heating castor oil at high temperature (about 250 ° C) with alkali. This treatment saponifies the castor oil to ricinoleic acid and then decomposes to produce capryl alcohol (2-octanol) and sebacic acid. Although the yield of sebacic acid is low, this route has been found to be cost competitive.

Receiving linoleate acid → alkali fusion at 250 ℃ → 2- octanol _{(CH 3 (CH 2) 5} CH (OH) CH 3) + sebacic acid _{(COOH (CH 2) 8 COOH} ) + H 2

The method is based on the caustic oxidation of castor oil. The type of reaction used affects the purity of the sebacic acid: the most modern conversion techniques result in high purity (there is a more outdated domestic handicraft conversion using a mixture of molten caustic soda and caustic soda).

Also, modern methods for higher yields use castor oil and molten caustic. It is reported that the type of reaction used affects the purity of sebacic acid, and that modern conversion techniques yields sebacic acid with higher purity.

Thermal hydrolysis of ricinoleic acid leads to heptaldehyde and undecenoic acid. Alkali fusion of this mixture leads to 10-hydroxydecanoic acid. At a temperature of 250-270 ° C, an increase of 2 moles of alkali per mole ricinoleate with 10-hydroxydecanoic acid produces capryl alcohol (also called 2-octanol; C8H18O) and sebacic acid.

In the actual reaction, the castor oil and fugitive are fed to the reaction vessel at a temperature of 180 to 270 캜 and proceed to a continuous reaction with the release of hydrogen to produce disodium sebacate and the saccharyl alcohol. When the reaction is complete, the soap is dissolved in water and oxidized to about pH 6. At this pH, the soap is converted to a water-insoluble free acid. The disodium sebacate is then partially neutralized with a halite which is soluble in water.

The oil and the water-soluble layer are separated. The water-soluble layer containing the 1/2 salt is oxidized to about pH 2 and the resulting sebacic acid is allowed to settle out of the solution. It is then filtered, washed with water and finally dried.

A number of process improvement methods have been described, which have the use of a boiling point or cresol mixture of 300 to 400 캜, including the use of white mineral oil. These materials enhance mixing by acting to reduce the viscosity of the reaction mixture.

The preparation of sebacic acid from adipic acid was developed by the Asai chemical industry in Japan and was also piloted in BASF, Germany. It produces high purity sebacic acid from adipic acid. These processes consist of three steps.

1) adipic acid is partially esterified to become monomethyl adipate. 2) Electrolysis of the potassium salt of monomethyl adipate in a mixture of methanol and water produces dimethyl sebacate. 3) The last step is the hydrolysis of dimethyl sebacate with sebacic acid.

The overall yield is reported to be about 85%.

The use of sebacic acid has been named from Latin sebaceus (resin candle) or sebum (resin) based on what is used in the manufacture of candles. One of the great uses of sebacic acid is the production of nylon 6-10. Cevanic acid and hexamethylene diisocyanate produce nylon 6-10 by reaction through condensation polymerization.

Derivatives such as sebacic acid and azelaic acid have a variety of industrial uses such as plasticizers, lubricants, hydraulic oils, cosmetics, candles, and the like. They are used in the synthesis of polyamides and alkyd resins. The isomeric isosevacic acid has different applications in the production of extruded plastics, adhesives, polyesters, polyurethane resins and synthetic rubbers.

Sebacinic acid is also used as an intermediate for fragrances, preservatives and phaeaceous materials. Numerous esters can be obtained from thousands of potential starting materials.

It is used as a combination in corrosion inhibitors and lubricants in metalworking fluids. When mixed with amines, sebacic acid can provide a highly effective water-soluble corrosion inhibitor for metal-pore fluids.

The lithium hydroxystearate complex lubricant uses a dibasic acid such as sebacic acid for more specific performance parameters than the termination. These lubricants require esters of sebacic acid developed for specific performance criteria under changing conditions. Example: DOS (dioctyl sebacate) is highly functional in low temperature formulations and disodium sebacate (DSS) has been used to replace sodium nitrite in aluminum lubricants. Its fine particle size allows it to be added to the oil during the cooling period without any further processing. DMS / DBS (dimethyl sebacate / dibutyl sebacate) is a synthetic base stock that can replace mineral oil for environmentally friendly applications. DOS or DMS in complex lubricant improves operability and low temperature characteristics for application to aircraft, trucks, vehicles and devices exposed to Arctic conditions.

The ester of cevanic acid is also used in the production of plasticizers for vinyl resins and diethyl sebacate, a lubricating oil for jet lubrication oil and air-cooled combustion motors.

The two derivatives of sebacic acid are also used in a wide range of applications. Dibutyl Sebacate (DBS) - Di-n-bibutyl Sebacate (DBS) dissolves ethanol and ether into clear emulsion. This product is widely used as rocket propellant. It is non-toxic and used as packaging material in the food and pharmaceutical industries. It is also used as a cold-resistant plasticizer for synthetic resins and synthetic rubbers. Dioctyl Sebacate (DOS) - Dioctyl Sebacate (DMS) is a clear, flammable liquid with a unique fragrance. With low volatility, high resistance, light shielding and electrical insulation, the product is soluble in hydrocarbons, alcohols, ethers, benzenes and other organic solvents. It is mainly used in the synthetic rubber industry such as PVC, chloroethylene copolymer, nitrocellulose, ethylcellulose and plasticizer and is suitable for cold-resistant cable, artificial leather, thin film, paper material.

Accordingly, the inventors of the present invention have found that by using a zinc oxide (ZnO) catalyst during the reaction in order to improve the decomposition production yield of dicarboxylic acid, the production amount of by-products such as fatty acid is reduced and the loss during the process is reduced, The present inventors have completed the present invention by confirming that the yield of the final dicarboxylic acid in the castor oil is improved to 40-45%, which is 50% or more.

It is an object of the present invention to provide a method for producing a biopolymer based material using a vegetable oil, and more particularly, to provide a high yield production method of sebacic acid as a dicarboxylic acid using castor oil.

In order to accomplish the above object, the present invention provides a method for producing a polyvinyl alcohol copolymer, comprising the steps of: 1) mixing castor oil with NaOH using zinc oxide (ZnO) as a catalyst; 2) cooling the reaction product to remove octanol, and adding sulfuric acid to the remaining solution to adjust the pH; 3) separating the oil component from the reactant and further adding sulfuric acid thereto to lower the pH; And 4) separating the dicarboxylic acid from the reactant. The present invention also provides a method for producing a dicarboxylic acid from a castor oil.

Hereinafter, the present invention will be described in detail.

In the process for producing a dicarboxylic acid from the castor oil of the present invention, the reaction of step 1) is preferably carried out at 350 to 400 ° C. for 7 to 8 hours in nitrogen gas, The pH of the step 2) is preferably adjusted to a pH of 5 to 6, and the pH of the step 3) is preferably lowered to a value of 1.4 to 1.8, and the separation of the step 4) In the reaction product, water in the lower layer portion is preferably removed by decantation, and the upper layer is preferably removed with a filter using activated carbon or activated clay.

In the method for producing a dicarboxylic acid from the castor oil of the present invention, it is preferable that the dicarboxylic acid is sebacic acid, and the catalytic zinc oxide (ZnO) And 50 to 200 parts by weight of NaOH are preferably added, and the purity of the zinc oxide (ZnO) is more preferably 50 to 60%.

In the production of the dicarboxylic acid from the conventional castor oil channel, only an NaOH is added without using an alkali catalyst separately. The dicarboxylic acid produced in the present invention is sebacic acid. Specifically, when catechol is reacted with NaOH, the dicarboxylic acid is hydrolyzed to produce ricinoleic acid. When the dicarboxylic acid is decomposed again, Acid sebacic acid is produced. Other dicarboxylic acids from the castor oil are hardly produced.

More specifically, the present invention is put into parts 50% NaOH 100 parts by weight of the castor oil to 100 parts by weight was put into a reactor equipped with a stirrer, that are compatible with the parts of the high-pressure ZnO 2 parts by weight as a catalyst discharge the air to the N ₂ gas in the N ₂ gas 350 The temperature is set at ~ 400 ° C and the temperature is maintained at 350-400 ° C. At this time, the pressure rises to about 70 to 80 kg / cm 2. After reacting for 7 ~ 8 hours in this state, the reactor is cooled to 100 ~ 150 ℃ through the cooling water, and the waste gas, octanol, is discharged and collected through a condenser. After discharging the waste gas, the contents are added to 1000 parts by weight of water, and 80 to 90% sulfuric acid is added thereto while the temperature is cooled to 80 to 90 ° C to adjust the pH to 5.5. Thereafter, the mixture is allowed to stand for 2 to 5 hours to separate the upper part having oil and the lower part having water-soluble components. When the upper part with the oil is separately extracted and the pH is adjusted to the acidity of about 1.4 to 1.8 by adding 80% to 90% sulfuric acid again, the dicarboxylic salt reacts with the sulfuric acid to produce the dicarboxylic acid and the gum (sodium sulfate, sodium sulfate) occurs. The upper layer containing a large amount of dicarboxylic acid is subjected to decantation, which is a separation method, to remove the remaining water layer and impurity layer. Subsequently, a small amount of impurities is removed using activated clay or activated carbon to prepare a dicarboxylic acid having a purity of 95% or more. At this time, the produced dicarboxylic acid can obtain a production yield of 50 to 55% of the initial amount of castor oil.

At this time, ZnO added as a catalyst is dissolved in sulfuric acid and treated with wastewater. Octanol produced as a by-product is subjected to vacuum distillation, and it is discharged at a constant temperature at 180-190 ° C (BP 194.5 ° C) according to the degree of vacuum without raising the temperature to obtain colorless transparent 2-octanol.

The production of sebacic acid, which is a dicarboxylic acid, from the castor oil using the zinc oxide according to the present invention as described above can reduce the production amount of by-products such as fatty acid and the loss during the process, .

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art may understand the present invention without departing from the scope and spirit of the present invention. It is not.

≪ Example 1 >

100 parts by weight of 50% NaOH was added to 100 parts by weight (OH value of 160) of castor oil, and 1 part by weight of ZnO with 55% purity was added thereto. Then, the mixture was filled with N ₂ gas and stirred at 350 ° C. The reaction time was 350 ° C for 7 hours. At this time, the pressure increased to 70 ~ 80 kg / ㎠. After completion of the reaction, the reaction mixture was cooled to 120 ° C through a capillary coil, and then octanol as a gaseous component was discharged. The resultant product was dissolved in 1000 parts by weight of water and sulfuric acid was added thereto to adjust the pH to 5.5. The upper part with oil was extracted and the pH was adjusted to 1.7 by adding sulfuric acid again, and the water layer in the lower part was removed and the upper part was separated. Activated carbon was injected into the separated upper layer oil, and after using the filter, impurities were removed to prepare a dicarboxylic acid. At this time, the content of dicarboxylic acid produced was over 95% and the yield of production was 45%.

≪ Example 2 >

100 parts by weight of 50% NaOH was added to 100 parts by weight (OH value of 160) of castor oil, and then 3 parts by weight of 55% ZnO was added. The mixture was filled with N ₂ gas and stirred at 350 ° C. The reaction time was 350 ° C for 7 hours. At this time, the pressure increased to 70 ~ 80 kg / ㎠. After completion of the reaction, the reaction mixture was cooled to 120 ° C through a capillary coil, and then octanol as a gaseous component was discharged. The resultant product was dissolved in 1000 parts by weight of water and sulfuric acid was added thereto to adjust the pH to 5.5. The upper part with oil was extracted and the pH was adjusted to 1.7 by adding sulfuric acid again, and the water layer in the lower part was removed by decantation and the upper part was separated. Activated carbon was injected into the separated upper layer oil, and after using the filter, impurities were removed to prepare a dicarboxylic acid. At this time, the content of dicarboxylic acid produced was over 95% and the yield of production was 50%.

≪ Example 3 >

After 100 parts by weight of 50% NaOH was added to 100 parts by weight (OH value of 160) of castor oil, 2 parts by weight of ZnO of 55% purity was added, filled with N ₂ gas and then set at 350 ° C while stirring. The reaction time was 350 ° C for 7 hours. At this time, the pressure increased to 70 ~ 80 kg / ㎠. After completion of the reaction, the reaction mixture was cooled to 120 ° C through a capillary coil, and then octanol as a gaseous component was discharged. The resultant product was dissolved in 1000 parts by weight of water and sulfuric acid was added thereto to adjust the pH to 5.5. The upper part with oil was extracted and the pH was adjusted to 1.7 by adding sulfuric acid again, and the water layer in the lower part was removed by decantation and the upper part was separated. Activated carbon was injected into the separated upper layer oil, and after using the filter, impurities were removed to prepare a dicarboxylic acid. At this time, the content of dicarboxylic acid produced was over 95% and the yield of production was 48%.

<Example 4>

After adding 100 parts by weight of 50% NaOH to 100 parts by weight of castor oil (OH value of 160), 3 parts by weight of ZnO of 90% purity was added, filled with N ₂ gas and then set at 350 ° C while stirring. The reaction time was 350 ° C for 7 hours. At this time, the pressure increased to 70 ~ 80 kg / ㎠. After completion of the reaction, the reaction mixture was cooled to 120 ° C through a capillary coil, and then octanol as a gaseous component was discharged. The resultant product was dissolved in 1000 parts by weight of water and sulfuric acid was added thereto to adjust the pH to 5.5. The upper part with oil was extracted and the pH was adjusted to 1.7 by adding sulfuric acid again, and the water layer in the lower part was removed by decantation and the upper part was separated. Activated carbon was injected into the separated upper layer oil, and after using the filter, impurities were removed to prepare a dicarboxylic acid. At this time, the content of dicarboxylic acid produced was over 95% and the yield of production was 50%.

<Comparative Example>

To 100 parts by weight of castor oil (OH value of 160) was added 100 parts by weight of 50% NaOH to the reactor, filled with N ₂ gas, and then set at 350 ° C while stirring. The reaction time was 350 ° C for 7 hours. After completion of the reaction, the reaction mixture was cooled to 120 ° C through a capillary coil, and then octanol as a gaseous component was discharged. The resultant product was dissolved in 1000 parts by weight of water and sulfuric acid was added thereto to adjust the pH to 5.5. The upper part with oil was extracted, and sulfuric acid was added again to adjust pH to 1.7, and the solution was allowed to stand to prepare a dicarboxylic acid stock solution.

Impurities were removed from the dicarboxylic acid stock solution using activated carbon. At this time, the content of dicarboxylic acid produced was more than 95% and the yield of production was 40%.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, This is possible.

Claims (8)

1) 100 parts by weight of castor oil and 50 to 200 parts by weight of NaOH were mixed in nitrogen gas at 350 to 400 ° C for 7 to 8 hours using 1 to 3 parts by weight of zinc oxide (ZnO) having a purity of 50 to 60% ;
2) cooling the reaction product to remove octanol, and adding sulfuric acid to the remaining solution to adjust the pH;
3) separating the oil component from the reactant and further adding sulfuric acid thereto to lower the pH; And
4) removing water from the lower part of the reaction product by decantation and removing the impurities by using a filter using activated carbon or activated clay to separate the dicarboxylic acid from the castor oil to obtain dicarboxylic acid &Lt; / RTI &gt;
delete The method for producing a dicarboxylic acid according to claim 1, wherein the cooling in step 2) is carried out at 100 to 150 ° C.
The method according to claim 1, wherein the pH of step 2) is adjusted to a pH of 5 to 6, and the pH of step 3) is lowered to a pH of 1.4 to 1.8. Way.
delete The method for producing a dicarboxylic acid according to claim 1, wherein the dicarboxylic acid is sebacic acid.
delete delete