KR102493012B1 - Purification method of feedstock for the olefin metathesis - Google Patents

Abstract

The present invention is a method for purifying a raw material for olefin metathesis reaction, which maximizes the reaction activity of a metathesis catalyst by removing catalyst toxic impurities in the raw material for olefin metathesis reaction to a high degree by contacting the raw material for olefin metathesis reaction with a metal particle mixture, comprising: manganese, A metal particle mixture prepared by supporting two or more transition metals selected from among iron, cobalt, and nickel on an unsupported or porous material is used.

Description

Olefin metathesis reaction raw material purification method {Purification method of feedstock for the olefin metathesis}

The present invention relates to a method for purifying natural oil and oil derivatives used as a reaction raw material in an olefin metathesis reaction and an olefin metathesis reaction using the purified raw material.

Olefin metathesis reaction is a reaction that can convert animal and plant oils and derivatives of animal and plant oils, which are natural resources with olefin functional groups, into industrially useful chemicals. there is.

In particular, among animal and vegetable oils, oleic acid and methyl oleate (MO), an oleic acid derivative, can synthesize alpha-olefin and alpha-omega-olefin carboxylic acids by cross-metathesis with ethylene, propylene, and butene, Since it can be converted into high-value substances such as dicarboxylic acid through self-metathesis, it is attracting attention as a useful raw material for metathesis in the chemical industry. Therefore, for this metathesis reaction, studies on catalysts including transition metals such as ruthenium, molybdenum, and tungsten are being actively conducted.

However, impurities inevitably included in the reaction raw material due to exposure to oxygen react with the catalyst, thereby significantly reducing the activity of the metathesis catalyst. This leads to a decrease in turnover number (TON), which is an indicator of catalytic activity. In particular, in the case of a highly active metathesis reaction of 30,000 TON or more, since the amount of catalyst used is 20 ppm or less, strict removal of toxic impurities contained in the reactants in the metathesis reaction is an important part for commercial application of the metathesis reaction.

Therefore, in order to maximize the activity of the metathesis catalyst to 30,000 TON or more, especially 50,000 TON or more, since the amount of catalyst used is 10 ppm or less, a method of reducing catalytic toxic impurities in the reactants to several ppm or less is essential. The most common of these methods is a method of removing impurities through alumina. A previously reported method is a method of using alumina at a concentration of about 1.5 wt.% or more compared to methyl oleate and undergoing a pretreatment process for at least one month (Angew. Chem. Int. Ed. 2015, 54, 1919-1923). However, such a method is not suitable because it takes too much time for purification and requires high-purity methyl oleate of 99% or more and has low industrial economic feasibility.

According to previous studies related to this, toxic impurities in metathesis catalysts in raw materials include peroxides and non-peroxides such as dyes and polar substances, and it is known that these impurities act as catalyst poisons and reduce catalyst activity. Specifically, typical catalyst poisons include peroxides, which are compounds inevitably generated when animal and vegetable oils, which are metathesis raw materials, meet oxygen in the air, peroxide radicals, which are oxygen-containing radicals, aldehyde compounds, and anisidine, phosphates, and sulfates.

In order to remove impurities from raw materials such as natural oils and oil derivatives, heat treatment is used to remove impurities in raw materials (U.S. Patent NO. 8,692,006 B2, 2014), using chemicals such as sodium bisulfite A method for removing impurities in the raw material by using a method (U.S. Patent NO. 8,642,824 B2, 2014) is proposed, and in order to remove various impurities, metal alkyl compounds, alumina, silica gel, montmorillonite clay, acid clay, bleaching earth, diatomaceous earth , A method of removing impurities from raw materials with various materials having strong adsorption properties for each impurity, such as zeolite, kaolin, acid anhydride, and activated carbon, was proposed (Korean Patent Publication No. 10-2015-0129681). However, in the case of this method, although the impurity content level of the raw material is reduced to a level at which the metathesis reaction is possible, the removal level of impurities is not high because a large amount of catalyst is required, the purification method is complicated, and the TON of the metathesis reaction is not high.

Therefore, there is still a need for technical development of a method for purifying raw materials for olefin metathesis reaction by highly removing catalytic toxic impurities to increase the efficiency of the metathesis catalyst.

US registered patent US 8,692,006 B2 (2014. 04. 08. registration) US Registered Patent US 8,642,824 B2 (2014. 02. 04. Registration) Korean Patent Publication No. 10-2015-0129681 (published on November 20, 2015)

Angew. Chem. Int. Ed. 2015, 54, 1919-1923

In order to solve the above problems, the present researchers aim to provide an efficient method for obtaining a purified raw material for olefin metathesis reaction by highly removing impurities that act as catalyst poisons in natural oil or oil derivative raw materials.

In addition, the present invention provides an efficient method for carrying out ethylene metathesis reaction even with a small amount of catalyst by using raw materials for olefin metathesis reaction purified by removing impurities that act as catalyst poisons in natural oil or oil derivative raw materials to a high degree. do.

In order to solve the above problems, a step of obtaining a purified raw material for olefin metathesis reaction by contacting the raw material for olefin metathesis reaction with a metal particle mixture to remove catalytic toxic impurities, wherein the metal particle mixture is manganese, iron, cobalt , It is intended to provide a method for purifying a raw material for olefin metathesis reaction, characterized in that metal particles containing two or more transition metals of nickel are mixed.

In one embodiment of the present invention, the metal particle mixture may be supported in a porous material.

In one embodiment of the present invention, the metal particle mixture includes at least two or more of iron, nickel, and cobalt, and the content ratio of metal component 1 and metal component 2 is 1: 5 to 5: 1, preferably 1: It can be 2 to 2:1.

In one embodiment of the present invention, the porous material may be any one or more selected from alumina, silica, titania, zirconium oxide, carbon black, graphene, and carbon nanotubes.

In one embodiment of the present invention, the porous material may be any one or more selected from alumina, silica, silica alumina, and zeolite.

In one embodiment of the present invention, the raw material for the olefin metathesis reaction may be any one selected from vegetable oil, animal oil, and derivatives thereof.

In one embodiment of the present invention, the raw material for the olefin metathesis reaction is oleic acid or an oleic acid derivative, 9-decenoic acid, methyl 9-decenoate, 10-undecenoate 10-undecenoic acid, methyl 10-undecenoate, 9-octadecenedioic acid, methyl 9-octadecenedioate, 12- 12-tridecenoic acid, methyl 12-tridecenoate, 13-tetradecenoic acid, methyl 13-tetradecenoate, It may be at least one selected from 11-dodecenoic acid and methyl 11-dodecenoate.

The present invention also provides a step of contacting a raw material for olefin metathesis reaction with a metal particle mixture to obtain a first-purified raw material for olefin metathesis reaction; and b) contacting the firstly purified raw material for olefin metathesis reaction with activated alumina particles to obtain a second purified raw material for olefin metathesis reaction, wherein the metal The particle mixture provides a method for purifying raw materials for olefin metathesis reaction, characterized in that metal particles containing two or more transition metals of manganese, iron, cobalt, and nickel are unsupported or supported on a porous material.

In addition, the present invention is a remover for removing catalytically toxic impurities in raw materials for olefin metathesis reaction, wherein the remover includes a metal particle mixture containing two or more transition metals among manganese, iron, cobalt, and nickel. A remover for removing catalytically toxic impurities in a raw material for an olefin metathesis reaction is provided.

In one embodiment of the present invention, the metal particle mixture of the remover may be supported on a porous material.

The present invention also provides a method for carrying out olefin metathesis reaction with a raw material for olefin metathesis reaction from which catalyst toxic impurities have been removed by purification according to the method of the present invention in the presence of a catalyst for olefin metathesis reaction.

In one embodiment of the present invention, the input amount of the catalyst for the olefin metathesis reaction may be 20 ppm or less.

The present invention is a simple operation of contacting toxic impurities of the metathesis catalyst that may be present in the raw material for olefin metathesis reaction with a metal particle mixture containing two or more transition metals of manganese, iron, cobalt, and nickel, and oil derivative raw material of the metathesis catalyst can effectively remove toxic impurities.

Therefore, if the method for purifying raw materials for olefin metathesis reaction according to the present invention is used, catalytic toxic impurities can be easily removed to easily purify low-purity raw materials for olefin metathesis reaction into high-purity ones. raw materials can also be used, which is economically advantageous.

In addition, when the metathesis reaction is performed using the raw material for the olefin metathesis reaction purified according to the present invention and the catalytic toxic impurities are removed, the amount of the metathesis catalyst is minimized (10 ppm or less) and the catalytic activity is maximized (50,000 TON or more). can

1 is a schematic diagram of a circulation purification system for raw materials for olefin metathesis reaction using a metal particle mixture in one embodiment of the present invention.
2 is a schematic diagram of a circulation and purification system for raw materials for olefin metathesis reaction using activated alumina in one embodiment of the present invention.
3 is a molecular structure of a catalyst for olefin metathesis reaction (Ru-CAAC, Ultra-Cat, etc.) used in an embodiment of the present invention.

Hereinafter, the configuration of the present invention, including a preferred embodiment, in which a person skilled in the art to which the present invention pertains can easily practice the present invention will be described in detail. In describing the principles of preferred embodiments of the present invention in detail, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is one well known and commonly used in the art.

Throughout the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

Terms used in this specification may be defined as follows.

The term "refining" used in the method of purifying the raw material for olefin metathesis reaction by removing impurities contained in the raw material for olefin metathesis reaction according to the present invention refers to the high purity of the raw material for olefin metathesis reaction by removing 100% of all impurities. It does not mean that the catalyst has a negative effect, but it means that the negative effect of the catalyst is mitigated and the efficiency of the catalyst is increased by reducing certain impurities that have a negative effect on the catalyst.

In addition, the term "impurity" used in the method for removing catalytically toxic impurities contained in the raw material for olefin metathesis reaction according to the present invention has a broad effect on the catalyst used for olefin metathesis and the catalyst metathesis reaction using natural oil raw materials. Indicates any impurities that may be present. The impurities include peroxides and non-peroxides such as pigments and polar substances, and specifically, peroxides, which are compounds inevitably generated when animal and vegetable oils, which are raw materials for olefin metathesis, meet oxygen in the air, peroxide radicals, which are radicals containing oxygen, and hydro It refers to peroxides, hydroxydienes, aldehyde compounds, epoxyhydroxy compounds, and anisidine, phosphates, and sulfates, and these impurities greatly reduce the activity of olefin metathesis catalysts, thereby lowering the metathesis reaction.

The present invention relates to a method for purifying raw materials for olefin metathesis reaction by highly removing impurities contained in raw materials for olefin metathesis reaction. Even in the presence of a metathesis catalyst, the catalytic activity of the metathesis reaction shows an excellent effect.

First, the method for purifying a raw material for olefin metathesis reaction according to the present invention includes the step of contacting the raw material for olefin metathesis reaction with a metal particle mixture to obtain a purified raw material for olefin metathesis reaction in order to highly remove catalytically toxic impurities in the raw material. The metal particle mixture is characterized in that metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel are mixed.

Hereinafter, a method for purifying a raw material for olefin metathesis reaction in which impurities toxic to the metathesis catalyst are highly removed from the raw material for olefin metathesis reaction according to the present invention will be described in detail.

The purification method according to the present invention includes the step of contacting the raw material for olefin metathesis reaction with a metal particle mixture to remove catalytic toxic impurities to obtain a purified raw material for olefin metathesis reaction, wherein the contact reaction with the raw material for olefin metathesis reaction The metal particle mixture may include two or more transition metals among manganese, iron, cobalt, and nickel as metal components, and the ability to remove impurities in the raw material for olefin metathesis reaction is determined depending on the type and content of the specified transition metal. .

Preferably, the metal component in the metal particle mixture may include iron and nickel at the same time, and more preferably, the metal component in the metal particle mixture includes iron, nickel, and cobalt to show high metathesis reaction catalytic activity, As a result, it shows a high conversion value.

Here, a turnover number (TON) is used as an indicator of the activity of the metathesis reaction catalyst, and the turnover number (TON) means a value obtained by dividing the number of moles of a metathesis product by the number of moles of a catalyst used in the metathesis reaction.

TON = (number of moles of product of metathesis reaction)/(number of moles of catalyst used)

In addition, as an embodiment, when the metal particle mixture simultaneously includes iron and nickel as metal components, the content ratio of iron and nickel is preferably 1: 5 to 5: 1, more preferably the iron and nickel A nickel content ratio of 1:2 to 2:1 indicates a high conversion value of the metathesis reaction.

The metal particle mixture may be used even when not supported on a carrier, but may be prepared by supporting the transition metal particles on a porous material for convenience of handling.

A manufacturing method thereof includes a) preparing a metal precursor mixture solution by dissolving two or more precursors of a transition metal in an appropriate solvent; b) preparing a slurry of the metal precursor mixture and the porous material by adding the porous material to the metal precursor mixture solution; c) drying the slurry to obtain a porous material containing a metal precursor mixture; d) obtaining a porous material containing a metal particle mixture by heat-treating the porous material containing the metal precursor mixture; and e) reducing and activating the metal particle mixture-containing porous material obtained through the heat treatment, but is not limited thereto.

Step a) is a step of preparing a metal precursor mixture solution by dissolving two or more types of transition metal precursors in an appropriate solvent.

The precursor of the transition metal refers to a metal salt that can be a source of an active transition metal because transition metal ions are coordinated with other organic materials, specifically, including two or more transition metal precursors among manganese, iron, cobalt, and nickel. , Two or more metal precursors may be used in combination.

The precursor of the transition metal may preferably be a transition metal precursor of nitrate, acetate, acetylacetoate, or carbonate.

At this time, as the solvent used in the process of dissolving two or more types of transition metal precursors in a solvent, an appropriate solvent in which the transition metal precursor can be easily dissolved may be used, and specifically, water or propanol, ethanol, methanol, acetone, tetrahydrofuran and Any suitable organic solvent may be used.

Step b) is a step of preparing a slurry of the metal precursor mixture solution and the porous material by adding the porous material to the metal precursor mixture solution.

At this time, the porous material used as the carrier of the transition metal may be a metal oxide such as alumina, silica, silica alumina, zeolite, titania, or zirconium oxide, or a porous carbon material such as carbon black, graphene, or carbon nanotube, Preferably, it is a porous material such as alumina, silica, silica alumina, or zeolite.

Step c) is a step of drying the slurry of the metal precursor mixture solution and the porous material to obtain a porous material containing the metal precursor mixture.

Specifically, in the drying process, it is preferable to perform the slurry in which the transition metal precursor solution and the porous material are mixed at a temperature of 30 to 150° C. for 1 hour or more, but is not limited thereto.

Step d) is a step of heat-treating the porous material containing the metal precursor mixture, and in this process, the metal precursor is converted into a metal oxide form.

Specifically, the heat treatment of the porous material containing the dried metal precursor mixture is preferably performed in an oven at a temperature of 100 to 400° C. for 3 hours or more, but is not limited thereto.

Finally, step e) is a step of reducing and activating the obtained porous material containing a mixture of metal particles, and converting the metal converted into an oxide form in step d) into a form suitable for purification of a raw material for metathesis decomposition. It is an essential process for

Specifically, the activation step is preferably performed at a temperature of 300 to 600 ° C. for 7 hours or more while introducing an inert mixed gas or pure hydrogen gas having a hydrogen concentration of 5% or more.

In the present invention, the material to be purified having impurities is a raw material for olefin metathesis reaction, and includes, for example, natural oil and natural oil derivatives having an olefin functional group. The olefin refers to an unsaturated hydrocarbon compound containing at least one carbon-carbon double bond.

As an example, any one selected from vegetable oil, animal oil, and derivatives thereof having an olefin functional group may be used as a raw material for the olefin metathesis reaction in the present invention.

The raw material for the olefin metathesis reaction is specifically, oleic acid or a methyl oleate derivative, such as 9-decenoic acid, methyl 9-decenoate, 10-undecenoic acid (10 -undecenoic acid), methyl 10-undecenoate, 9-octadecenedioic acid, methyl 9-octadecenedioate, 12-tridecenoic acid (12-tridecenoic acid), methyl 12-tridecenoate, 13-tetradecenoic acid, methyl 13-tetradecenoate, 11-dodecenoate It may be at least one selected from 11-dodecenoic acid and methyl 11-dodecenoate.

The present invention can obtain a purified raw material for olefin metathesis reaction by bringing the raw material for olefin metathesis reaction into contact with a metal particle mixture, and the purified raw material for olefin metathesis reaction has catalytic activity of the metathesis reaction even in the presence of a small amount of a metathesis catalyst. shows excellent effect.

As shown in FIG. 1 below, the contact reaction between the metal particle mixture and the raw material for olefin metathesis reaction is performed by supplying the raw material for olefin metathesis reaction to a tube filled with the metal particle mixture at a temperature of 30 to 200 ° C. for 1 hour or more contact can be made.

The amount of the raw material for olefin metathesis reaction supplied to the tube filled with the metal particle mixture may be 1 to 30 times greater than the weight of the catalytically active metal.

At this time, when the raw material for olefin metathesis reaction comes into contact with oxygen, impurities that have a fatal effect on the metathesis catalyst are generated, so the raw material for olefin metathesis reaction proceeds in an environment where it cannot come into contact with oxygen. Specifically, the entire purification system is inactive. It is possible to avoid contact with oxygen by supplying raw materials for olefin metathesis reaction in a state in which a positive pressure is applied by pressurizing with gas.

In addition, the present invention provides a method for purifying a raw material for olefin metathesis reaction, comprising: i) contacting the raw material for olefin metathesis reaction with a metal particle mixture to obtain a first-purified raw material for olefin metathesis reaction; and ii) obtaining a secondly purified raw material for olefin metathesis reaction by contacting the firstly purified raw material for olefin metathesis reaction with alumina particles, wherein the metal particle mixture is selected from among manganese, iron, cobalt, and nickel. As a mixture of two or more transition metal particles, it provides a method characterized by being in a non-supported form or a form supported in a porous material.

In this case, the contact reaction between the raw material for olefin metathesis reaction and the metal particle mixture in step i) is the same as described above.

A method for purifying a raw material for olefin metathesis reaction by removing impurities that may be present in the raw material for olefin metathesis reaction and acting as a catalyst poison for the catalyst for olefin metathesis reaction according to the present invention, wherein i) the raw material for olefin metathesis reaction is mixed with metal particles contacting the mixture to obtain a firstly purified raw material for olefin metathesis reaction; and ii) contacting the firstly purified raw material for olefin metathesis reaction with activated alumina particles to obtain a secondly purified raw material for olefin metathesis reaction; Impurities in the raw material for olefin metathesis can be removed at a higher rate through the secondary purification process of the raw material for metathesis reaction with activated alumina particles, and the second purified raw material for olefin metathesis reaction has better reactivity in metathesis reaction can represent

In step ii), the activated alumina is neutral alumina that is not acidic or basic, and preferably is porous neutral alumina having a specific surface area of 150 m ² /g or more and a pore size of 50 Å or more.

As shown in FIG. 2 below, in step ii), the raw material for olefin metathesis reaction, which has been primarily purified as a metal particle mixture, may be supplied to a tube filled with activated alumina and brought into contact with it at a temperature of 30 to 200 ° C. It can be carried out in contact for an hour or more.

The amount of the raw material for olefin metathesis reaction supplied to the tube filled with activated alumina may be 1 to 30 times greater than that of activated alumina.

At this time, in step ii), the entire purification system was pressurized with an inert gas to avoid contact with oxygen by supplying raw materials for olefin metathesis reaction in a state where a positive pressure was applied.

Therefore, the raw material for olefin metathesis reaction obtained through the secondary purification process of the raw material for olefin metathesis reaction, which was first purified from the contact reaction with the metal particle mixture, is an impurity that adversely affects the catalyst for olefin metathesis reaction. Since this is highly removed, it is possible to achieve a higher conversion number (TON) than conventional high vacuum multi-stage fractional distillation or alumina purification.

That is, when the metathesis reaction is performed using a raw material for olefin metathesis reaction from which impurities are highly removed, a larger amount of high added value is obtained as the yield increases with the same amount of catalyst than when a raw material for olefin metathesis reaction of low purity is used. The product can be obtained, and the effect of increasing economic efficiency is brought about by minimizing the amount of catalyst used and reducing the cost of separating and refining the catalyst from the product.

In addition, the present invention provides a remover for removing catalytically toxic impurities in a raw material for an olefin metathesis reaction, characterized in that it comprises a metal particle mixture in which metal particles containing two or more transition metals of manganese, iron, cobalt, and nickel are mixed. to provide.

The metal particle mixture of the remover may be supported in a porous material, and the porous material may be one or more selected from alumina, silica, silica alumina, zeolite, titania, zirconium oxide, carbon black, graphene, and carbon nanotubes. there is.

In addition, the present invention provides a method for metathesis reaction of raw materials and olefins obtained by the method for purifying the raw materials for olefin metathesis reaction, wherein the added catalyst has a very low content compared to the case of using raw materials that have not undergone a purification process. The reaction can be activated, and the conversion rate is high.

As an example, the catalyst input in the ethylene metathesis reaction according to the present invention can effectively perform the metathesis reaction even at 20 ppm or less, and preferably, the metathesis reaction can be performed even at 10 ppm or less.

At this time, as a catalyst in the ethylene metathesis reaction according to the present invention, Ru-CAAC [Ru-Cyclic Alkyl Amino Carbene], UltraCat [Ru-Bis (Cyclic Alkyl Amino Carbene)], and the like may be used.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

Examples 1-13

(1) Synthesis of Porous Materials Containing Metal Particle Mixtures

Based on the content of the transition metal in the porous material containing the metal particle mixture is 1 mmol / g, a metal-supported composite is synthesized in which single or two or more manganese, iron, nickel, and cobalt precursors are mixed in a predetermined molar ratio. At this time, the metal precursors used were Fe(NO ₃ ) ₃ 9H ₂ O, Ni(NO ₃ ) ₂ 6H ₂ O and Co(NO ₃ ) ₂ 6H ₂ O, and the molar ratio used in this example was Fe, Ni, Mn, Fe/Ni(4:1), Fe/Ni(1:1), Fe/Co(1:1), Co/Ni(1:1), Ni/Mn(1:1) , Fe/Ni/Co (1:1:1), and 40mmol metal precursors corresponding to each molar ratio were dissolved in 25mL ethanol to prepare a solution. At this time, the temperature was raised to 45° C. or higher to completely melt the transition metal precursor. In this way, 40 g of neutral alumina (activated, neutral, Brockmann I) was added to the solution in which the metal precursor was completely dissolved, mixed physically, and then dried in an oven at 70° C. for 1 hour. After that, it is put into a sintering furnace and heat-treated at 100 ° C for 3 hours and at 350 ° C for 5 hours. Then, as in the raw material purification system 1 shown in FIG. 1, 20 ml of the heat-treated transition metal/alumina was filled in a stainless steel tube with a diameter of 1/2 inch and a length of 30 cm, and hydrogen mixed nitrogen gas (23% hydrogen concentration) was supplied at 65 ml/ml. It was activated at 500° C. for 10 hours by supplying at a rate of min.

(2) Purification of methyl oleate using a mixture of metal particles

Methyl oleate was purified in the raw material purification system shown in FIG. 1 using the prepared porous material containing the metal particle mixture. Sigma-Aldrich's technical grade, 70% methyl oleate was fractionated to produce 96% pure methyl oleate, which was used as a raw material for metathesis reaction. Before refining raw materials, nitrogen was blown into the entire refining system to remove oxygen from the gas line and storage, and then a positive pressure of more than 1 atm was maintained with nitrogen gas to prevent oxygen from entering the system. After that, methyl oleate was added to the reaction raw material reservoir 1, and the stainless steel tube filled with the porous material containing the prepared metal particle mixture was heated to 50 ° C. While maintaining the temperature, 100 ml of methyl oleate was supplied through a pump at 8 mL/ml for 12 hours. methyl oleate was purified by feeding at a min rate. At this time, methyl oleate is circulated to raw material storage 1 after contact with the porous material containing the prepared metal particle mixture, and toxic impurities contained in the raw material are purified as the circulation contact time elapses, and the purified methyl oleate after 12 hours undergoes a metathesis reaction used as raw material.

(3) Secondary purification of methyl oleate using alumina

Secondary purification of methyl oleate was performed using alumina in the raw material purification system using activated alumina shown in FIG. 2 . 20 ml of porous neutral alumina (activated, neutral, Brockmann I, specific surface area 205 m ² /g, pore size 58 Å) was filled in a 1/2 inch diameter, 30 cm long stainless steel tube, and vacuumed to 10 mbar at 250 ° C for 10 hours. Activated. After that, the first purified methyl oleate as a metal supporting composite was added to the reaction raw material reservoir 2, and 100 ml of methyl oleate was supplied through a pump at a rate of 2 mL/min for 12 hours at room temperature at 25 ° C to purify methyl oleate. . At this time, methyl oleate is circulated to the raw material storage 2 after contact with activated alumina, and toxic impurities contained in the raw material are purified as the circulation contact time elapses, and the second purified methyl oleate after 12 hours is used as a raw material for the metathesis reaction. .

(4) Ethylene metathesis reaction of purified methyl oleate

Metathesis experiments were performed as follows. In a 20ml glass vial in a glove box, 5g of primary or secondary purified methyl oleate and 100mg of internal standard (IS, internal standard) dodecane and Ru-CAAC (made to order from Aperion or synthesized) or UltraCat (purchased from Aldrich) ) 10 ppm of metathesis catalyst (Ru-CAAC: 0.11 mg, UltraCat: 0.17 mg) was added. The vial containing the reactant was put into a 125ml stainless reactor and the reactor was fastened. The molecular structure of the metathesis catalyst used is shown in FIG. 3 . Thereafter, the reactor was taken out of the glove box, filled with 10 bar of ethylene, and stirred at 40° C. for 3 hours to proceed with the ethylene metathesis reaction. Quantitative analysis of the reacted material was performed by measuring the area of the product and unreacted material compared to the internal standard using gas chromatography (GC). After the sample passed through the DB-23 column, the product was analyzed through an FID detector. TON is a value obtained by dividing the number of moles of catalyst used by the number of moles of methyl 9-decenoate (9DCE) produced, and was used as an indicator of catalyst efficiency. The analysis results are shown in Table 1 below.

Comparative Examples 1-2

In order to compare the purification effect of removing impurities from the methyl oleate raw material, the metathesis reaction was performed under the same conditions as in Example 1 without refining the methyl oleate raw material, and the results are shown in Comparative Example 1 in Table 1 below. The results of the metathesis reaction using raw materials that had undergone a purification process using alumina without a purification process using a particle mixture are shown in Comparative Example 2 in Table 1 below.

Comparative Examples 3 to 5

In order to compare the purification effect of metal particle mixtures other than manganese, iron, nickel, and cobalt, vanadium (V), copper (Cu), and nickel/copper (Ni/ It was synthesized in the same manner except for changing to Cu (1/1)), and a metathesis reaction was performed under the same conditions as in Example 1, and the results are shown in Comparative Examples 3-5 in Table 1 below.

- Methyl oleate conversion rate (%) means the following.

Conversion rate = 100 - 100 x [(Number of moles of methyl oleate after reaction/Number of moles of methyl oleate initially added)]

- 1-decene + methyl 9-decennoate selectivity (%) means the following.

Selectivity = 100 x [(total number of moles of metathesis reaction product (1-decene + methyl 9-decenoate) / (total number of moles of metathesis reaction product + (2 x total number of moles of byproduct))]

/ In the calculation, the total number of moles of by-products must be multiplied by 2 because the by-products are catalytically prepared from two methyl oleates.

- TON is the number of conversions.

TON = number of moles of methyl 9-decenoate (9DCE) produced / number of moles of catalyst used

[Table 1] metathesis reaction results

As shown in Table 1, in Comparative Example 1 in which the metathesis reaction of methyl oleate from which impurities were not removed, the metathesis reaction did not proceed at all, and Examples 1 to 5 using raw materials purified with the metal particle mixture , 7, 9 to 11, it was confirmed that the conversion rate (TON) increased significantly compared to Comparative Example 2 purified only by activated alumina.

In addition, Examples 4 to 10 in which two or more metals are mixed show a tendency to increase activity more than when one metal is used, and the degree of activity increase at this time is the arithmetic average of the activities of two or more metals show more reactivity.

For example, the sum of the moles of Fe and Ni in the mixed metal of Fe and Ni of Example 5 uses the same number of moles as in Example 1 or Example 2 for each of the metals, Fe and Ni. That is, compared to Example 1, the number of moles of Fe in Example 5 corresponds to only 50%. However, the TON of Example 5 is 51,600, which is about 1.8 times the arithmetic average of 29,400 of Example 1 and 29,200 of Example 2, 29,300. This is due to the use of a mixed metal of Fe and Ni, which shows a higher effect than the case of using each metal alone, and it can be seen that the two or more metals show a synergistic effect with each other. In particular, the conversion rates of Examples 11 to 13 purified using a metal particle mixture prepared by mixing three types of metals at a ratio of Fe / Ni / Co (1: 1: 1) were 60,800 and 61,000, respectively. It was confirmed that the reactivity was maximized.

On the other hand, in the case of Comparative Example 5, when Ni and Cu were mixed, the TON was 4,200, which is much lower than the arithmetic average of 16,100 of the TON values in Ni and Cu single metals, synergistic effect due to the mixing of these two metals It was confirmed that it occurs only between specific metals.

Through these results, the method for removing toxic impurities in methyl oleate using the metal particle mixture according to the present invention can remove impurities more efficiently in less time than the previously known impurity removal method using alumina, and the minimum amount of catalyst It can be confirmed that the catalyst cost is reduced and the efficiency of the catalyst activity is increased by using the catalyst, and the productivity of the metathesis reaction is increased, which can be expected to reduce costs and increase efficiency in future industrial applications.

Examples 14 to 19: Impurity removal and metathesis reaction by purity of methyl oleate raw material using metal particle mixture

The raw material for methyl oleate was purified by purity using a metal particle mixture having a ratio of Fe/Ni (1:1) among active transition metals to remove impurities, and then a metathesis reaction was performed. Except for the purity of methyl oleate, all experimental conditions were carried out in the same manner as in Example 1. A total of three types of methyl oleate were used: Sigma-Aldrich technical grade, 96% methyl oleate obtained by fractional distillation of 70% methyl oleate, 90% methyl oleate from Acros and 70% technical grade methyl oleate from Sigma-Aldrich. did

[Table 2] metathesis reaction results

In Examples 14 to 19, after purifying methyl oleate having different purities, as a result of performing ethylene metathesis of the purified methyl oleate, the higher the purity, the higher the conversion rate (TON ) could be confirmed. In addition, when performing additional alumina purification, the higher the purity of the raw material, the higher the conversion rate (TON) increase rate. Eventually, after additional alumina purification, a high TON was secured overall.

Through these results, it was confirmed that the purification process through the metal-supported composite presented in the present invention is effective even in low-purity raw materials, and since metathesis reactions using various low-grade animal and plant oil raw materials are possible, it can be used industrially in the future. You can expect high value.

In the above, specific parts of the content of the present invention have been described in detail, and for those skilled in the art, these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be blind Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

obtaining a purified raw material for olefin metathesis reaction by contacting the raw material for olefin metathesis reaction with a metal particle mixture to remove catalytic toxic impurities,
The metal particle mixture is a mixture of metal particles containing two types of transition metals among manganese, iron, cobalt, and nickel,
A method for purifying raw materials for olefin metathesis reaction, characterized in that the molar ratio of metal component 1 and metal component 2 is 1: 5 to 5: 1.
According to claim 1,
A method for purifying a raw material for olefin metathesis reaction, characterized in that the metal particle mixture is supported in a porous material.
delete According to claim 2,
The method of purifying a raw material for olefin metathesis reaction, characterized in that the porous material is at least one selected from alumina, silica, silica alumina, zeolite, titania, zirconium oxide, carbon black, graphene, and carbon nanotubes.
According to claim 1,
The raw material for the metathesis reaction is a method for purifying a raw material for olefin metathesis reaction, characterized in that any one selected from vegetable oil, animal oil and derivatives thereof
According to claim 1,
The raw materials for the olefin metathesis reaction are 9-decenoic acid, methyl 9-decenoate, 10-undecenoic acid, methyl 10-undecenoate ( methyl 10-undecenoate, 9-octadecenedioic acid, methyl 9-octadecenedioate, 12-tridecenoic acid, methyl 12-tridecenoate Methyl 12-tridecenoate, 13-tetradecenoic acid, methyl 13-tetradecenoate, 11-dodecenoic acid, methyl 11- A method for purifying a raw material for olefin metathesis reaction, characterized in that at least one selected from dodecenoate (methyl 11-dodecenoate).
a) contacting a raw material for olefin metathesis reaction with a metal particle mixture to obtain a first-purified raw material for metathesis reaction; and
b) obtaining a secondly purified raw material for metathesis reaction by contacting the firstly purified raw material for olefin metathesis reaction with alumina particles;
The metal particle mixture is a state in which metal particles including two types of transition metals from among manganese, iron, cobalt, and nickel are not supported or supported in a porous material.
A method for purifying raw materials for olefin metathesis reaction, characterized in that the molar ratio of metal component 1 and metal component 2 is 1: 5 to 5: 1.
According to claim 7,
In step b), the activated alumina is neutral alumina that is neither acidic nor basic.
As a remover for removing catalyst toxic impurities in raw materials for olefin metathesis reaction,
The remover includes a metal particle mixture in which metal particles containing two types of transition metals among manganese, iron, cobalt, and nickel are mixed,
A remover for removing catalytically toxic impurities in a raw material for an olefin metathesis reaction, characterized in that the molar ratio of metal component 1 to metal component 2 is 1:5 to 5:1.
According to claim 9,
The metal particle mixture is a remover for removing catalytically toxic impurities in a raw material for an olefin metathesis reaction, characterized in that it is supported in a porous material.
a) preparing a metal precursor mixture solution by dissolving two types of transition metal precursors among manganese, iron, nickel, and cobalt in an appropriate solvent;
b) preparing a slurry of the metal precursor mixture and the porous material by adding the porous material to the metal precursor mixture solution;
c) drying the slurry to obtain a porous material containing a metal precursor mixture;
d) heat-treating the porous material containing the mixture of metal precursors to obtain a porous material containing a mixture of metal particles; and
e) reducing and activating the metal particle mixture-containing porous material obtained by the heat treatment;
In step a), the molar ratio of metal component 1 and metal component 2 is 1: 5 to 5: 1. To remove catalytic toxic impurities in the raw material for olefin metathesis reaction, wherein the metal particle mixture is supported on a porous material Method for manufacturing a remover for
In the olefin metathesis reaction method,
An olefin metathesis reaction is performed in the presence of a catalyst for olefin metathesis reaction using a raw material for olefin metathesis reaction from which catalytic toxic impurities have been removed by the method of any one of claims 1, 2, and 4 to 8 An olefin metathesis reaction method, characterized in that for carrying out.

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