KR20220087919A - Purification method of feedstock for the olefin metathesis - Google Patents

Abstract

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

Description

Purification method of feedstock for the olefin metathesis

The present invention relates to a method for purifying natural oils and oil derivatives used as reaction raw materials in an olefin metathesis reaction, and to 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 chemical substances. have.

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

However, impurities inevitably included in the reaction raw material due to exposure to oxygen, etc. react with the catalyst, thereby remarkably reducing the activity of the metathesis catalyst. This leads to a decrease in the turnover number (TON), which is an indicator of catalytic activity. In particular, in the case of high activity metathesis reaction of 30,000 TON or more, the amount of catalyst used is 20 ppm or less, so strictly removing toxic impurities contained in reactants in metathesis reaction is an important part for commercial application of 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, the amount of catalyst used is 10 ppm or less, so a method of reducing catalyst toxic impurities in the reactant to several ppm or less is essential. Among these methods, the most common method is to remove impurities through alumina. The previously reported method is a method that undergoes a pretreatment process of at least one month or more using about 1.5 wt.% or more of alumina compared to methyl oleate (Angew. Chem. Int. Ed. 2015, 54, 1919-1923). However, this method is not suitable because it takes too much time for purification, and requires high purity methyl oleate of 99% or more, so that industrial economic feasibility is low.

According to previous studies related to this, there are peroxide-based and non-peroxide-based impurities such as pigments and polar substances in the metathesis catalyst toxic impurities present in the raw material, and it is known that these impurities act as catalyst poisons and reduce the activity of the catalyst. Specifically, peroxide, a compound that is inevitably produced when animal and vegetable oils, which are raw materials for metathesis, meets oxygen in the air, radical peroxides containing oxygen, aldehyde compounds, and anisidine, phosphate, and sulfate are representative catalyst poisons.

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

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

US registered patent US 8,692,006 B2 (2014. 04. 08. registered) US Registered Patent US 8,642,824 B2 (Registered on 02.04. 2014) Republic of Korea Patent Publication 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 purified raw materials for olefin metathesis reaction by highly removing impurities acting as catalyst poisons in natural oil or oil derivative raw materials.

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

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

In one embodiment of the present invention, the metal particle mixture may be in a state supported on 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 to 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-undecenoic acid 10-undecenoic acid, methyl 10-undecenoate, 9-octadecenedioic acid, methyl 9-octadecenedioate, 12- Tridecenoic acid (12-tridecenoic acid), methyl 12-tridecenoate (methyl 12-tridecenoate), 13-tetradecenoic acid (13-tetradecenoic acid), methyl 13-tetradecenoate (methyl 13-tetradecenoate), It may be at least one selected from 11-dodecenoic acid and methyl 11-dodecenoate.

The present invention also comprises the steps of: a) contacting a raw material for olefin metathesis reaction with a metal particle mixture to obtain a primary purified raw material for olefin metathesis reaction; and b) contacting the first purified raw material for olefin metathesis reaction with activated alumina particles to obtain a second purified raw material for olefin metathesis reaction; The particle mixture provides a method of purifying a raw material for olefin metathesis reaction, characterized in that the metal particles including two or more transition metals among manganese, iron, cobalt, and nickel are supported in an unsupported state or in a state in which a porous material is supported.

In addition, the present invention is a remover for removing catalytic toxic impurities in a raw material for olefin metathesis reaction, wherein the remover includes a metal particle mixture in which metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel are mixed. It provides a removing agent for removing catalytic toxic impurities in the raw material for olefin metathesis reaction, characterized in that.

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

The present invention also provides a method of performing an olefin metathesis reaction with a raw material for an olefin metathesis reaction purified according to the method of the present invention to remove catalytic toxic impurities 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 metathesis catalyst toxic impurities that may exist in raw materials for olefin metathesis reaction with a metal particle mixture mixed with metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel, and oil derivative raw materials Metathesis catalyst toxic impurities can be effectively removed.

For this reason, if the purification method of the raw material for olefin metathesis reaction according to the present invention is used, catalyst toxic impurities can be easily removed to easily purify the raw material for the olefin metathesis reaction of low purity into a high purity one. of raw materials can also be used, which is economically advantageous.

In addition, if the metathesis reaction is performed using the raw material for olefin metathesis reaction purified according to the present invention from which catalytic toxic impurities have been removed, it is possible to minimize the amount of metathesis catalyst used (10 ppm or less) and maximize catalytic activity (50,000 TON or more). can

1 is a schematic diagram of a circulation purification system of a raw material for olefin metathesis reaction using a metal particle mixture in an embodiment of the present invention.
2 is a schematic diagram of a circulation purification system of a raw material for olefin metathesis reaction using activated alumina in an 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 preferred embodiments in which those of ordinary skill in the art to which the present invention pertains can easily practice the present invention will be described in detail. In the detailed description of the principle of the preferred embodiment of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof 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 those well known and commonly used in the art.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Terms used herein 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 is 100% removal of all impurities to achieve high purity of the raw material for olefin metathesis reaction It does not mean that certain impurities that have a negative effect on the catalyst are reduced, thereby alleviating the negative effects of the catalyst and increasing the efficiency of the catalyst.

In addition, the term "impurity" used in the method for removing catalytically toxic impurities contained in the raw material for olefin metathesis according to the present invention is extensively used for olefin metathesis and catalytic metathesis reaction using natural oil raw materials. Indicates any impurity that can give. The impurities include peroxide series and non-peroxide series such as pigments and polar substances. Specifically, peroxide, a compound that is inevitably generated when animal and vegetable oil, which is a raw material for olefin metathesis, meets oxygen in the air, radical peroxide radicals including oxygen, hydro Refers to peroxide, hydroxydiene, aldehyde compound, epoxyhydroxy compound, anisidine, phosphate, sulfate, etc. These impurities greatly reduce the activity of the olefin metathesis catalyst, thereby lowering the metathesis reaction.

The present invention relates to a method for purifying a raw material for olefin metathesis reaction by highly removing impurities contained in raw material for olefin metathesis reaction. The catalytic activity of the metathesis reaction is excellent even in the presence of a metathesis catalyst of

First, in the method for purifying a raw material for olefin metathesis reaction according to the present invention, in order to highly remove catalyst toxic impurities in the raw material, the raw material for olefin metathesis reaction is contacted with a metal particle mixture to obtain a purified raw material for olefin metathesis reaction. Including, the metal particle mixture is characterized in that the 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 that highly removes impurities toxic to metathesis catalyst in 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 a raw material for olefin metathesis reaction with a metal particle mixture to remove catalyst toxic impurities to obtain a purified raw material for olefin metathesis reaction, wherein the raw material for olefin metathesis reaction and the raw material for contact reaction The metal particle mixture may include two or more transition metals among manganese, iron, cobalt, and nickel as a metal component, and the ability to remove impurities in the raw material for olefin metathesis reaction is determined according to 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 three types of cobalt, so that the metathesis reaction catalytic activity is high, This indicates a high conversion value.

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

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

In addition, as an embodiment, when the metal particle mixture contains iron and nickel as metal components at the same time, 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 without being supported on a carrier, but may be prepared by supporting transition metal particles on a porous material for convenience of handling.

The preparation method includes: a) dissolving two or more transition metal precursors in an appropriate solvent to prepare a metal precursor mixture solution; b) adding a porous material to the metal precursor mixture solution to prepare a slurry of the metal precursor mixture and the porous material; c) drying the slurry to obtain a porous material containing a metal precursor mixture; d) heat-treating the metal precursor mixture-containing porous material to obtain a metal particle mixture-containing porous material; and e) reducing and activating the porous material containing the metal particle mixture obtained by 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 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 the transition metal ion is coordinated with another organic material, and specifically includes precursors of two or more transition metals among manganese, iron, cobalt, and nickel. , two or more metal precursors may be used in combination.

Preferably, the transition metal precursor may be a transition metal precursor of nitrate, acetate, acetylacetate or carbonate.

In this case, the solvent used in the process of dissolving two or more types of transition metal precursors in the solvent may be an appropriate solvent in which the transition metal precursor is well dissolved, 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 a porous material to the metal precursor mixture solution.

In this case, the porous material used as the carrier of the transition metal may be a metal oxide such as alumina, silica, silica alumina, zeolite, titania, 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 metal precursor mixture solution and the slurry of the porous material to obtain a metal precursor mixture-containing porous material.

Specifically, in the drying process, the slurry in which the transition metal precursor solution and the porous material are mixed is preferably performed 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 the metal particle mixture, and reducing the metal converted to oxide form in step d) is converted into a form suitable for refining the raw material for metathesis decomposition It is an essential process for

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

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

The raw material for the olefin metathesis reaction is specifically, oleic acid or a methyl derivative of oleic acid, for example, 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 (methyl 12-tridecenoate), 13-tetradecenoic acid (13-tetradecenoic acid), methyl 13-tetradecenoate (methyl 13-tetradecenoate), 11-dode It may be one or more selected from senoic acid (11-dodecenoic acid) and methyl 11-dodecenoate (methyl 11-dodecenoate).

According to the present invention, a purified raw material for olefin metathesis reaction can be obtained by contacting a raw material for olefin metathesis reaction with a metal particle mixture, and the purified raw material for olefin metathesis reaction has catalytic activity of metathesis reaction even in the presence of a small amount of metathesis catalyst It shows an excellent effect.

1, the contact reaction between the metal particle mixture and the raw material for the olefin metathesis reaction is performed by supplying the raw material for the 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 This can be done by contact.

The content of the raw material for the olefin metathesis reaction supplied to the tube filled with the metal particle mixture may be 1 to 30 times the weight of the metal having catalytic activity.

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. It is possible to avoid contact with oxygen by supplying the raw material for the olefin metathesis reaction in a state where 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 the steps of: i) contacting a raw material for olefin metathesis reaction with a metal particle mixture to obtain a primary purified raw material for olefin metathesis reaction; and ii) contacting the first purified raw material for olefin metathesis reaction with alumina particles to obtain a second purified raw material for olefin metathesis reaction; As a mixture of two or more transition metal particles, it provides a method characterized in that it is in an unsupported form or in a form supported on 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.

The method of purifying the raw material for olefin metathesis reaction by removing impurities acting as a catalyst poison of the catalyst for olefin metathesis reaction that may exist in the raw material for olefin metathesis reaction according to the present invention includes i) the raw material for olefin metathesis reaction with metal particles contacting the mixture to obtain a raw material for a primary purified olefin metathesis reaction; and ii) contacting the primary purified raw material for olefin metathesis reaction with activated alumina particles to obtain a secondary purified raw material for olefin metathesis reaction; Impurities in the raw material for olefin metathesis reaction 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 secondary purified raw material for olefin metathesis reaction has better reactivity in metathesis reaction can indicate

In step ii), the activated alumina is neutral alumina that is neither acidic nor basic, the activated alumina has 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 the olefin metathesis reaction, which is primarily purified as a metal particle mixture, may be supplied to a tube filled with activated alumina to be contacted, and at this time, at a temperature of 30 to 200 ℃ It can be carried out by contact for more than 1 hour.

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

At this time, even in step ii), the raw material for the olefin metathesis reaction was supplied while the entire purification system was pressurized with an inert gas to apply a positive pressure to avoid contact with oxygen.

Therefore, the raw material for olefin metathesis reaction obtained through the secondary purification process with activated alumina particles from the raw material for olefin metathesis reaction firstly purified from the contact reaction with the metal particle mixture is an impurity that adversely affects the catalyst for olefin metathesis reaction This high degree of removal can achieve a higher conversion number (TON) than conventional high-vacuum multi-stage fractionation or alumina refining.

That is, when the metathesis reaction is performed using the raw material for the olefin metathesis reaction from which impurities are highly removed, compared to the case where the raw material for the olefin metathesis reaction of low purity is used, as the yield increases with the same amount of the catalyst, a greater amount of high added value A product can be obtained, and it has the effect of increasing economic efficiency by minimizing the amount of catalyst used and reducing the cost of catalyst separation and purification from the product.

In addition, the present invention includes a metal particle mixture in which metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel are mixed. to provide.

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

In addition, the present invention provides a method for metathesis reaction of olefins with a raw material obtained by the purification method of the raw material for olefin metathesis reaction, wherein the catalyst added at this time is very low compared to the case of using a raw material that has not undergone the purification process. It can activate the reaction and shows a high conversion rate.

As an embodiment, the amount of 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.

In this case, as the 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)], etc. may be used.

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

Examples 1-13

(1) Synthesis of porous material containing metal particle mixture

The content of the transition metal in the porous material containing the metal particle mixture is based on 1 mmol/g, and a single or two or more kinds of manganese, iron, nickel, and cobalt precursors are mixed in a certain molar ratio to synthesize a metal-supported composite. 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 40 mmol metal precursor corresponding to each molar ratio was dissolved in 25 mL 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) is added to the solution in which the metal precursor is completely dissolved, mixed physically, and then dried in an oven at 70° C. for 1 hour. After that, it is put in a kiln and heat-treated at 100°C for 3 hours and at 350°C for 5 hours. After that, as in the raw material purification system 1 shown in FIG. 1, 20 ml of heat-treated transition metal/alumina was filled in a stainless steel tube having a diameter of 1/2 inch and a length of 30 cm, and hydrogen mixed nitrogen gas (hydrogen 23% concentration) was added to 65 ml/ It was activated at 500°C for 10 hours by feeding at a rate of min.

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

Methyl oleate purification was performed 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 fractionally distilled to produce 96% pure methyl oleate, which was used as a raw material for metathesis reaction. Before raw material refining, nitrogen was blown into the entire refining system to remove oxygen in the gas line and storage, and then a positive pressure of 1 atm or higher was maintained with nitrogen gas to prevent oxygen from entering the system. Then, methyl oleate was put into the reaction raw material storage 1, and the stainless steel tube filled with the prepared porous material containing the metal particle mixture was heated to 50 ° C. It was supplied at a rate of min to purify methyl oleate. At this time, the methyl oleate is circulated to the raw material storage 1 after contact with the prepared porous material containing the metal particle mixture, and as the circulation contact time passes, the toxic impurities contained in the raw material are purified, and the purified methyl oleate is metathesis reaction after 12 hours It was used as a 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 vacuum reduced to 10 mbar at 250° C. for 10 hours. activated. After that, the first purified methyl oleate as a metal support complex was put into the reaction raw material storage 2, and 100 ml of methyl oleate was supplied through a pump at a rate of 2 mL/min at 25° C. for 12 hours to purify the 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 has elapsed. .

(4) Ethylene metathesis reaction of purified methyl oleate

The metathesis experiment was performed as follows. In a Glover box, in a 20 ml glass vial, 5 g of primary or secondary purified methyl oleate and 100 mg of dodecane as an internal standard (IS, internal standard) and Ru-CAAC (customized supply or synthesis from Aperion) or UltraCat (purchased from Aldrich) ) 10ppm metathesis catalyst (Ru-CAAC: 0.11mg, UltraCat: 0.17mg) was added. The vial containing the reactant was placed in a 125ml stainless reactor and the reactor was fastened. The molecular structure of the metathesis catalyst used is shown in FIG. 3 . After that, the reactor was removed from 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 was performed on the finished material 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 the FID detector. TON is a value obtained by dividing the number of moles of the catalyst used by the number of moles of methyl 9-decenoate (9DCE) produced, and this 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 of Table 1 below, and the metal Comparative Example 2 of Table 1 shows the results of metathesis reaction using a raw material that has undergone a purification process by alumina without a purification process by a particle mixture.

Comparative Examples 3-5

In order to compare the purification effect of a mixture of metal particles other than manganese, iron, nickel, and cobalt, in the method for synthesizing a porous material containing a mixture of metal particles, only the types of metal are vanadium (V), copper (Cu) and nickel/copper (Ni/ Cu(1/1)) was synthesized in the same manner, and the metathesis reaction was performed under the same conditions as in Example 1, and the results are shown in Comparative Examples 3-5 of Table 1 below.

- Methyl oleate conversion (%) means the following.

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

- 1-decene+methyl 9-decenenoate Selectivity (%) means the following.

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

/ In the calculation, the total number of moles of by-products must be multiplied by two, since the by-products are produced from two methyl oleates by a catalyst.

- TON refers to the number of next conversions.

TON = moles of methyl 9-decenoate (9DCE) produced / 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 from the metal particle mixture , 7, 9-11, it was confirmed that the conversion rate (TON) was significantly increased compared to Comparative Example 2 purified only by activated alumina.

In addition, in Examples 4 to 10, in which two or more metals are mixed, the activity tends to increase more than when one type of metal is used. more reactive.

For example, in the mixed metal of Fe and Ni of Example 5, the sum of moles of Fe and Ni uses the same number of moles as those of Example 1 or Example 2 for Fe and Ni, respectively, of the metal. That is, compared to Example 1, the number of moles of Fe in Example 5 corresponds only to 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, which is 29,300. This shows a higher effect than when each single metal is used due to the use of a mixed metal of Fe and Ni, and it can be seen that the two or more metals exhibit a synergistic effect having a synergistic effect with each other. In particular, the conversion rates of Examples 11 to 13, which were purified using a metal particle mixture prepared by mixing three metals in 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 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. was confirmed to occur only between specific metals.

Through these results, the method for removing toxic impurities in methyl oleate using a metal particle mixture according to the present invention enables more efficient removal of impurities in less time and a minimum amount of catalyst compared to the conventionally known method for removing impurities using alumina. It can be confirmed that the productivity of metathesis reaction is increased through reduction of catalyst cost and efficiency of catalyst activity by using

Examples 14-19: Removal of impurities and metathesis reaction by purity of methyl oleate raw material using a metal particle mixture

The methyl oleate raw material was purified by purity using a metal particle mixture in 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 the same as in Example 1. There are three types of methyl oleate used: Sigma-Aldrich technical grade, 96% methyl oleate by fractional distillation of 70% methyl oleate, Acros 90% methyl oleate, and Sigma-Aldrich technical grade 70% methyl oleate are used. did.

[Table 2] Metathesis reaction results

In Examples 14 to 19, as a result of performing ethylene metathesis reaction of purified methyl oleate after purifying methyl oleate having different purities, the higher the purity, the higher the conversion rate (TON) ) was found to represent. In addition, when additional alumina purification was performed, the increase rate of the conversion rate (TON) was higher as the purity of the raw material was rather low.

Through these results, it was confirmed that the refining process through the metal-supported complex presented in the present invention is effective even with low-purity raw materials, and since metathesis reaction using low-grade various animal and plant oil raw materials is possible, it can be used industrially in the future The value can be expected to be high.

Above, a specific part of the content of the present invention has been described in detail, for those of ordinary skill in the art, this specific description is only a preferred embodiment, and the scope of the present invention is not limited thereby. will swear Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

Claims (12)

Contacting the raw material for olefin metathesis reaction with a metal particle mixture to remove catalyst toxic impurities to obtain a purified raw material for olefin metathesis reaction,
The metal particle mixture is a method of purifying a raw material for olefin metathesis reaction, characterized in that it is a mixture of metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel.
According to claim 1,
A method for purifying a raw material for olefin metathesis reaction, characterized in that the metal particle mixture is supported on a porous material.
According to claim 1,
The metal particles include two components from among manganese, iron, nickel and cobalt,
A method of purifying a raw material for olefin metathesis reaction, characterized in that the content ratio of metal component 1 and metal component 2 is 1: 5 to 5: 1.
3. The method of claim 2,
The porous material is a method of purifying a raw material for olefin metathesis reaction, characterized in that 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 an olefin metathesis reaction, characterized in that any one selected from vegetable oil, animal oil, and derivatives thereof
According to claim 1,
The raw material for the olefin metathesis reaction is 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-tride Cenoate (methyl 12-tridecenoate), 13-tetradecenoic acid (13-tetradecenoic acid), methyl 13-tetradecenoate (methyl 13-tetradecenoate), 11-dodecenoic acid (11-dodecenoic acid), methyl 11- A method of purifying a raw material for olefin metathesis reaction, characterized in that at least one selected from dodecenoate (methyl 11-dodecenoate).
a) Metal raw materials for olefin metathesis reaction contacting the particle mixture to obtain a primary purified raw material for metathesis reaction; and
b) contacting the first purified raw material for olefin metathesis reaction with alumina particles to obtain a second purified raw material for metathesis reaction;
the metal The particle mixture is a method of purifying a raw material for olefin metathesis reaction, characterized in that the metal particles including two or more transition metals among manganese, iron, cobalt, and nickel are supported in an unsupported state or a porous material.
8. The method of claim 7,
The method for purifying a raw material for olefin metathesis reaction, characterized in that the activated alumina in step ii) is neutral alumina, not acidic or basic.
As a remover for removing catalytic toxic impurities in raw materials for olefin metathesis reaction,
The removing agent for removing catalytic toxic impurities in the raw material for olefin metathesis reaction, characterized in that it comprises a metal particle mixture in which metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel are mixed.
10. The method of claim 9,
The metal particle mixture is a remover for removing toxic impurities from the catalyst in the raw material for olefin metathesis reaction, characterized in that it is supported on a porous material.
a) preparing a metal precursor mixture solution by dissolving at least two transition metal precursors in an appropriate solvent;
b) preparing a slurry of the metal precursor mixture and the porous material by adding a 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 metal precursor mixture to obtain a porous material containing the metal particle mixture; and
e) reducing and activating the porous material containing the metal particle mixture obtained by the heat treatment;
A method for producing a removing agent for removing catalytic toxic impurities in a raw material for olefin metathesis reaction, wherein the metal particle mixture is supported on a porous material, comprising:
In the olefin metathesis reaction method,
9. Olefin metathesis, characterized in that the olefin metathesis reaction is performed in the presence of a catalyst for olefin metathesis reaction using a raw material for olefin metathesis reaction purified by any one of claims 1 to 8 from which catalyst toxic impurities have been removed reaction method.

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