KR102588214B1 - Method for regenerating metal particle mixture for purifying feedstock for olefin metathesis - Google Patents

Abstract

The present invention relates to a method for regenerating a metal particle mixture for purifying raw materials for olefin metathesis reaction, and is a metal particle mixture in which catalyst poison-causing substances and impurities are absorbed and removed from raw materials such as natural oil and oil derivatives used as raw materials for olefin metathesis reaction. It relates to a method for regenerating metal particle mixtures for refining raw materials for olefin metathesis reactions so that they can be recycled and reused, and a method for purifying raw materials for olefin metathesis reactions using the same.

Description

Method for regenerating metal particle mixture for purifying feedstock for olefin metathesis}

The present invention relates to a method for regenerating a metal particle mixture for purifying raw materials for olefin metathesis reaction, and is a metal particle mixture in which catalyst poison-causing substances and impurities are absorbed and removed from raw materials such as natural oil and oil derivatives used as raw materials for olefin metathesis reaction. It relates to a method of regenerating a metal particle mixture for refining raw materials for olefin metathesis reaction so that it can be recycled and reused.

Olefin metathesis is a reaction that can convert natural resources with olefin functional groups, such as animal and plant oils and derivatives of animal and plant oils, into industrially useful chemicals, and has recently become a core technology in new industries for a sustainable society and climate change response. 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 through cross-metathesis reactions with ethylene, propylene, and butene. It can be converted into high value-added substances such as dicarboxylic acid and long-chain linear olefin through self-metathesis reaction, and is attracting attention as a raw material for metathesis reaction useful in the chemical industry. Therefore, for this metathesis reaction, research on catalysts containing transition metals such as ruthenium, molybdenum, and tungsten is actively being conducted.

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

Therefore, in order to maximize the activity of the metathesis catalyst to more than 30,000 TON, especially to more than 40,000 TON, the amount of catalyst used is less than 10 ppm, so a method of reducing catalyst toxic impurities in the reactant to less than a few ppm is essential. The most common of these methods is to remove impurities through alumina. The previously reported method uses about 1.5 wt.% or more of alumina compared to methyl oleate and undergoes a pretreatment process of at least one month (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 more than 99%, resulting in low industrial economic feasibility.

According to previous research in this regard, toxic impurities for metathesis catalysts present in raw materials include peroxides and non-peroxides such as pigments and polar substances, and it is known that these impurities act as catalyst poisons and reduce the activity of the catalyst. Specifically, peroxide, a compound inevitably generated when animal and vegetable oil, which is a raw material for metathesis, meets oxygen in the air, peroxide radical, which is a radical 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 for removing impurities in raw materials (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 white clay, bleached earth, and diatomaceous earth are used. , presented a method of removing impurities from raw materials using various substances with strong adsorption properties for each impurity, such as zeolite, kaolin, acid anhydride, and activated carbon (Korea Patent Publication No. 10-2015-0129681).

However, as described above, chemicals used to remove impurities from raw materials such as natural oils and oil derivatives, or metal alkyl compounds, alumina, silica gel, montmorillonite clay, acid white clay, bleached earth, diatomaceous earth, zeolite, kaolin, and acid anhydride. In the case of materials with strong adsorption such as activated carbon, they cannot be regenerated by a single method such as simple washing, firing, and activation treatment due to the adsorption and reaction of irreversible impurities, and require multi-step complex washing, firing, and advanced activation treatment. As a result, the recycling cost increases significantly from the initial synthesis cost, making it difficult to reuse, and when these materials are discarded after one-time use, a large amount of solid waste is generated, resulting in loss not only from an environmental perspective, but also from an economic perspective. To solve this problem, in U.S. Patent Publication No. 2020-0385324 (publication date: December 10, 2020), an adsorbent that adsorbs impurities present in olefin feedstock can be used by regenerating it at 180 to 500°C with nitrogen gas at normal pressure. is starting. However, the above method is limited to the case of adsorbing isobutanal and acetone that exist as impurities in the olefin feedstock. Therefore, if impurities causing catalyst toxicity other than isobutanal and acetone are adsorbed on the adsorbent, they are completely desorbed or removed. There are limitations in regenerating the adsorbent.

Therefore, the development of a technology that desorbs or removes impurities from an adsorbent that highly adsorbs impurities, including catalytic toxic substances, from raw materials for olefin metathesis reaction in a simple manner to enable regeneration and repeated use of the adsorbent is necessary for commercial application. .

(0001) US registered patent US 8,692,006 B2 (registered on April 8, 2014) (0002) US registered patent US 8,642,824 B2 (registered on February 4, 2014) (0003) Republic of Korea Patent No. 10-2015-0129681 (published on November 20, 2015) (0004) U.S. Patent Publication No. 2020-0385324 (Published Date: 2020.12.10.)

(0001) Angew. Chem. Int. Ed. 2015, 54, 1919-1923

In order to solve the above problems, the present invention removes catalyst poison-causing substances and impurities in the raw materials for olefin metathesis reaction to a high degree so that the metal particle mixture that purifies the raw material for olefin metathesis reaction can be used repeatedly rather than one-time treatment. The purpose is to provide a method for regenerating metal particle mixtures for raw material purification.

In addition, the purpose of the present invention is to provide a method for purifying raw materials for olefin metathesis reaction by regenerating the used metal particle mixture and using it again to purify raw materials for olefin metathesis reaction.

In order to solve the above problem, the present invention provides a method for regenerating a metal particle mixture used in purifying raw materials for an olefin metathesis reaction, wherein the metal particle mixture used in refining raw materials for an olefin metathesis reaction is heated at a temperature of 200 to 440° C., 1 to 100° C. A method for regenerating a metal particle mixture for purifying raw materials for olefin metathesis reaction is provided, which is characterized in that it is vacuum washed under a pressure of mbar and then regenerated by hydrogen activation at 250 to 440°C.

In one embodiment, the hydrogen activation treatment uses a mixed gas of hydrogen and an inert gas, and the hydrogen may be included in an amount of 10 to 70% by volume.

In one embodiment, the metal particle mixture may be a mixture of metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel. Preferably, the metal particles include two or more transition metals among manganese, iron, nickel, and cobalt. It contains components, and the content ratio of metal component 1 and metal component 2 may be 1:5 to 5:1.

In one embodiment, the metal particle mixture may be supported on a porous material. Preferably, the porous material is alumina, silica, silica alumina, zeolite, titania, zirconium oxide, carbon black, graphene, and carbon nanotubes. It may be one or more selected from among.

In one embodiment, the raw material for the olefin metathesis reaction may be any one selected from vegetable oils, animal oils, and derivatives thereof, and preferably the raw material for the olefin metathesis reaction is 9-decenoic acid. , methyl 9-decenoate, 10-undecenoic acid, methyl 10-undecenoate, 9-octadecenedioic acid ), methyl 9-octadecenedioate, 12-tridecenoic acid, methyl 12-tridecenoate, 13-tetradecenoic acid (13- It may be one or more selected from tetradecenoic acid, methyl 13-tetradecenoate, 11-dodecenoic acid, and methyl 11-dodecenoate.

In addition, the present invention includes the steps of i) contacting the raw material for the olefin metathesis reaction with a metal particle mixture to purify the raw material for the olefin metathesis reaction; ii) reactivating the metal particle mixture used in the purification step by vacuum washing and hydrogen activation; and iii) reusing the reactivated metal particle mixture to purify raw materials for olefin metathesis reaction, wherein the metal particle mixture includes metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel. A method for purifying raw materials for olefin metathesis reaction is provided, which is characterized in that the raw material is supported in a supported state or a porous material.

In one embodiment, after step i), the purified raw material for the olefin metathesis reaction may be further purified by contacting it with activated alumina particles. Preferably, the activated alumina may be neutral alumina.

The present invention can improve process efficiency by regenerating a contaminated metal particle mixture through a simple process in the process of adsorbing or removing impurities including catalytic toxic substances from raw materials for olefin metathesis reaction.

In addition, the regenerated metal particle mixture maintains performance similar to that of the new adsorbent, i.e., highly active purification performance even after regeneration, so that it can be reused for refining raw materials for olefin metathesis reaction through regeneration, making it economical as well as disposal. There is also an environmental advantage as the generation of toxic metal particle mixtures is minimized.

Moreover, when vacuum washing and hydrogen activation treatment are performed at low temperature according to the present invention, the regeneration rate of the metal particle mixture is higher compared to the conventional regeneration method, so higher activity purification performance can be maintained, and thus, the olefin purified using this method can be metathesized. When reaction raw materials are used in a metathesis reaction, a high conversion number (TON) can be achieved.

Figure 1 is a schematic diagram of a circulation purification system for raw materials for olefin metathesis reaction using a metal particle mixture in an embodiment of the present invention.

Hereinafter, the configuration of the invention, including preferred embodiments, will be described in detail so that those skilled in the art can easily implement the invention. In explaining in detail the principles of a preferred embodiment of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout the specification of the present application, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

Terms used in this specification may be defined as follows.

In the specification of the present invention, "purification" does not mean high purity of the raw material for olefin metathesis reaction by removing 100% of all impurities, but rather reduces specific impurities that have a negative impact on the catalyst to alleviate the negative impact of the catalyst and improve the catalyst's It means increasing efficiency.

In addition, the term "impurity" in the specification of the present invention broadly refers to any impurity that may affect the catalytic metathesis reaction using catalysts used for olefin metathesis and natural oil raw materials. The impurities include peroxide series and non-peroxide series such as pigments and polar substances. Specifically, peroxide, which is a compound inevitably generated when animal and vegetable oil, which is a raw material for olefin metathesis, meets oxygen in the air, peroxide radical, which is a radical containing oxygen, and hydro It refers to peroxides, hydroxydienes, aldehyde compounds, epoxyhydroxy compounds, anisidine, phosphates, and sulfates. These impurities greatly reduce the activity of the olefin metathesis catalyst, thereby lowering the metathesis reaction.

Impurities in the raw materials for the olefin metathesis reaction defined above can be removed through contact with the activated metal particle mixture of the present invention, and the raw materials for the olefin metathesis reaction purified through this can undergo highly active metathesis without reducing the activity of the olefin metathesis catalyst. The reaction can be carried out.

However, the metal particle mixture is contaminated during the process of adsorbing and removing the above impurities when purifying the raw materials for the olefin metathesis reaction, thereby reducing the activity of purifying the raw materials for the olefin metathesis reaction.

Therefore, the present invention provides a method for regenerating a metal particle mixture for purifying the raw material for the olefin metathesis reaction so that the contaminated metal particle mixture can be repeatedly reused during the process of absorbing or removing impurities including catalyst toxin-causing substances from the raw material for the olefin metathesis reaction. to provide.

The present invention is described in more detail below.

In the method for regenerating the metal particle mixture used in refining the raw material for the olefin metathesis reaction of the present invention, the metal particle mixture used in the purification of the raw material for the olefin metathesis reaction is vacuum washed at 200 to 440° C. and under a pressure of 1 to 100 mbar. It provides a method for regenerating a metal particle mixture for purifying raw materials for olefin metathesis reaction, which is characterized in that the metal particle mixture is regenerated by hydrogen activation treatment at 250 to 440°C.

Specifically, in the present invention, in order to regenerate a mixture of metal particles contaminated with impurities during the purification process of raw materials for olefin metathesis reaction, the metal particle mixture is first washed in a vacuum. Here, vacuum refers to an industrial vacuum, meaning a pressure below atmospheric pressure, and the difference from atmospheric pressure is called the degree of vacuum. Therefore, the degree of vacuum refers to the gauge pressure of pressure below atmospheric pressure.

The present invention can process metal particle mixtures in a vacuum of 1 to 100 mbar and at a low temperature of 200 to 440°C. The vacuum cleaning varies depending on the case, but generally it is preferable to clean for 1 to 10 hours.

The metal particle mixture is washed in a vacuum, which has the advantage of quickly and effectively removing excess raw materials and impurities contained in the metal particle mixture during the purification process of raw materials for olefin metathesis reaction, and further, washing at a relatively low temperature of 200 to 440°C. As this progresses, thermal decomposition and carbonization of the reaction raw materials and adsorbed organic impurities on the metal particle mixture do not occur, so that secondary contamination caused by the thermal decomposition and carbonization can be prevented, as well as the metal particles. Since the mixture is not damaged, its purification performance for raw materials for olefin metathesis reaction can be maintained even after regeneration.

The vacuum washed metal particle mixture is subjected to hydrogen activation.

The hydrogen activation treatment activates the metal particle mixture at a temperature of 250 to 440 ℃ with a mixed gas in which hydrogen is diluted with an inert gas. It is performed at a relatively low temperature of 250 to 440 ℃, and the metal particle mixture is unwashed. The remaining organic impurities and reaction raw materials can be removed without thermal decomposition and carbonization, thereby preventing secondary contamination caused by thermal decomposition and carbonization and damage to the metal particle mixture that may occur during this process. Accordingly, the metal particle mixture recovered through the above process can maintain its purification performance even when reused for refining raw materials for olefin metathesis reaction. The hydrogen activation treatment at this time may vary depending on the case, but can be performed for 1 to 10 hours.

In addition, the hydrogen activation treatment is carried out using a hydrogen gas mixture of hydrogen and an inert gas. The inert gas may be one or more selected from helium, neon, argon, krypton, xenon, and nitrogen, and is preferably nitrogen. . In the hydrogen-diluted mixed gas, it is preferable that hydrogen is contained in an amount of 10 to 70% by volume. If the hydrogen mixture gas contains less than 10% by volume of hydrogen, the activation treatment effect is low and a long treatment time is required. If it exceeds 70% by volume, excessive activation of the metal particle mixture occurs and a side reaction of hydrogen decomposition of the raw materials occurs. There is a problem. In addition, the hydrogen flow rate may vary depending on the case, but is generally preferably set to 10 to 200 GHSV (Gas Hour Space Velocity, hr ^-1 ).

The metal particle mixture regenerated by this process can effectively purify raw materials for olefin metathesis reaction as it maintains high activity purification performance even after regeneration, and raw materials for olefin metathesis reaction purified through this process can be used even in the presence of a small amount of metathesis catalyst. It exhibits excellent catalytic activity and reactivity.

Moreover, a higher conversion number (TON) can be achieved than existing high-temperature nitrogen washing, organic solvent washing, and high-temperature hydrogen activation regeneration methods, and as the yield increases from the same amount of catalyst, a larger amount of high value-added products can be obtained. This 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.

This may cause damage to the metal particle mixture and contaminants generated by carbonization or thermal decomposition of the organic impurities remaining on the metal particle mixture when washed or hydrogen activated at high temperature, thereby damaging the purification performance of the regenerated metal particle mixture. Moreover, during nitrogen cleaning, there is no cleaning effect at low temperatures, and carbonization and thermal decomposition occurs at high temperatures. When cleaning with organic solvents, a large amount of organic solvent waste liquid is generated, and after cleaning with organic solvents, vacuum cleaning or nitrogen gas is generated. This is because additional cleaning is required.

At this time, the metal particle mixture may contain two or more transition metals among manganese, iron, cobalt, and nickel as a metal component, and may remove impurities in the raw materials for the olefin metathesis reaction depending on the type and content of the specified transition metal. ability is determined.

Preferably, the metal component in the metal particle mixture may contain both iron and nickel, and more preferably, the metal component in the metal particle mixture includes three types of iron, nickel, and cobalt, so that the metathesis reaction catalyst activity is high, Accordingly, it shows a high conversion value.

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

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

Also, as an example, when the metal particle mixture simultaneously contains iron and nickel as metal components, the content ratio of iron and nickel is preferably 1:5 to 5:1, and more preferably, the iron and nickel content ratio is 1:5 to 5:1. The nickel content ratio of 1:2 to 2:1 indicates a high conversion value of the metathesis reaction.

The metal particle mixture can be used without being supported on a carrier, but for convenience of handling, it can be prepared by supporting transition metal particles on a porous material.

The manufacturing 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 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 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 transition metal precursors in an appropriate solvent.

The transition metal precursor 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 two or more transition metal precursors among manganese, iron, cobalt, and nickel. , two or more types of metal precursors can be used in combination.

Preferably, transition metal precursors of nitrate, acetate, acetylacetoate, and carbonate can be used as the transition metal precursor.

At this time, the solvent used in the process of dissolving two or more types of transition metal precursors in a solvent may be an appropriate solvent in which the transition metal precursor can be easily dissolved. Specifically, water, 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.

At this time, the porous material used as a carrier for 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 slurry of the metal precursor mixture solution and the porous material to obtain a porous material containing the metal precursor mixture.

Specifically, the drying process is preferably performed on a slurry mixed with a transition metal precursor solution and a porous material 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 during this process, the metal precursor is converted into a metal oxide form.

Specifically, 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) to a form suitable for purification of raw materials for metathesis decomposition. It is an essential process to do this.

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

In the present invention, substances to be purified containing impurities are raw materials for olefin metathesis reaction, and include, 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 oils, animal oils, 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 materials for the olefin metathesis reaction are specifically oleic acid or oleic acid methyl derivatives, such as 9-decenoic acid, methyl 9-decenoate, and 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-dode It may be one or more types selected from 11-dodecenoic acid and methyl 11-dodecenoate.

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

As another example of the present invention, a method for purifying raw materials for olefin metathesis reaction is provided by regenerating the used metal particle mixture and using it again to purify raw materials for olefin metathesis reaction.

Specifically, i) purifying the raw material for the olefin metathesis reaction by contacting the raw material for the olefin metathesis reaction with a metal particle mixture; ii) reactivating the metal particle mixture used in the purification step by vacuum washing and hydrogen activation; and iii) reusing the reactivated metal particle mixture to purify raw materials for olefin metathesis reaction, wherein the metal particle mixture includes metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel. A method for purifying raw materials for olefin metathesis reaction is provided, which is characterized in that the raw material is supported in a supported state or a porous material.

Figure 1 is a schematic diagram of a circulation purification system for raw materials for olefin metathesis reaction using a metal particle mixture in an embodiment of the present invention, which will be described in detail below with reference to this.

In the present invention, step i) is a step of purifying the raw material for the olefin metathesis reaction by contacting the raw material for the olefin metathesis reaction with the metal particle mixture. As shown in FIG. 1, the metal particle mixture and the olefin metathesis reaction The contact reaction of the raw material may be performed by supplying the raw material for the olefin metathesis reaction to a tube filled with the metal particle mixture and contacting the tube at a temperature of 30 to 200° C. for 1 hour or more.

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

At this time, when the raw materials for the olefin metathesis reaction come into contact with oxygen, impurities that have a fatal effect on the metathesis catalyst are generated, so the process is carried out in an environment where the raw materials for the olefin metathesis reaction cannot come into contact with oxygen, and specifically, the entire purification system is inactivated. Contact with oxygen can be avoided by supplying raw materials for olefin metathesis reaction while pressurizing with gas and applying positive pressure.

When the metathesis reaction is performed using raw materials for olefin metathesis reaction from which impurities have been highly removed due to the purification step, the amount of catalyst increases as the yield increases from the same amount of catalyst compared to the case where raw materials for olefin metathesis reaction of low purity are used. High value-added products can be obtained, and economic efficiency is increased by minimizing the amount of catalyst used and reducing the cost of catalyst separation and purification from the product.

In addition, the present invention provides a remover for removing catalytic toxic impurities in raw materials for olefin metathesis reaction, which includes a metal particle mixture mixed with metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel. to provide.

The metal particle mixture of the remover may be supported on 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 olefins with raw materials obtained through the purification method of raw materials for olefin metathesis reaction, wherein the added catalyst is used at a very low content compared to the case of using raw materials that have not gone through the purification process. It can activate the reaction and shows a high conversion rate.

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

At this time, the catalyst for the ethylene metathesis reaction according to the present invention may be Ru-CAAC [Ru-Cyclic Alkyl Amino Carbene], UltraCat [Ru-Bis (Cyclic Alkyl Amino Carbene)], etc.

In this way, the impurities removed through the purification method of the present invention encompass the peroxide series and the non-peroxide series such as pigments and polar substances, and specifically, peroxide, which is a compound inevitably generated when animal and vegetable oils, which are raw materials for olefin metathesis, meet oxygen in the air. , refers to oxygen-containing radicals such as peroxide radical, hydroperoxide, hydroxydiene, aldehyde compound, epoxyhydroxy compound, anisidine, phosphate, and sulfate, and these impurities are removed through contact with the activated metal particle mixture of the present invention. However, after purifying the metathesis reaction raw materials, the metal particle mixture is contaminated with these impurities and the purification activity is reduced, so simple regeneration and repeated use are possible. A method is required.

Step ii) is a step of reactivating the metal particle mixture used in the purification step by vacuum washing and hydrogen activation treatment. Since it is the same as the vacuum washing and hydrogen activation treatment described above, detailed description is omitted.

In addition, after step i), additional purification may be optionally performed on the purified raw material for the olefin metathesis reaction, and the additional purification is performed by contacting the raw material for the olefin metathesis reaction purified in step i) with activated alumina particles. can do. Through this, impurities in the raw materials for the olefin metathesis reaction can be removed at a higher rate, and the additionally purified raw materials for the olefin metathesis reaction can exhibit better reactivity in the metathesis reaction. At this time, the activated alumina is neutral alumina that is neither acidic nor basic. It is preferable that the activated alumina has a specific surface area of 150 m ² /g or more and a porous neutral alumina with a pore size of 50 Å or more.

In the present invention, step iii) is a step of reusing the reactivated metal particle mixture to purify raw materials for olefin metathesis reaction.

The metal particle mixture reactivated in step ii) has an environmental and economic advantage in that it can be recycled and reused, minimizing the generation of waste metal particle mixture, and furthermore, it maintains highly active purification performance even after regeneration, thereby producing olefin. The raw materials for the metathesis reaction can be effectively purified, and through this, a high conversion number (TON) can be achieved in the metathesis reaction using the purified raw materials for the olefin metathesis reaction.

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.

1. Synthesis of metal particle mixture for purification of raw materials for olefin metathesis reaction

Based on the transition metal content of 1 mmol/g in the porous material containing the metal particle mixture, we aim to synthesize a metal-supporting composite containing single or two or more manganese, iron, nickel, and cobalt precursors mixed in a certain mole 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 40 mmol metal precursor corresponding to the molar ratio of Fe/Ni/Co (1:1:1) was dissolved in 25 mL ethanol to prepare a solution. At this time, the temperature was raised above 45°C to completely melt the transition metal precursor. Add 40 g of neutral alumina (activated, neutral, Brockmann I) to the solution in which the metal precursor is completely dissolved, mix physically, and dry in an oven at 70°C for 1 hour. Afterwards, it is placed in a kiln and heat treated at 100°C for 3 hours and at 350°C for 5 hours. Then, as in raw material purification system 1 shown in FIG. 1, 7 g of heat-treated transition metal/alumina was filled into 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 added. It was supplied at a rate of 65 ml/min and activated at 500°C for 10 hours.

2. Purification of metathesis raw material (methyl oleate) by metal particle mixture

Methyl oleate was purified in the raw material purification system shown in FIG. 1 using the porous material containing the metal particle mixture prepared above. Sigma-Aldrich's technical grade, 70% methyl oleate, was fractionally distilled to produce 96% purity methyl oleate and used as a raw material for metathesis reaction. Before refining raw materials, nitrogen was blown into the entire purification system to remove oxygen in the gas line and storage. Afterwards, a positive pressure of over 1 atm was maintained with nitrogen gas to prevent oxygen from entering the system. Afterwards, methyl oleate was added to the reaction raw material reservoir 1, and the stainless steel tube filled with the prepared metal particle mixture-containing porous material was heated to 50°C and 40 ml of methyl oleate was pumped through the pump for 12 hours while maintaining the temperature. Methyl oleate was purified by supplying at a rate of mL/min. At this time, methyl oleate is circulated in raw material storage 1 after contact with the prepared porous material containing the metal particle mixture. As the circulation contact time passes, toxic impurities contained in the raw material are purified, and after 12 hours, the purified methyl oleate undergoes a metathesis reaction. Used as raw material. The purification system containing the porous material containing the metal particle mixture used in this way was refilled with 40 ml of new methyl oleate, purified by circulation in the same manner, and reused several times. The methyl oleate purified in this way was used as a metathesis reaction raw material. The metathesis reactivity following reuse of the porous material containing the metal particle mixture was confirmed.

3. Regeneration and effectiveness of used metal particle mixtures

The porous material containing the metal particle mixture, which was reused once in the metathesis raw material purification, was regenerated by the methods of Examples 1 to 3 and Comparative Examples 1 to 4 below, respectively, and then reused for methyl oleate purification, and was added to the purified methyl oleate. The metathesis reaction was performed as follows, and the degree of regeneration of the porous material containing the metal particle mixture was confirmed from the metathesis reaction results.

The results are shown in Table 1 below.

(Example 1)

A vacuum pump was connected to a tube filled with 7 g of the metal particle mixture reused once for raw material purification, and the vacuum pump was vacuumed at 5 mbar. Maintain vacuum and nitrogen flow at 5ml/min and raise temperature to 300°C. This condition is maintained for 4 hours and residual methyl oleate (MO) and organic impurities are washed. Afterwards, the vacuum was released, a nitrogen mixture gas with a hydrogen concentration of 50% was supplied at a flow rate of 20 ml/min, the temperature was raised to 350°C, and the temperature was raised to 350°C and maintained for 4 hours to activate. After activation, lower the tube temperature to 60°C and stop supplying hydrogen-mixed nitrogen gas.

(Example 2)

A vacuum pump was connected to a tube filled with 7 g of the metal particle mixture, which was reused once for raw material purification, and the vacuum pump was pumped at 5 mbar. Maintain vacuum and nitrogen flow at 5 ml/min and raise temperature to 250°C. Maintain this state for 4 hours to wash away residual methyl oleate and organic impurities. Afterwards, the vacuum was released, a nitrogen gas mixture with a hydrogen concentration of 50% was supplied at a flow rate of 20 ml/min, the temperature was raised to 300°C, and the temperature was raised to 300°C and maintained for 4 hours to activate. After activation, lower the tube temperature to 60°C and stop supplying hydrogen-mixed nitrogen gas.

(Example 3)

After purifying the raw material using the metal particle mixture regenerated (reactivated) once according to Example 2, the once regenerated metal particle mixture was regenerated a second time by the method of Example 2. .

(Comparative Example 1) Nitrogen gas cleaning and high-temperature hydrogen activation regeneration

The tube filled with the 7 g metal particle mixture, which was reused once for raw material purification, was heated to 500°C for 2 hours while supplying nitrogen gas at 20 ml/min, and when it reached 500°C, it was maintained for 2 hours to remove any remaining material in the mixture. Methyl oleate and organic impurities are washed away. Then, at 500°C, a nitrogen gas mixture with a hydrogen concentration of 50% was supplied at a flow rate of 20 ml/min and maintained for 4 hours to activate. After activation, lower the tube temperature to 60°C and stop supplying hydrogen-mixed nitrogen gas.

(Comparative Example 2) High-temperature hydrogen activation regeneration after organic solvent washing

The tube filled with the 7 g metal particle mixture, which was reused once for raw material purification, is washed with 200 ml of ethanol at a rate of 20 ml/min at 60°C to clean the remaining methyl oleate and organic impurities for 2 hours. After cleaning, nitrogen was supplied at 20 ml/min, the temperature was raised to 500°C, and nitrogen gas mixture with a hydrogen concentration of 50% was supplied at 500°C at a flow rate of 20 ml/min and maintained for 4 hours to activate. After activation, lower the tube temperature to 60°C and stop the gas supply.

(Comparative Example 3) High-temperature hydrogen activation regeneration after low-temperature vacuum cleaning

A vacuum pump is connected to the tube filled with 7 g metal particle mixture, which was reused once for raw material purification, and the temperature is raised to 300°C while maintaining a vacuum of 5 mbar and a nitrogen flow of 5 ml/min. Maintain this state for 4 hours and wash away methyl oleate and organic impurities. Afterwards, the vacuum was released, a nitrogen gas mixture with a hydrogen concentration of 50% was supplied at a flow rate of 20 ml/min, the temperature was raised to 500°C, and the temperature was maintained at 500°C for 4 hours to activate. After activation, lower the tube temperature to 60°C and stop supplying hydrogen-mixed nitrogen gas.

(Comparative Example 4) Low-temperature hydrogen activation regeneration after high-temperature vacuum washing

A vacuum pump is connected to the tube filled with 7 g metal particle mixture, which was reused once for raw material purification, and the temperature is raised to 450°C while maintaining a vacuum of 5 mbar and a nitrogen flow of 5 ml/min. Maintain this state for 4 hours and wash away methyl oleate and organic impurities. Afterwards, the vacuum is released, a nitrogen gas mixture with a hydrogen concentration of 50% is supplied at a flow rate of 20 ml/min, the temperature is lowered to 350°C, and activation is performed at 350°C for 4 hours. After activation, lower the tube temperature to 60°C and stop the gas supply.

(Control group 1) New use

A nitrogen gas mixture with a hydrogen concentration of 50% was supplied to the prepared metal particle mixture at a flow rate of 20 ml/min, the temperature was raised to 350° C. and maintained for 4 hours to activate the metal particle mixture. After activation, the tube temperature was lowered to 60°C, the supply of hydrogen-mixed nitrogen gas was stopped, and the activated metal particle mixture was first used to purify raw materials.

(Control group 2) Reuse once

The metal particle mixture used in Control 1 was reused for raw material purification without regeneration or activation process.

(Control group 3) Reused 2 times

The metal particle mixture used in Control Group 1 was used twice in succession to purify raw materials without regeneration.

(Ethylene metathesis reaction of purified methyl oleate)

The metathesis experiment was performed as follows. Methyl oleate purified using 5 g of the metal particle mixture from the examples and comparative examples or methyl oleate purified from the control group and dodecane as an internal standard (IS) in a 20 ml glass vial in a glove box. 100 mg and 10 ppm (Ru-CAAC: 0.11 mg, UltraCat: 0.17 mg) of Ru-CAAC (custom-produced or synthesized by Aperion) or UltraCat (purchased from Aldrich) metathesis catalyst were added. The vial containing the reactant was placed in a 125 ml stainless steel reactor and the reactor was fastened. The molecular structure of the metathesis catalyst used is shown in Figure 2. Afterwards, the reactor was taken out of the glove box, charged 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). The sample was passed through a DB-23 column and the product was analyzed through an FID detector. TON is the number of moles of catalyst used divided 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.

- 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 + 9DCE selection rate (%) means:

Selectivity = 100

In the above calculation, the total number of moles of byproduct must be multiplied by 2 because the byproduct is catalytically prepared from two methyl oleates.

- TON refers to the number of next conversions.

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

In Table 1 below, MO refers to methyl oleate and 9DCE refers to methyl 9-decenoate.

As shown in Table 1 above, when reusing as is without a regeneration method, it can be seen that TON decreases to 71.9% when reused once (control group 2) and to 51.0% when reused twice (control group 3). This indicates that the performance of the porous material containing the metal particle mixture gradually deteriorates due to contamination with impurities. This is thought to be because the metal material, which is the core of purification, adsorbs and reacts with impurities present in methyl oleate, and the state of the metal surface is no longer suitable for removing impurities. Therefore, various methods were applied to regenerate it, and it was confirmed that the regeneration efficiency differed depending on the method.

Among them, the low-temperature hydrogen activation method (Examples 1 to 3) after low-temperature vacuum washing showed a performance recovery rate of about 95% compared to the initial performance. The reason why low-temperature vacuum washing and low-temperature hydrogen activation regeneration methods showed the best performance is that residual reaction raw materials and adsorbed impurities are effectively removed at low temperatures (200 ~ 380℃), and thermal decomposition of organic adsorbates, which is expected to be a side effect during cleaning and activation, is prevented. It is expected that carbonization did not occur.

However, when transition metal cleaning or hydrogen activation regeneration was performed at high temperature (400 to 600°C) (Comparative Examples 3 and 4), the remaining organic materials were thermally decomposed and the metal particles present in the alumina carbonized the organic materials at high temperature to form impurities. It is interpreted that the impurity purification performance decreases by deepening the contamination of the particle surface, which is effective for removal.

Claims (11)

In the method of regenerating a mixture of metal particles used to purify raw materials for olefin metathesis reaction,
The metal particle mixture used to purify the raw material for the olefin metathesis reaction is vacuum washed at 200 to 440 ° C. and a pressure of 1 to 100 mbar, and then regenerated by hydrogen activation at 250 to 440 ° C. Method for regenerating metal particle mixtures for refining raw materials.
According to claim 1,
The hydrogen activation treatment is a hydrogen mixed gas mixed with hydrogen and an inert gas, and the hydrogen is contained in 10 to 70% by volume. A method of regenerating a metal particle mixture for purifying raw materials for olefin metathesis reaction.
According to claim 1,
A method of regenerating a metal particle mixture for purifying raw materials for an olefin metathesis reaction, wherein the metal particle mixture is a mixture of metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel.
According to claim 3,
The metal particles contain two components from manganese, iron, nickel and cobalt,
A method of regenerating a metal particle mixture for purifying raw materials for olefin metathesis reaction, characterized in that the content ratio of metal component 1 and metal component 2 is 1:5 to 5:1.
According to claim 1,
A method of regenerating a metal particle mixture for purifying raw materials for an olefin metathesis reaction, wherein the metal particle mixture is supported on a porous material.
According to claim 5,
A method of regenerating a metal particle mixture for purifying raw materials for olefin metathesis reaction, wherein 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,
A method of regenerating a metal particle mixture for purifying raw materials for olefin metathesis reaction, wherein the raw material for olefin metathesis reaction is 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, and methyl 10-undecenoate ( methyl 10-undecenoate), 9-octadecenedioic acid, methyl 9-octadecenedioate, 12-tridecenoic acid, methyl 12-tridecenoic acid Methyl 12-tridecenoate, 13-tetradecenoic acid, methyl 13-tetradecenoate, 11-dodecenoic acid, methyl 11- A method for regenerating a metal particle mixture for purifying raw materials for olefin metathesis reaction, characterized in that it is at least one selected from dodecenoate (methyl 11-dodecenoate).
i) Purifying the raw material for the olefin metathesis reaction by contacting the raw material for the olefin metathesis reaction with a metal particle mixture;
ii) reactivating the metal particle mixture used in the purification step by vacuum washing and hydrogen activation; and
iii) reusing the reactivated metal particle mixture to purify raw materials for olefin metathesis reaction,
The metal particle mixture is a method of purifying raw materials for olefin metathesis reaction, characterized in that the metal particles containing two or more transition metals among manganese, iron, cobalt, and nickel are unsupported or supported on a porous material.
According to clause 9,
A method for purifying raw materials for olefin metathesis reaction, characterized in that after step i), the purified raw material for olefin metathesis reaction is further purified by contacting it with activated alumina particles.
According to claim 10,
A method for purifying raw materials for olefin metathesis reaction, wherein the activated alumina is neutral alumina.