KR102011283B1 - Supported transition metal selenide catalyst, process for producing same, and process for producing urethane using same - Google Patents

Abstract

One embodiment of the present invention is a metal supported selenide (MSe ₂ ) supported catalyst for producing urethane, characterized in that it comprises a solid support and a metal selenide (MSe ₂ ) is adsorbed and supported on the surface of the solid support and Provided is a method for preparing the same, a method for preparing urethane using the metal selenide (Mse ₂ ) supported catalyst, and a urethane prepared thereby.

Description

Supported transition metal selenide catalyst, process for producing same, and process for producing urethane using same}

The present invention relates to a supported catalyst on which metal selenide (MSe ₂ , M = metal) is supported, and more specifically, metal seleide used to prepare urethane (also called carbamate) by reaction of nitro compound and carbon monoxide. The present invention relates to a supported catalyst supported by amide, a method for preparing the same, and a method for preparing urethane using the same.

Polyurethane resin is a plastic with a three-dimensional structure. It is a plastic with high tensile strength and resistance to chemicals, and has excellent chemical durability. It is used in various industrial fields such as electrical insulators, structural materials, and open insulation, and has good elasticity. It is also widely used as a substitute. Urethane is used as a starting material for various materials such as synthetic fibers and synthetic rubber as a preparation material for producing polyurethane. Furthermore, urethane itself is used in various ways as a material for manufacturing various chemicals such as pesticides, herbicides, insecticides, and pharmaceuticals.

Generally, the phosgene manufacturing method is used to manufacture urethane. The phosgene manufacturing method is a method of producing urethane as a final product through a step of reacting an amine compound with phosgene to prepare an isocyanate. However, the phosgene manufacturing method has to use phosgene, which is a highly toxic substance, and thus it is not easy to handle the reactants, and there is a problem that the reaction is not completed in one step one vessel, and a large amount of hydrogen chloride is generated as a reaction byproduct. There was also a problem of poor yield.

In connection with the phosgene method, Japanese Patent No. 1994-062544 (hereinafter referred to as Reference 1) has disclosed a 2-step process by a urethane synthesis method using no phosgene, which is a highly toxic substance. In the first step of the 2-step process, an aromatic first amine, an aromatic nitro compound, and carbon monoxide are added to a catalyst under a solvent, followed by reaction to prepare a substituted urea, and after the first step, the substituted urea is removed from the reactant of the first step. Disclosed is a method of preparing a urethane from an amine compound, including a second step of separating and recovering and then reacting an organic compound containing a hydroxyl group. However, the 2-step process is complicated in the reaction step, it is difficult to proceed the reaction in one container at once, there was a process cumbersome to neutralize the hydrogen chloride produced after the reaction with a basic material.

In connection with the 2-step process, U.S. Patent Publication No. 2009-0275771 (hereinafter referred to as Reference 2) discloses the oxidation of carbohydrates of amino compounds under a mixed gas of carbon monoxide and oxygen to improve the complexity of the process step in the 2-step process. It has been disclosed a method of producing urethane by nilation. However, the mixed gas of carbon monoxide and oxygen has a difficulty in controlling the partial pressure, and there is a disadvantage that an explosion of an oxidant is caused under high temperature oxidation reaction conditions.

Therefore, there is a demand for developing a technology for synthesizing urethanes economically while being able to solve the above-mentioned disadvantages of the prior arts.

Japanese Patent No.1994-062544 United States Patent Application Publication No. 2009-0275771

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a supported catalyst having a metal selenide supported thereon, a method of preparing the supported catalyst, and a method of preparing a urethane using the supported catalyst, which enables the production of urethane through a simple process.

Unlike the existing urethane manufacturing method that goes through two or more stages, when using a metal selenide-supported catalyst, urethane can be prepared directly in one step by using nitro compound, carbon monoxide, and alcohol compound as a reaction, and the reaction is simple and Since it can proceed in a container, urethane can be manufactured economically in terms of time and cost.

In addition, when urethane is manufactured by the conventional method, there is a problem that the safety of the process is threatened in a dangerous environment because it uses toxic toxic, or an oxidizing agent which may be explosive, but uses a metal selenide-supported catalyst. In this case, all of the reactants used in the process are not at risk of explosion and can be safely carried out as a non-toxic material.

The technical problem to be achieved by the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned above may be clearly understood by those skilled in the art from the following description. There will be.

In order to achieve the above technical problem, an embodiment of the present invention, a solid carrier; And metal selenide (MSe ₂ , M = metal) adsorbed and supported on the surface of the solid carrier to provide a metal selenide (MSe ₂ ) supported catalyst for producing urethane.

In one embodiment of the present invention, the metal is divalent iron (Fe (II)), trivalent iron (Fe (III)), mono-copper (Cu (I)), bi-copper (Cu (II) )), Nickel (Ni), chromium (Cr), zinc (Zn) and manganese (Mn) may be any one selected from.

In one embodiment of the present invention, the solid support is alumina (Al ₂ O ₃ ), ceria (CeO ₂ ), activated carbon (AC), montmorillonite (Montmorillonite), silica (SiO ₂ ), magnesium oxide (MgO ), Zeolite (Zeolite) and manaseite (Hydrotalcite) may be any one or more selected from.

In one embodiment of the present invention, the metal selenide (MSe ₂ ) may be contained from 2wt% to 10wt%.

In order to achieve the above technical problem, an embodiment of the present invention comprises the steps of preparing a first solution by mixing a metal compound, selenium dioxide (SeO ₂ ) and a stabilizer; Injecting a solid carrier into the first solution; Injecting carbon monoxide into the first solution into which the solid carrier is introduced; And metal selenide (MSe ₂ ) adsorbed on the surface of the solid support to carry and react the solid support and the carbon monoxide added to the first solution. (MSe ₂ ) It is possible to provide a supported catalyst production method.

In one embodiment of the present invention, the metal compound is a metal halide compound (MX _a ), the metal halide compound (MX _a ), iron chloride (II) (FeCl ₂ ), iron chloride (III) (FeCl ₃ ), It may be one of nickel chloride (NiCl ₂ ), chromium chloride (CrCl ₃ ) and manganese chloride (MnCl ₂ ).

In another embodiment of the present invention, the metal halide compound (MX _a ) is any one of iron bromide (FeBr ₃ ), nickel bromide (NiBr ₂ ), chromium bromide (CrBr ₃ ) and manganese bromide (MnBr ₂ ) It may be.

In one embodiment of the present invention, the stabilizer may be an amine compound or a quaternary ammonium compound.

In another embodiment of the present invention, the amine-based compound or the quaternary ammonium-based compound is, cetyl trimethyl ammonium bromide (CTAB), tetraethylammonium chloride (TBAC: Tetra-n-Butyl Ammonium Chloride), tetra Butylammonium bromide (TBAB: Tetra-n-ButylAmmonium Bromide), tetrabutylphosphonium bromide (TBPB: Tetra-n-ButylPhosphonium Bromide), polyvinylpyrrolidone (PVP: PolyVinylPyrrolidone), choline chloride, pyridine Pyridine, Tetraethylammonium chloride, Imidazole, dimethylaminopyridine and at least one selected from 2,2-bipyridyl It may be.

In one embodiment of the present invention, the solvent of the first solution may be an alcohol solvent.

In another embodiment of the present invention, the pressure of the carbon monoxide may be 200psig to 1600psig.

In one embodiment of the present invention, in the step of preparing the metal selenide (MSe ₂ ) supported catalyst, the reaction temperature may be 100 ℃ to 200 ℃, the reaction time may be 1 hour to 6 hours.

In order to achieve the above technical problem, an embodiment of the present invention comprises the steps of preparing a metal selenide (MSe ₂ ) supported catalyst; Preparing a reactant consisting of a nitro compound, carbon monoxide and an alcohol solvent; And carbonylating the reactant under the metal selenide (MSe ₂ ) supported catalyst.

In one embodiment of the present invention, the molar ratio of the metal selenide (MSe ₂ ) supported catalyst may be from 1/1000 to 1/20 of the reactant.

In another embodiment of the invention, the step of carbonylating, the carbon monoxide may be a pressure of 200psig to 1600psig.

In one embodiment of the present invention, the carbonylating may be performed for 1 hour to 6 hours at a temperature condition of 100 ℃ to 200 ℃.

In order to achieve the above technical problem, the present invention may be a reaction proceeding in a single step in a single vessel.

In order to achieve the above technical problem, another embodiment of the present invention can provide a urethane prepared according to the production method.

According to an embodiment of the present invention, the urethane can be produced in a simple manner using a metal supported selenide (MSe ₂ ) supported catalyst in a single step in a single step, and thus the urethane can be produced in an economical manner in terms of time and cost. Can be prepared.

In addition, according to an embodiment of the present invention, urethane may be safely manufactured without using an oxidizing agent such as nitro compound, carbon monoxide, and alcohol solvent, without the risk of explosion, without using an oxidizing agent.

Furthermore, according to an embodiment of the present invention, unlike the conventional catalyst, a metal selenide (MSe ₂ ) catalyst is used and supported to provide a metal selenide (MSe ₂ ) supported catalyst, the metal than when not supported The amount of selenide (MSe ₂ ) may be reduced to less than 1/50 times, and a relatively small amount of byproducts may be generated after the reaction, as well as urethane yield and selectivity, and the metal selenide (MSe ₂₎ may be increased. ) The recovery rate of the supported catalyst is also high, so that it can be used several times in the reaction, and thus, urethane can be produced economically.

The effects of the present invention are not limited to the above-described effects, but should be understood to include all the effects deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a flow chart showing a metal selenide (MSe ₂ ) supported catalyst production method for producing urethane.
2 is a flowchart illustrating a method of preparing urethane using a metal selenide (MSe ₂ ) supported catalyst.
3 and 4 are photographs showing SEM images of the metal selenide (MSe ₂ ) supported catalyst.
5 and 6 are photographs showing TEM images of a metal selenide (MSe ₂ ) supported catalyst.
7 and 8 are graphs illustrating the EDX data of the metal selenide (MSe ₂ ) supported catalyst.
9 is a graph showing urethane yield according to reaction time (h) when using a metal selenide (MSe ₂ ) supported catalyst.

Hereinafter, with reference to the accompanying drawings will be described the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, coupled)" with another part, it is not only "directly connected" but also "indirectly connected" with another member in between. "Includes the case. In addition, when a part is said to "include" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, action, component, part, or combination thereof described on the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In one embodiment of the present invention, the polyurethane comprising a metal selenide (MSe ₂₎ that is adsorbed supported on the surface of the solid carrier and the carrier of the solid for producing a metal selenide (MSe ₂₎ supported A catalyst can be provided.

The solid supporting material is a material for stably dispersing and maintaining a compound formed of the metal selenide (Mse ₂ ), and generally a solid material may be used. In particular, a solid support for use as a supported catalyst generally uses a porous or large area material for highly dispersed support to increase the exposed surface area so that the function of the catalyst can be activated. In addition, the solid support may use a thermally and chemically stable material to maintain a constant shape and function in the chemical reaction.

For example, the solid support may be alumina (Al ₂ O ₃ ), ceria (CeO ₂ ), activated carbon (AC), montmorillonite, silica (SiO ₂ ), magnesium oxide (MgO), zeolite (Zeolite) And manaseite (Hydrotalcite) may be any one or more selected from. In this case, zeolite may be zeolite (ZSM-5), zeolite 4A, or the like, but the zeolite type is not limited to the above listed types. Furthermore, the solid support is not limited to the materials listed above, and any solid support may be used as long as it is a porous material or a solid material having a large surface area and which does not cause a chemical or physical reaction so as to disperse the catalyst material highly. It can be used as a delay.

In the metal selenide (MSe ₂ ), M denotes a transition meatal (M), and metal selenide means a compound of selenium (Se) and a metal.

The metal may be any one of transition metals. Also called the transition element to be used, generally means the d-zone element of the periodic table. The periodic table includes all Group 3 to 12 elements. Transition metals generally form complexes.

For example, the metal constituting the metal selenide (MSe ₂ ) is divalent iron (Fe (II)), trivalent iron (Fe (III)), monovalent copper (Cu (I)), 2 It may be any one selected from kauri (Cu (II)), nickel (Ni), chromium (Cr), zinc (Zn) and manganese (Mn). However, it is not limited to the metals listed above, and may form any compound with selenium (Se), and any metal that may play a role in increasing the activity of the urethane manufacturing reaction may be included.

At this time, the metal selenide (MSe ₂ ) may be adsorbed on the surface of the solid support, which is due to the adsorption of the metal selenide (MSe ₂ ) and the solid support with each other by physical and chemical bonds As the solid carrier generally has a porous form, the metal selenide (MSe ₂ ) may be positioned in each of the pores constituting the porous surface, and the chemical bond is formed through the reaction according to the following. It is generated between the carrier and the metal selenide (MSe ₂ ) it is possible to stably support the metal selenide (Mse ₂ ).

In one embodiment of the present invention, the metal selenide (MSe ₂ ) may be included 2wt% to 10wt%. The weight percent (wt%) is a metal selenide (MSe ₂₎ is a metal selenide bearing (MSe ₂₎ that calculates, based on the weight of the entire supported catalyst, containing a metal selenide (MSe ₂₎ in the range It is preferable to form a metal selenide (MSe ₂ ) supported catalyst, and if it contains less than the above range, the reactants may not proceed sufficiently in the remaining state, and the reaction rate may be significantly reduced, and exceeds the above range. In this case, the reaction rate is the same as or less than the case of using the catalyst within the above range, whereas the metal selenide (MSe ₂ ) supported catalyst does not contribute to the activation of the reaction and remains, which is economic in terms of cost of the process. Since there may be a problem, it is preferable to fall within the above range.

The metal selenide (MSe ₂ ) supported catalyst may be a heterogeneous catalytically active species that is insoluble in an organic solvent including the above-mentioned solvent, and may be formed of black solid particles.

1 is a flow chart showing a metal selenide (MSe ₂ ) supported catalyst production method for producing urethane.

Referring to FIG. 1, a step of preparing a first solution by mixing a metal compound, selenium dioxide (SeO ₂ ), and a stabilizer (S110), and injecting a solid carrier into the first solution (S120) Injecting carbon monoxide into the first solution into which the carrier is added (S130) and reacting the solid carrier and the carbon monoxide injected into the first solution to adsorb the metal selenide (MSe ₂ ) to the surface of the solid carrier. It is possible to provide a method for preparing a metal selenide (MSe ₂ ) supported catalyst for producing urethane, comprising the step (S140) of being supported.

First, in the step (S110) of preparing a first solution by mixing a metal compound, selenium dioxide (SeO ₂ ) and a stabilizer,

The metal compound, selenium dioxide (SeO ₂ ) and the stabilizer may be considered as a preparation material for preparing the metal selenide (MSe ₂ ) catalyst in the future.

More specifically, the metal compound may be _a metal halide compound (MX _a ) (M is a metal, X is a halogen element, a may mean an integer of any one of 1 to 3, wherein a is Depending on the cation index when the metal is in the ionic state).

For example, the halogen element X may be any one selected from F, Cl, Br, and I, and in particular, Cl, Br may be used.

Specifically, when X is Cl in the metal halide compound (MX _a ), one of iron chloride (FeCl ₃ ), nickel chloride (NiCl ₂ ), chromium chloride (CrCl ₃ ) and manganese chloride (MnCl ₂ ) Although not limited to the metal chloride compounds listed above, other metals may be used, and metal chloride compounds may also be included accordingly.

In another example, when X is Br in the metal halide compound (MX _a ), any one of iron bromide (FeBr ₃ ), nickel bromide (NiBr ₂ ), chromium bromide (CrBr ₃ ) and manganese bromide (MnBr ₂ ) It may be one, but is not limited to the metal bromide compounds listed above, other metals may be used, and thus metal bromide compounds may also be included.

The metal compound may be a di-copper (Cu (II)) compound or a mono-copper (I) compound,

For example, the cupric (Cu (II)) compound includes copper chloride (CuCl- ₂ ), copper sulfate (CuSO ₄ ), copper acetate (Cu (COOCH ₃ ) ₂ ) and copper nitrate trihydrate (Cu ( NO ₃ ) ₂ ) 3 H ₂ O) is at least one selected from,

For another example, the cuprous (I) compound may be copper chloride (CuCl). In the case of copper, the cation valence may vary when ionized (Cu ⁺¹ or Cu ⁺² ) and thus, when forming the compound, the material may also vary.

Next, a stabilizer is a ligand, which forms a complex through coordination bonds with the metal compound, and reduces the metal compound and the selenium dioxide (SeO ₂ ) in the presence of carbon monoxide, and thus is prepared accordingly. By reducing the size of the catalytic material to increase the specific surface area, to stabilize the particles to increase the catalytic activity, it may serve to help the production of solid particles to prepare a solid catalyst.

For example, an amine compound or a quaternary ammonium compound can be used as the stabilizer.

More specifically, the amine-based compound or the quaternary ammonium-based compound, cetyl trimethyl ammonium bromide (CTAB), tetraethylammonium chloride (TBAC: Tetra-n-Butyl Ammonium Chloride), tetrabutyl ammonium bromide (TBAB) Tetra-n-ButylAmmonium Bromide, tetrabutylphosphonium bromide (TBPB: Tetra-n-ButylPhosphonium Bromide), polyvinylpyrrolidone (PVP: PolyVinylPyrrolidone), choline chloride, pyridine, tetraethyl It may be at least one selected from ammonium chloride (Tetraethylammonium chloride), imidazole, dimethylaminopyridine (4- (Dimethylamino) pyridine) and 2,2-bipyridyl (2,2-Bipyridyl).

For another example, the metal compound, selenium dioxide (SeO ₂ ) and the stabilizer may be mixed in a mass ratio of 1: 4: 0.3, but is not limited to the mass ratio, specific metal compounds and stabilizers, solvent used. And reaction conditions.

In another example, the solvent of the first solution may be an alcohol solvent (ROH). In this case, R may be an alkyl group having 1 to 4 carbon atoms, and ROH may be a monohydric alcohol having one hydroxyl group (-OH) in the entire alkyl group, but is not limited thereto and has two hydroxyl groups (-OH). Dihydric alcohol, or trihydric alcohol having three hydroxyl groups (—OH). Furthermore, since the solid carrier is supported on the first solution according to the following method, the same solvent may be used until the reaction is completed through each step.

For example, the alcohol solvent is methanol (CH ₃ OH), ethanol (C ₂ H ₅ OH), propanol (C ₃ H ₈ OH), n-butanol (C ₄ H ₉ OH), iso-butanol (C ₄ H ₉ OH) and tert-butanol (C ₄ H ₉ OH)) may be any one or more selected from, but is not limited thereto.

 In the step (S120) of injecting a solid carrier to the first solution,

For example, a solid support material is a material that stably disperses and maintains a compound formed of the metal selenide (Mse ₂ ), and generally a solid material may be used. In particular, a solid support for use as a supported catalyst generally uses a porous or large area material for highly dispersed support to increase the exposed surface area so that the function of the catalyst can be activated. In addition, the solid support may use a thermally and chemically stable material to maintain a constant shape and function in the chemical reaction.

For example, the solid support may be alumina (Al ₂ O ₃ ), ceria (CeO ₂ ), activated carbon (AC), montmorillonite, silica (SiO ₂ ), magnesium oxide (MgO), zeolite (Zeolite) And manaseite (Hydrotalcite) may be any one or more selected from. However, the solid support is not limited to the above-listed materials, and solid supports are not limited so long as they are porous materials or solid materials having a large surface area and which do not cause chemical or physical reactions so as to disperse the catalyst material highly. It can be used as a delay.

As another example, the solid carrier may be added to the first solution, followed by stirring for about 10 minutes to 1 hour, thereby adsorbing a substance mixed in the first solution to the solid carrier. The stirring time is sufficient if the material mixed in the first solution is adsorbed to the solid carrier and is not necessarily limited to the above time range. In this case, the solid carrier and the first solution is mixed with the material may be chemically and physically combined and adsorbed. Since the solid carrier generally has a porous form, the metal selenide (MSe ₂ ) may be located in each of the pores constituting the porous surface, and the chemical bond is supported by the solid carrier as it is subjected to the reaction according to the following. Is generated between the metal selenide (MSe ₂ ) and the metal selenide (Mse ₂ ) may be supported.

In the step (S130) of injecting carbon monoxide into the first solution in which the solid carrier is added,

The first solution may be prepared through the step S110 in one vessel reactor, when the solid carrier is added in the same reactor, carbon monoxide may be directly injected into the reactor, and the carbon monoxide is in the form of a gas. It can be injected to have a certain level or more pressure. Therefore, the supported catalyst can be produced at one time in one container. Furthermore, after the preparation of the metal selenide (Mse ₂ ) supported catalyst according to the above process and the following process, the reactant may be added immediately to prepare the urethane, thus preparing the catalyst, as well as preparing the urethane using the catalyst. Everything can be done in a single container.

The pressure of the injected carbon monoxide (CO) may be 200psig to 1600psig. When the pressure of the carbon monoxide is injected below the above range, even if the reaction is performed according to the following last step (S140), the metal selenide (MSe ₂ ) supported catalyst may not be prepared in a desired yield, and the pressure of the carbon monoxide is in the above range. If the amount is exceeded, there is a possibility that side reactions may occur, and even after the metal selenide (MSe ₂ ) -supported catalyst is prepared, the residual amount of carbon monoxide may be high, so the process may not operate economically. It may be desirable to control the injection of carbon monoxide within the range.

In the step (S140) in which the metal carrier (MSe ₂ ) is adsorbed and supported on the surface of the solid carrier by reacting the solid carrier and the carbon monoxide introduced into the first solution.

For example, the first solution, in which the metal compound, selenium dioxide (SeO ₂ ), and the stabilizer are mixed, may be considered to contain precursor materials for preparing a metal selenide (MSe ₂ ) supported catalyst. It is not possible to prepare the supported catalyst immediately after the step (S120) of injecting the solid carrier into the first solution, and the precursor materials contained in the first solution are located on the surface of the solid carrier. that is, carbon monoxide is introduced and, to is a certain time after the reaction time in the range of the metallic selenide (Mse ₂₎ on the surface of the carrier of said solid under specific temperature conditions absorption is presented in the metal selenide (Mse ₂ Supported catalyst can be prepared.

In this case, the metal selenide (MSe ₂ ) and the solid support are adsorbed to each other by physical and chemical bonds through the reaction, and the solid support generally has a porous form, thereby forming a porous surface. The metal selenide (MSe ₂ ) may be located in each of the pores, and the chemical bond is generated between the solid carrier and the metal selenide (MSe ₂ ) while undergoing a reaction according to the following. Mse ₂ ) can be supported stably.

In another example, after the carbon monoxide is injected, the reaction temperature is 100 ° C. to 200 ° C., and the solid carrier and carbon monoxide on which the first solution is loaded may be reacted for 1 to 6 hours. The reaction temperature is a temperature range suitable for the support of the solid support on which carbon monoxide and the first solution are loaded to support the metal selenide (MSe ₂ ) on the solid support. It may be set differently depending on the type, and is not necessarily limited to the reaction proceeds within the temperature range. In addition, the reaction time may be set differently according to the kind of the first solution to be injected and the type of the solid carrier, and the reaction time range is within the general time range in which the reaction proceeds and the reaction is necessarily within the time range. It is not limited to proceeding.

For example, the metal selenide (MSe ₂ ) may be included from 2wt% to 10wt%. The weight percent (wt%) is a metal selenide (MSe ₂₎ is to be calculated based on the metal selenide (MSe ₂₎ by weight of the total supported catalyst supported thereon, it is contained a metal selenide (MSe ₂₎ in the range It is preferable to form a metal selenide (MSe ₂ ) supported catalyst, and if it contains less than the above range, the reactant may not proceed sufficiently in a remaining state and thus the reaction rate may be significantly reduced. In this case, the reaction rate is the same as or less than the case of using a catalyst within the above range, whereas the metal selenide (MSe ₂ ) -supported catalyst does not contribute to the activation of the reaction and remains, which is not economical in terms of cost of the process. The problem may be present, it is preferably included in the above range.

The metal selenide (MSe ₂ ) supported catalyst prepared through each step of the preparation method may be a heterogeneous catalytically active species that is insoluble in an organic solvent including the aforementioned solvent, and may be formed of black solid particles.

2 is a flowchart illustrating a method of preparing urethane using a metal selenide (MSe ₂ ) supported catalyst.

Referring to Figure 2, preparing a metal selenide (MSe ₂ ) supported catalyst (S210), preparing a reactant consisting of a nitro compound, carbon monoxide and alcohol solvent (S220) and the metal selenide (MSe ₂ ) Carbonylation reaction of the reactants under a supported catalyst may be provided a urethane manufacturing method comprising the step (S230).

The urethane is also called carbamate, and may be prepared by the same process as in Scheme 1 below.

Scheme 1

Based on Scheme 1, R-NO ₂ can be seen as a nitro compound, R'OH can be seen as an alcohol solvent, catalyst is a metal selenide (MSe ₂ ) supported catalyst, and the result is urethane It can be seen that carbon dioxide is generated as a byproduct.

First, in the preparing of the metal selenide (MSe ₂ ) supported catalyst (S210), the metal selenide (MSe ₂ ) supported catalyst may be prepared by the above-described method.

Next, in the step of preparing a reactant consisting of a nitro compound, carbon monoxide and an alcohol solvent (S220),

As the reactant, the nitro compound may be any compound having a nitro functional group (-NO ₂ ). For example, a substance having a nitro group attached to a benzene compound, such as nitrobenzene, may be used. However, the present invention is not limited to the above-mentioned substance, and in addition to the nitro functional group, all compounds having a nitro functional group may be used as reactants of the reaction unless the substance further has a separate functional group capable of participating in the reaction.

For example, the molar ratio of the metal selenide (MSe ₂ ) supported catalyst may be 1/1000 to 1/20 of the reactant. The range of the molar ratio depends on the optimum amount of the metal selenide (MSe ₂ ) supported catalyst to allow the reaction to occur, but is not limited to the above range, depending on the overall conditions of the reaction, in order to proceed with the reaction In addition, the metal selenide (MSe ₂ ) supported catalyst may be further added, or the metal selenide (MSe ₂ ) supported catalyst below the above range may be added.

In addition, the pressure of the carbon monoxide (CO) may be 200psig to 1600psig.

Carbon monoxide in this step is an essential reactant for the carbonyl reaction, and can react with a metal selenide (MSe ₂ ) supported catalyst at high pressure to form a metal carbonyl compound as a reaction intermediate. The metal carbonyl compound and the nitro compound may be reacted to prepare the final product urethane (the metal selenide (MSe ₂ supported catalyst is recovered again and does not finally participate in the reaction).

When the pressure of the carbon monoxide (CO) is less than the pressure range, it is not possible to react with the metal selenide (MSe ₂ ) supported catalyst to form a metal carbonyl compound, so that the reaction to prepare the final product of the urethane can not proceed, Yields of urethane may not be prepared. In addition, when the pressure range is exceeded, urethane may be manufactured in a certain yield or more, but carbon monoxide that does not participate in the reaction may be left as a by-product, and thus the by-product may be generated in a high pressure environment. It is preferable to proceed with reaction within the range.

As another example, the reaction temperature for the carbonylation reaction is 100 ℃ to 200 ℃, it is possible to react the solid carrier and carbon monoxide on which the first solution is supported for 1 hour to 6 hours. The reaction temperature is an appropriate temperature range for the carbonylation reaction to be carried out, and may be set differently according to the metal selenide (MSe ₂ ) supported catalyst and the kind of the reactant, and the reaction may be limited within the temperature range. It is not. In addition, the reaction time may be set differently according to the kind of the first solution to be injected and the type of the solid carrier, and the reaction time range is within the general time range in which the reaction proceeds and the reaction is necessarily within the time range. It is not limited to proceeding.

Urethane manufacturing method according to an embodiment of the present invention is a reaction proceeding in a single step in a single-pot (one-pot), the urethane is produced through a one-step reaction in one reactor without having to prepare the reactor for each step It is possible to produce urethane economically in terms of time and cost to enter the process due to the simple process-wide steps.

According to one embodiment of the present invention can provide a urethane prepared according to the above method.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail using an Example and a comparative example. These examples are provided for the purpose of more specifically illustrating embodiments of the invention and are not intended to limit the scope of the invention.

3 and 4 are SEM images of a metal selenide (MSe ₂ ) supported catalyst. More specifically, in FIG. 3, the metal selenide (MSe ₂ ) is CuSe ₂ and the solid carrier is AC. . In the case of Figure 4, the metal selenide (MSe ₂ ) is FeSe ₂ , the carrier is Al ₂ O ₃ .

5 and 6 are photographs showing TEM images of a metal selenide (MSe ₂ ) supported catalyst. More specifically, in the case of Figure 5, the metal selenide (MSe ₂ ) is CuSe ₂ , the solid carrier is AC. In the case of Figure 6, the metal selenide (MSe ₂ ) is FeSe ₂ , the solid carrier is Al ₂ O ₃ . Referring to FIG. 5, it can be seen that CuSe ₂ is well dispersed in nano size, and referring to FIG. 6, it can be seen that FeSe ₂ is well dispersed in nano size.

7 and 8 are graphs illustrating the EDX data of the metal selenide (MSe ₂ ) supported catalyst. More specifically, in the case of Figure 7, the metal selenide (MSe ₂ ) is CuSe ₂ , the solid support is AC. In the case of Figure 8, the metal selenide (MSe ₂ ) is FeSe ₂ , the solid carrier is Al ₂ O ₃ . Referring to the EDX data of FIG. 7, it can be seen that the ratio of Cu: Se is 1: 2. Referring to the EDX data of FIG. 8, it can be seen that the ratio of Fe: Se is 1: 2.

[ Example  One] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% CuSe ₂ Supported Catalyst Preparation-Alumina ( Al ₂ O ₃ Solid) On support  use

① Dissolve 0.1 g of CuCl ₂ , 0.33 g of SeO ₂ , and 0.1 g of CTAB (1: 4: 0.3) in 30 ml methanol. ② Put 3.1 g of solid carrier (Al ₂ O ₃ ) into the solution and stir for 30 minutes. ③ Inject carbon monoxide (CO) 82 bar (1200 psi) into the reactor and react at 160 ^o C for 4 hours. ④ Wash and filter with soxhlet using methanol as solvent. ⑤ Wash with methanol three times or more and dry for 12 hours under vacuum.

[ Example  2] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% CuSe ₂ Supported Catalyst Preparation-Silica ( SiO ₂ ) -solid commercial On support  use

Manufactured in the same manner as in Example 1, but prepared by changing only the type of the solid carrier to silica (SiO ₂ ) -commercial.

[ Example  3] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% CuSe ₂ Supported Catalyst Preparation-Activated Carbon (AC) On support  use

Manufactured in the same manner as in Example 1, but prepared by changing only the type of the solid carrier to activated carbon (AC).

[ Example  4] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% CuSe ₂ Supported Catalyst Preparation- Ceria ₂ )  Solid On support  use

Prepared in the same manner as in Example 1, but prepared by changing only the type of the solid carrier to ceria (CeO ₂ ).

 [ Example  5] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% CuSe ₂ Supported Catalyst Preparation-Silica ( SiO ₂ ) -110 solid On support  use

Prepared in the same manner as in Example 1, but prepared by changing only the type of the solid carrier to silica (SiO ₂ ) -110.

[ Example  6] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% CuSe ₂ Supported Catalyst Preparation-Silica ( SiO ₂ ) -240 solid On support  use

Prepared in the same manner as in Example 1, but prepared by changing only the type of the solid carrier to silica (SiO ₂ ) -240.

[ Example  7] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% CuSe ₂ Supported Catalyst Preparation-Magnesium Oxide (MgO) On support  use

Prepared in the same manner as in Example 1, but prepared by changing only the type of the solid carrier to magnesium oxide (MgO).

[ Example  8] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% CuSe ₂ Supported Catalyst Preparation- Manaseite (Hydrotalcite)  Solid On support  use

Manufactured in the same manner as in Example 1, only the type of the solid carrier is prepared by changing to manaseite (Hydrotalcite).

[ Example  9] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% CuSe ₂ Supported Catalyst Preparation-Montmorillonite Solid On support  use

Prepared in the same manner as in Example 1, but prepared by changing only the kind of the solid carrier to Montmorillonite (Montmorillonite).

[ Example  10] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% Fese ₂ Supported Catalyst Preparation-Alumina ( Al ₂ O ₃ Solid) On support  use

Manufactured in the same manner as in Example 1, prepared by changing the metal selenide (MSe ₂ ) to FeSe ₂ , and the type of the solid carrier to alumina (Al ₂ O ₃ ).

[ Example  11] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% Fese ₂ Supported Catalyst Preparation-Silica ( SiO ₂ ) -solid commercial On support  use

Prepared in the same manner as in Example 1, except that the metal selenide (MSe ₂ ) is changed to FeSe ₂ , and the type of the solid carrier is changed to silica (SiO ₂ )-commercial.

[ Example  12] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% Fese ₂ Supported Catalyst Preparation-Activated Carbon (AC) On support  use

Manufactured in the same manner as in Example 1, prepared by changing the metal selenide (MSe ₂ ) to FeSe ₂ , and the type of the solid carrier to activated carbon (AC).

[ Example  13] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% Fese ₂ Supported Catalyst Preparation- Ceria ₂ )  Solid On support  use

Manufactured in the same manner as in Example 1, prepared by changing the metal selenide (MSe ₂ ) to FeSe ₂ , and the type of the solid carrier to ceria (CeO ₂ ).

[ Example  14] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% Fese ₂ Supported Catalyst Preparation-Montmorillonite Solid On support  use

Manufactured in the same manner as in Example 1, prepared by changing the metal selenide (MSe ₂ ) to FeSe ₂ , and the type of the solid carrier to montmorillonite (Montmorillonite).

[ Example  15] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% Fese ₂ Supported Catalyst Preparation-Silica ( SiO ₂ ) -110 solid On support  use

Prepared in the same manner as in Example 1, prepared by changing the metal selenide (MSe ₂ ) to FeSe ₂ , and the type of the solid carrier to silica (SiO ₂ ) -110.

[ Example  16] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% Fese ₂ Supported Catalyst Preparation-Silica ( SiO ₂ ) -240 solid On support  use

Prepared in the same manner as in Example 1, prepared by changing the metal selenide (MSe ₂ ) to FeSe ₂ , and the type of the solid carrier to silica (SiO ₂ ) -240.

[ Example  17] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% Fese ₂ Supported Catalyst Preparation-Zeolites in Solid On support  use

Manufactured in the same manner as in Example 1, prepared by changing the metal selenide (MSe ₂ ) to FeSe ₂ and the type of the solid carrier to Zeolite (Zeolite).

[ Example  18] Metal selenide ( MSe ₂ Supported Catalyst Preparation

5wt% Fese ₂ Supported Catalyst Preparation- Manganese Cobalt Spinel ( MnCo ₂ O ₄ ) Solid On support  use

Prepared in the same manner as in Example 1, prepared by changing the metal selenide (MSe ₂ ) to FeSe ₂ , and the type of the solid carrier to manganese cobalt spinel (MnCo ₂ O ₄ ) .

[ Experimental Example  One] Metal selenide ( MSe ₂ ) Preparation of Urethane Using Supported Catalyst

₂ g of a metal selenide (MSe ₂ ) supported catalyst prepared according to Examples 1 to 18 were added to 20 mmol of nitrobenzene (NB) in 30 ml of methanol, and then 82 bar (1200 psi) of carbon monoxide (CO) was injected into the reactor. The reaction was carried out at 160 ^o C for 4 hours to prepare methylphenyl carbamate (MPC: Methyl N- phenyl carbamate) (carbamate corresponds to the same material as urethane), and the experimental results thereof are shown in Table 1 below.

turn Conv. (%) Conversion Rate (Y _MPC (%)) Yield (S _MPC (%)) Example  One 100 82.9 82.9 Example 2 62.3 51.0 81.9 Example  3 100 75.2 75.2 Example  4 97.2 87.7 90.2 Example 5 68.2 62.6 91.8 Example 6 59.5 57.7 97.0 Example 7 87.8 11.5 13.1 Example 8 21.2 0 0 Example 9 52.2 43.3 83.2 Example 10 100 91.6 91.6 Example 11 78.4 71.5 91.3 Example 12 100 75.9 75.9 Example 13 18.2 12.4 68.3 Example 14 50.8 43.2 85.0 Example 15 76.4 71.7 93.8 Example 16 100 86.7 86.7 Example 17 11.7 8.1 69.3 Example 18 9.3 1.9 20.5 Example 19 100 88.7 88.7

Based on the results of the above examples, when the metal selenide (MSe ₂ ) to CuSe ₂ , Example 1 using activated alumina (Al ₂ O ₃ ) as a solid support, the activated carbon (AC) Example 3 used as a support, Example 4 using ceria (CeO ₂ ) as a solid support it can be seen that the catalytic activity is relatively higher than the other examples.

In addition, when metal selenide (MSe ₂ ) is FeSe ₂ , Example 10 using alumina (Al ₂ O ₃ ) as a solid support, Example 12 using activated carbon (AC) as a solid support, and silica (SiO) _It can be seen that Example 16, which uses ₂ ) as a solid carrier, has a relatively higher catalytic activity compared to other examples.

Therefore, it can be seen that the urethane production yield may vary depending on the type of metal selenide and the type of the solid carrier.

[ Example  3-1] prepared by varying the reaction time Metal selenide ( MSe ₂ Supported Catalyst Preparation

Prepared in the same manner as in Example 3, but prepared by changing the catalyst production time (reaction time in the step of preparing the catalyst) from 4 hours to 10 hours.

[ Example  4-1] prepared by varying the reaction time Metal selenide ( MSe ₂ Supported Catalyst Preparation

Prepared in the same manner as in Example 4, but prepared by changing the catalyst preparation time from 4 hours to 10 hours.

[ Experimental Example  2] Catalyst  Manufactured with different time Metal selenide ( MSe ₂ ) Preparation of Urethane Using Supported Catalyst

Prepared in the same manner as in Experimental Example 1, compared to Example 3 and Example 3-1, and compared with Example 4 and Example 4-1 to carry out the metal selenide (MSe ₂ ) by varying the catalyst production time The yield in the case of preparing a catalyst is compared.

turn Conv. (%) Conversion Rate (Y _MPC (%)) Yield (S _MPC (%)) Example 3 100 75.2 75.2 Example 3-1 94.0 86.8 92.3 Example 4 97.2 87.7 90.2 Example 4-1 100 79.0 79.0

Phenyl carbamate according to the Catalyst Preparation Time: a review of (MPC Methyl N -phenyl carbamate) yield changes result, it is possible to check that each yield almost without a difference, the catalyst preparation time difference between the change in catalyst activity, and hence yields It can be seen that it does not significantly affect.

[ Experimental Example  3] Metal selenide ( MSe ₂ ) Urethane production by changing reaction time using supported catalyst

To prepare a urethane in the same manner as in Experimental Example 1, but using a metal selenide (MSe ₂ ) supported catalyst prepared according to Example 3 reaction time for preparing methylphenyl carbamate (MPC: Methyl N -phenyl carbamate) Only by changing the urethane was prepared. The results are shown in FIG. 9.

9 is a graph showing the yield of urethane (Methyl N- phenyl carbamate) according to reaction time (h) when a metal selenide (MSe ₂ ) supported catalyst is used. Metal selenide (MSe ₂ ) supported catalyst prepared according to Example 3 was used.

Referring to Figure 9, as the reaction time increases it was confirmed that the conversion and the yield was increased, when the reaction for 8 hours to improve the yield of methylphenyl carbamate (MPC: Methyl N -phenyl carbamate) to 96.9% I could confirm it.

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is represented by the following claims, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present invention.

Claims (4)

delete Solid carrier; And
It characterized in that it comprises a metal selenide (MSe ₂ ) which is adsorbed and supported on the surface of the solid carrier,
The metal is any one selected from mono-copper (Cu (I)) and bi-copper (Cu (II)),
The solid carrier is characterized in that it comprises alumina (Al ₂ O ₃ ), ceria (CeO ₂ ) or activated carbon (AC),
Metal selenide (MSe ₂ ) is characterized in that it comprises 2wt% to 10wt%,
Metal selenide (MSe ₂ ) supported catalyst for producing urethane used for producing urethane by reaction of nitro compound and carbon monoxide.
Solid carrier; And
It characterized in that it comprises a metal selenide (MSe ₂ ) which is adsorbed and supported on the surface of the solid carrier,
The metal is any one selected from divalent iron (Fe (II)) and trivalent iron (Fe (III)),
The solid carrier is characterized in that it comprises alumina (Al ₂ O ₃ ), activated carbon (AC) or silica (SiO ₂ ),
Metal selenide (MSe ₂ ) is characterized in that it comprises 2wt% to 10wt%,
Metal selenide (MSe ₂ ) supported catalyst for producing urethane used for producing urethane by reaction of nitro compound and carbon monoxide.
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