KR20180116196A - Supported transition metal selenide catalyst, process for producing same, and process for producing urethane using same - Google Patents

Abstract

According to an embodiment of the present invention, provided are a metal selenide (MSe_2) supported catalyst for producing urethane and a method for producing the same, wherein the catalyst comprises a solid supporting material and metal selenide (MSe_2) supported by being adsorbed onto a surface of the solid supporting material. Moreover, the present invention provides a method for producing urethane by using the metal selenide (MSe_2) supported catalyst and urethane manufactured thereby.

Description

[0001] The present invention relates to a metal-selenide catalyst, a supported metal-selenide catalyst, a process for producing same, and a process for producing same,

The present invention relates to a supported catalyst on which metal selenide (MSe ₂ , M = metal) is supported, and more particularly, to a supported catalyst comprising a metal selenide (hereinafter referred to as " Supported catalyst supported on a support, a process for producing the catalyst, and a process for producing urethane using the same.

Polyurethane resin is a type of plastic with a three-dimensional structure. It is a plastic with high physical tensile strength, good chemical resistance and excellent chemical durability. It is used in various industrial fields such as electric insulation, structural material, It is widely used as a substitute. Urethane is used as a starting material for various materials such as synthetic fibers and synthetic rubbers as a preparation material for producing polyurethane. Furthermore, urethane itself is widely used as a material for manufacturing various chemicals such as pesticides, herbicides, insecticides, medicines and the like.

Generally, a phosgene process is used to produce urethane. The phosgene production process is a process for producing an isocyanate by reacting an amine compound with phosgene to produce urethane as a final product. However, since the phosgene production method requires the use of phosgene, which is a toxic substance, it is difficult to handle the reactants, the reaction can not be completed in a single stage vessel at once, and there is a problem that a large amount of hydrogen chloride is generated as a reaction by- There was also a problem that the yield was poor.

Regarding the phosgene process, Japanese Patent Registration No. 1994-062544 (hereinafter referred to as Reference 1) has disclosed a 2-step process using a urethane synthesis method which does not use phosgene, which is a toxic substance. In the first step of the 2-step process, the aromatic urea amine, the aromatic nitro compound, and the carbon monoxide are added to the reaction mixture in the presence of a solvent to prepare a substituted urea, Separating and recovering the organic urea solution, and purifying the organic solvent to react with an organic compound containing a hydroxyl group, thereby producing urethane from the amine compound. However, the 2-step process has a complicated reaction step, and it is difficult for the reaction to proceed in one vessel at a time, and there is a complication in the process of neutralizing the generated hydrogen chloride with a basic substance.

In order to improve the complexity of the process step in the 2-step process, U.S. Published Patent Application No. 2009-0275771 (hereinafter referred to as Document 2) relates to the above 2-step process. In order to improve the complexity of the process step, A process for producing urethane by nitration has been disclosed. However, the mixed gas of carbon monoxide and oxygen has a difficulty in controlling the partial pressure and has a disadvantage in that there is a risk of explosion of an oxidizing agent and the like in a high temperature oxidation reaction condition.

Accordingly, there is a need to develop a technology for economically producing urethane having a high yield while solving the disadvantages of the above-described conventional techniques.

Japanese Patent No. 1994-062544 U.S. Published Patent Application No. 2009-0275771

SUMMARY OF THE INVENTION The present invention provides a supported catalyst on which a metal selenide is supported to produce urethane through a simple process, a method for producing the supported catalyst, and a method for producing the urethane using the supported catalyst.

Unlike the conventional urethane manufacturing process, the metal-selenide supported catalyst can be used to produce urethane in a single step using a nitro compound, carbon monoxide and an alcohol compound as a reaction material, It is possible to proceed in the container, thereby making it possible to economically manufacture urethane in terms of time and cost.

In addition, when the urethane produced by the conventional method is used, toxic phosgene is used, or an oxidizing agent which may cause explosion is used. In this case, the safety of the process is threatened in a dangerous environment. However, the use of a metal- In case the reactants used in the process are all free from the risk of explosion and can be safely carried out as a non-toxic substance.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

According to an aspect of the present invention, there is provided an image forming apparatus comprising: a solid carrier; And a metal selenide (MSe ₂ , M = metal) adsorbed on and supported on the surface of the solid support, thereby providing a metal selenide (MSe ₂ ) supported catalyst for urethane production.

In one embodiment of the present invention, the metal is selected from the group consisting of Fe (II), Fe (III), Cu (I), Cu ), Nickel (Ni), chrome (Cr), zinc (Zn), and manganese (Mn).

In one embodiment of the present invention, the solid carrier includes at least one of alumina (Al ₂ O ₃ ), ceria (CeO ₂ ), activated carbon (AC), montmorillonite, silica (SiO ₂ ) ), Zeolite (Zeolite) and mannateite (Hydrotalcite).

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

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: 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 support is charged; And a step of reacting the solid carrier and the carbon monoxide introduced into the first solution to adsorb and support the metal selenide (MSe ₂ ) on the surface of the solid support, characterized in that the metal selenide (MSe ₂ ) supported catalyst.

In one embodiment of the present invention, the metal compound is a metal halide (MX _a), the metal halide (MX _a) is, iron (Ⅱ) (FeCl _2), ferric chloride (Ⅲ) (FeCl _3), And may be any 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 ) Lt; / RTI >

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 compound or the quaternary ammonium compound may be at least one selected from the group consisting of Cetyl Trimethyelmonium Bromide (CTAB), Tetra-n-Butylmonium Chloride (TBAC) (TBAB: Tetra-n-Butylphosphonium bromide), polyvinylpyrrolidone (PVP), choline chloride, pyridine Pyridine, tetraethylammonium chloride, imidazole, 4- (dimethylamino) pyridine, and 2,2-bipyridyl. Lt; / RTI >

In an 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 200 psig to 1600 psig.

In one embodiment of the present invention, in the step of preparing the metal-selenide (MSe ₂ ) supported catalyst, the reaction temperature is 100 ° C to 200 ° C, and the reaction time is 1 hour to 6 hours.

According to an aspect of the present invention, there is provided a method for preparing a metal-selenide (MSe ₂ ) supported catalyst, Preparing a reactant comprising a nitro compound, carbon monoxide and an alcohol solvent; And subjecting the reactant to a carbonylation reaction 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 1/1000 to 1/20 of the reactant.

In another embodiment of the present invention, the carbonylating step may be such that the pressure of the carbon monoxide is 200 psig to 1600 psig.

In one embodiment of the present invention, the carbonylating step may be carried out at a temperature of 100 ° C to 200 ° C for 1 hour to 6 hours.

In order to accomplish the above object, the present invention may be a single step reaction in a single vessel.

In order to accomplish the above object, another embodiment of the present invention can provide urethane which is produced according to the above production method.

According to the embodiment of the present invention, urethane can be produced by a simple method through a single step in a single container using the metal-selenide (MSe ₂ ) supported catalyst, Can be prepared.

Also, according to the embodiment of the present invention, it is possible to safely manufacture urethane without the risk of explosion by using only reactants such as nitro compound, carbon monoxide and alcohol solvent without using an oxidizer or the like which is dangerous for explosion.

Further, according to the embodiment of the present invention, unlike the existing catalyst, a metal selenide (MSe ₂ ) catalyst is used and supported to support a metal selenide (MSe ₂ ) The amount of selenide (MSe ₂ ) added can be reduced to less than 1/50, the byproduct after reaction can be relatively reduced, the urethane yield and selectivity are increased, and the metal selenide (MSe ₂ ) Recovery rate of the supported catalyst is also high, so that it can be used many times in the reaction, so that the urethane can be economically produced.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

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

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when an element is referred to as " comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, 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 Catalyst can be provided.

The solid supporting material is a material which disperses and retains a compound formed of the metal selenide (Mse ₂ ) in a stable state, and generally, a solid material can be used. Particularly, a solid carrier to be used as a supported catalyst generally has a large porosity or a large area so as to be highly dispersed and supported so that the exposed surface area becomes large so that the function of the catalyst can be activated. In addition, solid carriers can be thermally and chemically stable to maintain certain shapes and functions in chemical reactions.

For example, the solid carrier may be selected from alumina (Al ₂ O ₃ ), ceria (CeO ₂ ), activated carbon (AC), montmorillonite, silica (SiO ₂ ), magnesium oxide (MgO), zeolite And hydrotalcite. [0033] The term " hydrotalcite " The zeolite may be zeolite (ZSM-5), zeolite (4A) or the like, but the zeolite is not limited to the above listed zeolite. Further, the solid carrier is not limited to the above listed materials, and may be a porous material or a solid material having a large surface area so as to highly disperse the catalyst material, and a material that does not cause a chemical or physical reaction, It can be used as a delay.

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

The metal may be any one of transition metals. Also referred to as the transition element to be used, it generally refers to the d-zone element of the periodic table. In the periodic table, all elements from Group 3 to Group 12 are included. Transition metals generally form complexes.

For example, the metal constituting the metal selenide (MSe ₂ ) may be at least one selected from the group consisting of divalent iron (Fe (II)), trivalent iron (Fe (III) And may be any one selected from the group consisting of brazing alloy (Cu (II)), nickel (Ni), chrome (Cr), zinc (Zn) and manganese (Mn). However, the present invention is not limited to the metals listed above, but may be any metal capable of forming a compound with selenium (Se) and capable of increasing the activity of the urethane production reaction.

At this time, the metal selenide (MSe ₂ ) may be adsorbed on the surface of the solid support. This is because the metal selenide (MSe ₂ ) and the solid support are adsorbed to each other by physical and chemical bonding Since the solid support has a generally porous structure, the metal selenide (MSe ₂ ) may be positioned in each of the pores constituting the porous surface, and the chemical bond may be bonded to the solid support It is generated between the bearing member and the metal selenide (MSe ₂₎ wherein the metal selenide (Mse ₂₎ is able to be reliably supported.

In one embodiment of the present invention, the metal selenide (MSe ₂ ) may be contained in an amount of 2 wt% to 10 wt%. 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 (MSe ₂ ) supported catalyst. If the amount of the catalyst is less than the above range, the reaction may not proceed sufficiently in the state where the reactants remain, so that the reaction rate may be significantly reduced, (MSe ₂ ) supported catalyst does not contribute to the activation of the reaction and is remained, which is economical in view of the cost of the process However, it is preferable that the above-mentioned range is included.

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

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

Referring to FIG. 1, a solid solution is prepared by mixing a metal compound, selenium dioxide (SeO ₂ ), and a stabilizer to form a first solution (S110), and injecting a solid support into the first solution (S120) (S130) injecting carbon monoxide into the first solution into which the support is charged, and reacting the solid support and the carbon monoxide introduced into the first solution to adsorb the metal selenide (MSe ₂ ) on the surface of the solid support (MSe ₂ ) supported catalyst for urethane production according to the present invention.

In the first, a metal compound, and selenium dioxide (SeO ₂₎ and a step (S110) of mixing to prepare a first solution of a stabilizer,

The metal compound, selenium dioxide (SeO ₂ ) and stabilizer can be regarded 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 be an integer of 1 to 3, Depending on the cation index when the metal is in the ionic state).

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

Specifically, when X is Cl in the above metal halide (MX _a), ferric chloride (FeCl _3), any one be of nickel chloride (NiCl _2), chloride, chromium (CrCl ₃₎ and manganese chloride (MnCl ₂₎ However, it is not limited to the metal chloride compounds listed above, but other metals may be used, and accordingly metal chloride compounds may also be included.

None of the other, for example, the metal halide (MX _a) when X is Br, bromide, iron (FeBr _3), bromide, nickel (NiBr _2), bromide, chromium (CrBr ₃₎ and hydrobromic manganese (MnBr ₂₎ in the But it is not limited to the metal bromide compounds listed above, but other metal may be used, and the metal bromide compound may be also included.

The metal compound may be a two-family metal (Cu (II)) compound or a one-family metal (I) compound,

For example, the two-family cupric (Cu (II)) compound can be prepared by reacting copper chloride (CuCl- ₂ ), copper sulfate (CuSO ₄ ), copper acetate (Cu (COOCH ₃ ) ₂ ) and copper nitrate trihydrate NO ₃ ) ₂ ) 3H ₂ O), and more preferably,

In another embodiment, the compound of formula (I) may be copper chloride (CuCl). In the case of copper, ionization can change the cationic valence (Cu ^{+ 1} or Cu ^{+ 2} ), so if the compound is made, the substance can also be different.

Next, a stabilizer is used as a ligand to form a complex through coordination bond with the metal compound. The metal compound and the selenium dioxide (SeO ₂ ) are reduced in the presence of carbon monoxide, The size of the catalyst material may be reduced to increase the specific surface area, stabilize the particles to increase the catalytic activity, and may assist in the generation of solid particles to produce a solid catalyst.

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

More specifically, the amine compound or the quaternary ammonium compound may be at least one selected from the group consisting of Cetyl Trimethyelmonium Bromide (CTAB), Tetra-n-Butylmonomethyl Chloride (TBAC), Tetrabutylammonium Bromide (Tetra-n-Butylmmonium Bromide), tetrabutylphosphonium bromide (TBPB), polyvinylpyrrolidone (PVP), choline chloride, pyridine, tetraethyl May be one selected from the group consisting of ammonium chloride, trimethylammonium chloride, imidazole, dimethylamino pyridine and 2,2-bipyridyl.

For example, the metal compound, SeO ₂ and stabilizer may be mixed in a mass ratio of 1: 4: 0.3. However, the mass ratio is not limited to the above-mentioned mass ratio, but the specific metal compound and stabilizer, , Reaction conditions, and the like.

As 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 not limited thereto, and two hydroxyl groups (-OH) Dihydric alcohols, or trihydric alcohols having three hydroxyl groups (-OH). Further, since the solid carrier is supported on the first solution by 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)), but the present invention is not limited thereto.

 In the step of injecting a solid support into the first solution (S120)

For example, a solid supporting material is a substance that disperses and retains a compound formed of the metal selenide (Mse ₂ ) in a stable state, and generally, a solid material can be used. Particularly, a solid carrier to be used as a supported catalyst generally has a large porosity or a large area so as to be highly dispersed and supported so that the exposed surface area becomes large so that the function of the catalyst can be activated. In addition, solid carriers can be thermally and chemically stable to maintain certain shapes and functions in chemical reactions.

For example, the solid carrier may be selected from alumina (Al ₂ O ₃ ), ceria (CeO ₂ ), activated carbon (AC), montmorillonite, silica (SiO ₂ ), magnesium oxide (MgO), zeolite And hydrotalcite. [0033] The term " hydrotalcite " However, the solid carrier is not limited to the above listed materials, and may be a porous material or a solid material having a large surface area so as to highly disperse the catalyst material, and a solid material It can be used as a delay.

In another example, the solid carrier may be added to the first solution, and then stirred for about 10 minutes to about 1 hour to adsorb the substance mixed in the first carrier to the solid carrier. The stirring time may be sufficient for the solid carrier to adsorb the substance mixed in the first solution and is not necessarily limited to the time range. At this time, the solid carrier and the first solution may be mixed and chemically and physically combined to be adsorbed. Since 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 may be formed on the solid carrier And the metal selenide (MSe ₂ ), so that the metal selenide (Mse ₂ ) can be supported.

In the step of injecting carbon monoxide into the first solution into which the solid support is charged (S130)

The first solution may be prepared in step S110 in one container reactor, and carbon monoxide may be directly injected into the reactor when the solid carrier is charged in the same reactor. So as to have a pressure higher than a certain level. Therefore, it becomes possible to produce the supported catalyst in one container at one time. Further, since the urea can be prepared by adding the reaction material immediately after the metal-selenide (Mse ₂ ) supported catalyst is prepared according to the above process and the following process, it is possible to produce the urethane using the catalyst, Can be carried out in a single vessel.

The pressure of the carbon monoxide (CO) injected may be 200 psig to 1600 psig. When the pressure of the carbon monoxide is less than the above range, the metal-selenide (MSe ₂ ) supported catalyst may not be produced at a desired yield even if the reaction is carried out according to the following last step (S140) There is a possibility that a side reaction may occur, and since the residual amount of carbon monoxide may be large even after the metal-selenide (MSe ₂ ) supported catalyst is prepared, the process may not be economically operated, It may be desirable to inject carbon monoxide while controlling the pressure of the carbon monoxide.

(S140) in which metal selenide (MSe ₂ ) is adsorbed and supported on the surface of the solid support by reacting the solid support charged with the first solution and the carbon monoxide,

For example, precursor materials for preparing a metal-selenide (MSe ₂ ) supported catalyst may be contained in the first solution in which the metal compound, selenium dioxide (SeO ₂ ) and stabilizer are mixed. It is not possible to prepare the supported catalyst immediately after the step of injecting the solid support into the first solution (S120), and the precursor materials contained in the first solution are not located on the surface of the solid support The metal selenide (Mse ₂ ) is adsorbed on the surface of the solid support through a reaction time of a certain time under the specific temperature condition shown below, and the metal selenide (Mse ₂ ) Supported catalyst can be produced.

At this time, due to the fact that the metal selenide (MSe ₂ ) and the solid support are adsorbed to each other by physical and chemical bonding through the reaction, the solid support generally has a porous form, The metal selenide (MSe ₂ ) may be positioned in each of the pores, and a chemical bond is generated between the solid support and the metal selenide (MSe ₂ ) as a result of the following reaction, Mse ₂ ) can be stably supported.

In another example, after the carbon monoxide is injected, the reaction temperature may be 100 ° C to 200 ° C, and the solid carrier and the carbon monoxide on which the first solution is supported may be reacted for 1 hour to 6 hours. The reaction temperature is a temperature range suitable for allowing carbon monoxide (MSe ₂ ) to be supported on the solid support by reacting with carbon monoxide and a solid support on which the first solution is supported, And the reaction is not necessarily limited to proceed within the temperature range. Also, the reaction time may be set differently depending on the type of the first solution to be injected and the type of the solid carrier, and the reaction time range is within a general time range in which the reaction proceeds, The present invention is not limited to this.

For example, the metal selenide (MSe ₂ ) may be contained in an amount of 2 wt% to 10 wt%. 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 the metal-selenide (MSe ₂ ) supported catalyst. If the amount of the catalyst is less than the above range, the reaction can not proceed sufficiently in the state where the reactant remains, so that the reaction rate can be remarkably decreased. (MSe ₂ ) supported catalyst does not contribute to the reaction activation and remains, which is not economical in view of the cost of the process. However, the reaction rate is the same as or slightly different from that in the case of using the catalyst within the above range May be present within the above-mentioned range.

The metal selenide (MSe ₂ ) supported catalyst prepared through each step of the above production method may be a heterogeneous catalytic active species which is insoluble in an organic solvent including the above-mentioned solvent, and may be formed of black solid particles.

2 is a flowchart showing a method for producing urethane using a metal-selenide (MSe ₂ ) supported catalyst.

2, a metal selenide (MSe ₂₎ preparing a supported catalyst (S210), a nitro compound, carbon monoxide and a step (S220), and the metal to prepare the reaction product consisting of an alcohol solvent selenide (MSe ₂₎ And a step (S230) of carbonylating the reactant under a supported catalyst.

The urethane is also called a carbamate, and can be produced through a process as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

Based on the above reaction formula 1, R-NO ₂ can be regarded as a nitro compound, R'OH can be regarded as an alcohol solvent, and the catalyst is a metal selenide (MSe ₂ ) supported catalyst, And it can be confirmed that carbon dioxide is generated as a by-product.

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

Next, in step S220 of preparing a reactant composed of a nitro compound, carbon monoxide and an alcohol solvent,

As the reactant, any compound having a nitro functional group (-NO ₂ ) may be used as the nitro compound. For example, a nitro group-containing substance such as nitrobenzene may be used. However, the present invention is not limited to the above-mentioned materials, and in the case where the compound other than the nitro functional group is not a substance having a separate functional group capable of participating in the reaction, any compound having a nitro functional group may be used as a reaction substance of 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 molar ratio ranges according to the optimum amount of the metal-selenide (MSe ₂ ) -supporting catalyst that enables the reaction to take place, but is not limited to the above range. Depending on the conditions of the reaction, (MSe ₂ ) supported catalyst may be further added, or the metal-selenide (MSe ₂ ) supported catalyst may be added in an amount less than the above range.

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

The carbon monoxide in the above step can be reacted with a metal selenide (MSe ₂ ) supported catalyst at a high pressure to form a metal carbonyl compound as a reaction intermediate material, The metal carbonyl compound and the nitro compound react with each other to produce a final product urethane (the metal-selenide (MSe ₂ ) supported catalyst is not recovered and finally does not participate in the reaction).

If the pressure of the carbon monoxide (CO) is less than the above-mentioned pressure range, the metal carbonyl compound (MSe ₂ ) can not react with the supported catalyst to form a metal carbonyl compound. The urethane of the yield can not be produced. When the pressure exceeds the above-mentioned range, it is possible to produce urethane having a certain yield or more. However, since carbon monoxide which has not participated in the reaction as a byproduct may be left behind and by-products may be generated in a high pressure environment, It is preferable to carry out the reaction within the range.

For example, the reaction temperature for the carbonylation reaction may be 100 ° C to 200 ° C, and the solid carrier and carbon monoxide on which the first solution is supported may be reacted for 1 hour to 6 hours. The reaction temperature is an appropriate temperature range for progressing the carbonylation reaction and can be set differently depending on the kind of the catalyst and the metal-selenide (MSe ₂ ) -supporting catalyst, It is not. Also, the reaction time may be set differently depending on the type of the first solution to be injected and the type of the solid carrier, and the reaction time range is within a general time range in which the reaction proceeds, The present invention is not limited to this.

The urethane production method according to an embodiment of the present invention is a reaction that proceeds in a single step in a one-pot process, in which a urethane is produced through one-step reaction in one reactor without preparing the reactor in each step As a matter of fact, the urethane can be economically produced in terms of the time and cost involved in the process by simplifying the overall steps of the process.

According to one embodiment of the present invention, it is possible to provide the urethane produced according to the above method.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. It is to be understood that these embodiments are provided for the purpose of illustrating the embodiments of the present invention more specifically and needless to say that the scope of the present invention is not limited thereto.

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 support is AC . In the case of Fig. 4, the metal selenide (MSe ₂ ) is FeSe ₂ and the support is Al ₂ O ₃ .

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

7 and 8 are graphs showing the EDX data of the metal-selenide (MSe ₂ ) supported catalyst. More specifically, in the case of FIG. 7, the metal selenide (MSe ₂ ) is CuSe ₂ , and the solid carrier is AC. In the case of Fig. 8, the metal selenide (MSe ₂ ) is FeSe ₂ and 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

5 wt% CuSe ₂ Supported Catalyst Preparation - Alumina ( Al ₂ O ₃ ) To solid As a support sieve  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 of methanol. (2) 3.1 g of a solid carrier (Al ₂ O ₃ ) is added to the solution and stirred for 30 minutes. (3) Carbon monoxide (CO) 82 bar (1200 psi) is injected into the reactor and reacted at 160 ^° C for 4 hours. ④ Wash with soxhlet using methanol as solvent and filter. ⑤ Wash again with methanol more than 3 times and dry in vacuum for 12 hours.

[ Example  2] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% CuSe ₂ Preparation of Supported Catalyst - Silica ( SiO ₂ ) -commercial solid As a support sieve  use

(SiO ₂ ) - commercial, and only the kind of the solid carrier was changed to silica (SiO ₂ ) - commercial.

[ Example  3] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% CuSe ₂ Preparation of supported catalyst - Activated carbon (AC) As a support sieve  use

(AC) in the same manner as in Example 1, except that only the kind of the solid carrier was changed to activated carbon (AC).

[ Example  4] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% CuSe ₂ Supported catalyst preparation - Ceria ₂ )  Solid As a support sieve  use

Was prepared in the same manner as in Example 1 except that only the kind of the solid carrier was changed to ceria (CeO ₂ ).

 [ Example  5] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% CuSe ₂ Preparation of Supported Catalyst - Silica ( SiO ₂ ) -110 to solid As a support sieve  use

Carried out, but that of Example 1, prepared in the same way, only the type of the solid carrier of silica (SiO ₂₎ - are prepared by changing to 110.

[ Example  6] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% CuSe ₂ Preparation of Supported Catalyst - Silica ( SiO ₂ ) -240 to solid As a support sieve  use

(SiO ₂ ) -240 in the same manner as in Example 1, except that only the kind of the solid carrier was changed to silica (SiO ₂ ) -240.

[ Example  7] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% CuSe ₂ Preparation of supported catalyst - Magnesium oxide (MgO) As a support sieve  use

(MgO) was prepared in the same manner as in Example 1, except that only the kind of the solid carrier was changed to magnesium oxide (MgO).

[ Example  8] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% CuSe ₂ Supported catalyst preparation - The Hydrotalcite  Solid As a support sieve  use

Was prepared in the same manner as in Example 1 except that only the kind of the solid carrier was changed to a hydrotalcite.

[ Example  9] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% CuSe ₂ Preparation of supported catalyst - Montmorillonite (Montmorillonite) As a support sieve  use

The procedure of Example 1 was repeated except that only the solid carrier was changed to montmorillonite.

[ Example  10] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% FeSe ₂ Supported Catalyst Preparation - Alumina ( Al ₂ O ₃ ) To solid As a support sieve  use

(MSe ₂ ) was changed to FeSe ₂ , and the kind of the solid carrier was changed to alumina (Al ₂ O ₃ ).

[ Example  11] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% FeSe ₂ Preparation of Supported Catalyst - Silica ( SiO ₂ ) -commercial solid As a support sieve  use

(MSe ₂ ) was changed to FeSe ₂ , and the kind of the solid carrier was changed to silica (SiO ₂ ) - commercial.

[ Example  12] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% FeSe ₂ Preparation of supported catalyst - Activated carbon (AC) As a support sieve  use

(MSe ₂ ) was changed to FeSe ₂ , and the kind of the solid carrier was changed to activated carbon (AC).

[ Example  13] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% FeSe ₂ Supported catalyst preparation - Ceria ₂ )  Solid As a support sieve  use

(MSe ₂ ) was changed to FeSe ₂ , and the kind of the solid carrier was changed to ceria (CeO ₂ ) in the same manner as in Example 1.

[ Example  14] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% FeSe ₂ Preparation of supported catalyst - Montmorillonite (Montmorillonite) As a support sieve  use

(MSe ₂ ) was changed to FeSe ₂ , and the kind of the solid carrier was changed to montmorillonite.

[ Example  15] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% FeSe ₂ Preparation of Supported Catalyst - Silica ( SiO ₂ ) -110 to solid As a support sieve  use

(MSe ₂ ) was changed to FeSe ₂ , and the kind of the solid carrier was changed to silica (SiO ₂ ) -110 in the same manner as in Example 1.

[ Example  16] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% FeSe ₂ Preparation of Supported Catalyst - Silica ( SiO ₂ ) -240 to solid As a support sieve  use

(MSe ₂ ) was changed to FeSe ₂ , and the kind of the solid carrier was changed to silica (SiO ₂ ) -240 in the same manner as in Example 1.

[ Example  17] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% FeSe ₂ Supported catalyst preparation - Zeolite (Zeolite) As a support sieve  use

(MSe ₂ ) was changed to FeSe ₂ , and the kind of the solid carrier was changed to zeolite.

[ Example  18] Metal selenide ( MSe ₂ ) Supported catalyst preparation

5 wt% FeSe ₂ Supported catalyst preparation - Manganese cobalt spinel ( MnCo ₂ O ₄ ) To solid As a support sieve  use

(MSe ₂ ) was changed to FeSe ₂ , and the kind of the solid carrier was changed to manganese cobalt spinel (MnCo ₂ O ₄ ) .

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

₂ g of the metal selenide (MSe ₂ ) supported catalyst prepared according to the above Examples 1 to 18 in 20 mmol of Nitrobenzene (NB) was placed in 30 ml of methanol, then 82 cc of carbon monoxide (CO) (1200 psi) 160 ^o C for 4 hours and allowed to react at-phenyl carbamate: were prepared (MPC Methyl N -phenyl carbamate) are shown in Table 1 below the results thereof (this corresponds to a carbamate is the same material as polyurethane).

turn Conversion (Conv. (%)) Conversion rate (Y _MPC (%)) The 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-described embodiments, it can be seen that when the metal selenide (MSe ₂ ) is CuSe ₂ , the activated carbon (AC) of Example 1 using alumina (Al ₂ O ₃ ) It can be confirmed that Example 4 using ceria (CeO ₂ ) used as a support as a solid support has a relatively higher catalytic activity as compared with other Examples.

Further, metal selenide When the (MSe ₂₎ as FeSe _2, alumina (Al ₂ O ₃₎ an embodiment with Example 10, the activated carbon (AC) with body of solid-supported body of the solid-supported Example 12, silica (SiO ₂ ) was used as a solid support, the catalyst activity was relatively higher in Example 16 than in the other Examples.

Accordingly, it can be confirmed that the urethane production yield can be varied depending on the kind of the metal selenide and the kind of the solid carrier.

[ Example  3-1] The reaction time Metal selenide ( MSe ₂ ) Supported catalyst preparation

The catalyst was prepared in the same manner as in Example 3 except that the catalyst preparation time (reaction time in the step of preparing the catalyst) was changed from 4 hours to 10 hours.

[ Example  4-1] < / RTI > Metal selenide ( MSe ₂ ) Supported catalyst preparation

Was prepared in the same manner as in Example 4, except that the catalyst preparation time was changed from 4 hours to 10 hours.

[ Experimental Example  2] Catalyst  Manufactured at different times Metal selenide ( MSe ₂ ) Urethane Production Using Supported Catalyst

(MSe ₂ ) was carried on the catalyst production time different from that of Example 4 and Example 4-1 by comparing Example 3 with Example 3-1, The yields in the case of preparing the catalyst are compared.

turn Conversion (Conv. (%)) Conversion rate (Y _MPC (%)) The 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

The yield of methyl phenylcarbamate (MPC: methyl N- phenyl carbamate) was investigated according to the catalyst preparation time. As a result, it was found that the yields of catalysts were almost the same, It can be confirmed that there is no significant influence on

[ Experimental Example  3] Metal selenide ( MSe ₂ ) ≪ / RTI > supported catalyst to produce urethane

(MSe ₂ ) supported catalyst prepared according to Example 3 was used in the same manner as in Experimental Example 1, and the reaction time for producing methylphenylcarbamate (MPC: Methyl N- phenyl carbamate) To produce urethane. The results are shown in Fig.

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

Referring to FIG. 9, it was confirmed that the conversion and yield were increased as the reaction time was increased, and the yield of methylphenylcarbamate (MPC: Methyl N- phenyl carbamate) was improved to 96.9% I could confirm.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (4)

A solid support; And
And a metal selenide (MSe ₂ ) adsorbed and supported on the surface of the solid carrier,
The metal is any one selected from among divalent iron (Fe (II)), trivalent iron (Fe (III)), 1 family Cu (I) and 2 family Cu (II) (MSe ₂ ) supported catalyst for urethane production.
The method according to claim 1,
(Al ₂ O ₃ ), ceria (CeO ₂ ), or activated carbon (AC), when the metal is one family (Cu (I)) or two families (Cu (MSe ₂ ) supported catalyst for urethane production.
The method according to claim 1,
When the metal is divalent iron (Fe (Ⅱ)) or a trivalent iron (Fe (Ⅲ)), carrier of the solid is alumina (Al ₂ O _3), activated carbon for (AC) or silica (SiO ₂₎ (MSe ₂ ) supported catalyst for urethane production.
The method according to claim 1,
Metal selenide (MSe ₂₎ is a urethane-producing metal selenide, characterized in that contained 2wt% to 10wt% (MSe ₂₎ supported catalyst.

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