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WO2018182102A1 - Catalyseur supporté à base de séléniure métallique, procédé de préparation associé et procédé de préparation d'uréthane faisant appel audit catalyseur - Google Patents

Catalyseur supporté à base de séléniure métallique, procédé de préparation associé et procédé de préparation d'uréthane faisant appel audit catalyseur Download PDF

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WO2018182102A1
WO2018182102A1 PCT/KR2017/008285 KR2017008285W WO2018182102A1 WO 2018182102 A1 WO2018182102 A1 WO 2018182102A1 KR 2017008285 W KR2017008285 W KR 2017008285W WO 2018182102 A1 WO2018182102 A1 WO 2018182102A1
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mse
supported catalyst
metal selenide
metal
urethane
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Korean (ko)
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김용진
박인
박제성
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Korea Institute of Industrial Technology KITECH
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Korea Institute of Industrial Technology KITECH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0573—Selenium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/08—Separation; Purification; Stabilisation; Use of additives

Definitions

  • 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.
  • 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.
  • 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. There was also a problem of poor yield.
  • Reference 1 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.
  • 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.
  • 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.
  • 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.
  • U.S. Patent Publication No. 2009-0275771 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.
  • Patent Document 1 Japanese Patent No. 1994-062544
  • Patent Document 2 United States Patent Publication No. 2009-0275771
  • 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.
  • urethane 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.
  • 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.
  • 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.
  • the metal selenide (MSe 2 ) may be contained from 2wt% to 10wt%.
  • 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.
  • 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 ).
  • 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.
  • the stabilizer may be an amine compound or a quaternary ammonium compound.
  • 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.
  • CAB cetyl trimethyl ammonium bromide
  • TBAC Tetraethylammonium chloride
  • TBAC Tetra-n-But
  • the solvent of the first solution may be an alcohol solvent.
  • the pressure of the carbon monoxide may be 200psig to 1600psig.
  • the reaction temperature may be 100 °C to 200 °C
  • the reaction time may be 1 hour to 6 hours.
  • 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.
  • the molar ratio of the metal selenide (MSe 2 ) supported catalyst may be from 1/1000 to 1/20 of the reactant.
  • the step of carbonylating, the carbon monoxide may be a pressure of 200psig to 1600psig.
  • the carbonylating may be performed for 1 hour to 6 hours at a temperature condition of 100 °C to 200 °C.
  • the present invention may be a reaction proceeding in a single step in a single vessel.
  • another embodiment of the present invention can provide a urethane prepared according to the production method.
  • 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.
  • MSe 2 metal supported selenide
  • 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.
  • an oxidizing agent such as nitro compound, carbon monoxide, and alcohol solvent
  • 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.
  • MSe 2 metal selenide
  • FIG. 2 is a flowchart illustrating a method of preparing urethane using a metal selenide (MSe 2 ) supported catalyst.
  • FIG 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.
  • FIG. 7 and 8 are graphs illustrating the EDX data of the metal selenide (MSe 2 ) supported catalyst.
  • 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.
  • 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.
  • the solid support may use a thermally and chemically stable material to maintain a constant shape and function in the chemical reaction.
  • 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.
  • zeolite may be zeolite (ZSM-5), zeolite 4A, or the like, but the zeolite type is not limited to the above listed types.
  • 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.
  • M denotes a transition meatal (M)
  • 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.
  • 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.
  • 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
  • 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 ).
  • 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.
  • 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.
  • MSe 2 metal selenide
  • 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.
  • 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.
  • 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).
  • MX a metal halide compound
  • the halogen element X may be any one selected from F, Cl, Br, and I, and in particular, Cl, Br may be used.
  • metal chloride compound MX a
  • FeCl 3 iron chloride
  • NiCl 2 nickel chloride
  • CrCl 3 chromium chloride
  • MnCl 2 manganese chloride
  • any one of iron bromide (FeBr 3 ), nickel bromide (NiBr 2 ), chromium bromide (CrBr 3 ) and manganese bromide (MnBr 2 ) 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,
  • 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,
  • the cuprous (I) compound may be copper chloride (CuCl).
  • CuCl copper chloride
  • the cation valence may vary when ionized (Cu +1 or Cu +2 ) and thus, when forming the compound, the material may also vary.
  • 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.
  • a stabilizer 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.
  • an amine compound or a quaternary ammonium compound can be used as the stabilizer.
  • 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).
  • CAB cety
  • 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.
  • the solvent of the first solution may be an alcohol solvent (ROH).
  • R may be an alkyl group having 1 to 4 carbon atoms
  • 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).
  • the same solvent may be used until the reaction is completed through each step.
  • 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.
  • 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.
  • 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.
  • the solid support may use a thermally and chemically stable material to maintain a constant shape and function in the chemical reaction.
  • 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.
  • 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.
  • 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.
  • the solid carrier and the first solution is mixed with the material may be chemically and physically combined and adsorbed.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 It is not limited to proceeding.
  • 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.
  • 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.
  • FIG. 2 is a flowchart illustrating a method of preparing urethane using a metal selenide (MSe 2 ) supported catalyst.
  • 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.
  • 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.
  • the metal selenide (MSe 2 ) supported catalyst may be prepared by the above-described method.
  • the nitro compound may be any compound having a nitro functional group (-NO 2 ).
  • a substance having a nitro group attached to a benzene compound, such as nitrobenzene may be used.
  • 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.
  • 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.
  • 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.
  • 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).
  • the pressure of the carbon monoxide (CO) is less than the pressure range, the metal selenide (MSe 2) react with the supported catalyst metal carbonyl can not form a compound can not also take place after the reaction for preparing the final products of polyurethane, the desired Yields of urethane may not be prepared.
  • 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.
  • the reaction temperature for the carbonylation reaction is 100 °C to 200 °C, 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.
  • 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 It is not limited to proceeding.
  • Urethane manufacturing method 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.
  • FIG. 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 .
  • FIG. 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.
  • FIG. 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 1 100 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
  • Example 16 which uses 2 ) as a solid carrier, has a relatively higher catalytic activity compared to other examples.
  • the urethane production yield may vary depending on the type of metal selenide and the type of the solid carrier.
  • 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.
  • FIG. 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Selon un mode de réalisation, la présente invention concerne : un catalyseur supporté à base de séléniure métallique (MSe2) servant à préparer de l'uréthane, le catalyseur comprenant un support solide et un séléniure métallique (MSe2) adsorbé et supporté sur la surface du support solide ; un procédé de préparation associé ; un procédé de préparation d'uréthane faisant appel au catalyseur supporté à base de séléniure métallique (MSe2) ; et un uréthane ainsi préparé.
PCT/KR2017/008285 2017-03-29 2017-08-01 Catalyseur supporté à base de séléniure métallique, procédé de préparation associé et procédé de préparation d'uréthane faisant appel audit catalyseur Ceased WO2018182102A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112121827A (zh) * 2020-09-21 2020-12-25 哈尔滨理工大学 一种高效电催化合成氨FeSe2/MoSe2纳米片及其制备方法和应用
CN114345378A (zh) * 2021-12-08 2022-04-15 青岛农业大学 一种塑化剂降解方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102414147B1 (ko) * 2020-12-04 2022-06-28 한국생산기술연구원 카보네이트 유도체 제조용 셀레늄계 촉매 시스템 및 그를 이용한 카보네이트 유도체의 제조방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3956360A (en) * 1973-06-21 1976-05-11 Atlantic Richfield Company Process for the manufacture of urethanes
US4258201A (en) * 1979-01-29 1981-03-24 Halcon Research And Development Corp. Process for the manufacture of carbamates
KR20150027560A (ko) * 2013-09-04 2015-03-12 부산대학교 산학협력단 입자 크기 및 조성을 제어할 수 있는 구리 셀레나이드의 제조방법

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3147231A (en) 1960-01-04 1964-09-01 Monsanto Co Preparation of a catalyst comprising iron selenide dispersed on a porous support
DE2808980A1 (de) 1978-03-02 1979-09-13 Bayer Ag Verfahren zur herstellung von urethanen
KR100277207B1 (ko) 1998-04-03 2001-01-15 박호군 셀레늄 촉매계를 이용한 카바메이트의 제조방법
KR101776101B1 (ko) 2016-10-12 2017-09-08 한국생산기술연구원 니트로화합물로부터 우레탄을 제조하기 위한 Cu-Se계 촉매 및 이를 이용한 우레탄의 제조방법
KR101828431B1 (ko) 2016-10-12 2018-02-13 한국생산기술연구원 니트로화합물로부터 우레탄을 제조하기 위한 Fe-Se계 촉매 및 이를 이용한 우레탄의 제조방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3956360A (en) * 1973-06-21 1976-05-11 Atlantic Richfield Company Process for the manufacture of urethanes
US4258201A (en) * 1979-01-29 1981-03-24 Halcon Research And Development Corp. Process for the manufacture of carbamates
KR20150027560A (ko) * 2013-09-04 2015-03-12 부산대학교 산학협력단 입자 크기 및 조성을 제어할 수 있는 구리 셀레나이드의 제조방법

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JANG, SEONGWAN: "Facile preparation and control of Cu-Se compounds with various preparation conditions", JOURNAL OF THE KOREAN PHYSICAL SOCIETY, vol. 66, no. 2, pages 171 - 174, XP035439459, DOI: doi:10.3938/jkps.66.171 *
NGUYEN, TRAM HUYNH ET AL.: "Ferric selenide as catalyst for reductive carbonylation of nitrobenzene for generating urethanes", KOREA NATIONAL CLEANER PRODUCTION CENTER FALL CONFERENCE- POSTER PRESENTATION, 28 September 2016 (2016-09-28) *
TRAN, VY ANH ET AL.: "Copper selenide as catalyst system for reductive carbonylation of nitrobenzene for generating urethanes", KOREA NATIONAL CLEANER PRODUCTION CENTER FALL CONFERENCE- POSTER PRESENTATION, 28 September 2016 (2016-09-28) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112121827A (zh) * 2020-09-21 2020-12-25 哈尔滨理工大学 一种高效电催化合成氨FeSe2/MoSe2纳米片及其制备方法和应用
CN112121827B (zh) * 2020-09-21 2023-09-19 哈尔滨理工大学 一种高效电催化合成氨FeSe2/MoSe2纳米片及其制备方法和应用
CN114345378A (zh) * 2021-12-08 2022-04-15 青岛农业大学 一种塑化剂降解方法
CN114345378B (zh) * 2021-12-08 2023-04-25 青岛农业大学 一种塑化剂降解方法

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