Composite and method for producing composite

Abstract

To provide a new material suitable for a catalyst for reaction of an amine compound and carbon dioxide or the like.SOLUTION: A composite includes a compound A having a chemical element M-oxygen double bond and a carrier to carry the compound A. The chemical element M is a metal element or P. The carrier includes a compound B having a cation with an ionic radius larger than 60.5 pm. The cation is, for instance, a metal cation.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composite and a method for producing the composite. [Background technology]

[0002] In recent years, techniques have been developed to synthesize useful compounds using carbon dioxide as a raw material. For example, Non-Patent Document 1 discloses a method for synthesizing vanadium(V) oxytriisopropoxide (VO(O i In Non-Patent Document 1, it is disclosed that a urea compound is synthesized by reacting an amine compound with carbon dioxide in the presence of VO(O i Pr)3 functions as a catalyst to promote the reaction between amine compounds and carbon dioxide. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Toshiyuki Moriuchi et al., "Oxovanadium(V)-catalyzed amination of carbon dioxide under ambient pressure for the synthesis of ureas", RSC Adv., 2021, 11, 27121-27125. Summary of the Invention [Problem to be solved by the invention]

[0004] There is a need for new materials suitable for catalyzing reactions such as those between amine compounds and carbon dioxide. [Means for solving the problem]

[0005] The present invention provides a compound A having an element M-oxygen double bond; a carrier supporting the compound A; Equipped with The element M is a metal element or P, The carrier provides a complex comprising compound B having a cation with an ionic radius greater than 60.5 pm.

[0006] Furthermore, the present invention provides a step of contacting a compound A having an element M-oxygen double bond with a support to support the compound A on the support, The element M is a metal element or P, The carrier contains a compound B having a cation with an ionic radius of greater than 60.5 pm. [Effects of the Invention]

[0007] According to the present invention, a new material suitable for use as a catalyst in the reaction of an amine compound with carbon dioxide, etc., can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0008] The complex according to the first aspect of the present invention comprises: a compound A having an element M-oxygen double bond; a carrier supporting the compound A; Equipped with The element M is a metal element or P, The support comprises a compound B having a cation with an ionic radius greater than 60.5 pm.

[0009] In a second aspect of the present invention, for example, in the complex according to the first aspect, the cation is a metal cation.

[0010] In a third aspect of the present invention, for example, in the composite according to the second aspect, the metal cation comprises at least one selected from the group consisting of magnesium ions, cerium ions, zirconium ions, sodium ions, calcium ions, manganese ions, cobalt ions, lanthanum ions, zinc ions, potassium ions, indium ions, niobium ions, barium ions, strontium ions, iron ions, and yttrium ions.

[0011] In a fourth aspect of the present invention, for example, in the composite according to the second or third aspect, the compound B comprises a metal oxide having the metal cation.

[0012] In a fifth aspect of the present invention, for example, in the composite according to any one of the first to fourth aspects, the compound B includes at least one selected from the group consisting of MgO and CeO2.

[0013] In a sixth aspect of the present invention, for example, in the composite according to any one of the first to fifth aspects, the element M is V, Fe, Mo, Ta, Nb, Ti, W, or P.

[0014] In a seventh aspect of the present invention, for example, in the composite according to any one of the first to sixth aspects, the compound A includes at least one selected from the group consisting of NH4VO3 and Na3VO4.

[0015] In an eighth aspect of the present invention, for example, in the complex according to any one of the first to seventh aspects, the content of the compound A is 0.05 wt % or more.

[0016] In a ninth aspect of the present invention, for example, the complex according to any one of the first to eighth aspects is used to promote the reaction of an amine compound with at least one selected from the group consisting of carbon dioxide, carbonates, and hydrogencarbonates.

[0017] A method for producing a composite according to a tenth aspect of the present invention includes the steps of: a step of contacting a compound A having an element M-oxygen double bond with a support to support the compound A on the support, The element M is a metal element or P, The support comprises a compound B having a cation with an ionic radius greater than 60.5 pm.

[0018] In an eleventh aspect of the present invention, for example, in the production method according to the tenth aspect, the step is carried out by drying a mixture of the carrier and the solution containing compound A.

[0019] The present invention will be described in detail below, but the following description is not intended to limit the present invention to a specific embodiment.

[0020] <Embodiments of the composite> The composite of this embodiment includes compound A having an element M-oxygen double bond and a support supporting compound A. In compound A, element M is a metal element or P. The support contains compound B having a cation with an ionic radius of greater than 60.5 pm. The composite can function as a catalyst having catalytic activity for the reaction R between an amine compound and at least one selected from the group consisting of carbon dioxide, carbonates, and hydrogencarbonates.

[0021] (Compound A) Compound A is preferably a compound capable of promoting the above-mentioned reaction R. Compound A is typically supported on the surface of a support.

[0022] As described above, compound A has an element M-oxygen double bond. The number of element M-oxygen double bonds in one molecule of compound A may be 1 or more, for example, 1 to 5. The number of element M-oxygen double bonds in one molecule of compound A is preferably 1. However, in some cases, the number of element M-oxygen double bonds in one molecule of compound A may be 2 or more.

[0023] As described above, the element M is a metal element or P. The element M is preferably a metal element. The element M may be V, Fe, Mo, Ta, Nb, Ti, W, or P, or may be V, Fe, Mo, Ta, Nb, Ti, or W, or may be V, Fe, Mo, or Nb, or may be V. As an example, it is preferable that the element M is V and the compound A has a vanadium-oxygen double bond.

[0024] In a preferred embodiment of the present invention, compound A may be an oxide of element M or an inorganic salt containing element M. Examples of compound A include NH4VO3, Na3VO4, (NH4)2MoO4, and (NH4)6Mo7O 24 4H2O, (NH4) 10 W 12 O 41 5H2O, Na6O 39 W 12 Compound A preferably contains at least one selected from the group consisting of NH4VO3 and Na3VO4, and particularly preferably contains Na3VO4.

[0025] In another preferred embodiment of the present invention, compound A may be a complex having a ligand that coordinates with element M.

[0026] Examples of the ligand include a hydrocarbon group which may have a substituent, an oxyhydrocarbon group which may have a substituent, and a halogen.

[0027] The number of carbon atoms in the hydrocarbon group is not particularly limited as long as it is at least 1. The number of carbon atoms in the hydrocarbon group may be, for example, 20 or less, 15 or less, 10 or less, 5 or less, or 3 or less.

[0028] The hydrocarbon group may be a linear or branched chain hydrocarbon group. The chain hydrocarbon group may be an alkyl group, an alkenyl group, or an alkynyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, and a sec-butyl group. Examples of the alkenyl group include a vinyl group and an allyl group. Examples of the alkynyl group include an ethynyl group.

[0029] Examples of the substituent on the hydrocarbon group include halogen, amino, alkoxy, alkyl ester, carboxyl, ketone, and hydroxyl groups.

[0030] Examples of hydrocarbon groups contained in the oxyhydrocarbon group include those described above. The oxyhydrocarbon group may be an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an isopropoxy group. Examples of the substituent of the oxyhydrocarbon group include those described above for the hydrocarbon group. Examples of the oxyhydrocarbon group having a substituent include a group derived from triethanolamine (TEA).

[0031] Examples of halogen include fluorine, chlorine, bromine, and iodine, and an example is chlorine.

[0032] The ligand is preferably an isopropoxy group, an ethyl group, an ethoxy group, chlorine, TEA, an acetylacetonate group (C5H7O2), or the like.

[0033] The number of ligands can be adjusted appropriately depending on the type of element M. The number of ligands may be 1 or more, for example, 1 to 5. The number of ligands may be 3 or 4. The number of ligands is preferably 3.

[0034] Compound A may be a compound represented by the following formula (1): L n VO (1)

[0035] In formula (1), L's are each independently a hydrocarbon group which may have a substituent, an oxyhydrocarbon group which may have a substituent, or a halogen, and n is a natural number of 1 to 5. At least two selected from the plurality of L's may be linked to each other.

[0036] Examples of the hydrocarbon group which may have a substituent and the oxyhydrocarbon group which may have a substituent are those mentioned above.

[0037] In formula (1), n ​​may be 3 or 4. n is preferably 3.

[0038] In formula (1), L is preferably an alkoxy group, more preferably an isopropoxy group.

[0039] A specific example of Compound A is vanadium(V) oxytriisopropoxide (VO(O i Pr)3), VO(OEt)3, VO(OEt)Cl2, VOCl3, VO(TEA), VO(C5H7O2)2, TiO(C5H7O2)2, MoO2(C5H7O2)2, etc.

[0040] In the composite, the content of compound A is, for example, 0.05 wt% or more, and may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 8 wt% or more, or even 10 wt% or more. The upper limit of the content of compound A may be, for example, 50 wt% or less, 30 wt% or less, or even 20 wt% or less.

[0041] (Carrier) The carrier is preferably a solid capable of supporting compound A. In this specification, the term "solid" refers to a substance that is in a solid state at 20°C under atmospheric pressure.

[0042] As described above, the carrier contains compound B having a cation D1 with an ionic radius of greater than 60.5 pm. In the complex, compound B is preferably different from compound A. In this specification, the "ionic radius" is a value based on the definition described in Shannon et al., Acta A 32 (1976) 751. The ionic radius is usually determined by the type of cation, the valence of the cation, and the coordination number of the cation.

[0043] In compound B, the ionic radius of cation D1 may be greater than 60.5 pm as described above, 61 pm or more, 63 pm or more, 65 pm or more, 68 pm or more, 70 pm or more, 75 pm or more, 80 pm or more, 85 pm or more, 90 pm or more, 95 pm or more, or even 100 pm or more. The upper limit of the ionic radius of cation D1 is not particularly limited, and may be, for example, 200 pm or less, or 150 pm or less. In some cases, the ionic radius of cation D1 may be 100 pm or less.

[0044] The valence of the cation D1 is, for example, 1 to 6, and preferably 1 to 4. The valence of the cation D1 may be 3 or less, or 2 or less, depending on the case.

[0045] Cation D1 is preferably a metal cation, preferably containing at least one selected from the group consisting of magnesium ions, cerium ions, zirconium ions, sodium ions, calcium ions, manganese ions, cobalt ions, lanthanum ions, zinc ions, potassium ions, indium ions, niobium ions, barium ions, strontium ions, iron ions, and yttrium ions, more preferably containing at least one selected from the group consisting of magnesium ions and cerium ions, and particularly preferably containing magnesium ions.

[0046] Compound B further has an anion D2 bonded to cation D1. Examples of anion D2 include oxide ions, hydroxide ions, carbonate ions, and phosphate ions, with oxide ions being preferred.

[0047] Compound B preferably has a metal cation as cation D1 and an oxide ion as anion D2, i.e., compound B preferably contains a metal oxide having a metal cation.

[0048] Specific examples of metal oxides include MgO (ionic radius of magnesium ion: 72 pm), CeO2 (ionic radius of cerium ion: 97 pm), ZrO2 (ionic radius of zirconium ion: 78 pm), CaO (ionic radius of calcium ion: 100 pm), MnO (ionic radius of manganese ion: 67 to 83 pm), CoO (ionic radius of cobalt ion: 65 to 74.5 pm), Fe2O3 (ionic radius of iron ion: 78 pm), and YO3 (ionic radius of yttrium ion: 90 pm). Compound B preferably contains at least one selected from the group consisting of MgO and CeO2, and particularly preferably contains MgO.

[0049] Compound B may be a compound other than a metal oxide, such as a hydroxide salt such as NaOH (ionic radius of sodium ion: 102 pm), a carbonate salt such as CaCO3 (ionic radius of calcium ion: 112 pm), or a hydroxyphosphate salt such as Ca5(PO4)3(OH) (ionic radius of calcium ion: 118 pm).

[0050] The carrier may contain compound B as a main component. In this specification, "main component" means the component contained in the carrier in the largest amount by weight. The content of compound B in the carrier may be, for example, 80 wt% or more, 90 wt% or more, 95 wt% or more, or even 99 wt% or more. The carrier may be essentially composed of compound B.

[0051] In the composite, the carrier content may be, for example, 99.9 wt% or less, 99.5 wt% or less, 99 wt% or less, 97 wt% or less, 95 wt% or less, 92 wt% or less, or even 90 wt% or less. The lower limit of the carrier content may be, for example, 50 wt% or more, 70 wt% or more, or even 80 wt% or more.

[0052] The shape of the carrier is not particularly limited, and may be, for example, particulate. In this specification, particulate includes spherical, ellipsoidal, scaly, fibrous, and the like.

[0053] (complex) The complex is typically a solid. In particular, the complex preferably has low solubility in a solvent (e.g., a polar solvent) used in the reaction R between the amine compound and at least one selected from the group consisting of carbon dioxide, carbonates, and hydrogencarbonates. In other words, the complex preferably can maintain a solid state during the progress of the reaction R.

[0054] The shape of the complex is not particularly limited, and may be, for example, particulate.

[0055] (Method of manufacturing the composite) The method for producing the complex of this embodiment preferably includes a step of bringing the above-mentioned compound A into contact with a carrier to support compound A on the carrier.

[0056] The above steps can be carried out, for example, by the following method. First, a support is prepared. The support may be subjected to a calcination treatment in advance. The calcination treatment can be carried out, for example, using a muffle furnace. The conditions for the calcination treatment are not particularly limited, and for example, the calcination temperature is 100°C to 1000°C and the calcination time is 1 minute to 24 hours. The calcination treatment may be carried out in air.

[0057] Next, a solution L containing compound A is prepared. The solution L preferably contains a solvent capable of dissolving compound A. Examples of the solvent include water and organic solvents. Next, the support is mixed with the solution L containing compound A, thereby bringing compound A into contact with the support. The mixing of the support and solution L can be carried out, for example, by immersing the support in solution L. It is preferable that when the support is immersed in solution L, the support is hardly dissolved in solution L. However, a part of the support may be dissolved in solution L.

[0058] Next, the mixture of the carrier and solution L is dried to produce a composite in which compound A is supported on the carrier. The mixture is preferably dried under conditions that remove the solvent contained in solution L. The mixture may be dried in a reduced pressure atmosphere (particularly a vacuum atmosphere). The mixture may also be dried by heating the mixture. Compound A may be supported on the carrier by ion exchange with compound B contained in the carrier.

[0059] The prepared composite may be further subjected to a calcination treatment. The calcination treatment conditions include those described above. The composite may be further subjected to a pulverization treatment or a molding process. Examples of molding processes include spray granulation, compression molding, and extrusion molding using an extruder. By using the pulverization treatment or molding process, the composite can be easily adjusted to a desired shape and size. For example, a particulate composite can be obtained by spray granulation, a tablet-shaped composite can be obtained by compression molding, and an extruded-shaped composite can be obtained by extrusion molding.

[0060] In the manufacturing method of this embodiment, the produced composite does not need to be further washed, although the composite may be further washed.

[0061] (Use of the complex) The complex is preferably used to promote the reaction R between an amine compound and at least one selected from the group consisting of carbon dioxide, carbonates, and hydrogencarbonates. As described above, the complex can function as a catalyst having catalytic activity for the reaction R.

[0062] When compound A is used alone, compound A tends to dissolve in the reaction solution of reaction R and function as a homogeneous catalyst. On the other hand, the composite of the present embodiment is less soluble in the reaction solution of reaction R and tends to function as a solid catalyst. The composite as a solid catalyst has the advantage that it can be easily recovered from the reaction solution after reaction R is carried out and is easily reused.

[0063] A specific example of reaction R is a reaction in which a urea compound is synthesized from an amine compound and carbon dioxide. However, the product of reaction R is not limited to a urea compound and may be an isocyanate compound, a urethane compound, or the like. The composite may also be used to promote reactions other than the above reaction R.

[0064] Reaction R for synthesizing a urea compound from an amine compound and carbon dioxide will be described in detail below. In reaction R, the amine compound is a compound having an amino group. In the amine compound, the amino group is preferably capable of reacting with carbon dioxide, and is preferably a primary amino group or a secondary amino group, and is particularly preferably a primary amino group. The amino group may be protected by a protecting group. The number of amino groups in the amine compound may be one or two or more.

[0065] The amine compound may contain a cyclic structure. The amine compound may contain one cyclic structure or two or more cyclic structures. The cyclic structure may or may not contain a heteroatom. The cyclic structure may be an aliphatic ring or an aromatic ring.

[0066] In the amine compound, the nitrogen atom contained in the amino group may or may not be directly bonded to a cyclic structure. In the amine compound, the nitrogen atom contained in the amino group may be directly bonded to an aromatic ring. The amine compound may be a primary amine compound or a secondary amine compound in which the amino group and the aromatic ring are directly bonded.

[0067] Specific examples of the amine compound include ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, cyclohexylamine, cyclopentylamine, phenylmethylamine, 2-phenylethylamine (phenethylamine), 1-phenylethylamine, 2-phenylpropylamine, 3-phenylpropylamine, 3,3-diphenylpropylamine, 2-(4-methylphenyl)ethylamine, 2-(4-bromophenyl)ethylamine, 2-(4-trifluoromethylphenyl)ethylamine, 3-ethoxypropylamine, 1-adamantanamine, 4-methoxyaniline (p-anisidine), tetrahydrofuran-2-methaneamine, hexamethylenediamine, 1,5-pentamethylenediamine, toluenediamine, 4,4'-methylenedianiline, tetrahydrofuranamine, etc. When structural isomers exist in the compounds exemplified above, the structural isomers are also included in the examples. The amine compound is preferably p-anisidine, phenethylamine, or the like.

[0068] Reaction R may be carried out in the presence of at least one solvent selected from the group consisting of organic solvents and water. The solvent is preferably an organic solvent. The solvent may be a mixed solvent of an organic solvent and water. The solvent may be a polar solvent or a non-polar solvent. In this specification, a non-polar solvent is a solvent having a relative dielectric constant of 8.0 or less at 25°C. A polar solvent is a solvent having a relative dielectric constant of more than 8.0 at 25°C.

[0069] Examples of non-polar solvents include toluene, benzene, xylene, hexane, 1,4-dioxane, tetrahydrofuran, ethyl acetate, cyclopentyl methyl ether, and mixed solvents thereof.

[0070] Examples of polar solvents include acetonitrile, dimethyl sulfoxide, dichloromethane, propylene carbonate, methanol, ethanol, dimethylacetamide, and mixed solvents thereof, with dimethylacetamide (DMA) being preferred.

[0071] In reaction R, components other than compound A and the solvent may be present. Examples of the other components include a base and a dehydrating agent.

[0072] The base may be an inorganic base or an organic base. Examples of inorganic bases include hydride salts such as sodium hydride and lithium hydride; hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and barium hydroxide; and ammonia. Examples of organic bases include nitrogen-containing compounds such as N,N-diisopropylethylamine (DIEA), diazabicycloundecene (DBU), 1,8-bis(dimethylamino)naphthalene, and N-ethyldiisopropylamine.

[0073] The base may also function as a dehydrating agent. For example, when sodium hydride is used as the base, it may be converted to sodium hydroxide by reaction and function as a dehydrating agent.

[0074] The dehydrating agent may be a molecular sieve.

[0075] In reaction R, the reaction temperature is, for example, 50° C. or higher, and may be 80° C. or higher, 100° C. or higher, or even 130° C. or higher. The reaction temperature is, for example, the boiling point of the solvent used or lower, and may be 160° C. or lower, or even 150° C. or lower.

[0076] In reaction R, the reaction time is not particularly limited and is, for example, 10 minutes or more, 1 hour or more, 3 hours or more, 5 hours or more, 10 hours or more, 15 hours or more, or even 24 hours or more. The upper limit of the reaction time is, for example, 48 hours or less.

[0077] Reaction R is preferably carried out in an atmosphere containing carbon dioxide. This atmosphere may be a pressurized atmosphere. Alternatively, carbon dioxide may be supplied to a solution containing an amine compound by bubbling carbon dioxide into the solution.

[0078] The reaction R may be carried out using a batch reactor or a flow reactor (for example, a plug flow reactor (PFR) or a continuous stirred tank reactor (CSTR)).

[0079] In reaction R, a urea compound is typically produced by reacting one mole of carbon dioxide with two moles of an amine compound. In the urea group (-NX-CO-NX-: X is, independently of each other, a hydrogen atom or any substituent) contained in the urea compound, the carbonyl moiety (-CO-) is derived from carbon dioxide, and the amine moiety (-NX-) is derived from the amine compound. [Example]

[0080] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0081] Example 1 First, 450 mg of particles containing ZrO2 (ZrO2 particles, Fujifilm Wako Pure Chemical Industries, Ltd., 264-01482) were prepared as Compound B. Next, these particles (support) were placed in a muffle furnace and fired at 700°C for 5 hours.

[0082] Next, 50 mg of NH4VO3 was prepared as compound A. Compound A was mixed with 10 mL of distilled water, and compound A was dissolved in the distilled water using ultrasound. Next, a support was immersed in the resulting solution, and the two were mixed to bring compound A into contact with the support. Water was removed from the resulting mixture using an evaporator, and the mixture was dried. This produced a composite in which compound A was supported on a support. The content of compound A in the composite was 4.5 wt%.

[0083] The composite was further fired in a muffle furnace at 500°C for 5 hours. The fired composite was ground in a mortar to obtain the composite of Example 1. The obtained composite was stored in a glove box.

[0084] (Examples 2 to 8 and Comparative Examples 1 and 2) The composites of Examples 2 to 8 and Comparative Examples 1 and 2 were obtained in the same manner as in Example 1, except that the types of compound A and compound B contained in the carrier were changed as shown in Table 1. In each of the obtained composites, the content of compound A was 4.5 wt %.

[0085] [evaluation] The catalytic activity of the prepared complex for reaction R, which synthesizes a urea compound from an amine compound and carbon dioxide, was examined using the following method. First, the complex, 0.15 mmol of phenethylamine as the amine compound, 0.03 mmol of N-ethyldiisopropylamine as the base, 0.4 g of molecular sieves (MS3A) as a dehydrating agent, and 5 mL of dimethylacetamide as the solvent were placed in a reaction vessel. The amount of the complex was adjusted so that the amount of compound A present in the reaction vessel was 0.03 mmol.

[0086] Next, carbon dioxide was introduced into the reaction vessel, creating a pressurized atmosphere of 0.5 MPa. In this state, the reaction vessel was heated until the temperature inside the reaction vessel reached 130°C, and the reaction vessel was stirred. Sampling was performed 3 hours after the start of stirring, and the yield of the urea compound was calculated based on the amount of the amine compound added to the reaction vessel. For the composite of the example, sampling was also performed 24 hours after the start of stirring, and the yield of the urea compound was calculated.

[0087] [Table 1]

[0088] The details of the carriers used in the examples and comparative examples are as follows. Examples 1 and 4: ZrO2 particles, Fujifilm Wako Pure Chemical Industries, Ltd., 264-01482 Examples 2 and 5: CeO2 particles, Fujifilm Wako Pure Chemical Industries, Ltd., 030-01882 Examples 3 and 6 to 8: MgO particles, Fujifilm Wako Pure Chemical Industries, Ltd., 131-00282 Comparative Example 1: SiO2 particles, manufactured by Kanto Chemical Co., Ltd., 37562-84 Comparative Example 2: Al2O3 particles, Fujifilm Wako Pure Chemical Industries, Ltd., 592-13765

[0089] (Reference examples 1~6) In the above evaluation, we investigated how the yield of the urea compound changed when no complex was used (Reference Example 1), when only Compound A was used instead of the complex (Reference Example 2), and when only a carrier was used instead of the complex (Reference Examples 3 to 6). In Reference Example 2, 0.03 mmol of Compound A was added to the reaction vessel. In Reference Examples 3 to 6, 35 mg of a carrier was added to the reaction vessel.

[0090] [Table 2]

[0091] The details of the carriers used in the Reference Examples are as follows: Reference Example 3: ZrO2 particles, Fujifilm Wako Pure Chemical Industries, Ltd., 264-01482 Reference Example 4: TiO2 particles, Fujifilm Wako Pure Chemical Industries, Ltd., 207-13642 Reference Example 5: CeO2 particles, Fujifilm Wako Pure Chemical Industries, Ltd., 030-01882 Reference Example 6: MgO particles, Fujifilm Wako Pure Chemical Industries, Ltd., 131-00282

[0092] As can be seen from Tables 1 and 2, the composite of the example in which compound A was supported on a carrier containing compound B having a cation with an ionic radius larger than 60.5 pm exhibited catalytic activity for reaction R that was equal to or greater than that of Reference Example 2 in which compound A was used alone. On the other hand, the composite of Comparative Example 1 did not exhibit catalytic activity for reaction R. Furthermore, the composite of Comparative Example 2 had poorer catalytic activity than Reference Example 2.

[0093] The composites of the Examples did not dissolve in the reaction solution of Reaction R and functioned as solid catalysts. The composites of the Examples can be easily recovered from the reaction solution and can be easily reused. On the other hand, in Reference Example 2, Compound A dissolved in the reaction solution. [Industrial Applicability]

[0094] The composite of this embodiment can be used as a catalyst to promote the reaction between an amine compound and carbon dioxide.

Claims

1. a compound A having an element M-oxygen double bond; A carrier supporting the compound A; Equipped with The element M is a metal element or P, The support comprises a compound B having a cation with an ionic radius of greater than 60.5 pm.

2. The complex of claim 1 , wherein the cation is a metal cation.

3. 3. The composite according to claim 2, wherein the metal cation comprises at least one selected from the group consisting of magnesium ions, cerium ions, zirconium ions, sodium ions, calcium ions, manganese ions, cobalt ions, lanthanum ions, zinc ions, potassium ions, indium ions, niobium ions, barium ions, strontium ions, iron ions, and yttrium ions.

4. The complex of claim 2 , wherein compound B comprises a metal oxide having the metal cation.

5. The compound B is MgO and CeO 2 The complex according to claim 1, comprising at least one selected from the group consisting of:

6. 2. The composite of claim 1, wherein the element M is V, Fe, Mo, Ta, Nb, Ti, W, or P.

7. The compound A is NH 4 VO 3 and Na 3 VO 4 The complex according to claim 1, comprising at least one selected from the group consisting of:

8. The composite according to claim 1 , wherein the content of compound A is 0.05 wt % or more.

9. 2. The complex according to claim 1, which is used to promote the reaction of an amine compound with at least one selected from the group consisting of carbon dioxide, carbonates, and hydrogencarbonates.

10. a step of contacting a compound A having an element M-oxygen double bond with a support to support the compound A on the support, The element M is a metal element or P, The method for producing a complex, wherein the support comprises a compound B having a cation with an ionic radius of greater than 60.5 pm.

11. The method according to claim 10 , wherein the step is carried out by drying a mixture of the carrier and the solution containing compound A.

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