WO2020244140A1 - 氢甲酰化催化剂及其制备方法和应用 - Google Patents

氢甲酰化催化剂及其制备方法和应用 Download PDF

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WO2020244140A1
WO2020244140A1 PCT/CN2019/115850 CN2019115850W WO2020244140A1 WO 2020244140 A1 WO2020244140 A1 WO 2020244140A1 CN 2019115850 W CN2019115850 W CN 2019115850W WO 2020244140 A1 WO2020244140 A1 WO 2020244140A1
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metal
group
hydroformylation catalyst
catalyst according
active component
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PCT/CN2019/115850
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English (en)
French (fr)
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王勇
王哲
巩玉同
吴雷
于丽丽
李浩然
陈志荣
马啸
毛建拥
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浙江新和成股份有限公司
浙江大学
山东新和成药业有限公司
山东新和成维生素有限公司
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Priority to DE112019003554.1T priority Critical patent/DE112019003554T5/de
Priority to US17/258,439 priority patent/US20220080400A1/en
Publication of WO2020244140A1 publication Critical patent/WO2020244140A1/zh

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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • 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
    • B01J37/04—Mixing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/18—Carbon
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

Definitions

  • the invention relates to the technical field of catalysts, in particular to a hydroformylation catalyst and its preparation method and application.
  • the hydroformylation of olefins is one of the main methods for preparing aldehydes. Hydroformylation was first discovered by O. Roelen in 1938 at Ruhrchemie Chemical Company in Germany. The first generation of hydroformylation catalytic process uses cobalt carbonyl as a catalyst. Co 2 (CO) 8 is first dissolved in the reaction solution. Under the reaction conditions, the formed HCo(CO) 4 is considered to be the active species in the reaction. Species are easily decomposed to produce CO, and need to be stable under higher CO pressure.
  • the second-generation hydroformylation catalytic process uses phosphorus ligands to improve the stability of catalytically active species, which can effectively reduce the pressure required for the reaction and increase the proportion of normal aldehydes.
  • phosphorus ligands will cause a decrease in catalyst activity and accelerate the hydrogenation reaction of olefins and product aldehydes, resulting in a decrease in aldehyde selectivity.
  • the third-generation hydroformylation catalytic process is an oil-soluble rhodium ligand complex catalyst with metal Rh as the active center.
  • This type of catalyst can greatly improve the reaction efficiency.
  • the Rh catalyst modified by triphenylphosphine is used. Mild, high normal aldehyde selectivity, olefin hydrogenation and other side reactions are greatly reduced, but its disadvantage is that the product and the catalyst are in a homogeneous liquid phase, the separation of the product and the catalyst and the recovery of the catalyst are difficult, and the distillation product is separated Catalysts often lead to problems such as product polymerization, catalyst decomposition and deactivation.
  • the fourth-generation hydroformylation catalytic process uses a water-soluble phosphorus ligand and an oil-water two-phase reaction system.
  • the catalyst exists in the water phase and the product aldehyde is in the oil phase. After the reaction, the catalyst and the product can be effectively separated by standing still. Due to the low mass transfer efficiency of the two-phase reaction, which affects the catalytic effect, it is necessary to add a phase transfer agent, but the addition of the phase transfer agent will cause emulsification and increase the difficulty of phase separation.
  • the present invention provides a hydroformylation catalyst comprising an active component and a carrier supporting the active component.
  • the active component includes a transition metal as a central atom and a polyhydroxy aromatic ring group combined with the transition metal
  • the transition metal and the polyhydroxy aromatic ring group are bonded by at least one of a metal-hydroxyl coordination bond and a metal-oxygen covalent bond, and the active component includes at least one of the metal -Hydroxyl coordination bond and at least one of said metal-oxygen covalent bond.
  • the transition metal and the same polyhydroxy aromatic ring group are bonded via a metal-hydroxyl coordination bond and a metal-oxygen covalent bond, and the hydroxyl group is preferably a phenolic hydroxyl group.
  • the active component has a structure as shown in formula (1):
  • M is the transition metal
  • the bond between OH and M is the metal-hydroxyl coordination bond
  • the bond between O and M is the metal-oxygen covalent bond
  • R is H or Substituent groups, 1 ⁇ n ⁇ 3, preferably, the R is a substituent group containing a hydroxyl group; when n>1, R on each benzene ring is independently selected from H or a substituent group.
  • n 3
  • the structure of the active component is as shown in formula (2):
  • the active component has a structure as shown in formula (3):
  • M is the transition metal
  • the bond between OH and M is the metal-hydroxyl coordination bond
  • the bond between O and M is the metal-oxygen covalent bond
  • R1 and R2 are independent Is selected from H or a substituent group, 1 ⁇ m1+m2 ⁇ 12, m1 ⁇ 1, m2 ⁇ 1, preferably, said R1 and R2 are independently selected from a substituent group containing a hydroxyl group.
  • a plurality of the active components are cross-linked by hydrogen bonds formed between the hydroxyl groups on the polyhydroxy aromatic ring groups to form a network.
  • the hydroxyl group on the polyhydroxy aromatic ring group of the active component is bonded to the carrier through a hydrogen bond.
  • the active ingredient is 0.1% to 20% of the mass of the carrier.
  • the invention also provides a preparation method of the hydroformylation catalyst, which comprises the following steps:
  • the pH of the mixed solution is adjusted to 8-11 by an alkaline substance to obtain the hydroformylation catalyst.
  • the preparation method of the hydroformylation catalyst further includes the step of modifying the carrier with a chemical group, and the chemical group includes one or more of a hydroxyl group, a mercapto group, and an amino group.
  • the carrier is selected from one or more of activated carbon, silicon dioxide and metal oxides, and the metal oxides are preferably Al 2 O 3 , MoO 3 , WO 3 , V 2 One or more of O 5 , VO 2 , MgO and ZnO.
  • the metal precursor is selected from (NH 4 ) 2 RuCl 6 , RuCl 3 , C 15 H 21 O 6 Ru, H 12 Cl 6 N 3 Rh, RhN 3 O 9 , RhCl 3 ⁇ 3H One or more of 2 O.
  • the polyhydroxy aromatic ring compound is an aromatic hydrocarbon ring compound containing two or more hydroxyl groups.
  • the hydroxyl group is preferably a phenolic hydroxyl group, and the phenolic hydroxyl group is preferably an ortho-position phenolic hydroxyl group.
  • the polyhydroxy aromatic ring compound is selected from one or more of catechol, phloroglucinol, and tannic acid.
  • the mass ratio of the polyhydroxy aromatic ring group to the metal precursor is 0.1:1 to 50:1.
  • the mass ratio of the carrier to the metal precursor is 5 to 1,000.
  • the present invention further improves the application of the hydroformylation catalyst in the hydroformylation reaction of olefins or alkynes.
  • a polyhydroxy aromatic ring group is connected to a transition metal with catalytic activity to form an active component, and a solid-phase carrier carries the active component to realize the heterogeneity of a homogeneous catalyst.
  • the catalyst is after the reaction It is easy to separate and recover, and can be directly used in continuous gas phase production. Due to the existence of the carrier, the steric hindrance around the transition metal is extremely large, which can realize the highly selective hydroformylation reaction and effectively control the linear products and branched chains. Distribution of products.
  • the polyhydroxy aromatic ring group and the transition metal can be bonded through metal-hydroxyl coordination bond or metal-oxygen covalent bond.
  • the active component formed includes both metal-hydroxyl coordination bond and metal -Oxygen covalent bond, this kind of bonding is more stable than all the coordination bonds, the transition metal as the central atom is not easy to fall off, agglomerate or lose; and due to the common metal-oxygen covalent bond and metal-hydroxyl coordination bond
  • the transition metal element presents a unique electronic structure and geometric structure, which can further improve the activity of the catalyst.
  • the hydroformylation is obtained through metal precursors that can be dissociated to form transition metal ions, polyhydroxy aromatic ring compounds, and carriers under alkaline conditions with a pH of 8-11.
  • Acylation catalyst Under the basic conditions of pH 8-11, the hydroxy group of the polyhydroxy aromatic ring compound can be partially dissociated to form the dissociation of the polyhydroxy aromatic ring group from the metal precursor in the hydroformylation catalyst A part of the hydroxyl group dissociates into an oxygen anion and a transition metal ion to form a non-coordinated covalent bond, and the other part of the undissociated hydroxyl group forms a coordination with the transition metal ion under coordination.
  • the preparation method of the hydroformylation catalyst provided by the embodiment of the present invention is simple, feasible and easy to operate, and the prepared hydroformylation catalyst has a stable structure and is easy to separate and recover.
  • Figure 1 is a schematic structural diagram of a hydroformylation catalyst prepared in an embodiment of the present invention
  • Figure 2 is a transmission electron micrograph of a hydroformylation catalyst prepared in an embodiment of the present invention.
  • an embodiment of the present invention provides a hydroformylation catalyst comprising an active component 20 and a carrier 10 carrying the active component.
  • the active component 20 includes a transition metal 22 as a central atom and The transition metal-bonded polyhydroxy aromatic ring group 24, the transition metal 22 and the polyhydroxy aromatic ring group 24 are at least one of a metal-hydroxyl coordination bond and a metal-oxygen covalent bond
  • the active component 20 includes at least one metal-hydroxyl coordination bond and at least one metal-oxygen covalent bond.
  • a polyhydroxy aromatic ring group is connected to a transition metal with catalytic activity to form an active component, and a solid-phase carrier carries the active component to realize the heterogeneity of a homogeneous catalyst.
  • the catalyst is after the reaction It is easy to separate and recover, and can be directly used in continuous gas phase production. Due to the existence of the carrier, the steric hindrance around the transition metal is extremely large, which can realize the highly selective hydroformylation reaction and effectively control the linear products and branched chains. Distribution of products.
  • the polyhydroxy aromatic ring group and the transition metal can be bonded through metal-hydroxyl coordination bond or metal-oxygen covalent bond.
  • the active component formed includes both metal-hydroxyl coordination bond and metal -Oxygen covalent bond, this kind of bonding is more stable than all the coordination bonds, the transition metal as the central atom is not easy to fall off, agglomerate or lose; and due to the common metal-oxygen covalent bond and metal-hydroxyl coordination bond
  • the transition metal element presents a unique electronic structure and geometric structure, which can further improve the activity of the catalyst.
  • the polyhydroxy aromatic ring group is preferably a rigid structure containing a benzene ring, which can stabilize the microstructure of the active component and is not easily deformed.
  • the polyhydroxy aromatic ring group and the transition metal can be combined with at least one of a metal-hydroxyl coordination bond and a metal-oxygen covalent bond to form the active components of different structures.
  • the transition metal and the same polyhydroxy aromatic ring group are bonded through a metal-hydroxyl coordination bond and a metal-oxygen covalent bond, and the hydroxyl group is preferably a phenolic hydroxyl group.
  • the active component has the structure shown in formula (1):
  • M is the transition metal
  • the bond between OH and M is the metal-hydroxyl coordination bond
  • the bond between O and M is the metal-oxygen covalent bond, 1 ⁇ n ⁇ 3.
  • n is 1 or 3, and further, n is 3.
  • R is H or a substituent group, and the substituent group includes a C1-C10 alkyl group and a C6-C20 aryl group.
  • the R is halogen, amino, carboxyl, hydroxy substituted C1-C10 alkyl or C6-C20 aryl. More preferably, the R is a C1-C10 alkyl group or a C6-C20 aryl group substituted by a hydroxy group.
  • the hydroxy-substituted C1-C10 alkyl group or C6-C20 aryl group may have one or more hydroxy groups substituted, and preferably contain 1-3 hydroxy groups.
  • the R on each benzene ring may be the same or different, and the R on each benzene ring is independently selected from H or a substituent group.
  • n 3
  • the structure of the active component is shown in formula (2):
  • the active component has a structure as shown in formula (3):
  • M is the transition metal
  • the bond between OH and M is the metal-hydroxyl coordination bond
  • the bond between O and M is the metal-oxygen covalent bond, 1 ⁇ m1+ m2 ⁇ 12, m1 ⁇ 1, m2 ⁇ 1, preferably 1 ⁇ m1+m2 ⁇ 6.
  • R1 and R2 may be the same or different.
  • R1 and R2 are independently selected from H or a substituent group, and the substituent group includes a C1-C10 alkyl group and a C6-C20 aryl group.
  • the R1 and R2 are halogen, amino, carboxyl, hydroxy substituted C1-C10 alkyl or C6-C20 aryl. More preferably, the R1 and R2 are C1-C10 alkyl groups or C6-C20 aryl groups substituted with hydroxy groups.
  • the hydroxy-substituted C1-C10 alkyl group or C6-C20 aryl group may have one or more hydroxy groups substituted, and preferably contain 1-3 hydroxy groups.
  • the multiple active components are cross-linked by hydrogen bonds formed between the hydroxyl groups on the polyhydroxy aromatic ring groups to form a network, which surrounds the transition metal to further prevent the transition
  • the shedding, agglomeration and loss of metals make the catalyst more stable.
  • the surface of the carrier has one or more functional groups among hydroxyl, amino and mercapto groups.
  • the hydroxyl group on the polyhydroxy aromatic ring group of the active component can be combined with the carrier through hydrogen bonds, and the binding between the active component and the carrier can be made better due to the hydrogen bond. firm.
  • the active component in the hydroformylation catalyst is 0.1% to 20%, preferably 0.2% to 2%, of the mass of the carrier.
  • the embodiment of the present invention also provides a method for preparing a hydroformylation catalyst, which includes the following steps:
  • the hydroformylation is obtained through metal precursors that can be dissociated to form transition metal ions, polyhydroxy aromatic ring compounds, and carriers under alkaline conditions with a pH of 8-11.
  • Acylation catalyst Under the basic conditions of pH 8-11, the hydroxy group of the polyhydroxy aromatic ring compound can be partially dissociated to form the dissociation of the polyhydroxy aromatic ring group from the metal precursor in the hydroformylation catalyst
  • a part of the hydroxyl group dissociates into an oxygen anion and a transition metal ion to form a non-coordinated covalent bond, and the other part of the undissociated hydroxyl group forms a coordination with the transition metal ion under coordination.
  • Position bonds to form the active component, and the carrier immobilizes the active component to obtain the hydroformylation catalyst.
  • the metal precursor is selected from but not limited to (NH 4 ) 2 RuCl 6 , RuCl 3 , C 15 H 21 O 6 Ru, H 12 C 16 N 3 Rh, RhN 3 O 9 , RhCl 3 .3H 2 O One or more, preferably RuCl 3 and RhCl 3 ⁇ 3H 2 O.
  • the polyhydroxy aromatic ring compound is preferably an aromatic hydrocarbon ring compound containing two or more hydroxyl groups.
  • the hydroxyl group is preferably a phenolic hydroxyl group, such as hydroquinone, catechol, phloroglucinol, tannic acid and the like.
  • the phenolic hydroxyl group is preferably an ortho-phenolic hydroxyl group, such as catechol, tannic acid and the like.
  • the hydroformylation catalyst has an active component structure as shown in formula (1). More preferably, the polyhydroxy aromatic ring compound is tannic acid. Tannic acid contains a large number of hydroxyl groups and hydroxyl bonds, which can be more firmly combined with the carrier, and the polyhydroxy aromatic ring formed by tannic acid The groups are easier to crosslink to form a network.
  • the support is selected from but not limited to one or more of activated carbon, silicon dioxide and metal oxides, and the metal oxides can be selected from Al, Ti, Zr, Ce, Mo, W, V, Mg, Oxides of one or more elements among Ca, Cr, Mn, Fe, Zn, Ga, Ge, Sn, Bi, Y, Nb, La, and Re are preferably Al 2 O 3 , MoO 3 , WO 3 , One or more of V 2 O 5 , VO 2 , MgO and ZnO.
  • the morphology of the carrier is not limited.
  • the carrier is granular, and the particle size of the granular carrier is 6 nm to 250 ⁇ m.
  • the catalyst is a porous support, and the pore size of the support is 0.2 nm to 100 nm.
  • the preparation method of the hydroformylation catalyst further includes the step of modifying the carrier with chemical groups.
  • the surface of the carrier can be modified with hydroxyl and amino groups by chemical methods or plasma treatment. , Sulfhydryl and other chemical groups, the surface of the carrier is modified with the chemical groups to make the hydroformylation catalyst more firmly supported.
  • the mass ratio of the polyhydroxy compound to the metal precursor is 0.1:1-50:1. In one embodiment, the mass ratio of the catalyst carrier to the metal precursor is 5:1 to 1000:1.
  • the solvent is a solvent that can dissolve the metal precursor and the polyhydroxy aromatic ring compound, and includes water, ethanol, cycloethane, and the like.
  • the mixed solution can be uniformly mixed by stirring or shaking.
  • the metal precursor is first dissolved in the solvent to form a solution
  • the carrier is first added to the solution, and the carrier is combined with the carrier through the operation steps of stirring or shaking.
  • the polyhydroxy aromatic ring compound is added for mixing.
  • the alkaline substance may be selected from one or more of Na 2 CO 3 , NaHCO 3 , NaOH, and NH 3 ⁇ H 2 O.
  • the solid of the alkaline substance can be formulated into a solution with a certain concentration when adjusting the pH and added dropwise to the mixed solution.
  • the pH of the mixed solution is adjusted to 8-11, it is allowed to stand at room temperature for 2 to 12 hours, and then filtered, and the obtained solid is washed and dried to obtain the hydroformylation catalyst.
  • the solid It is dried at 70°C to 90°C, and the drying time is preferably 24h to 48h.
  • the invention also provides an application of the hydroformylation catalyst in the hydroformylation reaction of olefins and alkynes.
  • the hydroformylation catalyst can be used for the hydroformylation of propylene to produce n-butanol, 2-ethylhexanol and other higher alcohols; the hydroformylation of heptene to produce octanol; and the hydroformylation of mixed olefins
  • Chemical reaction produces C 8 ⁇ C 10 alcohols and C 12 ⁇ C 16 alcohols used for plasticizers and synthetic detergents;
  • the hydroformylation reaction of propyne produces methyl methacrylate (MMA), the monomer of organic glass.
  • MMA methyl methacrylate
  • Example 2 It is basically the same as Example 1, except that the metal precursor added is RhCl 3 ⁇ 3H 2 O.
  • Example 2 It is basically the same as Example 1, except that the added catalyst support is silica.
  • Example 2 It is basically the same as Example 1, except that the metal precursor added is RhCl 3 ⁇ 3H 2 O, and the catalyst support added is silica.
  • Example 2 It is basically the same as Example 1, except that the polyhydroxy aromatic ring compound added is hydroquinone.
  • Example 2 It is basically the same as Example 1, except that the polyhydroxy aromatic ring compound added is pyrogallol and the catalyst carrier is silica.
  • Example 2 It is basically the same as Example 1, except that the pH of the solution is 6-7.
  • hydroformylation catalysts prepared in Examples 1-6 can all efficiently catalyze the formylation reaction of alkenes or alkynes.
  • the hydroformylation catalyst prepared in Example 4 and the hydroformylation catalyst prepared in the comparative example are used in the following. Comparison of catalytic effects in acylation reactions.
  • the hydroformylation catalyst prepared in Example 4 and the comparative example was used as the catalyst to catalyze the formylation reaction of propylene, and the reaction conditions were the same.
  • the specific reaction conditions are as follows: a 500 mL autoclave is used, 50 mg of catalyst, 10 mL deionized water, 0.4 MPa of propylene, 1 MPa of carbon monoxide, and 1 MPa of hydrogen are added to the autoclave, the reaction temperature is 100° C., and the reaction time is 6 h.
  • the hydroformylation catalyst prepared in Example 4 and the comparative example was used as a catalyst to catalyze the formylation reaction of isobutylene, and the reaction conditions were the same.
  • the specific reaction conditions were as follows: a 500mL autoclave was used, 50mg of catalyst, 10mL of deionized water, 0.2MPa of isobutylene, 1MPa of carbon monoxide, and 1MPa of hydrogen were added to the autoclave, the reaction temperature was 100°C, and the reaction time was 6h.
  • the hydroformylation catalyst prepared in Example 4 and the comparative example was used as a catalyst to catalyze the formylation reaction of isobutylene, and the reaction conditions were the same.
  • the specific reaction conditions are: using a 500mL autoclave, add 50mg of catalyst, 10mL of n-hexane, 30mmol of 1-heptene, 1MPa of carbon monoxide, 1MPa of hydrogen, a reaction temperature of 100°C, and a reaction time of 8h into the autoclave.

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Abstract

一种氢甲酰化催化剂及制备方法和应用，该氢甲酰化催化剂包括活性组分(20)和承载所述活性组分(20)的载体(10)，所述活性组分(20)包括作为中心原子的过渡金属(22)以及与所述过渡金属(22)结合的多羟基芳环基团(24)，所述过渡金属(22)与所述多羟基芳环基团(24)之间通过金属-羟基配位键和金属-氧共价键中的至少一种结合，所述活性组分(20)中包括至少一个所述金属-羟基配位键和至少一个所述金属-氧共价键。

Description

氢甲酰化催化剂及其制备方法和应用
相关申请
本申请要求2019年6月6日申请的，申请号为201910492315.5，名称为“氢甲酰化催化剂及其制备方法和应用”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本发明涉及催化剂技术领域，特别是涉及一种氢甲酰化催化剂及其制备方法和应用。
背景技术
烯烃的氢甲酰化反应是制备醛类物质的主要方法之一。氢甲酰化最早由O.Roelen于1938年在德国Ruhrchemie化学公司发现。第一代氢甲酰化催化工艺以羰基钴为催化剂，Co 2(CO) 8首先溶解在反应液中，在反应条件下，形成的HCo(CO) 4被认为是反应的活性物种，但是该物种极易分解产生CO，需要在较高的CO压力下才能得以稳定存在。
第二代氢甲酰化催化工艺采用磷配体提升催化活性物种的稳定性，可有效降低反应所需压力，提高正构醛的比例。但磷配体会导致催化剂活性的下降，而且会加速烯烃及产物醛的加氢反应，造成醛选择性的下降。
第三代氢甲酰化催化工艺是以金属Rh为活性中心的油溶性铑配体络合物催化剂，该类催化剂可大大提升反应效率，如采用三苯基膦改性的Rh催化剂，反应条件温和，正构醛选择性高，烯烃加氢等副反应都极大降低，但其缺点是产物与催化剂是处在均一的液相中，产物与催化剂的分离以及催化剂的回收困难，蒸馏产物分离催化剂常会导致产物聚合、催化剂分解失活等问题。
第四代氢甲酰化催化工艺采用水溶性的磷配体和油-水两相反应体系，催化剂存在于水相，产物醛位于油相，反应后静置即可有效分离催化剂和产物，但由于两相反应传质效率较低，影响催化效果，需要加入相转移剂，但相转移剂的加入会导致乳化现象而增加相分离难度。
因此，如何获得活性高同时还能够分离回收的催化剂是我们亟待解决的问题。
发明内容
基于此，有必要提供一种氢甲酰化催化剂及其制备方法和应用。
本发明提供一种氢甲酰化催化剂，包括活性组分和承载所述活性组分的载体，所述活性组分包括作为中心原子的过渡金属以及与所述过渡金属结合的多羟基芳环基团，所述过渡金属与所述多羟基芳环基团之间通过金属-羟基配位键和金属-氧共价键中的至少一种结合，所述活性组分中包括至少一个所述金属-羟基配位键和至少一个所述金属-氧共价键。
在其中一个实施例中，所述过渡金属与同一所述多羟基芳环基团之间通过金属-羟基配位键和金属-氧共价键结合，所述羟基优选为酚羟基。
在其中一个实施例中，所述活性组分具有如式(1)所示的结构：
Figure PCTCN2019115850-appb-000001
式(1)中M为所述过渡金属，OH与M之间的键为所述金属-羟基配位键，O与M之间的键为所述金属-氧共价键，R为H或取代基团，1≤n≤3，优选的，所述R为含有羟基的取代基团；n>1时，每个苯环上的R独立的选自H或取代基团。
在其中一个实施例中，n为3，所述活性组分结构如式(2)所示：
Figure PCTCN2019115850-appb-000002
在其中一个实施例中，所述活性组分具有如式(3)所示的结构：
Figure PCTCN2019115850-appb-000003
式(3)中M为所述过渡金属，OH与M之间的键为所述金属-羟基配位键，O与M之间的键为所述金属-氧共价键，R1与R2独立的选自H或取代基团，1≤m1+m2≤12，m1≥1，m2≥1，优选的，所述R1与R2独立的选自含有羟基的取代基团。
在其中一个实施例中，多个所述活性组分之间通过所述多羟基芳环基团上的羟基之间形成的氢键交联形成网络。
在其中一个实施例中，所述活性组分的所述多羟基芳环基团上的羟基与所述载体之间 通过氢键结合。
在其中一个实施例中，所述活性组分为所述载体质量的0.1％至20％。
本发明还提供一种氢甲酰化催化剂的制备方法，包括以下步骤：
提供载体、金属前驱体和多羟基芳环化合物在溶剂中形成的混合溶液，所述金属前驱体能够在所述溶剂中解离形成过渡金属离子；
通过碱性物质调节所述混合溶液pH至8～11，得到所述氢甲酰化催化剂。
在其中一个实施例中，所述氢甲酰化催化剂的制备方法还包括对所述载体进行化学基团修饰的步骤，所述化学基团包括羟基、巯基、氨基中的一种或多种。
在其中一个实施例中，所述载体选自活性碳、二氧化硅和金属氧化物中的一种或多种，所述金属氧化物优选为Al 2O 3、MoO 3、WO 3、V 2O 5、VO 2、MgO、ZnO中的一种或多种。
在其中一个实施例中，所述金属前驱体选自(NH 4) 2RuCl 6、RuCl 3、C 15H 21O 6Ru、H 12Cl 6N 3Rh、RhN 3O 9、RhCl 3·3H 2O中的一种或多种。
在其中一个实施例中，所述多羟基芳环化合物为含有两个或两个以上羟基的芳烃环化合物，所述羟基优选为酚羟基，所述酚羟基优选为邻位酚羟基。
在其中一个实施例中，所述多羟基芳环化合物选自邻苯二酚、间苯三酚、单宁酸中的一种或多种。
在其中一个实施例中，所述多羟基芳环基团与所述金属前驱体的质量比为0.1:1至50:1。
在其中一个实施例中，所述载体与所述金属前驱体的质量比为5至1000。
本发明进一步提高一种所述的氢甲酰化催化剂在烯烃或炔烃的氢甲酰化反应中的应用。
本发明提供的氢甲酰化催化剂，以多羟基芳环基团连接具有催化活性的过渡金属形成活性组分，固相载体承载活性组分，实现均相催化剂的多相化，催化剂在反应后易于分离回收，可直接用于气相连续化生产，并且由于载体的存在，使过渡金属周围的空间位阻极大，可实现高选择性的氢甲酰化反应，有效调控直链产物和支链产物的分布。多羟基芳环基团与过渡金属之间既可通过金属-羟基配位键结合，又可通过金属-氧共价键结合，形成的活性组分中既包括金属-羟基配位键又包括金属-氧共价键，这样的结合方式比全部以配位键结合更稳定，作为中心原子的过渡金属不易脱落、团聚或流失；并且由于金属-氧共价键和金属-羟基配位键的共同作用，过渡金属元素呈现出独特的电子结构和几何结构，可进一步提高催化剂的活性。
本发明实施例提供的氢甲酰化催化剂制备方法，通过可解离形成过渡金属离子的金属 前驱体、多羟基芳环化合物以及载体在pH为8～11的碱性条件下得到所述氢甲酰化催化剂。多羟基芳环化合物在pH为8～11的碱性条件下，其羟基基团可发生部分解离形成所述氢甲酰化催化剂中的所述多羟基芳环基团与金属前驱体解离出的过渡金属离子结合，所述羟基基团一部分解离为氧负离子与过渡金属离子形成非配位共价键，另一部分没解离的羟基基团在配位作用下与过渡金属离子形成配位键，从而形成所述活性组分，载体固载所述活性组分得到所述氢甲酰化催化剂。本发明实施例提供的氢甲酰化催化剂制备方法，简单可行，易操作，制得的氢甲酰化催化剂结构稳定、易分离回收。
附图说明
图1为本发明实施例制备的氢甲酰化催化剂结构示意图；
图2为本发明实施例制备的氢甲酰化催化剂的透射电镜图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下通过实施例，并结合附图，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
请参阅图1，本发明实施例提供一种氢甲酰化催化剂，包括活性组分20和承载所述活性组分的载体10，所述活性组分20包括作为中心原子的过渡金属22以及与所述过渡金属结合的多羟基芳环基团24，所述过渡金属22与所述多羟基芳环基团24之间通过金属-羟基配位键和金属-氧共价键中的至少一种结合，所述活性组分20中包括至少一个所述金属-羟基配位键和至少一个所述金属-氧共价键。
本发明提供的氢甲酰化催化剂，以多羟基芳环基团连接具有催化活性的过渡金属形成活性组分，固相载体承载活性组分，实现均相催化剂的多相化，催化剂在反应后易于分离回收，可直接用于气相连续化生产，并且由于载体的存在，使过渡金属周围的空间位阻极大，可实现高选择性的氢甲酰化反应，有效调控直链产物和支链产物的分布。多羟基芳环基团与过渡金属之间既可通过金属-羟基配位键结合，又可通过金属-氧共价键结合，形成的活性组分中既包括金属-羟基配位键又包括金属-氧共价键，这样的结合方式比全部以配位键结合更稳定，作为中心原子的过渡金属不易脱落、团聚或流失；并且由于金属-氧共价键和金属-羟基配位键的共同作用，过渡金属元素呈现出独特的电子结构和几何结构，可进一步提高催化剂的活性。
所述多羟基芳环基团优选为含有苯环的刚性结构，可使所述活性组分微观结构稳定而不易变形。
所述多羟基芳环基团与所述过渡金属之间通过金属-羟基配位键和金属-氧共价键中的至少一种结合可形成不同结构的所述活性组分。
在一实施例中，所述过渡金属与同一所述多羟基芳环基团之间通过金属-羟基配位键和金属-氧共价键结合，所述羟基优选为酚羟基。所述活性组分具有如式(1)所示的结构：
Figure PCTCN2019115850-appb-000004
式(1)中M为所述过渡金属，OH与M之间的键为所述金属-羟基配位键，O与M之间的键为所述金属-氧共价键，1≤n≤3，优选的，n为1或3，更进一步的，n为3。
R为H或取代基团，所述取代基团包括C1-C10的烷基、C6-C20的芳基。优选的，所述R为卤素、氨基、羧基、羟基取代的C1-C10的烷基或C6-C20的芳基。更优选的，所述R为羟基取代的C1-C10的烷基或C6-C20的芳基。所述的羟基取代的C1-C10的烷基或C6-C20的芳基可以有1个或多个羟基取代，优选的含有1-3个羟基。
n>1时，每个苯环上的R可以相同，也可不同，每个苯环上的R独立的选自H或取代基团。
优选的，n为3，所述活性组分结构如式(2)所示：
Figure PCTCN2019115850-appb-000005
在另一实施例中，所述活性组分具有如式(3)所示的结构：
Figure PCTCN2019115850-appb-000006
式(3)中M为所述过渡金属，OH与M之间的键为所述金属-羟基配位键，O与M之间的键为所述金属-氧共价键，1≤m1+m2≤12，m1≥1，m2≥1，优选的1≤m1+m2≤6。
上述的R1、R2可以相同、也可不同，R1与R2独立的选自H或取代基团，所述取代基团包括C1-C10的烷基、C6-C20的芳基。优选的，所述R1、R2为卤素、氨基、羧基、羟基取代的C1-C10的烷基或C6-C20的芳基。更优选的，所述R1、R2为羟基取代的C1-C10的烷基或C6-C20的芳基。所述的羟基取代的C1-C10的烷基或C6-C20的芳基可以有1个或多个羟基取代，优选的含有1-3个羟基。
在一实施例中，所述多个活性组分之间通过所述多羟基芳环基团上的羟基之间形成的氢键交联形成网络，将所述过渡金属包围，进一步防止所述过渡金属的脱落、团聚以及流失问题，使催化剂更稳定。
在一实施例中，所述载体表面具有羟基、氨基及巯基中的一种或多种官能团。所述活性组分的所述多羟基芳环基团上的羟基与所述载体之间可通过氢键结合，由于氢键的作用可使所述活性组分和所述载体之间的结合更牢固。
在一实施例中，所述氢甲酰化催化剂中所述活性组分为所述载体质量的0.1％至20％，优选为0.2％至2％。
本发明实施例还提供一种氢甲酰化催化剂的制备方法，包括以下步骤：
S10，提供载体、金属前驱体和多羟基芳环化合物在溶剂中形成的混合溶液，所述金属前驱体能够在所述溶剂中解离形成过渡金属离子；
S20，通过碱性物质调节所述混合溶液pH至8～11，得到所述氢甲酰化催化剂。
本发明实施例提供的氢甲酰化催化剂制备方法，通过可解离形成过渡金属离子的金属前驱体、多羟基芳环化合物以及载体在pH为8～11的碱性条件下得到所述氢甲酰化催化剂。多羟基芳环化合物在pH为8～11的碱性条件下，其羟基基团可发生部分解离形成所述氢甲酰化催化剂中的所述多羟基芳环基团与金属前驱体解离出的过渡金属离子结合，所述羟基基团一部分解离为氧负离子与过渡金属离子形成非配位共价键，另一部分没解离的羟基基团在配位作用下与过渡金属离子形成配位键，从而形成所述活性组分，载体固载所述活性组分得到所述氢甲酰化催化剂。
所述金属前驱体选自但不限于(NH 4) 2RuCl 6、RuCl 3、C 15H 21O 6Ru、H 12C l6N 3Rh、RhN 3O 9、RhCl 3·3H 2O中的一种或多种，优选为RuCl 3和RhCl 3·3H 2O。
所述多羟基芳环化合物优选为含有两个或两个以上羟基的芳烃环化合物。所述羟基优选为酚羟基，例如对苯二酚、邻苯二酚、间苯三酚、单宁酸等。所述酚羟基优选为邻位酚羟基，例如邻苯二酚、单宁酸等。所述多羟基芳环化合物中含有邻位酚羟基时，所述氢甲酰化催化剂具有如式(1)所示的活性组分结构。更优选的，所述多羟基芳环化合物为单宁酸，单宁酸中含有大量的羟基和羟键，能够与所述载体更牢固的结合，同时单宁酸形成的所述多羟 基芳环基团之间更容易交联形成网络。
所述载体选自但不限于活性碳、二氧化硅和金属氧化物中的一种或多种，所述金属氧化物可选自Al、Ti、Zr、Ce、Mo、W、V、Mg、Ca、Cr、Mn、Fe、Zn、Ga、Ge、Sn、Bi、Y、Nb、La、Re中的一种或多种元素的氧化物，优选为Al 2O 3、MoO 3、WO 3、V 2O 5、VO 2、MgO、ZnO中的一种或多种。所述载体的形貌不限，在一实施例中，所述载体为颗粒状，所述颗粒状载体的粒径为6nm至250μm。在一实施例中，所述催化剂为多孔载体，所述载体的孔径为0.2nm至100nm。
在一实施例中，所述氢甲酰化催化剂的制备方法还包括对所述载体进行化学基团修饰的步骤，可采用化学方法或等离子体处理等方法将所述载体表面修饰上羟基、氨基、巯基等化学基团，所述载体表面修饰所述化学基团可使所述氢甲酰化催化剂的固载更牢固。
在一实施例中，所述多羟基化合物与所述金属前驱体的质量比为0.1:1～50:1。在一实施例中，所述催化剂载体与所述金属前驱体的质量比为5:1～1000:1。
步骤S10中，所述溶剂为可溶解所述金属前驱体和所述多羟基芳环化合物的溶剂，包括水、乙醇、环乙烷等。
制备所述混合溶液时，可通过搅拌或振荡等方式使所述混合溶液混合均匀。为使其混合均匀，优选的，先将所述金属前驱体溶解在所述溶剂中形成溶液，先向所述溶液中加入所述载体，通过搅拌或振荡的操作步骤使所述载体与所述金属前驱体混合均匀后，再加入所述多羟基芳环化合物进行混合。
步骤S20中，所述碱性物质可选自Na 2CO 3、NaHCO 3、NaOH、NH 3·H 2O中的一种或多种。为防止沉淀的生成，优选的，调节pH时可将所述碱性物质的固体配制成一定浓度的溶液逐滴加入所述混合溶液。
所述混合溶液pH调节至8～11后，在室温条件下静置2小时至12小时，然后进行过滤，将得到的固体洗涤干燥得所述氢甲酰化催化剂，优选的，将所述固体置于70℃～90℃下干燥，干燥时间优选为24h～48h。
本发明还提供一种所述的氢甲酰化催化剂在烯烃和炔烃的氢甲酰化反应中的应用。例如所述的氢甲酰化催化剂可用于丙烯氢甲酰化反应生产正丁醇、2-乙基己醇及其它高碳醇；庚烯氢甲酰化反应生产辛醇；混合烯烃氢甲酰化反应生产用于增塑剂和合成洗涤剂的C 8～C 10醇和C 12～C 16醇；丙炔的氢甲酰化反应反应生产有机玻璃的单体甲基丙烯酸甲酯(MMA)。
实施例1
称取20mg RuCl 3溶于40mL水中，加入1g活性炭，搅拌10分钟后，加入300mg单宁酸，搅拌10分钟；
逐滴加入0.1M的NaOH溶液直至溶液pH在10左右，继续反应2h；
反应结束后过滤得到固体，将固体洗涤，置于70度下干燥24h，得到氢甲酰化催化剂。
实施例2
与实施例1基本相同，不同之处在于，加入的金属前驱体为RhCl 3·3H 2O。
实施例3
与实施例1基本相同，不同之处在于，加入的催化剂载体为二氧化硅。
实施例4
与实施例1基本相同，不同之处在于，加入的金属前驱体为RhCl 3·3H 2O，加入的催化剂载体为二氧化硅。
实施例5
与实施例1基本相同，不同之处在于，加入的多羟基芳环化合物为对苯二酚。
实施例6
与实施例1基本相同，不同之处在于，加入的多羟基芳环化合物为均苯三酚，催化剂载体为二氧化硅。
对比例
与实施例1基本相同，不同之处在于，溶液pH为6～7。
实施例1-6制备的氢甲酰化催化剂均可高效催化烯烃或炔烃的甲酰化反应，以下以实施例4制备的氢甲酰化催化剂与对比例制备的氢甲酰化催化剂在甲酰化反应中的催化效果对比。
应用例1
Figure PCTCN2019115850-appb-000007
采用实施例4和对比例中制备的氢甲酰化催化剂作为催化剂催化丙烯的甲酰化反应，反应条件相同。具体反应条件为：采用500mL高压反应釜中，在高压反应釜中加入催化剂50mg，10mL去离子水，丙烯0.4MPa，一氧化碳1MPa，氢气1MPa，反应温度为100℃，反应时间6h。反应结束后经测试，使用实施例4中制备的氢甲酰化催化剂作为催化剂时，丙烯转化率为96％，正丁醛选择性为96％，正丁醛/异丁醛的比例为28；使用对比例中制备的氢甲酰化催化剂作为催化剂时，丙烯转化率为93％，正丁醛选择性为49％，正丁醛/异丁醛的比例为4，丙烷的选择性为39％。
应用例2
Figure PCTCN2019115850-appb-000008
采用实施例4和对比例中制备的氢甲酰化催化剂作为催化剂催化异丁烯的甲酰化反应，反应条件相同。具体反应条件为：采用500mL高压反应釜，在高压反应釜中加入催化剂50mg，10mL去离子水，异丁烯0.2MPa，一氧化碳1MPa，氢气1MPa，反应温度为100℃，反应时间6h。反应结束后经测试，使用实施例4中制备的氢甲酰化催化剂作为催化剂时，异丁烯转化率为98％，异戊醛选择性为97％；使用对比例中制备的氢甲酰化催化剂作为催化剂时，异丁烯转化率为91％，异戊醛选择性为54％，异戊醛/新戊醛的比例为9，异丁烷选择性为40％。
应用例3
Figure PCTCN2019115850-appb-000009
采用实施例4和对比例中制备的氢甲酰化催化剂作为催化剂催化异丁烯的甲酰化反应，反应条件相同。具体反应条件为：采用500mL高压反应釜，在高压反应釜中加入催化剂50mg，10mL正己烷，1-庚烯30mmol，一氧化碳1MPa，氢气1MPa，反应温度为100℃，反应时间8h。反应结束后经测试，使用实施例4中制备的氢甲酰化催化剂作为催化剂时，1-庚烯转化率为99％，正辛醛选择性为98％；使用对比例中制备的氢甲酰化催化剂作为催化剂时，1-庚烯转化率为82％，正辛醛选择性为47％，正丁醛/异丁醛的比例为3.3，正庚烷的选择性为39％。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (17)

  1. 一种氢甲酰化催化剂，其特征在于，包括活性组分和承载所述活性组分的载体，所述活性组分包括作为中心原子的过渡金属以及与所述过渡金属结合的多羟基芳环基团，所述过渡金属与所述多羟基芳环基团之间通过金属-羟基配位键和金属-氧共价键中的至少一种结合，所述活性组分中包括至少一个所述金属-羟基配位键和至少一个所述金属-氧共价键。
  2. 根据权利要求1所述的氢甲酰化催化剂，其特征在于，所述过渡金属与同一所述多羟基芳环基团之间通过金属-羟基配位键和金属-氧共价键结合，所述羟基优选为酚羟基。
  3. 根据权利要求1所述的氢甲酰化催化剂，其特征在于，所述活性组分具有如式(1)所示的结构：
    Figure PCTCN2019115850-appb-100001
    式(1)中M为所述过渡金属，OH与M之间的键为所述金属-羟基配位键，O与M之间的键为所述金属-氧共价键，R为H或取代基团，1≤n≤3，优选的，所述R为含有羟基的取代基团；n>1时，每个苯环上的R独立的选自H或取代基团。
  4. 根据权利要求3所述的氢甲酰化催化剂，其特征在于，n为3，所述活性组分结构如式(2)所示：
    Figure PCTCN2019115850-appb-100002
  5. 根据权利要求1所述的氢甲酰化催化剂，其特征在于，所述活性组分具有如式(3)所示的结构：
    Figure PCTCN2019115850-appb-100003
    式(3)中M为所述过渡金属，OH与M之间的键为所述金属-羟基配位键，O与M之 间的键为所述金属-氧共价键，R1与R2独立的选自H或取代基团，1≤m1+m2≤12，m1≥1，m2≥1，优选的，所述R1与R2独立的选自含有羟基的取代基团。
  6. 根据权利要求1至5任一项所述的氢甲酰化催化剂，其特征在于，多个所述活性组分之间通过所述多羟基芳环基团上的羟基之间形成的氢键交联形成网络。
  7. 根据权利要求1至5任一项所述的氢甲酰化催化剂，其特征在于，所述活性组分的所述多羟基芳环基团上的羟基与所述载体之间通过氢键结合。
  8. 根据权利要求1至5任一项所述的氢甲酰化催化剂，其特征在于，所述活性组分为所述载体质量的0.1％至20％。
  9. 一种氢甲酰化催化剂的制备方法，其特征在于，包括以下步骤：
    提供载体、金属前驱体和多羟基芳环化合物在溶剂中形成的混合溶液，所述金属前驱体能够在所述溶剂中解离形成过渡金属离子；
    通过碱性物质调节所述混合溶液pH至8～11，得到所述氢甲酰化催化剂。
  10. 根据权利要求9所述的氢甲酰化催化剂的制备方法，其特征在于，还包括对所述载体进行化学基团修饰的步骤，所述化学基团包括羟基、巯基、氨基中的一种或多种。
  11. 根据权利要求9所述的氢甲酰化催化剂的制备方法，其特征在于，所述载体选自活性碳、二氧化硅和金属氧化物中的一种或多种，所述金属氧化物优选为Al 2O 3、MoO 3、WO 3、V 2O 5、VO 2、MgO、ZnO中的一种或多种。
  12. 根据权利要求9所述的氢甲酰化催化剂的制备方法，其特征在于，所述金属前驱体选自(NH 4) 2RuCl 6、RuCl 3、C 15H 21O 6Ru、H 12C l6N 3Rh、RhN 3O 9、RhCl 3·3H 2O中的一种或多种。
  13. 根据权利要求9所述的氢甲酰化催化剂的制备方法，其特征在于，所述多羟基芳环化合物为含有两个或两个以上羟基的芳烃环化合物，所述羟基优选为酚羟基，所述酚羟基优选为邻位酚羟基。
  14. 根据权利要求9所述的氢甲酰化催化剂的制备方法，其特征在于，所述多羟基芳环化合物选自邻苯二酚、间苯三酚、单宁酸中的一种或多种。
  15. 根据权利要求9所述的氢甲酰化催化剂的制备方法，其特征在于，所述多羟基芳环基团与所述金属前驱体的质量比为0.1:1至50:1。
  16. 根据权利要求9所述的氢甲酰化催化剂的制备方法，其特征在于，所述载体与所述金属前驱体的质量比为5:1至1000:1。
  17. 一种如权利要求1至8任一项所述的氢甲酰化催化剂在烯烃或炔烃的氢甲酰化反应中的应用。
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