CN106140303B - One kind is containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its preparation and application - Google Patents

One kind is containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its preparation and application Download PDF

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CN106140303B
CN106140303B CN201510158032.9A CN201510158032A CN106140303B CN 106140303 B CN106140303 B CN 106140303B CN 201510158032 A CN201510158032 A CN 201510158032A CN 106140303 B CN106140303 B CN 106140303B
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phosphine
catalyst
organophosphorus ligand
organic mixed
heterogeneous catalyst
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CN106140303A (en
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丁云杰
李存耀
严丽
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • 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
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    • Y02P20/50—Improvements relating to the production of bulk chemicals

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Abstract

The invention discloses a kind of hierarchical porous structures containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its preparation and in the just different application than in aldehyde production of interior olefin hydroformylation height; using one of metal Rh, Co or Ir, two kinds, three kinds as active component in the heterogeneous catalyst; using hierarchical porous structure containing the organic mixed polymers of phosphine as carrier, organic mixed polymers containing phosphine is copolymerized by the multiple tooth organophosphorus ligand containing alkylene and monodentate organophosphorus ligand.Such coordination bond type heterogeneous catalyst is suitable for fixed bed, slurry bed system, in the reactors such as bubbling bed and trickle bed.Heterogeneous catalyst provided by the invention has performance well in interior hydroformylation of olefin; internal olefin is first isomerized to end group alkene under the action of such catalyst; hydroformylation reaction occurs again and is selectively generating corresponding n-alkanal; therefore product aldehyde is just different than high; 15 can be higher than, Determination of Alkane Content is lower than 1% in obtained product.

Description

One kind is containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its preparation and application
Technical field
The invention belongs to heterogeneous catalysis and field of fine chemical, and in particular to a kind of organic mixed polymers-metal multiphase containing phosphine Catalyst and preparation method thereof is with it in the just different application than in aldehyde production of interior olefin hydroformylation height.
Background technique
Hydroformylation of olefin (Hydroformylation, also known as OXO-Synthesis) refers to transition-metal-carbonyl Alkene and synthesis gas (CO/H under complex-catalyzed2) generate higher than a raw material olefin carbon aldehyde reaction, be to realize earliest Industrial even phase complex catalysis process.The continuous development of hydroformylation of olefin mainly has benefited from petro chemical industry It pushes, petroleum cracking technique and Fischer-Tropsch synthesis technology generate a large amount of alkene, provide for hydroformylation reaction Cheap synthesis material makes its industrialization have material base；The product aldehyde of hydroformylation of olefin is very useful simultaneously Chemical intermediate, it can be used to synthesis of carboxylic acid and corresponding ester and fatty amine etc., most important purposes is that it can add hydrogen It is converted to alcohol, alcohol itself can be used as organic solvent, plasticizer and surfactant etc. and be widely used in field of fine chemical.
Patent CN1319580A describes a variety of bidentate phosphite ligands with larger space steric hindrance, these ligands with Rh and Co etc. is coordinated the hydroformylation reaction of the higher olefins of homogeneous catalyst, the selectivity with the just different ratio of higher aldehyde.But Homogeneous catalyst is not easily recycled and ligand synthesis is more difficult.
Patent CN1210514A reports the Rh complex compound catalyst of hydroformylation of olefin, and Rh complex compound is using more The organonitrogen compound of tooth makees ligand, containing the tertiary nitrogen group that at least one can be protonated in weak acid in ligand, but catalyst Equally face the problem of being not easily recycled.
In patent CN102911021A, Rh complex and biphenyl backbone or dinaphthalene skeleton biphosphine ligand and triphen are utilized The composite catalyst system of base phosphine or phosphite ester triphenylmethyl methacrylate monophosphorus ligand composition is catalyst, in linear alkene hydroformylation reaction Middle n-alkanal selectivity with higher, reduces the dosage of expensive biphosphine ligand, but catalyst system is still in this way Homogeneous, catalyst can not reuse.
Cooperate in patent CN1986055A also with bis-phosphite and triphenylphosphine and Rh, forms composite catalyzing body System, in the hydroformylation reaction of propylene, n-butanal and isobutylaldehyde molar ratio are greater than 20, significantly extend bisphosphite ligands Service life, hence it is evident that reduce the dosage of triaryl phosphine, but substantially or homogeneous reaction, equally face catalyst recycling benefit With difficult problem.
2001, Holger Klein et al. (Angew.Chem.Int.Ed.2001,40, No.18) synthesized NAPHOS Good choosing is achieved in end group alkene and internal olefin hydroformylation reaction after the homogeneous ligand of type, such ligand and Rh complexing Selecting property (the just different ratio of product aldehyde is very high).But substantially still homogeneous reaction, catalyst recycle difficult, high carbene to catalyst system Hydrocarbon includes that internal olefin hydroformylation reaction cost is very high.
The Billig et al. of UCC company (Union Carbide Corporation) has synthesized Biphephos ligand, and the ligand is in propylene hydrogen It is had excellent performance in formylation reaction, Arno Behr and Christian Vogl et al. utilizes the further system of Biphephos ligand Ground has studied hydroformylation reaction (the Journal of Molecular of catalysis internal olefin and end group alkene after the ligand and Rh cooperation Catalysis A:Chemical,2003,206,179-184；2005,232,41-44；2005,226,215-219), product aldehyde Stereoselectivity it is good, and Arno Behr and Christian Vogl also done in terms of two-phase olefin hydroformylation it is some Explore work.But always without fundamentally solving the problems, such as Immobilized homogenous catalyst, catalyst inactivation quickly, and does not have There is the recycling for realizing catalyst.
The hydroformylation of internal olefin is always the difficult point studied and hot spot, and chemists are being applied to internal olefin hydrogen first The homogeneous multidentate ligand synthesis aspect of acylation reaction has poured into a large amount of painstaking effort, but there is presently no specifically in internal olefin hydrogen The heterogeneous catalyst and technique of formylation reaction occur.
Summary of the invention
To solve the above-mentioned problems, the purpose of the present invention is to provide a kind of organic mixed polymers-metal heterogeneous catalysis containing phosphine Agent and its interior olefin hydroformylation height it is just different than aldehyde production in application.
The technical scheme is that：
A kind of organic mixed polymers-metal heterogeneous catalyst containing phosphine, with one of metal Rh, Co or Ir, two kinds, three kinds of works For active component, using organic mixed polymers containing phosphine as carrier, metal loading is 0.01~10wt% in catalyst, organic mixed containing phosphine Polymers is copolymerized by the multiple tooth organophosphorus ligand containing alkylene and the monodentate organophosphorus ligand containing alkylene, active metal For exposed p-shaped at multiple coordinate bond, the catalyst of formation is high just in the production of interior olefin hydroformylation in component and mixed copolymer carrier It is different more excellent than being showed in aldehyde technique.
The alkylene is preferably vinyl, and the multiple tooth organophosphorus ligand containing alkylene is containing vinyl Bidentate phosphites organophosphor ligand, the monodentate organophosphorus ligand containing alkylene are that the triphenylphosphine containing vinyl is matched Body.
Organic mixed copolymer carrier has hierarchical porous structure, and specific surface area is 100~3000m2/ g, simultaneously containing big Hole, mesoporous and micropore, 0.1~5.0cm of Kong Rongwei3/ g, pore-size distribution is in 0.2~50.0nm.
The heterogeneous catalyst is after mixing multiple tooth organophosphorus ligand and monodentate organophosphorus ligand, using solvent hot polymerization It is legal, cause the alkylene in organophosphorus ligand through radical initiator and polymerization reaction occurs, generation contains with hierarchical porous structure The organic mixed polymers of phosphine is stirred as carrier, the presoma of active component with carrier in organic solvent, and active component has with containing phosphine Machine mixes p-shaped exposed in copolymer carrier into multiple coordinate bond, after boiling off volatile solvent, obtains the heterogeneous catalysis of coordination bond type Agent.
The preparation method of heterogeneous catalyst is：
A) at 273~473K, inert gas atmosphere, in organic solvent, monodentate organophosphorus ligand is added and multiple tooth has Whether machine Phosphine ligands, addition crosslinking agent or not, add radical initiator, and after mixing, it is small to stir the mixture for 0.1~100 When, preferred mixing time range is 0.1~50 hour；
B) mixed solution made from step a) is transferred in synthesis autoclave, 273~473K, under inert gas atmosphere, Using solvent thermal polymerization method, 1~100 hour progress polymerization reaction is stood, obtains a kind of organic mixed polymers containing phosphine；
C) the mixed polymers for obtaining step b), vacuum abstraction solvent is at room temperature to get to hierarchical porous structure Organic mixed polymers containing exposed P, i.e., the carrier of the described heterogeneous catalyst；
D) at 273~473K, inert gas atmosphere, in the solvent containing active component presoma, step c) is added Obtained organic mixed copolymer carrier stirs 0.1~100 hour, preferably mixing time range 0.1~50 hour, and later, vacuum is taken out Except organic solvent, heterogeneous catalyst is obtained.
Organic solvent described in step a) is benzene, toluene, tetrahydrofuran, methanol, ethyl alcohol, dichloromethane or chloroform Middle one or more；The crosslinking agent is styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodo- One or more of tri- acetylenylbenzene of methane, paraformaldehyde or 1,3,5-；The radical initiator is peroxidating Cyclohexanone, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile or azobisisoheptonitrile it is one or two kinds of with On.
The molar ratio of monodentate organophosphorus ligand and multiple tooth organophosphorus ligand described in step a) is 0.01:1~100:1, In the case where crosslinking agent addition, the molar ratio of monodentate organophosphorus ligand and crosslinking agent is 0.01:1~10:1, monodentate organic phosphine The molar ratio of ligand and radical initiator is 300:1~10:1, before aggregating into organic mixed polymers, monodentate organophosphorus ligand is having Concentration range in solvent is 0.01-1000g/L.
Solvent described in step d) is water, benzene, toluene, tetrahydrofuran, methanol, ethyl alcohol, dichloromethane or chloroform Middle one or more, the active component are one of Rh, Co, Ir, two or three, and wherein the presoma of Rh is Rh(CH3COO)2、RhH(CO)(PPh3)3、Rh(CO)2(acac)、RhCl3；The presoma of Co is Co (CH3COO)2、Co(CO)2 (acac)、Co(acac)2、CoCl2；The presoma of Ir is Ir (CO)3(acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4.It urges Metal loading range is 0.01~10wt% in agent.
The catalyst for the organic mixed copolymer carrier supported active metals containing P prepared is used for internal olefin hydroformylation reaction In, catalytic activity is high, and product selectivity is good, can be used for fixed bed, slurry bed system, in bubbling bed and drip bed reaction technique.Reaction 323~573K of temperature, 0.1~10.0MPa of reaction pressure, 100~20000h of gas space velocity-1, 0.01~10.0h of liquid hourly space velocity (LHSV)-1.The main component of reaction raw materials synthesis gas is H2And CO, (H2+ CO) volume content be 20~100%, H2/ CO volume ratio is 0.5 ~5.0.Feed internal olefins are mainly derived from the C of the processes such as petroleum catalytic pyrolysis, F- T synthesis, oil refinery dry gas recycling4~C20's Alkene, double bond can be located on 2~No. 10 positions of carbochain.This technique and method adaptability to raw material are strong, can be C4~C20It is interior One of alkene (including end group alkene) or several, material purity are 20~100%, and product is predominantly one more than raw material olefin The n-alkanal of a carbon atom.
Reaction principle of the invention：
The present invention will on the aromatic ring of typical biphosphine ligand such as Biphephos introduce vinyl (Vinyl) group, i.e., one Multiple tooth organophosphorus ligand (Vinyl Biphephos) of the kind containing vinyl is used as polymerized monomer, and solvent is utilized in autoclave Thermal polymerization is copolymerized to be formed with high surface area and multistage pore canal with monodentate organophosphorus ligand such as three (4- vinyl benzene) base phosphine Organic mixed polymers of structure can be used as catalysis due to having a large amount of Ps of the exposure containing lone pair electrons in organic mixed polymer backbone Agent carrier and active transition metal ion unoccupied orbital form multiple coordinate bond, and then form catalytic active site.In the catalyst, Organic phosphine mixes polymers and is provided simultaneously with the dual function of carrier and ligand, and active metal component high dispersive is and highly concentrated in the carrier Exposed p-shaped is spent into multiple coordinate bond.Active metal component is mixed in copolymer carrier with monatomic form high dispersive in organic phosphine, significantly Improve the utilization efficiency of metal.And active component not easily runs off, catalyst life is long, and the multiple tooth Phosphine ligands in skeleton have aobvious The stereoeffect of work, the catalyst prepared are remarkably improved the stereoselectivity of product.
Contain P in the organic mixed copolymer carrier skeleton of catalyst provided by the present invention, organic mixed polymers has both ligand and load The dual function of body；Active metal component can be dispersed in this high surface area hierarchical porous structure in a manner of monatomic or ion In organic mixed copolymer carrier, metal utilization efficiency is substantially increased.Carrier organic phosphine mixes the monophosphorus ligand structure in polymer backbone Unit makes mixed polymers have higher P concentration, is easy to form double or multi-metal-P coordinate bond, the coordination with active metal component Key has stronger chemical bonding ability, so that active component not easily runs off.
Beneficial effects of the present invention are：
Contain multiple tooth and monodentate organophosphorus ligand structural unit in heterogeneous catalyst skeleton of the present invention, wherein monodentate Organophosphorus ligand makes on the surface of mixed polymers in the presence of higher exposed P, and multiple tooth Phosphine ligands then have significant stereoeffect, activity Exposed p-shaped on metallic atom or ion and mixed polymers is at multiple coordinate bond, and active component not easily runs off, the active group of catalyst It is divided into Rh, Co or Ir, such catalyst stereoselectivity with higher, mixing polymers has high-specific surface area hierarchical porous structure, Has the dual function of carrier and ligand, active metal component may mix copolymer carrier in organic phosphine with monatomic form high dispersive In duct or on surface, the utilization efficiency of metal component is improved.
Such coordination bond type heterogeneous catalyst is suitable for fixed bed, slurry bed system, the reaction process such as bubbling bed and trickle bed, sheet Invent provided by internal olefin hydroformylation production corresponding aldehyde technique and method, can be used fixed bed, slurry bed system, bubbling bed and The reaction process such as trickle bed, internal olefin are isomerized to end group alkene in hydroformylation reaction first, and then are selectively generating attached Value added higher n-alkanal can solve long-standing reactivity and choosing during internal olefin hydroformylation reaction heterogeneouss Selecting property is poor and metal component is lost the problems such as serious.
Heterogeneous catalyst provided by the invention has performance well in interior hydroformylation of olefin, and internal olefin is herein It is first isomerized to end group alkene under the action of class catalyst, then hydroformylation reaction occurs and is selectively generating corresponding positive structure Aldehyde, therefore product aldehyde is just different than high, can be higher than 15, Determination of Alkane Content is lower than 1% in obtained product, which stablizes Property it is good, catalyst and reactant, the separation of product are simple and efficiently.The production cost of n-alkanal is greatly reduced, is interior alkene Hydrocarbon hydroformylation reaction provides new industrialization technology.
Detailed description of the invention
In Fig. 1, A figure is the biphosphine ligand of typical alkylene functionalization, and B figure is Vinyl Biphephos structural representation Figure.
Fig. 2 is Vinyl Biphephos polymerization technique route schematic diagram.
Fig. 3 is the signal of typical the monodentate organophosphorus ligand and multiple tooth organophosphorus ligand and crosslinking agent used in polymerization Figure, wherein L1-L16 is monodentate organophosphorus ligand, and L17-L19 is multiple tooth organophosphorus ligand, and L20 and L21 are crosslinking agent.
Fig. 4 is Vinyl Biphephos ligand1H spectrum.
Fig. 5 is Vinyl Biphephos ligand13C spectrum.
Fig. 6 is Vinyl Biphephos ligand31P spectrum.
Fig. 7 is the high resolution mass spectrum of Vinyl Biphephos ligand.
Fig. 8 is N2The catalyst thermogravimetric curve that embodiment 1 synthesizes under atmosphere.
Specific embodiment
Following embodiments better illustrate the present invention, but do not limit invention which is intended to be protected.
Embodiment 1
At 298K and inert gas shielding atmosphere, 10.0 grams of Vinyl Biphephos monomers (attached drawing 1) are dissolved in In 100.0ml tetrahydrofuran solvent, while 2.5g co-monomer three (4- vinyl benzene) base phosphine (L1) is added, adds into above-mentioned solution Enter 1.0 grams of radical initiator azodiisobutyronitriles, stirs 2 hours.The solution being stirred is moved in autoclave, in 373K and It is polymerize for 24 hours under inert gas shielding atmosphere using solvent thermal polymerization method.Solution after above-mentioned polymerization is cooled to room temperature, room Warm condition vacuum takes solvent away to get to being copolymerized by Vinyl Biphephos and three (4- vinyl benzene) base phosphine organic monomers Organic phosphine mixes copolymer carrier.Fig. 2 is the schematic diagram of the organic mixed copolymer carrier polymerization technique route of Vinyl Biphephos.It weighs 3.13 milligrams of three rhodium carbonyls of acetylacetone,2,4-pentanedione are dissolved in 10.0ml tetrahydrofuran solvent, be added 1.0 grams by Vinyl Biphephos and Organic mixed copolymer carrier that three (4- vinyl benzene) base phosphines are copolymerized, by this mixture in 298K and inert gas shielding atmosphere Lower stirring 24 hours, then vacuum takes solvent away at room temperature, that is, obtains and be applied to the excellent of internal olefin hydroformylation reaction Good catalyst.
Embodiment 2
In example 2, in addition to weighing 10.0 grams of co-monomers three (4- vinyl benzene) base phosphine (L1), 2.5 grams of lists altogether are substituted Body three (4- vinyl benzene) base phosphine (L1), remaining catalyst synthesis processes are same as Example 1.
Embodiment 3
In embodiment 3,1.0 grams of free radicals initiations are substituted in addition to weighing 0.1 gram of radical initiator azodiisobutyronitrile Outside agent azodiisobutyronitrile, remaining catalyst synthesis processes is same as Example 1.
Embodiment 4
In example 4, other than substituting 100.0ml tetrahydrofuran solvent with 50.0ml tetrahydrofuran solvent, remaining Catalyst synthesis processes are same as Example 1.
Embodiment 5
In embodiment 5, other than substituting 100.0ml tetrahydrofuran solvent with 100.0ml dichloromethane solvent, remaining Catalyst synthesis processes are same as Example 1.
Embodiment 6
In embodiment 6, other than substituting 373K polymerization temperature with 393K polymerization temperature, remaining catalyst synthesis processes It is same as Example 1.
Embodiment 7
In embodiment 7, in addition to 12h polymerization time substitution for 24 hours other than polymerization time, remaining catalyst synthesis processes with Embodiment 1 is identical.
Embodiment 8
In embodiment 8, other than adding 10.0 grams of L20 as crosslinking agent, remaining catalyst synthesis processes and reality It is identical to apply example 1.
Embodiment 9
In embodiment 9, other than adding 1.0 grams of styrene as crosslinking agent, remaining catalyst synthesis processes with Embodiment 1 is identical.
Embodiment 10
In embodiment 10, weighs 14.05 milligrams of acetylacetone,2,4-pentanedione dicarbapentaborane cobalt substitution three rhodium carbonyls of acetylacetone,2,4-pentanedione and be dissolved in Outside 10.0ml tetrahydrofuran solvent, remaining catalyst synthesis processes is same as Example 1.
Embodiment 11
In embodiment 11, weighs 2.05 milligrams of acetylacetone,2,4-pentanediones, three carbonyl iridium substitution three rhodium carbonyl of acetylacetone,2,4-pentanedione and be dissolved in Outside 10.0ml tetrahydrofuran solvent, remaining catalyst synthesis processes is same as Example 1.
Embodiment 12
By in the catalyst 0.5g fixed bed reactors of above-mentioned preparation, both ends are packed into quartz sand.Micro feed pump is pumped into 2- Octene, flow 0.1ml/min, mass flowmenter control synthesis gas (H2:CO=1:1) air speed 1000h-1, in 373K, 1MPa Under the conditions of carry out hydroformylation reaction.Reaction is collected through the cooling collecting tank of ice bath.Obtained liquid product, which uses, is furnished with HP-5 The HP-7890N gas chromatographic analysis of capillary column and fid detector, makees internal standard using normal propyl alcohol.The tail gas that collecting tank comes out is adopted On-line analysis is carried out with the HP-7890N gas-chromatography equipped with Porapak-QS column and TCD detector.Reaction result is listed in table 1.
Embodiment 13
Catalyst 0.5g prepared by embodiment 1 is encased in the paste state bed reactor of 50ml capacity, and be added 30ml oneself Aldehyde is slurry liquid, is passed through reaction mixture gas (H2:CO:C3H6=1:1:1), in 393K, 1.0MPa, reaction mixture gas air speed 2000h-1Hydroformylation reaction is carried out under the conditions of being 750 revs/min with stirring rate.Reaction is gone through one equipped with 60ml cooling The collecting tank of ionized water, which absorbs, to be collected, and is all dissolved in the water of collecting tank with the reaction product and slurry liquid of tail gas entrainment.It is other With embodiment 12, data are listed in table 1.
Different catalysts described in embodiment 12 are prepared according to the step of embodiment 1-11, the catalysis of embodiment 13 Agent is prepared according to the step of embodiment 1.
The specific surface area of catalyst and 2- octene response data synthesized in 1 embodiment 1-13 of table
* it is 0.1ml/min, synthesis gas (CO that experiment condition, which is 100 DEG C, 1MPa, 2- octene flows,:H2=1:1) air speed 1000h-1, TOF calculate when think that all metals are active sites.* indicates that reaction temperature is 230 DEG C.The work of embodiment 10 Property group be divided into Co, the active component of embodiment 11 is Ir.The data of embodiment 13 are the slurry reactor data of propylene.

Claims (9)

1. a kind of organic mixed polymers-metal heterogeneous catalyst containing phosphine, it is characterised in that：In the heterogeneous catalyst with metal Rh, One of Co or Ir, two kinds, three kinds be used as active component, using organic mixed polymers containing phosphine as carrier, contain the organic mixed polymers of phosphine by Multiple tooth organophosphorus ligand containing alkylene and the monodentate organophosphorus ligand containing alkylene are copolymerized, and metal is carried on a shoulder pole in catalyst Load ranges are 0.01~10wt%；The multiple tooth organophosphorus ligand containing alkylene is：
The monodentate organophosphorus ligand containing alkylene is：
One of.
2. catalyst described in accordance with the claim 1, it is characterised in that：Organic mixed copolymer carrier has multi-stage porous knot Structure, specific surface area are 100~3000m2/ g contains macropore, mesoporous and micropore, 0.1~5.0cm of Kong Rongwei simultaneously3/ g, aperture point Cloth is in 0.2~50.0nm.
3. catalyst described in accordance with the claim 1, it is characterised in that：The heterogeneous catalyst is by multiple tooth organophosphorus ligand After the mixing of monodentate organophosphorus ligand, using solvent thermal polymerization method, cause the alkene in organophosphorus ligand through radical initiator Polymerization reaction occurs for base, and generating has hierarchical porous structure containing the organic mixed polymers of phosphine as carrier, the presoma and load of active component Body stirs in organic solvent, and active component, at multiple coordinate bond, is boiled off and waved with containing p-shaped exposed in the organic mixed copolymer carrier of phosphine After hair property solvent, the heterogeneous catalyst of coordination bond type is obtained.
4. a kind of preparation method of any catalyst of claim 1-3, it is characterised in that：
A) at 273~473K, inert gas atmosphere, in organic solvent, monodentate organophosphorus ligand and multiple tooth organic phosphine is added Whether ligand, addition crosslinking agent or not, add radical initiator, after mixing, stir the mixture for 0.1~100 hour；
B) mixed solution made from step a) is transferred in synthesis autoclave, 273~473K, under inert gas atmosphere, is used Solvent thermal polymerization method stands 1~100 hour progress polymerization reaction, obtains a kind of organic mixed polymers containing phosphine；
C) the mixed polymers for obtaining step b), vacuum abstraction solvent is at room temperature to get to having hierarchical porous structure containing There are organic mixed polymers of exposed P, i.e., the carrier of the described heterogeneous catalyst；
D) at 273~473K, inert gas atmosphere, in the solvent containing active component presoma, step c) is added and obtains Organic mixed copolymer carrier, stir 0.1~100 hour, later, vacuum extract organic solvent, obtain heterogeneous catalyst.
5. preparation method according to claim 4, it is characterised in that：Organic solvent described in step a) be benzene, toluene, It is tetrahydrofuran, methanol, ethyl alcohol, one or more kinds of in dichloromethane or chloroform；The crosslinking agent is styrene, second One of alkene, propylene, divinylbenzene, dimethoxymethane, tri- acetylenylbenzene of diiodomethane, paraformaldehyde or 1,3,5- or It is two or more；The radical initiator is cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azo The one or more of bis-isobutyronitrile or azobisisoheptonitrile.
6. preparation method according to claim 4, it is characterised in that：Monodentate organophosphorus ligand described in step a) and more The molar ratio of tooth organophosphorus ligand is 0.01:1~100:1, in the case where crosslinking agent addition, monodentate organophosphorus ligand and crosslinking The molar ratio of agent is 0.01:1~10:1, the molar ratio of monodentate organophosphorus ligand and radical initiator is 300:1~10:1, gather Before synthesizing organic mixed polymers, the concentration range of monodentate organophosphorus ligand in organic solvent is 0.01-1000g/L.
7. preparation method according to claim 4, it is characterised in that：Solvent described in step d) be water, benzene, toluene, It is tetrahydrofuran, methanol, ethyl alcohol, one or more kinds of in dichloromethane or chloroform, the active component be Rh, Co, One or more of Ir, wherein the presoma of Rh is Rh (CH3COO)2、RhH(CO)(PPh3)3、Rh(CO)2(acac)、 RhCl3；The presoma of Co is Co (CH3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2；The presoma of Ir is Ir (CO)3 (acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4, metal loading range is 0.01~10wt% in catalyst.
8. preparation method according to claim 4, it is characterised in that：Step a) and d) in mixing time range be 0.1 ~50 hours.
9. just different than in aldehyde production in interior olefin hydroformylation height according to any heterogeneous catalyst of claim 1-3 Using, it is characterised in that：The hydroformylation reaction of internal olefin, reaction temperature be 323~573K, reaction pressure be 0.1~ 10.0MPa, gas space velocity are 100~20000h-1, liquid hourly space velocity (LHSV) is 0.01~10.0h-1, main group of reaction raw materials synthesis gas It is divided into H2And CO, (H2+ CO) volume content be 20~100%, H2/ CO volume ratio is 0.5~5.0, feed internal olefins C4~C20 Alkene, double bond is located on 2~No. 10 positions of carbochain, and internal olefin feed purity is 20~100%, and product predominantly compares raw material The n-alkanal of the more carbon atoms of alkene.
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