CN106140303A - One contains the organic mixed polymers-metal heterogeneous catalyst of phosphine and preparation thereof and application - Google Patents

One contains the organic mixed polymers-metal heterogeneous catalyst of phosphine and preparation thereof and application Download PDF

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CN106140303A
CN106140303A CN201510158032.9A CN201510158032A CN106140303A CN 106140303 A CN106140303 A CN 106140303A CN 201510158032 A CN201510158032 A CN 201510158032A CN 106140303 A CN106140303 A CN 106140303A
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catalyst
phosphine
organophosphorus ligand
mixed polymers
organic mixed
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CN106140303B (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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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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

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Abstract

The invention discloses a kind of hierarchical porous structure and contain the organic mixed polymers-metal heterogeneous catalyst of phosphine and preparation thereof and the application in internal olefin hydroformylation system the most different high ratio aldehyde produces; in described heterogeneous catalyst using the one in metal Rh, Co or Ir, two kinds, three kinds as active component; using hierarchical porous structure containing the organic mixed polymers of phosphine as carrier, form by the multiple tooth organophosphorus ligand containing alkylene and monodentate organophosphorus ligand copolymerization containing the organic mixed polymers of phosphine.This type of coordination of bonding heterogeneous catalyst is applicable to fixed bed, and slurry bed system, in the reactor such as bubbling bed and trickle bed.The heterogeneous catalyst that the present invention provides has well performance in internal olefin hydroformylation reaction; internal olefin is first isomerized to end group alkene under the effect of this type of catalyst; hydroformylation reaction is occurred to be selectively generating corresponding n-alkanal again; therefore the most different ratio of product aldehyde is high; can be higher than 15, in the product obtained, Determination of Alkane Content is less than 1%.

Description

One contains the organic mixed polymers-metal heterogeneous catalyst of phosphine and preparation thereof and application
Technical field
The invention belongs to heterogeneous catalysis and field of fine chemical, be specifically related to a kind of containing the organic mixed polymers of phosphine- Metal heterogeneous catalyst and preparation method thereof and its internal olefin hydroformylation height the most different ratio aldehyde produce in Application.
Background technology
Hydroformylation of olefin (Hydroformylation, also known as OXO-Synthesis) refers to transition Alkene under metal carbonyl complex catalysis and synthesis gas (CO/H2) generate than raw material olefin a high carbon The reaction of aldehyde, is to realize industrial even phase complex catalysis process the earliest.Hydroformylation of olefin Development mainly have benefited from the promotion of petro chemical industry, petroleum cracking technique and Fischer-Tropsch synthesis technique produces substantial amounts of alkene, provides cheap for hydroformylation reaction Synthesis material so that it is industrialization has possessed material base；The product aldehyde of hydroformylation of olefin simultaneously Being very useful 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 be hydroconverted into alcohol, and alcohol itself can be as organic solvent, plasticizer and table Face activating agent etc. is widely used in field of fine chemical.
Patent CN1319580A describes the multiple bidentate phosphite ligands with larger space steric hindrance, These parts are coordinated the hydroformylation reaction of the higher olefins of homogeneous catalyst with Rh and Co etc., have relatively The selectivity of the most different ratio of high aldehyde.But homogeneous catalyst is not easily recycled and part synthesis more difficulty.
Patent CN1210514A reports the Rh complex compound catalyst of hydroformylation of olefin, Rh complexation Thing is to use multiple tooth organonitrogen compound to make part, can be by matter in weak acid containing at least one in part The tertiary nitrogen group of sonization, but catalyst faces the problem being not easily recycled equally.
In patent CN102911021A, utilize Rh coordination compound and biphenyl backbone or dinaphthalene skeleton biphosphine ligand, And the composite catalyst system of triphenylphosphine or phosphite ester triphenylmethyl methacrylate monophosphorus ligand composition is catalyst, In linear alkene hydroformylation reaction, n-alkanal has higher selectivity, which decreases price and holds high The consumption of expensive biphosphine ligand, but catalyst system and catalyzing or homogeneous, catalyst cannot reuse.
Coordinating with Rh also with bis-phosphite and triphenylphosphine in patent CN1986055A, composition is multiple Closing catalyst system and catalyzing, in the hydroformylation reaction of propylene, hutanal and isobutylaldehyde mol ratio are more than 20, Significantly extend the service life of bisphosphite ligands, hence it is evident that reduce the consumption of triaryl phosphine, but Substantially still, homogeneous reaction, faces the problem that catalyst recycles difficulty equally.
Calendar year 2001, Holger Klein et al. (Angew.Chem.Int.Ed.2001,40, No.18) Synthesize the homogeneous part of NAPHOS type, at end group alkene and internal olefin hydrogen after such part and Rh complexation Formylation reaction achieves good selectivity (the most different ratio of product aldehyde is the highest).But catalyst system and catalyzing Substantially still, homogeneous reaction, catalyst reclaims difficulty, and higher olefins includes that internal olefin hydroformylation is anti- Answer cost the highest.
Billig of UCC company (Union Carbide Corporation) et al. has synthesized Biphephos part, and this is joined Body is excellent performance in propene hydroformylation reaction, and Arno Behr and Christian Vogl et al. utilize Biphephos part the most systematically have studied and is catalyzed internal olefin and end group after this part coordinates with Rh The hydroformylation reaction of alkene (Journal of Molecular Catalysis A:Chemical, 2003, 206,179-184；2005,232,41-44；2005,226,215 219), the solid of product aldehyde Selectivity is good, and Arno Behr and Christian Vogl also does in terms of biphase olefin hydroformylation Some explore work.But the problem the most fundamentally solving Immobilized homogenous catalyst, Catalysqt deactivation quickly, and is not carried out the recycling of catalyst.
The difficult point of the hydroformylation of internal olefin always research and focus, chemists are being applied to The homogeneous multidentate ligand synthesis aspect of internal olefin hydroformylation reaction has poured into a large amount of painstaking effort, but at present The most it is not specifically designed for heterogeneous catalyst and technique in internal olefin hydroformylation reaction to occur.
Summary of the invention
In order to solve the problems referred to above, it is an object of the invention to provide a kind of organic mixed polymers-metal Han phosphine Heterogeneous catalyst and internal olefin hydroformylation system high the most different produce than aldehyde in application.
The technical scheme is that
A kind of organic mixed polymers-metal heterogeneous catalyst Han phosphine, with the one in metal Rh, Co or Ir, two Kind, three kinds as active component, with organic mixed polymers containing phosphine as carrier, metal loading in catalyst It is 0.01～10wt%, containing the organic mixed polymers of phosphine by the multiple tooth organophosphorus ligand containing alkylene with containing alkene The monodentate organophosphorus ligand copolymerization of alkyl forms, the p-shaped that active metal component is exposed with mixed copolymer carrier Becoming multiple coordinate bond, it is the most different than table in aldehyde technique that the catalyst of formation produces height in internal olefin hydroformylation Existing excellent.
Described alkylene is preferably vinyl, and the described multiple tooth organophosphorus ligand containing alkylene is Bidentate phosphites organophosphor ligand containing vinyl, the described monodentate organophosphite ligand containing alkylene Body is the triphenylphosphine ligand containing vinyl.
Described organic mixed copolymer carrier has hierarchical porous structure, and specific surface area is 100～3000m2/ g, with Shi Hanyou macropore, mesopore and micropore, pore volume is 0.1～5.0cm3/ g, pore-size distribution is 0.2～50.0nm.
Described heterogeneous catalyst is by after multiple tooth organophosphorus ligand and the mixing of monodentate organophosphorus ligand, adopts Using solvent thermal polymerization method, the alkylene in radical initiator causes organophosphorus ligand occurs polymerization anti- Should, generate and there is hierarchical porous structure containing the organic mixed polymers of phosphine as carrier, the presoma of active component with Carrier stirs in organic solvent, and active component becomes many with containing p-shaped exposed in the organic mixed copolymer carrier of phosphine Weight coordinate bond, after boiling off volatile solvent, obtains being coordinated the heterogeneous catalyst of of bonding.
The preparation method of heterogeneous catalyst is:
A) 273～473K, under inert gas atmosphere, in organic solvent, monodentate organophosphite ligand is added Body and multiple tooth organophosphorus ligand, interpolation or without cross-linking agent, add radical initiator, mixing After, stirring the mixture for 0.1～100 hour, preferred mixing time scope is 0.1～50 hour；
B) it is transferred to mixed solution prepared for step a) synthesize in autoclave, 273～473K, indifferent gas Under bromhidrosis atmosphere, use solvent thermal polymerization method, stand and carry out polyreaction in 1～100 hour, obtain one and contain The organic mixed polymers of phosphine；
C) the mixed polymers obtained by step b), vacuum extracts solvent at ambient temperature, is i.e. had The organic mixed polymers containing exposed P of hierarchical porous structure, the carrier of the most described heterogeneous catalyst；
D) 273～473K, under inert gas atmosphere, in the solvent containing active component presoma, Add the organic mixed copolymer carrier that step c) obtains, stir 0.1～100 hour, preferably mixing time scope 0.1～50 hour, afterwards, vacuum extracted organic solvent, obtains heterogeneous catalyst.
Organic solvent described in step a) is benzene, toluene, oxolane, methanol, ethanol, dichloro In methane or chloroform one or more；Described cross-linking agent be styrene, ethylene, propylene, In divinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3,5-tri-acetylenylbenzene One or more；Described radical initiator is cyclohexanone peroxide, diphenyl peroxide first One or more of acyl, tert-butyl hydroperoxide, azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The mol ratio of the monodentate organophosphorus ligand described in step a) and multiple tooth organophosphorus ligand is 0.01:1～100:1, in the case of cross-linking agent adds, monodentate organophosphorus ligand and cross-linking agent mole Ratio is 0.01:1～10:1, and monodentate organophosphorus ligand with the mol ratio of radical initiator is 300:1～10:1, before aggregating into organic mixed polymers, monodentate organophosphorus ligand concentration in organic solvent Scope is 0.01-1000g/L.
Solvent described in step d) is water, benzene, toluene, oxolane, methanol, ethanol, dichloro In methane or chloroform one or more, described active component is in Rh, Co, Ir Kind, two or three, 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.In catalyst, metal loading scope is 0.01～10wt%.
The catalyst containing the organic mixed copolymer carrier supported active metals of P prepared is for internal olefin hydrogen first In acylation reaction, catalysis activity is high, and product selectivity is good, can be used for fixed bed, slurry bed system, bubbling In bed and trickle bed reaction process.Reaction temperature 323～573K, reaction pressure 0.1～10.0MPa, gas Air speed 100～20000h-1, liquid hourly space velocity (LHSV) 0.01～10.0h-1.The key component of reaction raw materials synthesis gas is H2And CO, (H2+ CO) volume content is 20～100%, H2/ CO volume ratio is 0.5～5.0.Feed internal olefins It is mainly derived from the C of the processes such as oil catalytic pyrolysis, F-T synthesis, oil refinery dry gas recovery4～C20Alkene, Double bond may be located on 2～No. 10 positions of carbochain.This technique and method adaptability to raw material are strong, Ke Yiwei C4～C20One (including end group alkene) or several in internal olefin, material purity is 20～100%, product master It to be the n-alkanal of many carbon atoms than raw material olefin.
The reaction principle of the present invention:
The present invention will introduce vinyl (Vinyl) on the aromatic ring of typical biphosphine ligand such as Biphephos Group, a kind of multiple tooth organophosphorus ligand (Vinyl Biphephos) containing vinyl is as polymerization Monomer, utilizes solvent thermal polymerization method in autoclave, with monodentate organophosphorus ligand such as three (4-vinyl Benzene) base phosphine copolymerization is formed has the organic mixed polymers of high surface and multi-stage artery structure, owing to this is organic Mixed polymer backbone has a large amount of P exposing and containing lone pair electrons, can be as catalyst carrier and activity mistake Cross metal ion unoccupied orbital and form multiple coordinate bond, and then form catalytic active site.In this catalyst, Organic phosphine mixes polymers and is provided simultaneously with the dual-use function of carrier and part, and active metal component high dispersive is in this In carrier, p-shaped exposed with high concentration becomes multiple coordinate bond.Active metal component is with monatomic form high score Dissipate in organic phosphine mixes copolymer carrier, substantially increase the utilization ratio of metal.And active component is difficult to Running off, catalyst life is long, and the multiple tooth Phosphine ligands in skeleton has significant stereoeffect, prepares The catalyst come is remarkably improved the stereo selectivity of product.
Containing P in the organic mixed copolymer carrier skeleton of catalyst provided by the present invention, organic mixed polymers has concurrently Part and the dual-use function of carrier；Active metal component can be dispersed in the way of monatomic or ion In the organic mixed copolymer carrier of this high surface area hierarchical porous structure, substantially increase metal utilization ratio. Carrier organic phosphine mixes the monophosphorus ligand construction unit in polymer backbone makes mixed polymers have higher P concentration, Easy and active metal component forms double or multi-metal-P coordinate bond, and this coordinate bond has stronger Chemical bonding ability so that active component not easily runs off.
The invention have the benefit that
Containing multiple tooth and monodentate organophosphorus ligand structure list in heterogeneous catalyst skeleton of the present invention Unit, wherein monodentate organophosphorus ligand makes to there is higher exposed P, multiple tooth Phosphine ligands on the surface of mixed polymers Then there is significant stereoeffect, active metal atom or ion and become many with the exposed p-shaped on mixed polymers Weight coordinate bond, active component not easily runs off, and the active component of catalyst is Rh, Co or Ir, and this type of is urged Agent has higher stereo selectivity, and mixed polymers has high-specific surface area hierarchical porous structure, possesses carrier With the dual-use function of part, active metal component may be mixed poly-in organic phosphine with monatomic form high dispersive In thing carrier duct or on surface, improve the utilization ratio of metal component.
This type of coordination of bonding heterogeneous catalyst is applicable to fixed bed, slurry bed system, bubbling bed and trickle bed etc. Reaction process, internal olefin hydroformylation provided by the present invention produces technique and the method for corresponding aldehyde, can Using fixed bed, slurry bed system, the reaction process such as bubbling bed and trickle bed, internal olefin is anti-in hydroformylation Should first be isomerized to end group alkene, and then be selectively generating the n-alkanal that added value is higher, permissible Solve long-standing reactivity and poor selectivity during internal olefin hydroformylation reaction heterogenize, And metal component runs off the problem such as serious.
The heterogeneous catalyst that the present invention provides has well performance in internal olefin hydroformylation reaction, Internal olefin is first isomerized to end group alkene under the effect of this type of catalyst, then hydroformylation reaction occurs Being selectively generating corresponding n-alkanal, therefore the most different ratio of product aldehyde is high, can obtain higher than 15 In product, Determination of Alkane Content is less than 1%, this heterogeneous catalyst good stability, catalyst and reactant, product Separation simple and also efficiently.Greatly reduce the production cost of n-alkanal, for internal olefin hydroformylation Reaction provides new industrialization technology.
Accompanying drawing explanation
In Fig. 1, A figure is the biphosphine ligand of typical alkylene functionalization, and B figure is Vinyl Biphephos Structural representation.
Fig. 2 is Vinyl Biphephos polymerization technique route schematic diagram.
Fig. 3 is the typical monodentate organophosphorus ligand and multiple tooth organophosphorus ligand and crosslinking used in polymerization The schematic diagram of agent, wherein, L1-L16 is monodentate organophosphorus ligand, and L17-L19 is monodentate organophosphite ligand Body, L20 and L21 is cross-linking agent.
Fig. 4 is Vinyl Biphephos part1H composes.
Fig. 5 is Vinyl Biphephos part13C composes.
Fig. 6 is Vinyl Biphephos part31P composes.
Fig. 7 is the high resolution mass spectrum of Vinyl Biphephos part.
Fig. 8 is N2The catalyst thermogravimetric curve of embodiment 1 synthesis under atmosphere.
Detailed description of the invention
The present invention is better illustrated by following embodiment, but is not intended to the claimed model of the present invention Enclose.
Embodiment 1
Under 298K and inert gas shielding atmosphere, by (attached for 10.0 grams of Vinyl Biphephos monomers Fig. 1) it is dissolved in 100.0ml tetrahydrofuran solvent, is simultaneously introduced 2.5g co-monomer three (4-vinyl benzene) Base phosphine (L1), adds 1.0 grams of radical initiator azodiisobutyronitriles in above-mentioned solution, stirs 2 Hour.The solution being stirred is moved in autoclave, utilizes under 373K and inert gas shielding atmosphere Solvent thermal polymerization method carries out being polymerized 24h.Solution after above-mentioned polymerization is cooled to room temperature, room temperature condition Vacuum takes solvent away, i.e. obtains by Vinyl Biphephos and three (4-vinyl benzene) the organic list of base phosphine The organic phosphine of body copolymerization mixes copolymer carrier.Fig. 2 is that the organic mixed copolymer carrier of Vinyl Biphephos gathers Close the schematic diagram of technology path.Weigh 3.13 milligrams of acetylacetone,2,4-pentanedione three rhodium carbonyls and be dissolved in 10.0ml tetrahydrochysene In THF solvent, add 1.0 grams by Vinyl Biphephos and three (4-vinyl benzene) base phosphine copolymerization The organic mixed copolymer carrier obtained, stirs 24 under 298K and inert gas shielding atmosphere by this mixture Hour, vacuum takes solvent away the most at ambient temperature, i.e. obtains that to be applied to internal olefin hydroformylation anti- The excellent catalyst answered.
Embodiment 2
In example 2, except weighing 10.0 grams of co-monomers three (4-vinyl benzene) base phosphine (L1), Substitute 2.5 grams of co-monomers three (4-vinyl benzene) base phosphine (L1), remaining catalyst synthesis processes and reality Execute example 1 identical.
Embodiment 3
In embodiment 3, except weighing 0.1 gram of radical initiator azodiisobutyronitrile replacement 1.0 Outside gram radical initiator azodiisobutyronitrile, remaining catalyst synthesis processes is same as in Example 1.
Embodiment 4
In example 4, molten except substituting 100.0ml oxolane with 50.0ml tetrahydrofuran solvent Outside agent, remaining catalyst synthesis processes is same as in Example 1.
Embodiment 5
In embodiment 5, except substituting 100.0ml oxolane with 100.0ml dichloromethane solvent Outside solvent, remaining catalyst synthesis processes is same as in Example 1.
Embodiment 6
In embodiment 6, in addition to substituting 373K polymerization temperature with 393K polymerization temperature, remaining Catalyst synthesis processes is same as in Example 1.
Embodiment 7
In embodiment 7, in addition to substituting 24h polymerization time with 12h polymerization time, remaining is urged Agent building-up process is same as in Example 1.
Embodiment 8
In embodiment 8, except add 10.0 grams of L20 as cross-linking agent in addition to, remaining catalyst Building-up process is same as in Example 1.
Embodiment 9
In embodiment 9, except add 1.0 grams of styrene as cross-linking agent in addition to, remaining catalysis Agent building-up process is same as in Example 1.
Embodiment 10
In embodiment 10, weigh 14.05 milligrams of acetylacetone,2,4-pentanedione dicarbapentaborane cobalts and substitute acetylacetone,2,4-pentanedione three carbonyl Base rhodium is dissolved in outside 10.0ml tetrahydrofuran solvent, and remaining catalyst synthesis processes is same as in Example 1.
Embodiment 11
In embodiment 11, weigh 2.05 milligrams of acetylacetone,2,4-pentanedione three carbonyl iridium and substitute acetylacetone,2,4-pentanedione three carbonyl Base rhodium is dissolved in outside 10.0ml tetrahydrofuran solvent, and remaining catalyst synthesis processes is same as in Example 1.
Embodiment 12
By in the catalyst 0.5g fixed bed reactors of above-mentioned preparation, two ends load quartz sand.Trace enters Material pump pumps into 2-octene, and its flow is 0.1ml/min, and mass flowmenter controls synthesis gas (H2: CO=1:1) Air speed 1000h-1, under the conditions of 373K, 1MPa, carry out hydroformylation reaction.React through ice bath cooling Collecting tank is collected.Obtained fluid product uses is furnished with HP-5 capillary column and fid detector HP-7890N gas chromatographic analysis, uses normal propyl alcohol to make internal standard.Collecting tank tail gas out uses to be furnished with The HP-7890N gas chromatogram of Porapak-QS post and TCD detector carries out on-line analysis.Reaction result It is listed in table 1.
Embodiment 13
Catalyst 0.5g embodiment 1 prepared is encased in the paste state bed reactor of 50ml capacity, And to add 30ml hexanal be slurry liquid, it is passed through reaction mixture gas (H2:CO:C3H6=1:1:1), at 393K, 1.0MPa, reaction mixture gas air speed 2000h-1Hydrogen is carried out under the conditions of being 750 revs/min with stir speed (S.S.) Formylation reaction.React to absorb through a collecting tank equipped with the deionized water of 60ml cooling and collect, with Product and slurry liquid that tail gas is carried secretly are all dissolved in the water of collecting tank.The other the same as in Example 12, Data are listed in table 1.
Different catalysts described in embodiment 12 prepares according to the step of embodiment 1-11, real The catalyst executing example 13 prepares according to the step of embodiment 1.
The specific surface area of catalyst synthesized in table 1 embodiment 1-13 and 2-octene response data
* experiment condition is 100 DEG C, and 1MPa, 2-octene flow is 0.1ml/min, synthesis gas (CO:H2=1:1) air speed 1000h-1, when TOF calculates Think that all of metal is all avtive spot.* represents that reaction temperature is 230 DEG C.The active component of embodiment 10 is Co, embodiment 11 Active component is Ir.The data of embodiment 13 are the slurry reactor data of propylene.

Claims (10)

1. organic mixed polymers-metal heterogeneous catalyst Han phosphine, it is characterised in that: described heterogeneous catalysis In agent using the one in metal Rh, Co or Ir, two kinds, three kinds as active component, to have containing phosphine It is carrier that machine mixes polymers, and organic mixed polymers containing phosphine by the multiple tooth organophosphorus ligand containing alkylene and contains The monodentate organophosphorus ligand copolymerization of alkylene forms, and in catalyst, metal loading scope is 0.01～10wt%.
2. according to the catalyst described in claim 1, it is characterised in that: described alkylene is vinyl Functional group.
3. according to the catalyst described in claim 1, it is characterised in that: described is many containing alkylene Tooth organophosphorus ligand is the bidentate phosphites organophosphor ligand containing vinyl, described containing alkene The monodentate organophosphorus ligand of base is the triphenylphosphine ligand containing vinyl.
4. according to the catalyst described in claim 1, it is characterised in that: described organic mixed polymers carries Body has hierarchical porous structure, and specific surface area is 100～3000m2/ g, contains macropore, mesopore and micro-simultaneously Hole, pore volume is 0.1～5.0cm3/ g, pore-size distribution is 0.2～50.0nm.
5. according to the catalyst described in claim 1, it is characterised in that: described heterogeneous catalyst is After multiple tooth organophosphorus ligand and monodentate organophosphorus ligand being mixed, use solvent thermal polymerization method, through freedom Base initiator causes the alkylene generation polyreaction in organophosphorus ligand, generates and has hierarchical porous structure Organic mixed polymers containing phosphine stirs with carrier in organic solvent as carrier, the presoma of active component, Active component becomes multiple coordinate bond with containing p-shaped exposed in the organic mixed copolymer carrier of phosphine, boils off volatility After solvent, obtain being coordinated the heterogeneous catalyst of of bonding.
6. the preparation method of the arbitrary described catalyst of claim 1-5, it is characterised in that:
A) 273～473K, under inert gas atmosphere, in organic solvent, monodentate organophosphite ligand is added Body and multiple tooth organophosphorus ligand, interpolation or without cross-linking agent, add radical initiator, mixing After, stirring the mixture for 0.1～100 hour, preferred mixing time scope is 0.1～50 hour；
B) it is transferred to mixed solution prepared for step a) synthesize in autoclave, 273～473K, indifferent gas Under bromhidrosis atmosphere, use solvent thermal polymerization method, stand and carry out polyreaction in 1～100 hour, obtain one Containing the organic mixed polymers of phosphine；
C) the mixed polymers obtained by step b), vacuum extracts solvent at ambient temperature, is i.e. had The organic mixed polymers containing exposed P of hierarchical porous structure, the carrier of the most described heterogeneous catalyst；
D) 273～473K, under inert gas atmosphere, in the solvent containing active component presoma, Add the organic mixed copolymer carrier that step c) obtains, stir 0.1～100 hour, preferably mixing time model Enclosing 0.1～50 hour, afterwards, vacuum extracts organic solvent, obtains heterogeneous catalyst.
7. according to the preparation method described in claim 6, it is characterised in that: having described in step a) Machine solvent is a kind of in benzene, toluene, oxolane, methanol, ethanol, dichloromethane or chloroform Or it is two or more；Described cross-linking agent is styrene, ethylene, propylene, divinylbenzene, dimethoxy One or more in methylmethane, diiodomethane, paraformaldehyde or 1,3,5-tri-acetylenylbenzene； Described radical initiator be cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, One or more of azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).
8. according to the preparation method described in claim 6, it is characterised in that: the list described in step a) The mol ratio of tooth organophosphorus ligand and multiple tooth organophosphorus ligand is 0.01:1～100:1, adds at cross-linking agent In the case of, monodentate organophosphorus ligand is 0.01:1～10:1 with the mol ratio of cross-linking agent, monodentate organic phosphine Part is 300:1～10:1 with the mol ratio of radical initiator, before aggregating into organic mixed polymers, and monodentate Organophosphorus ligand concentration range in organic solvent is 0.01-1000g/L.
9. according to the preparation method described in claim 6, it is characterised in that: molten described in step d) Agent is a kind of in water, benzene, toluene, oxolane, methanol, ethanol, dichloromethane or chloroform Or two or more, described active component is one or more in Rh, Co, Ir, wherein Rh Presoma be Rh (CH3COO)2、RhH(CO)(PPh3)3、Rh(CO)2(acac)、RhCl3；Co's Presoma 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 scope in catalyst It is 0.01～10wt%.
10. described produce than aldehyde internal olefin hydroformylation height is the most different according to claim 1-5 is arbitrary In application, it is characterised in that: the hydroformylation reaction of internal olefin, reaction temperature is 323～573K, Reaction pressure is 0.1～10.0MPa, and gas space velocity is 100～20000h-1, liquid hourly space velocity (LHSV) is 0.01～10.0h-1, the key component of reaction raw materials synthesis gas is H2And CO, (H2+ CO) volume content is 20～100%, H2/ CO volume ratio is 0.5～5.0, and feed internal olefins is C4～C20Alkene, double bond is positioned at On 2～No. 10 positions of carbochain, internal olefin feed purity is 20～100%, and product is mainly ratio raw material alkene The n-alkanal of the many carbon atoms of hydrocarbon.
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