CN104710288B - A kind of method utilizing hydroformylation of olefin to produce high-carbon aldehyde - Google Patents
A kind of method utilizing hydroformylation of olefin to produce high-carbon aldehyde Download PDFInfo
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- CN104710288B CN104710288B CN201310675693.XA CN201310675693A CN104710288B CN 104710288 B CN104710288 B CN 104710288B CN 201310675693 A CN201310675693 A CN 201310675693A CN 104710288 B CN104710288 B CN 104710288B
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- 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
- C07C45/505—Asymmetric hydroformylation
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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
- B01J31/24—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
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- 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
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Abstract
The present invention relates to a kind of method utilizing hydroformylation of olefin to produce high-carbon aldehyde, it is characterised in that described method makes with C in the presence of being included in solid heterogeneous catalyst6～C20Olefin feedstock and synthesis gas carry out hydroformylation reaction in trickle bed; wherein said solid heterogeneous catalyst is made up of metal component and organic ligand polymer; described metal component is one or more in metal Rh, Ir or Co; described organic ligand polymer is the polymer with bigger serface and hierarchical porous structure that the organic ligand monomer containing P and alkylene and optional N generates after solvent thermal polymerization method is polymerized, and described metal component and the P atom in described organic ligand polymer backbone or N form coordinate bond and exist with the state of single atomic dispersion.The method reaction process is simple, it is adaptable to industrialization large-scale production, and reactivity and selectivity are excellent, and the most different comparison of product aldehyde is high.
Description
Technical field
The present invention relates to one utilizes hydroformylation of olefin to produce high-carbon aldehyde (i.e. the aldehyde of carbon more than 6)
Method, belong to heterogeneous catalysis technology field.
Background technology
Typical atom economic reaction during hydroformylation reaction, its catalytic process and the research of catalyst
The history of existing nearly 60 years.At present, whole world aldehyde and alcohol about more than 1,000 ten thousand tons every year is to make
With the production of olefin hydroformylation technology.This reaction can make raw material alkene under less exacting terms
Hydrocarbon generates aldehyde, and product aldehyde can be hydroconverted into alcohol further.Homogeneous catalysis system is in gentle reaction
Under the conditions of there is higher catalysis activity and the selectivity of purpose product, but catalyst is with reaction mass
Separation problem difficulty, hinders the heavy industrialization application of homogeneous catalysis system.Heterogeneous catalysis is with equal
Phase catalytic phase is that catalyst can be easily separated with reaction mass than maximum advantage, and the subject matter existed is
Severe reaction conditions, reactivity is relatively low.The focus that hydroformylation is mainly studied at present is concentrated
Developing a kind of novel heterogeneous catalysis agent so that it is both there is catalyst and the reactant of heterogeneous catalysis
Expect segregative advantage, there is again the high reaction activity of homogeneous catalysis and the reaction condition of gentleness.
Balue etc. (J.Mol.Catal.A:Chem, 1999,137:193-203) utilize cation exchange tree
Fat, as carrier, forms heterogeneous catalyst, following of styrene hydroformylation by immobilized rhodium sulphur compound
Ring experiment shows, this heterogeneous catalyst poor stability, and the phenomenon that Rh runs off is the most serious.Zeelie etc.
(Appl.Catal.A:Gen, 2005,285:96-109) by styrene and styrene diphenylphosphine is modified in
On polyethylene fibre, then by Rh (acac) (CO)2It is anchored on adorned polyethylene fibre, ethylene
The result of hydroformylation shows, this catalyst is at 100 DEG C, and under the conditions of 5bar, conversion ratio is higher but urges
Agent stability is bad, and after reaction 50h, reactivity drastically declines, and catalysqt deactivation phenomenon is more
Seriously.
Ricken etc. (J.Mol.Catal.A:Chem, 2006,257:78-88) are by part
NIXANTPHOS carries out different sense dough and modifies, the part modified and Rh (acac) (CO)2
Being carried on altogether on polyglycereol polymer, the experiment of 1-octene hydroformylation shows, this catalyst at 80 DEG C,
Under the conditions of 20bar, conversion ratio can reach about 90%.But, commercially available or by conventional
Polymer support prepared by styrene radical polymerization is owing to gel formation, polymer are swelling, polymer
In skeleton, the loading of phosphorus part is limited and the problem such as catalytic active component loss seriously limits this
The commercial Application of class catalyst
CN102281948A report a kind of Polymer-supported transition-metal catalyst complex and
Using method, is prepared for having the Rh catalyst of the molten Polymer-supported of the energy of narrower molecular weight distribution.
But, prepared by catalyst, catalytic reaction and catalyst separation process the most complicated.Catalyst preparation needs
First control the polymer of the synthesizing soluble such as functional monomer and styrene, be re-introduced into part, final load
Rh catalyst.Catalytic reaction process needs add compressed gas.Catalyst uses the mode of nanofiltration
Separating from reactant mixture, reaction result is the most undesirable.
U.S.P.5585524 reports a kind of cobalt-based producing aldehyde compound for olefin hydroformylation
Complex catalyst system, this catalyst system uses the two-phase system of polar organic phase/organic facies, this
Sample cobalt-based complex is separated from organic facies by being dissolved in polar organic.This catalyst system
It is applied to the cobalt carbonyl catalyst of ethylene.And cobalt-based complex compound catalyst and organic solvent and product
Separate simple.U.S.P.5631392 has invented and a kind of has produced aldehyde compound for olefin hydroformylation
Bidentate phosphine metal catalyst system.
U.S.P.6184413 is the patent of California Institute of Technology's application, it was recently reported that a kind of load is catalyzed mutually
Agent, the load of this catalyst is highly polar, such as ethylene glycol or glycerol mutually；Its metal center is chirality
Sulfonated 2, double diphenylphosphine-1 of 2-, 1 pair of naphthalide complex, this complex dissolves in load phase
In, this kind of catalyst system and catalyzing can be used for having optically active asymmetric synthesis.
Kausik Mukhopadhyay etc. (Chem Mater, 2003,15:1766-1777) first use diphenyl
MCM-41 and MCM-48 molecular sieve outer surface is passivated processing by dichlorosilane, then uses 3-
Aminopropyl trimethoxysilane decorating molecule sieve inner surface, so can be by HRh (CO) (PPh3)3Select
Property immobilized in the inner surface of molecular sieve.The maximum bright spot of this research be author creative general
HRh(CO)(PPh3)3It is the most immobilized in the inner surface of MCM-41 and MCM-48 molecular sieve,
But from the point of view of the reaction effect of catalyst, this kind of heterogeneous catalytic system reactivity is relatively low, and circulation profit
Showing with experiment, the repeatable usability of catalyst is poor, and metal loss is the most serious.
Bassam El Ali etc. (Journal of Molecular Catalysis A:Chemical,
2006,250:153-162) by HRh (CO) (PPh3)3Immobilized on MCM-41 carrier while, also will
Heteropoly acid is immobilized, and on MCM-41 carrier, research shows, the existence of heteropoly acid not only can improve
The reactivity of hydroformylation, can effectively reduce the losing issue of metal, it is ensured that heterogeneous catalysis simultaneously
The stability of agent reaction.
N.Sudheesh etc. (Journal of Molecular Catalysis A:Chemical,
2008,296:61-70) by HRh (CO) (PPh3)3Catalyst in situ be encapsulated in HMS mesopore molecular sieve
In and be applied to the hydroformylation reaction of long-chain olefin.Author makees with the reaction in slurry bed system of the 1-hexene
For research emphasis, discuss temperature, carbon monoxide pressure of tension, hydrogen partial pressure and catalyst amount etc. to instead
The impact of activity, catalyst recycling experiment is answered to show that this catalyst has preferable repeatable utilization
Property.Subsequently, N.Sudheesh etc. (Applied Catalysis A:General,
2012,415-416:124-131) by HRh (CO) (PPh3)3In situ be encapsulated in HMS mesopore molecular sieve
In catalyst system and catalyzing be applied to the hydroformylation reaction of propylene, HMS mesopore molecular sieve is received as one
Meter level reactor, shows higher stability in recycling experiment, but same homogeneous catalysis system
Compare, reactivity there are still bigger gap.
Ki-Chang Song etc. (Catalysis Today, 2011,164:561-565) are by two kinds of methods pair
SBA-15 has carried out rear modification, a kind of method be first with diphenyl diethoxy silane to SBA-15
Outer surface be passivated processing, the most again with N-(2-amino-ethyl)-3-amino propyl methyl dimethoxy
The inner surface of SBA-15 is modified by base silane, passes through Rh4(CO)12With modifying in inner surface
Amino reacts, and reaches Rh4(CO)12Immobilized in the purpose of SBA-15.Another kind of method is straight
Connect and with N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, the surface of SBA-15 is carried out
Modify, pass through Rh4(CO)12React with modifying the amino in molecular sieve surfaces externally and internally, reach
Rh4(CO)12Immobilized in the purpose of SBA-15.Research shows, it is immobilized that the second processing method is formed
Changing catalyst and show more excellent activity and stability in hydroformylation reaction, author explains catalysis
Agent activity preferably reason is that surfaces externally and internally is modified simultaneously, can make Rh4(CO)12Evenly point
It is distributed in the surfaces externally and internally of molecular sieve, so that homogeneous catalyst has bigger free space.Author grinds
Studying carefully and show, the reason that heterogeneous catalyst n/i value is higher is the space steric effect of part, is conducive to
The generation of linear chain aldehyde.
Hanh Nguyen Thi Ha etc. (Catalysis Communications, 2012,25:136-141)
By Rh (acac) (CO)2It is prepared as supported ionic liquid phase heterogeneous catalyst with part TPPTS and applies
In the hydroformylation reaction of ethylene, author investigation ionic liquid content, reaction temperature and pressure etc. are right
The impact of catalysis activity, research shows, high ionic liquid content, is unfavorable for the reaction of hydroformylation
Activity, is characterized by FTIR, SEM and EDX analysis etc., illustrates that ionic liquid content is higher
Time inactivation main cause be that ionic liquid overflows from the duct of carrier, thus cause homogeneous catalyst
Loss, reactivity significance reduce.
US4252678 discloses the preparation of a kind of colloidal dispersion containing transition metal such as Rh, its
Middle transition metal component with the colloidal dispersion of 1.0 to 20.0 nanometers with use hydroxy-end capped (styrene
/ butadiene) catalyst system of functionalized copolymer composition, and the hydroformylation being applied to 1-octene is anti-
Should.Catalyst prepared by the method cannot be applied to fixed bed and trickle bed reactor, and catalyst with
Being difficult to of product separates.
CN102281948A report a kind of Polymer-supported transition-metal catalyst complex and
Using method, is prepared for having the Rh catalyst of the molten Polymer-supported of the energy of narrower molecular weight distribution.
But, prepared by catalyst, catalytic reaction and catalyst separation process the most complicated.Catalyst preparation needs
First control the polymer of the synthesizing soluble such as functional monomer and styrene, be re-introduced into part, final load
Rh catalyst.Catalytic reaction process needs add compressed gas.Catalyst uses the mode of nanofiltration
Separate from reactant mixture and reaction result is the most undesirable.
" research of the Suzuki coupling reaction of loaded palladium catalyst catalysis in microcapsule membrane " (Li Kaixiao,
China's excellent MA theses full-text database, the 8th phase) literary composition, report uses micro-at polystyrene
The microencapsulation material connecting phosphorus part in capsule membrane is carrier, prepares Pd base catalyst, is applied to
In Suzuki coupling reaction.But this microencapsulation material is copolymer material, it it not single polymeric material.?
In this catalyst, the dispersity of transition metal component does not describe.
In sum, the overall thought of the homogeneous heterogenize of the studies above is all to make organo-functional group with homogeneous
Catalyst action, so that homogeneous catalyst is immobilized on heterogeneous carrier, these methods occur at present
Greatest problem is exactly the losing issue of homogeneous catalyst, and the immobilized performance on carrier of homogeneous catalyst
The activity decrease problem gone out, the two problem is the homogeneous supported maximum bottleneck of restriction hydroformylation.
Summary of the invention
In order to solve the problems referred to above, it is an object of the invention to provide one by organic ligand polymer certainly
Carried metal heterogeneous catalyst produces the method for high-carbon aldehyde.
To this end, the present invention provides a kind of method utilizing hydroformylation of olefin to produce high-carbon aldehyde, its
Being characterised by, described method makes with C in the presence of being included in solid heterogeneous catalyst6～C20Olefin feedstock and
Synthesis gas carries out hydroformylation reaction in trickle bed, and wherein said solid heterogeneous catalyst is by metal group
Point and organic ligand polymer form, described metal component be the one in metal Rh, Ir or Co or
Several, described organic ligand polymer is the organic ligand list containing P and alkylene and optional N
The polymer with bigger serface and hierarchical porous structure that body generates after solvent thermal polymerization method is polymerized,
P atom in described metal component and described organic ligand polymer backbone or N formed coordinate bond and
Exist with the state of single atomic dispersion.
In a preferred embodiment, the reaction condition of described hydroformylation reaction is: reaction temperature
333～573K, reaction pressure 0.1～10.0MPa, gas volume air speed 100～20000h-1, liquid matter
Amount air speed 0.01～10.0h-1。
In a preferred embodiment, described synthesis gas derive from natural gas, coal, casing-head gas,
Coal bed gas or hydro carbons are the Gas-making of raw material.
In a preferred embodiment, the key component of described synthesis gas is H2And CO, H2With
The volume content of CO is 20～100%, H2/ CO volume ratio is 0.5～5.0.
In a preferred embodiment, described olefin feedstock with the mol ratio of described synthesis gas is
0.1: 1～1: 1.
In a preferred embodiment, described C6～C20Alkene be 1-hexene, 1-octene, 1-decene,
1-laurylene, 1-tetradecylene or styrene.
In a preferred embodiment, described metal component is in described solid heterogeneous catalyst gross weight
In account for 0.005～5.0%.
In a preferred embodiment, described metal component is in the gross weight of described solid heterogeneous catalyst
Amount accounts for 0.01～3.0%.
In a preferred embodiment, described organic ligand monomer is containing P and vinyl and to appoint
The organophosphorus ligand monomer of the N of choosing.
In a preferred embodiment, the specific surface area of described organic ligand polymer is
100～3000m2/ g, pore volume is 0.1～5.0cm3/ g, pore-size distribution is 0.2～50.0nm.
Beneficial effects of the present invention includes but not limited to following aspect:
The inventive method is compared with the production technology that existing hydroformylation produces organic aldehyde, owing to using
Solid heterogeneous catalyst in organic ligand polymer have the dual function of part and carrier concurrently, catalysis
Agent preparation process is simple；There is the urging of the self-supported metal of polymer of bigger serface and hierarchical porous structure
In agent, active metal component exists with the state of single atomic dispersion, the hydroformylation of such catalyst
Reactivity is high, and aldehyde product selectivity is good, is particularly due to microchannel in hierarchical porous structure and has and select
The function of type catalysis, in the hydroformylation reaction of higher olefins, the selectivity of n-alkanal and yield are significantly
Improve；Metal component defines chemical coordination key, Er Qie with P or N in organic ligand polymer
Catalyst after long-play remains in that the dispersity of this monometallic ion and is formed
Chemical bond, so showing the highest stability, not finding that metal component runs off, or joining
Body runs off；The catalyst of the present invention is being macroscopically heterogeneous catalyst, therefore, in recycle and reuse
With aspect has obvious superiority with reactant and product separate etc..
Accompanying drawing explanation
Fig. 1 is the synthetic technology of three (4-vinyl benzene) the base Phosphine ligands polymer monomer according to the present invention
The schematic diagram of route.
Fig. 2 is three (4-vinyl benzene) the base Phosphine ligands polymer monomer according to present invention synthesis1H
NMR spectra.
Fig. 3 is three (4-vinyl benzene) the base Phosphine ligands polymer monomer according to present invention synthesis31P
NMR spectra.
Fig. 4 is three (4-vinyl benzene) the base Phosphine ligands polymer support polymerization technique road according to the present invention
The schematic diagram of line.
Detailed description of the invention
The present invention produces grinding of the production method of high-carbon aldehyde (aldehyde of more than C6) in multiple hydroformylation
On the basis of studying carefully, use the self-supported active metal component of organic ligand polymer as solid heterogeneous
Agent, utilizes trickle bed production technology, probes into the reaction effect of high-carbon (C6-20) olefin hydroformylation.
Organic ligand polymer self-supported active metal component heterogeneous catalyst is by using introducing on aromatic ring
The organophosphorus ligand of thiazolinyl (such as vinyl), as polymerization monomer, utilizes solvent thermal in autoclave
Polymerization synthetic method, is polymerized to form the organic ligand polymerization with Large ratio surface and multi-stage artery structure
Thing, utilizes this organic ligand polymer to be in polymer backbone a large amount of P exposing and having lone pair electrons
And/or the coordinate bond effect of atom N and active transition metal ion unoccupied orbital, form new catalysis
Active sites, referred to herein as the catalyst of the self-supported active metal component of organic ligand polymer.This has
Machine ligand polymer is on the one hand as the part of active metal component, on the other hand as high-dispersion load
The carrier of the high-specific surface area of active metal component.By EXAFS,31P NMR, HRTEM and
The modern sign technical research such as FT-IR shows: at this type of by the self-supported metal of organic ligand polymer
In catalyst, active metal component exists with single atomic dispersion state, and metal ion is joined with organic
P and/or N in body polymer defines chemical bond, and in the catalyst after long-play
Remain in that the single atomic dispersion state of metal in this, illustrate that the active sites of homogeneous catalysis is in alkene hydrogen first
Acylation reaction plays effect, and can stably be present in organic ligand polymer, metal component
The chemical coordination key formed with P and/or N in organic ligand polymer solves active metallic ion
The problem being easy to run off.So that the present invention by the self-supported active metal component of organic ligand polymer
Catalyst there is possibility solve immobilized the occurred reactivity of homogeneous catalysis up to now and reduce
With the problem such as loss of active component, namely there is the prospect of the problem solving reaction stability difference.
Specifically, a kind of method utilizing hydroformylation of olefin to produce high-carbon aldehyde, described method
Make with C in the presence of being included in solid heterogeneous catalyst6～C20Olefin feedstock and synthesis gas are in trickle bed
Carrying out hydroformylation reaction, wherein said solid heterogeneous catalyst is polymerized by metal component and organic ligand
Thing forms, and described metal component is one or more in metal Rh, Ir or Co, described organic joins
Body polymer is that the organic ligand monomer containing P and alkylene and optional N is through solvent thermal polymerization method
The polymer with bigger serface and hierarchical porous structure generated after polymerization, described metal component and institute
State the P atom in organic ligand polymer backbone or N forms coordinate bond and the shape with single atomic dispersion
State exists.Preferably, the reaction condition of described hydroformylation reaction is: reaction temperature 333～573K,
Reaction pressure 0.1～10.0MPa, gas volume air speed 100～20000h-1, liquid quality air speed
0.01～10.0h-1。
In above-mentioned production method, the key component of synthesis gas is H2And CO, H2With CO's
Volume content is 20～100%, H2/ CO volume ratio is 0.5～5.0；The alkene used is C6～C20Alkene
Hydrocarbon, wherein preferred 1-hexene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene and styrene.
It is highly preferred that the mol ratio of described olefin feedstock and described synthesis gas is 0.1: 1～1: 1.
In above-mentioned production method, it is preferable that described organic ligand monomer is containing P and vinyl
And the organophosphorus ligand monomer of optional N, after initiator initiated polymerization, generate polymer make
For carrier.
Furthermore it is preferred that metal component accounts for 0.005～5.0wt.% in the gross weight of catalyst, excellent
Selecting 0.005～4.0wt.%, more preferably metal component accounts for 0.01～3.0wt.% in the gross weight of catalyst.
Preferably, in above-mentioned catalyst, the specific surface area of organic ligand polymer is 200～2000
m2/ g, pore volume is 0.5～5.0cm3/ g, pore-size distribution is 0.5～50.0nm.
The catalyst by the self-supported metal of organic ligand polymer that the present invention provides such as can pass through
Prepared by following methods:
A) under 293～473K and noble gas such as nitrogen or argon shield atmosphere, having containing above-mentioned
Machine ligand monomer, such as vinyl functionalization triphenylphosphine ligand or vinyl functionalization diphenyl pyridine radicals
In the organic solvent of Phosphine ligands, add radical initiator, stir 0.5～100 hour.Preferably,
Organic solvent therein can use in benzene, toluene, oxolane, methanol, ethanol or chloroform one
Kind or several mixed solvents, radical initiator can use cyclohexanone peroxide, diphenyl peroxide first
Acyl, tert-butyl hydroperoxide, the mixing of one or more of azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile)
Radical initiator.Preferably, described radical initiator and the weight ratio of described organic ligand monomer
It is 1: 500～1: 5；
B) in autoclave 293～473K and inert gas shielding atmosphere under utilize solvent thermal polymerization
Method, above-mentioned solution left standstill 0.5～carry out solvent thermal polymerization reaction in 100 hours；
C) the solution vacuum at ambient temperature after above-mentioned polymerization is extracted solvent, i.e. obtain that there is multipole
The organic phosphine polymer support containing P and optional N of the high surface of pore structure；
D) above-mentioned organic phosphine polymer support puts into the organic solvent containing metal component, and (it can be with
The solvent phase of above-mentioned steps a) is same) in, protect in 293～473K and noble gas such as nitrogen or argon
Protecting and stir 0.5～100 hour under atmosphere, be down to room temperature after stirring, vacuum is taken out at ambient temperature
Except solvent, the solid i.e. obtaining being made up of the described self-supported active metal component of organic ligand polymer is many
Phase catalyst.
The present invention catalyst prepare in, the organic ligand monomer of use can include but not limited to
One or more in Xia:
In order to better illustrate the preparation method of catalyst and answering in hydroformylation of olefin thereof
With, (wherein organic ligand monomer is only with three (4-vinyls to enumerate the preparation of some catalyst samples below
Benzene) explain as a example by base phosphine monomer (the most above-mentioned monomer L-2)) and application in reaction process
Embodiment, but the invention is not restricted to cited embodiment.Unless otherwise expressly specified, in the application
" percentage ratio " used is based on weight.
In the following embodiments, all of raw material is as follows:
H2/ CO gaseous mixture is (containing 50 volume %H2, 50 volume %CO): the middle bright chemical industry of sky grinds
Study carefully company limited of designing institute
1-laurylene, 1-tetradecylene, 1-decene, 1-octene, 1-hexene and styrene: Shanghai chemistry tries
Agent company, analytical pure
The specific surface area of sample and pore-size distribution measure in Quantachrome Instruments company
Carry out on Autosorb-1 Sorption Analyzer.Before test, sample 373K pretreatment 20 hours,
77K liquid nitrogen temperature carries out N2Adsorption-desorption is tested.
Embodiment 1
Under ice-water bath and nitrogen atmosphere, in the 100mL three neck round bottom flask with magnetic stick,
Being sequentially added into 0.5g magnesium powder, 10mL absolute ether, gained reactant mixture stirs 2 with this understanding
Hour, then it being added dropwise over 4g to bromstyrol and the mixed solution of 10mL absolute ether, gained is anti-
Answer mixture to stir with this understanding 2 hours, then be added dropwise over 6g Phosphorous chloride. and 10mL is anhydrous
The mixed solution of ether, gained reactant mixture stirs with this understanding 2 hours, adds 10mL
Water stirs 1 hour, then divides 3 extractive reaction mixture with 90mL diethyl ether solution, merges ether
Extract, rotary evaporation desolvation after filtration, prepared primary product purify through silica gel column chromatography,
I.e. making fixing phase with silica gel, eluting made by the mixed solvent of ethyl acetate/petroleum ether 1: 5 composition by volume
Liquid, prepares Bluish white viscous oil-like liquid, uses normal hexane recrystallization, prepares light yellow powder solid,
Yield is 40%.Fig. 1 is three (4-vinyl benzene) base Phosphine ligands polymer monomer synthetic technology route
Schematic diagram, Fig. 2 is three (4-vinyl benzene) base Phosphine ligands polymer monomer1H NMR spectra, Fig. 3
It it is three (4-vinyl benzene) base Phosphine ligands polymer monomer31P NMR spectra.The structure of this product and
Purity is three (4-vinyl benzene) base Phosphine ligands through NMR (Nuclear Magnetic Resonance) spectrum confirmation products obtained therefrom.
Embodiment 2
Protect under atmosphere at 298K and nitrogen gas, 10.0 gram of three (4-vinyl benzene) base phosphine is dissolved in
In 100.0ml tetrahydrofuran solvent, in above-mentioned solution, add 1.0 grams of radical initiator azos two different
Butyronitrile, stirs 2 hours.The solution being stirred is moved in autoclave, in 373K and nitrogen gas
Solvent thermal polymerization method is utilized to carry out being polymerized 24h under protection atmosphere.Solution after above-mentioned polymerization is cooled to
Room temperature, room temperature condition vacuum takes solvent away, i.e. obtains being formed by the polymerization of three (4-vinyl benzene) base phosphine
High surface area hierarchical porous structure organic ligand polymer support, Fig. 4 is that three (4-vinyl benzene) base phosphine is joined
The schematic diagram of body polymer support polymerization technique route, determines through analyzing, the polymerization of this ligand polymer
Degree n is 450-550, has the hierarchical porous structure including macropore, mesopore and micropore, the BET recorded
Specific surface area is 981m2/ g, pore volume is 1.45cm3/ g, pore-size distribution is 0.5～100.0nm.
Embodiment 3
Protect under atmosphere at 298K and nitrogen gas, weigh 3.14 milligrams of rhodium dicarbonyl acetylacetonates (I)
It is dissolved in the three-neck flask of 100.0ml tetrahydrofuran solvent, stirring and dissolving, adds 1.0 grams of embodiments 2
The organic ligand polymer formed by the polymerization of three (4-vinyl benzene) base phosphine of preparation, exists this mixture
Stirring 24 hours under 298K and nitrogen gas protection atmosphere, vacuum is taken away molten the most at ambient temperature
Agent, i.e. obtains by the solid heterogeneous catalyst of the self-supported metal component of organic ligand polymer.By above-mentioned
The heterogeneous catalyst prepared is applied to trickle bed 1-laurylene hydroformylation reaction.Trickle bed is internal diameter
For the stainless steel tube reactor of 9mm, loaded catalyst is 1.0ml, and synthesis gas pressure is 1.0MPa,
Volume space velocity is 5000h-1.1-laurylene double plunger micro pump squeezes into reactor, liquid quality air speed
For 1.47h-1, reaction temperature is 373K, and the cooled tank of reactor effluent is cooled to liquid product.
Liquid product was released after the regular hour, added internal standard substance normal propyl alcohol, at Agilent7890A gas
In phase chromatograph, (HP-5 capillary column, fid detector) is analyzed.Reaction result is listed in table 1.
Embodiment 4
In example 4,2.88h is changed into except liquid quality air speed-1Outside, remaining catalyst
Preparation process and hydroformylation reaction condition are same as in Example 3.Reaction result is listed in table 1.
Embodiment 5
In embodiment 5, in addition to synthesis gas pressure change is 2.0MPa, remaining catalyst
Preparation process and hydroformylation reaction condition are same as in Example 3.Reaction result is listed in table 1.
Embodiment 6
In embodiment 6, change into 393K except reaction temperature and liquid quality air speed is changed into
2.80h-1Outside, remaining catalyst preparation step and hydroformylation reaction condition are same as in Example 3.
Reaction result is listed in table 1.
Embodiment 7
In embodiment 7, in addition to olefin feedstock substitutes 1-laurylene with 1-tetradecylene, remaining
Catalyst preparation step and hydroformylation reaction condition are same as in Example 3.Reaction result is listed in table 1.
Embodiment 8
In embodiment 8, in addition to olefin feedstock substitutes 1-laurylene with 1-decene, remaining is urged
Agent preparation process and hydroformylation reaction condition are same as in Example 3.Reaction result is listed in table 1.
Embodiment 9
In embodiment 9, except olefin feedstock 1-octene substitutes 1-laurylene, and synthesize air pressure
Power is changed into outside 3.0MPa, remaining catalyst preparation step and hydroformylation reaction condition and reality
Execute example 3 identical.Reaction result is listed in table 1.
Embodiment 10
In embodiment 10, except olefin feedstock 1-hexene substitutes 1-laurylene, and synthesis gas
Pressure change is outside 3.0MPa, remaining catalyst preparation step and hydroformylation reaction condition with
Embodiment 3 is identical.Reaction result is listed in table 1.
Embodiment 11
In embodiment 11, except olefin feedstock styrene substitutes 1-laurylene, and synthesis gas
Pressure change is outside 3.0MPa, remaining catalyst preparation step and hydroformylation reaction condition with
Embodiment 3 is identical.
Table 1
From the result of above-mentioned table 1, the present invention use novel solid heterogeneous catalyst for alkene
It is simple that hydroformylation produces high-carbon aldehyde, reaction process and device, can carry out in conventional trickle bed
Reaction；It is applicable to C6～C20Multiple alkene；Hydroformylation reaction stable performance, yield is high, solves
Present in prior art or metal component runs off, or part runs off, or catalyst is difficult to
The problems such as recycle and reuse, have wide prospects for commercial application.
Below to the present invention have been described in detail, but the invention is not limited in tool described herein
Body embodiment.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, permissible
Make other changes and deformation.The scope of the present invention is defined by the following claims.
Claims (9)
1. one kind utilizes the method that hydroformylation of olefin produces high-carbon aldehyde, it is characterised in that described
Method makes with C in the presence of being included in solid heterogeneous catalyst6～C20Olefin feedstock and synthesis gas are at drip
Carrying out hydroformylation reaction in Chuan, wherein said solid heterogeneous catalyst is by metal component and organic ligand
Polymer form, described metal component is one or more in metal Rh, Ir or Co, described in have
Machine ligand polymer is that the organic ligand monomer containing P and alkylene and optional N is through solvent hot polymerization
The polymer with bigger serface and hierarchical porous structure generated after legal polymerization, described metal component
Coordinate bond is formed and with single atomic dispersion with the P atom in described organic ligand polymer backbone or N
State exist,
Wherein said organic ligand monomer is one or more in the following:
Method the most according to claim 1, it is characterised in that described hydroformylation reaction anti-
The condition is answered to be: reaction temperature 333～573K, reaction pressure 0.1～10.0MPa, gas volume air speed
100～20000h-1, liquid quality air speed 0.01～10.0h-1。
Method the most according to claim 1, it is characterised in that described synthesis gas derives from sky
So gas, coal, casing-head gas, coal bed gas or hydro carbons are the Gas-making of raw material.
Method the most according to claim 3, it is characterised in that the key component of described synthesis gas
For H2And CO, H2It is 20～100% with the volume content of CO, H2/ CO volume ratio is 0.5～5.0.
Method the most according to claim 4, it is characterised in that described olefin feedstock and described conjunction
The mol ratio becoming gas is 0.1:1～1:1.
Method the most according to claim 1, it is characterised in that described C6～C20Alkene is 1-
Hexene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene or styrene.
Method the most according to claim 1, it is characterised in that described metal component is described solid
Body heterogeneous catalyst gross weight accounts for 0.005～5.0%.
Method the most according to claim 6, it is characterised in that described metal component is described solid
The gross weight of body heterogeneous catalyst accounts for 0.01～3.0%.
Method the most according to claim 1, it is characterised in that described organic ligand polymer
Specific surface area is 100～3000m2/ g, pore volume is 0.1～5.0cm3/ g, pore-size distribution is 0.2～50.0nm.
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| CN107793304B (en) * | 2016-09-07 | 2021-03-16 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde by olefin with high selectivity |
| CN109776294B (en) * | 2017-11-14 | 2022-01-04 | 中国石油化工股份有限公司 | Olefin hydroformylation reaction method |
| CN109806911B (en) * | 2017-11-21 | 2022-01-21 | 中国科学院大连化学物理研究所 | Catalyst for preparing straight-chain aldehyde with high selectivity and preparation and application thereof |
| CN109836318B (en) * | 2017-11-27 | 2022-09-30 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde through olefin hydroformylation reaction |
| CN109395784B (en) * | 2018-11-19 | 2021-09-21 | 中国科学院兰州化学物理研究所 | Preparation and application of metal catalyst supported by phenolic resin modified carrier |
| CN112547128B (en) * | 2019-09-26 | 2023-07-21 | 中国石油化工股份有限公司 | Catalyst composition and preparation method of high-carbon aldehyde |
| CN112898122A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing isononyl alcohol from mixed octenes |
| CN112898138B (en) * | 2019-12-03 | 2022-09-27 | 中国科学院大连化学物理研究所 | High-value utilization method of Fischer-Tropsch product |
| CN112898139B (en) * | 2019-12-03 | 2022-10-04 | 中国科学院大连化学物理研究所 | Method for preparing n-valeraldehyde from Raffinate II |
| CN112892601A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing 1, 4-cyclohexane dicarbaldehyde from 3-cyclohexene-1-formaldehyde |
| CN111470962A (en) * | 2020-04-28 | 2020-07-31 | 浙江师范大学 | Method for preparing isononanoic acid from mixed isomeric octene |
| CN113717029A (en) * | 2020-05-26 | 2021-11-30 | 中国科学院大连化学物理研究所 | Method for preparing high-carbon alcohol from butene oligomer |
| CN114522740B (en) * | 2020-11-23 | 2023-10-13 | 中国科学院大连化学物理研究所 | Method for preparing 3-acetoxypropanol from vinyl acetate |
| CN114874082B (en) * | 2022-05-31 | 2023-08-04 | 中海油天津化工研究设计院有限公司 | Method for preparing high-carbon aldehyde by hydroformylation of mixed alpha olefin |
| CN115999629B (en) * | 2023-02-03 | 2024-09-06 | 中国科学院山西煤炭化学研究所 | Heterogeneous catalyst for preparing aldehyde by hydroformylation of alpha-olefin, preparation method and application thereof |
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