CN110280310A - A kind of heterogeneous catalyst, its preparation method and the application of hydroformylation and hydrogenation reaction - Google Patents
A kind of heterogeneous catalyst, its preparation method and the application of hydroformylation and hydrogenation reaction Download PDFInfo
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- CN110280310A CN110280310A CN201910661215.0A CN201910661215A CN110280310A CN 110280310 A CN110280310 A CN 110280310A CN 201910661215 A CN201910661215 A CN 201910661215A CN 110280310 A CN110280310 A CN 110280310A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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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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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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Abstract
The invention discloses the heterogeneous catalyst of a kind of hydroformylation and hydrogenation reaction, its preparation method and applications.The heterogeneous catalyst includes main active component and carrier, and the main active component includes rhodium and ruthenium, and the carrier is the porous polymer containing Phosphine ligands, and the main active component is dispersed in carrier in an atomic fashion.The present invention also provides a kind of methods of synthesis of dibasic alcohol comprising: in H2In/CO mixed atmosphere, makes to include that hydroformylation reaction occurs for the mixed system of unsaturated alcohol, the heterogeneous catalyst and solvent, then occur hydrogenation reaction in hydrogen atmosphere, obtain dihydric alcohol.Catalyst of the invention can one kettle way realize hydroformylation and plus two reaction process of hydrogen, be used for unsaturated alcohol high selectivity dihydric alcohol；And having many advantages, such as that preparation process is simple, the easily separated recycling of catalyst simultaneously repeatedly uses, and is suitable for industrial production.
Description
Technical field
The present invention relates to catalyst, more particularly to the heterogeneous catalyst and its preparation of a kind of hydroformylation and hydrogenation reaction
Method and the catalyst belong to catalyst preparation skill using unsaturated alcohol as the application in the method for Material synthesis dihydric alcohol
Art field.
Background technique
1,4-butanediol (Isosorbide-5-Nitrae-BDO) is a kind of important Organic chemical products, mainly for the production of tetrahydrofuran
(THF), gamma-butyrolacton (GBL), polybutylene terephthalate (PBT) (PBT), polytetramethylene ethylene glycol (PTMEG), polybutadiene
Sour butanediol ester (PBS) and polyurethane (PU) etc., furthermore, it may also be used for production vitamin B6, N-Methyl pyrrolidone (NMP),
Adipic acid, acetal and 1,3-butadiene etc. have wide in fields such as medicine, chemical industry, weaving, papermaking, automobile and household chemicals
General application prospect.
It is common method in chemical industry that alkene, which produces aldehyde and alcohol by hydroformylation reaction,.But in actual production process
In, alcoholic product, which is obtained, through the technique needs multiple steps, including hydroformylation of olefin that aldehyde, aldehyde purifying and aldehyde is made and adds hydrogen
Obtain alcohol.Hydroformylation, which is completed, by single catalyst and hydrogen two-step reaction is added to obtain alcohol product will be helpful to simplify work
Skill process (J.Am.Chem.Soc.2012,134,18746-18757).In the research to homogeneous catalyst system, it was demonstrated that rhodium-
Phosphine composition is the active catalyst of the reaction, and has good chemo-selective to hydroformylation product.However, rhodium system urges
The hydrogenation reaction activity of agent is very low, thus is difficult to realize further add intermediate product aldehyde hydrogen to obtain alcohol
(Catal.Sci.Technol,2012,2,773–777).Currently used technique be by aldehyde existing for the Ni catalyst under the conditions of
It carries out plus hydrogen obtains alcohol (US 20140005440A1).In the research to alkene, existing research personnel are matched using complexity is introduced
Body adds bimetallic mode for hydroformylation and hydrogenation reaction series connection, realizes alkene being converted into alcohol
(Angew.Chem.Int.Ed.2012,51,2178–2182；J.Am.Chem.Soc.2013,135,14306-14312；
J.Am.Chem.Soc.2012,134,18746-18757).However, there are catalyst to separate, returns for above-mentioned homogeneous catalysis system
It receives and the root problems such as reuse not yet achieves a solution.
The hydroformylation reaction (such as allyl alcohol) of unsaturated alcohol is the having more challenge of the task, because adding hydrogen first
It is easier under acylation condition with such as isomerization, hydrogenation, dehydration and condensation (generating acetal, hemiacetal) side reaction
(Ind.Eng.Chem.Res.2008,47,969-972).Therefore it is badly in need of developing a kind of heterogeneous catalyst to solve existing homogeneously to urge
Change the separation of catalyst present in reaction process, recycling and reuses the technological deficiencies such as difficulty.
Summary of the invention
The main purpose of the present invention is to provide a kind of one kettle ways to realize hydroformylation and hydrogenation reaction synthesis of dibasic alcohol
Heterogeneous catalyst and preparation method, to solve the separation of catalyst present in existing homogeneous catalytic reaction technique, recycling and repeat
Use the technological deficiencies such as difficulty.
Another object of the present invention is to provide the applications of the heterogeneous catalyst of the hydroformylation and hydrogenation reaction.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides the heterogeneous catalyst of a kind of hydroformylation and hydrogenation reaction, including main active component and
Carrier, the main active component include rhodium and ruthenium, and the carrier is the porous polymer containing Phosphine ligands, the main active component with
The form of atom is dispersed in carrier.
In some embodiments, the heterogeneous catalyst includes following component: 0.1~5wt% of rhodium, and ruthenium 0.2~
10wt%, rest part include carrier.
In some embodiments, the porous polymer containing Phosphine ligands will be matched containing phosphine by solvent thermal polymerization method
The organic monomer of body and alkenyl polymerize to form the high molecular polymer with porous structure.
The embodiment of the invention also provides the preparation methods of forgoing multiphase catalyst, the described method comprises the following steps:
S1. carrier is added in the organic solvent containing rhodium source and ruthenium source, reaction 10~for 24 hours is then stirred at room temperature；
S2. reaction solution step S1 finally obtained is filtered, is washed, and is dried in vacuo at room temperature, and the multiphase is obtained
Catalyst.
The embodiment of the invention also provides the heterogeneous catalysts of hydroformylation above-mentioned and hydrogenation reaction in unsaturated alcohol elder generation
The application in hydroformylation and hydrogenation reaction synthesis of dibasic alcohol occurs afterwards.
The embodiment of the invention also provides a kind of methods of synthesis of dibasic alcohol comprising:
The heterogeneous catalyst of hydroformylation and hydrogenation reaction above-mentioned is provided；
In H2In/CO mixed atmosphere, make include unsaturated alcohol, the heterogeneous catalyst and solvent mixed system in 60
3~10h of hydroformylation reaction occurs at~110 DEG C；Then in hydrogen atmosphere, at 80~130 DEG C occur hydrogenation reaction 4~
12h obtains dihydric alcohol.
Compared with prior art, of the invention to include: a little
1) heterogeneous catalyst provided by the invention is to pass through chemical bonding by active metal and the polymer containing Phosphine ligands
Mode is loaded, and obtains metal with the catalyst of atomic level high degree of dispersion.Match in use without additionally reusing
Body, and the reuse of active component and ligand is realized simultaneously.
2) two kinds of active components of catalyst rhodium of the present invention and ruthenium load altogether, realize a catalyst and complete hydrogen
Formylated and plus two reaction process of hydrogen obtain glycol products, help to save reaction process.
3) heterogeneous catalyst that the present invention improves has preparation method is simple, stability is good, post catalyst reaction is easy to divide
The advantages that from recycling and reuse, is suitble to industry amplification application.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is the transmission electron microscope dark field HAADF image of catalyst 1 in inventive embodiments 1；
Fig. 2 is the transmission electron microscope dark field HAADF image of catalyst 1 in inventive embodiments 1；
Fig. 3 is the imaging figure of selection area element Rh-L in Fig. 2；
Fig. 4 is the imaging figure of selection area element Ru-L in Fig. 2；
Fig. 5 is X-ray energy spectrum (EDX) figure of selection area in Fig. 2.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution as follows will be further explained the technical solution, its implementation process and principle etc..
The heterogeneous catalyst of a kind of hydroformylation and hydrogenation reaction that the one aspect of the embodiment of the present invention provides comprising
Main active component and carrier, the main active component include rhodium and ruthenium, and the carrier is the porous polymer containing Phosphine ligands, described
Main active component is dispersed in carrier in an atomic fashion.
In some embodiments, the catalyst includes following component: 0.1~5wt% of rhodium, 0.2~10wt% of ruthenium,
Remaining part point includes carrier.
In some embodiments, the porous polymer containing Phosphine ligands will be matched containing phosphine by solvent thermal polymerization method
The organic monomer of body and alkenyl polymerize to form the high molecular polymer with porous structure.
Further, the organic monomer includes three (4- vinyl benzene) base phosphines.
The other side of the embodiment of the present invention additionally provides the preparation method of forgoing multiphase catalyst, specifically include with
Lower step:
S1. carrier is added in the organic solvent containing rhodium source and ruthenium source, reaction 10~for 24 hours is then stirred at room temperature；
S2. reaction solution step S1 finally obtained is filtered, is washed, and is dried in vacuo 20~40h at room temperature, obtains institute
State heterogeneous catalyst.
In some embodiments, the rhodium source includes rhodium chloride, triphenylphosphine carbonyl hydrogenation Rh, dicarbapentaborane levulinic
Any one in ketone rhodium, acetylacetone,2,4-pentanedione carbonyl hydrogenation Rh, but not limited to this.
Further, the ruthenium source includes ruthenium trichloride, ten dicarbapentaborane, three ruthenium, 1- hydroxyl tetraphenyl-cyclopentadienyl group-hydrogen
Any one in four carbonyls, two ruthenium, three carbonyl dichloro- ruthenium (II) dimers, but not limited to this.
Further, the rhodium source and the concentration of ruthenium source in organic solvent are 2.5*10-4~1*10-2mol/L。
Further, the organic solvent is toluene.
The other side of the embodiment of the present invention additionally provides heterogeneous catalyst above-mentioned and hydrogen successively occurs in unsaturated alcohol
Application in formylated and hydrogenation reaction synthesis of dibasic alcohol.
The other side of the embodiment of the present invention additionally provides a kind of method of synthesis of dibasic alcohol comprising:
The heterogeneous catalyst of hydroformylation and hydrogenation reaction above-mentioned is provided；
In H2In/CO mixed atmosphere, make include unsaturated alcohol, the heterogeneous catalyst and solvent mixed system in 60
3~10h of hydroformylation reaction occurs at~110 DEG C；Then in hydrogen atmosphere, at 80~130 DEG C occur hydrogenation reaction 4~
12h obtains dihydric alcohol.
In some embodiments, the condition of the hydroformylation reaction is controlled at 70~90 DEG C of temperature, 3~6h of time,
H23~6MPa of/CO mixture pressure.
Further, the condition control of the hydroformylation reaction is at 80~90 DEG C of temperature, 4~6h of time, H2/ CO mixing
4~5MPa of atmospheric pressure.
In some embodiments, the condition control of the hydrogenation reaction is at 80~110 DEG C of temperature, 4~10h of time, hydrogen
4~7MPa of atmospheric pressure.
Further, the condition control of the hydrogenation reaction is at 90~100 DEG C of temperature, 4~7h of time, and Hydrogen Vapor Pressure 5~
6MPa。
In some embodiments, the unsaturated alcohol include allyl alcohol, 2- methallyl alcohol, 3- butene-2 -ol and
Any one in crotonyl alcohol, but not limited to this.
Further, the solvent is water.
Further, the H2/ CO gaseous mixture ratio is 0.5~2, preferably 1~1.5.
Further, the molar ratio of the unsaturated alcohol and rhodium is 500~1200:1, preferably 500~700:1.
Further, the molar ratio of the unsaturated alcohol and ruthenium is 250~600:1, preferably 250~350:1.
In some embodiments, the method also includes after reaction to the multiphase in the hybrid reaction system
The step of catalyst is separated.
Further, the separating step includes centrifugation and/or filtering.
By above-mentioned technical proposal, heterogeneous catalyst structure of the invention and property are stablized, and reaction stability is high, repeat
It uses；And have many advantages, such as that preparation method is simple, post catalyst reaction is easy to separate and recover and is recycled, it is more suitable for industry and puts
Big application.
Below with reference to several preferred embodiments, further details of the technical solution of the present invention, but the present invention is not
It is limited only to following embodiments.
Embodiment 1
By 52mg Rh (CO)2(acac)、100mg Ru2(CO)6Cl4With 1g polymer containing Phosphine ligands (POL-PPh3) addition
Into 40mL toluene, 20h is stirred at room temperature in air, filters after reaction, washed with excessive toluene, room temperature in vacuo is dry
It obtains catalyst 1 (characterization is shown in transmission electron microscope Fig. 1~4 and X-ray energy spectrum (EDX) figure).
Embodiment 2
By 52mg Rh (CO)2(acac)、80mg Ru3(CO)12With 1g polymer containing Phosphine ligands (POL-PPh3) be added to
In 40mL toluene, 20h is stirred at room temperature in air, filters after reaction, washed with excessive toluene, room temperature in vacuo is dry
Catalyst 2.
Embodiment 3
By 52mg Rh (CO)2(acac), 200mg 1- hydroxyl tetraphenyl-four carbonyl of cyclopentadienyl group-hydrogen, two ruthenium (Shvo '
S catalyst) and 1g polymer containing Phosphine ligands (POL-PPh3) be added in 40mL toluene, 20h is stirred at room temperature in air,
Filter, washed with excessive toluene after reaction, room temperature in vacuo it is dry catalyst 3.
Embodiment 4
By 52mg Rh (CO)2(acac)、78mg RuCl3With 1g polymer containing Phosphine ligands (POL-PPh3) it is added to 40mL
In toluene, 20h is stirred at room temperature in air, filters after reaction, washed with excessive toluene, room temperature in vacuo is so dry that be catalyzed
Agent 4.
Embodiment 5
By 5.2mg Rh (CO)2(acac)、10mg Ru2(CO)6Cl4With 1g polymer containing Phosphine ligands (POL-PPh3) addition
Into 40mL toluene, 20h is stirred at room temperature in air, filters after reaction, washed with excessive toluene, room temperature in vacuo is dry
Obtain catalyst 5.
Embodiment 6
By 10.4mg Rh (CO)2(acac)、20mg Ru2(CO)6Cl4With 1g polymer containing Phosphine ligands (POL-PPh3) addition
Into 40mL toluene, 20h is stirred at room temperature in air, filters after reaction, washed with excessive toluene, room temperature in vacuo is dry
Obtain catalyst 6.
Embodiment 7
By 26mg Rh (CO)2(acac)、50mg Ru2(CO)6Cl4With 1g polymer containing Phosphine ligands (POL-PPh3) be added to
In 40mL toluene, 20h is stirred at room temperature in air, filters after reaction, washed with excessive toluene, room temperature in vacuo is dry
Catalyst 7.
Embodiment 8
By 104mg Rh (CO)2(acac)、200mg Ru2(CO)6Cl4With 1g polymer containing Phosphine ligands (POL-PPh3) addition
Into 40mL toluene, 20h is stirred at room temperature in air, filters after reaction, washed with excessive toluene, room temperature in vacuo is dry
Obtain catalyst 8.
Catalyst performance test
One, inventor is respectively with the obtained heterogeneous catalyst of embodiment 1-8 for being catalyzed allyl alcohol hydroformylation and adding
Hydrogen reaction prepares dihydric alcohol:
Catalysis reaction carries out in pressure autoclave type reactor, respectively by allyl alcohol (AA) 128mg, catalyst, water 2.05ml
It is added in reaction kettle, uses H2It is replaced 3 times with the gaseous mixture (1:1) of CO, initial reaction pressure is 4MPa, reaction temperature 80
DEG C, the reaction time is 4 hours.It cools down after reaction, bleed off gas and reaction atmosphere is changed to pure H2, initial pressure is
5MPa, reaction temperature are 100 DEG C, and the reaction time is 5 hours.After be separated by filtration, filtrate carry out GC analysis (the results are shown in Table
1)。
Table 1: the reactivity worth result of different catalysts
| Embodiment | Catalyst amount | AA conversion ratio % | Glycol selectivity % |
| Embodiment 1 | 20mg | 100 | 85 |
| Embodiment 2 | 20mg | 100 | 72 |
| Embodiment 3 | 20mg | 100 | 7 |
| Embodiment 4 | 20mg | 100 | 49 |
| Embodiment 5 | 200mg | 100 | 41 |
| Embodiment 6 | 100mg | 100 | 66 |
| Embodiment 7 | 40mg | 100 | 83 |
| Embodiment 8 | 10mg | 100 | 46 |
The result shows that the load capacity of ruthenium source and metal selectively influences to show to catalyst reaction performance, especially dihydric alcohol
It writes.Using Ru2(CO)6Cl4Ruthenium source and moderate content of metal are conducive to improve the selectivity of dihydric alcohol.In addition, this case is invented
People investigated respectively substrate be 2- methallyl alcohol, 3- butene-2 -ol and crotonyl alcohol, with the molar ratio of substrate and rhodium be 500 and
700 (molar ratio of corresponding allyl alcohol and rhodium is 250 and 350), also hydroformylation temperature be 70~90 DEG C react respectively 4h,
6h, hydrogenation temperature are 90~110 DEG C, time 4h, 6h, 7h, and Hydrogen Vapor Pressure is that 6MPa is reacted, and dihydric alcohol has been made,
And conversion ratio and selectivity are consistent with above-described embodiment.
Embodiment 9
Catalyst 1 after participation binary alcohol synthesis reaction is filtered and is washed with toluene, it is anti-to put into high pressure again after dry
It answers in kettle, and allyl alcohol 128mg, 2.05ml water, CO/H is added2Level pressure is 4MPa after gaseous mixture displacement, and reaction 4 is small at 80 DEG C
When, atmosphere is switched to H again after cooling2, pressure 5MPa reacts 5 hours at 100 DEG C.Catalyst is reused 5 times, circulation
The reactivity worth data used are shown in Table 2.Catalyst 1 is able to maintain higher catalytic activity and selectivity of product, table after 5 repetitions
Bright catalyst 1 has preferable repeat performance.
Table 2: the repeat performance of catalyst 1
| Number of repetition | AA conversion ratio % | Glycol selectivity % |
| 1 | 100 | 84 |
| 2 | 100 | 82 |
| 3 | 100 | 77 |
| 4 | 100 | 73 |
| 5 | 100 | 63 |
Reference examples 1
Inventor also uses unsupported triphenylphosphine carbonyl hydrogenation Rh, Rh (CO)2(acac), three carbonyl dichloro-
The homogeneous catalysts such as ruthenium (II) dimer are added triphenylphosphine ligand thereto and allyl alcohol carry out reaction synthesis of dibasic alcohol,
Conversion ratio reaches 100%, and glycol is selectively 83%, suitable with result of the present invention, but the homogeneous catalyst after use can not
It reuses.
In conclusion heterogeneous catalyst structure of the invention and property are stablized, reaction stability is high, reusable；And
Have many advantages, such as that preparation method is simple, post catalyst reaction is easy to separate and recover and is recycled, is more suitable for industry amplification and applies.
In addition, inventor also refers to the mode of embodiment 1-8, with the other raw materials and condition listed in this specification
Etc. being tested, corresponding effect can also achieve, the structure and property of heterogeneous catalyst are stablized, and reaction stability is high, can weigh
It is multiple to use, it is suitble to industry amplification application.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (10)
1. the heterogeneous catalyst of a kind of hydroformylation and hydrogenation reaction, it is characterised in that described including main active component and carrier
Main active component includes rhodium and ruthenium, and the carrier is the porous polymer containing Phosphine ligands, and the main active component is with the shape of atom
Formula is dispersed in carrier.
2. heterogeneous catalyst according to claim 1, which is characterized in that the catalyst includes following component: rhodium 0.1~
5wt%, 0.2~10wt% of ruthenium, rest part include carrier.
3. the preparation method of heterogeneous catalyst described in any one of claim 1-2, which is characterized in that the method includes following
Step:
S1. carrier is added in the organic solvent containing rhodium source and ruthenium source, reaction 10~for 24 hours is then stirred at room temperature；
S2. reaction solution step S1 finally obtained is filtered, is washed, and is dried in vacuo at room temperature, and the heterogeneous catalysis is obtained
Agent.
4. preparation method according to claim 3, which is characterized in that the rhodium source includes rhodium chloride, triphenylphosphine carbonyl
Base hydrogenation Rh, dicarbonyl rhodium acetylacetonate, any one in acetylacetone,2,4-pentanedione carbonyl hydrogenation Rh；
And/or the ruthenium source includes ruthenium trichloride, ten dicarbapentaborane, three ruthenium, 1- hydroxyl tetraphenyl-four carbonyl of cyclopentadienyl group-hydrogen
Any one in two rutheniums, three carbonyl dichloro- ruthenium (II) dimers；
And/or the rhodium source and the concentration of ruthenium source in organic solvent are 2.5*10-4~1*10-2mol/L；
And/or the organic solvent is toluene.
5. in unsaturated alcohol hydroformylation and hydrogenation reaction synthesis of dibasic alcohol successively occur for heterogeneous catalyst described in claim 1
In application.
6. a kind of method of synthesis of dibasic alcohol, characterized by comprising:
The heterogeneous catalyst of hydroformylation and hydrogenation reaction of any of claims 1-2 is provided；
In H2In/CO mixed atmosphere, make include unsaturated alcohol, the heterogeneous catalyst and solvent mixed system in 60~110
3~10h of hydroformylation reaction occurs at DEG C；Then in hydrogen atmosphere, 4~12h of hydrogenation reaction occurs at 80~130 DEG C,
Obtain dihydric alcohol.
7. according to the method described in claim 6, it is characterized in that, the hydroformylation reaction condition control temperature 70~
90 DEG C, 3~6h of time, H2/ CO 3~6MPa of mixture pressure, preferably, 80~90 DEG C of temperature, 4~6h of time, H2/ CO mixing
4~5MPa of atmospheric pressure；
With or, the condition control of the hydrogenation reaction is at 80~110 DEG C of temperature, 4~10h of time, Hydrogen Vapor Pressure 4~7MPa is excellent
It is selected as, 90~100 DEG C of temperature, 4~7h of time, 5~6MPa of Hydrogen Vapor Pressure.
8. according to the method described in claim 6, it is characterized in that, the unsaturated alcohol includes allyl alcohol, 2- methallyl
Any one in alcohol, 3- butene-2 -ol and crotonyl alcohol；
And/or the solvent is water.
9. according to the method described in claim 6, it is characterized in that, the H2/ CO gaseous mixture ratio is 0.5~2, preferably 1
~1.5；
And/or the molar ratio of the unsaturated alcohol and rhodium is 500~1200:1, preferably 500~700:1；
And/or the molar ratio of the unsaturated alcohol and ruthenium is 250~600:1, preferably 250~350:1.
10. according to the method described in claim 6, it is characterized in that, the method also includes mixing after reaction to described
Close the step of heterogeneous catalyst in reaction system is separated；Preferably, the separating step includes centrifugation and/or filtering.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269086A (en) * | 2020-03-06 | 2020-06-12 | 厦门大学 | Application method of atomic-level dispersed ruthenium catalyst in catalytic hydrogenation |
| CN117000309A (en) * | 2023-08-25 | 2023-11-07 | 中国科学院兰州化学物理研究所 | Preparation method of phosphine-containing polyion liquid polymer supported Rh catalytic material |
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| CN117000309A (en) * | 2023-08-25 | 2023-11-07 | 中国科学院兰州化学物理研究所 | Preparation method of phosphine-containing polyion liquid polymer supported Rh catalytic material |
| CN117000309B (en) * | 2023-08-25 | 2024-02-02 | 中国科学院兰州化学物理研究所 | Preparation method of phosphine-containing polyion liquid polymer supported Rh catalytic material |
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