CN109776294A - A kind of hydroformylation of olefin method - Google Patents
A kind of hydroformylation of olefin method Download PDFInfo
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- CN109776294A CN109776294A CN201711118822.XA CN201711118822A CN109776294A CN 109776294 A CN109776294 A CN 109776294A CN 201711118822 A CN201711118822 A CN 201711118822A CN 109776294 A CN109776294 A CN 109776294A
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Abstract
The present invention provides a kind of hydroformylation of olefin methods; it is included in the presence of rhodium complex catalyst; alkene and synthesis gas are through first segment reaction and second segment reaction hydroformylation reaction generation aldehyde, and wherein the temperature of first segment reaction is at least 5 DEG C lower than the temperature that second segment reacts.The present invention controls the temperature of two-stage reaction using segmentation reaction, and reactant is made to carry out activity and stability that pre-reaction improves catalyst at a lower temperature, and the performance of catalyst is improved with this, reduces production cost.
Description
Technical field
The invention belongs to hydroformylation reaction technical fields, and in particular to it is steady that one kind is conducive to improvement rhodium complex catalyst
Qualitative and active hydroformylation of olefin method.
Background technique
Catalyst used in hydroformylation reaction is generally cobalt (Co) base or rhodium (Rh) base catalyst in industrial production, i.e.,
Using cobalt (Co) or rhodium (Rh) as the catalyst of metal active centres.But reaction condition is severe when due to using cobalt-base catalyst
It carves, side reaction is more, the poor selectivity of reaction product, and a variety of causes such as removal process complexity of energy consumption of reaction height and cobalt,
The catalyst used in hydroformylation reaction is mostly rhodium base catalyst now.
The selectivity of activity and institute's product aldehyde that rhodium base catalyst embodies during hydroformylation depends on catalyst
The combination and operating condition of presoma and ligand.Rhodium base catalyst is carried out in alkene formylation reaction, due to rhodium and other
The composition catalyst that substance is formed is very sensitive for the variation of state in reaction process, and catalyst is easy to inactivate, thus
It will affect the selectivity of reaction conversion ratio and product.
Chinese patent CN101293818 discloses a kind of hydroformylation process, by carrying out to mixed butylene hydroformylation
Two-stage reaction, by first segment react in unreacting material be sent into second segment reaction in the reaction was continued, solving internal olefin cannot have
The problem of validity response, improves alkene utilization rate, but does not relate to the improvement to catalyst activity and stability.Chinese patent
CN103814006 discloses a kind of hydroformylation process in the reaction with improved catalyst stability, by hydrogen first
It is added a kind of special α in acylation reaction, beta-unsaturated carbonyl compound inhibits the decomposition of ligand and catalyst, this method
The stability of catalyst is increased to a certain extent, but also increases reaction cost simultaneously.Chinese patent CN102123978 exists
Use the rhodium complex of calixarene bisphosphite as catalyst in embodiment 8 to 14, by changing the partial pressure of carbon monoxide,
1- octene hydroformylation is obtained into two or more aldehyde with the target N/I ratio that can be selected within the scope of 7-31, still
The patent is also not involved with the problems such as raising to catalyst activity and stability.
Summary of the invention
In order to improve the stability and activity of rhodium complex catalyst in hydroformylation reaction, the present invention provides a kind of new
Hydroformylation of olefin method, propose to mention using by the way of segmentation reaction by controlling the different temperature of two-stage reaction
The stability and activity of high rhodium complex catalyst.
Specifically, the present invention is carried out by using following technical solution:
A kind of hydroformylation of olefin method, is included in the presence of rhodium complex catalyst, alkene and synthesis gas warp
First segment reaction and second segment reaction generate aldehyde, and wherein first segment reaction temperature is at least 5 DEG C lower than second segment reaction temperature, preferably
First segment reaction temperature is at least 10 DEG C lower than second segment reaction temperature, and more preferable first segment reaction temperature is than second segment reaction temperature
Low at least 15 DEG C, the temperature of most preferably first segment reaction is 20 DEG C lower than the temperature that second segment reacts.
According to the preferred embodiment of the present invention, the temperature of first segment reaction is 50-135 DEG C, preferably 50-100 DEG C,
Preferably 60-80 DEG C, more preferably 70-80 DEG C;And/or the pressure of reaction is 0-8MPa, preferably 1-6MPa, more preferably 1-
3MPa;Time of reaction controls within 50min, such as 1-40min or 5-40min or 6-30min or 8-30min, preferably the
One section of reaction time is greater than 5min, preferably 10-25min, more preferably 10-20min, most preferably 15-20min.
According to the preferred embodiment of the present invention, the temperature of the second segment reaction is 55-140 DEG C, preferably 80-110
DEG C, more preferably 90-100 DEG C;And/or the pressure of reaction is 0-8MPa, preferably 1-6MPa, more preferably 1-3MPa;And/or
The time of reaction is 1-8h, preferably 1-5h, more preferably 1-3h.
It maintains the temperature of first segment reaction to be lower than the temperature of second segment reaction in the present invention, and controls first segment reaction temperature
At least 5 DEG C lower than second segment reaction temperature, preferably down to less 10 DEG C, preferably first segment reaction temperature is lower than second segment reaction temperature
At least 15 DEG C, more preferable first segment reaction temperature is at least 20 DEG C lower than second segment reaction temperature.First segment is controlled under normal circumstances
Reaction temperature and second segment temperature difference are not more than 40 DEG C, it is preferable that first segment reaction temperature and second segment temperature difference are not more than 30
℃.The temperature that such as can control first segment reaction can be 5-40 DEG C or 5-30 DEG C or 10-30 lower than the temperature that second segment reacts
DEG C or 10-25 DEG C or 10-20 DEG C or 15-20 DEG C.It is advantageous lower than second segment reaction temperature by control first segment reaction temperature
In the stability for improving catalyst, catalyst activity is set to maintain higher level always, the possible reason is the rhodium that the present invention uses
The combination between rhodium and ligand in composition catalyst is easy to be influenced and cause between ligand and rhodium by reaction condition
Coordinate bond fracture, so that the activity and stability of catalyst are influenced, from hydroformylation reaction of the invention using two-stage reaction
Mode, by first at a lower temperature carry out first segment reaction, at relatively low temperatures carry out pre-reaction with prevent rhodium with
The fracture of coordinate bond between ligand, keeps the stabilization of catalyst performance, catalyst activity is made to maintain higher level.
And preferably, reaction higher for second segment reaction temperature is lower compared to second segment reaction temperature anti-
It answers, in order to improve the performance of catalyst, it should the appropriate time for increasing first segment reaction, to avoid high reaction temperature to catalysis
The injury of agent performance.
In the present invention, first segment reaction and second segment reaction can carry out in same reactor, can also go here and there at two
It is carried out in the reactor of connection.For the sake of easy to operate, preferably using identical anti-in first segment reaction and second segment reaction
Answer pressure.
According to the preferred embodiment of the present invention, second is increased to instead from the first reaction temperature by the way of gradually heating up
Answer temperature.Preferably, the second reaction temperature is increased to from the first reaction temperature with the speed of 3-6 DEG C/min.
According to the preferred embodiment of the present invention, the alkene is C2-C12Alkene, preferably C5-C12Alkene, preferably
C6-C12Alkene, more preferably C6-C10Alkene, in the specific embodiment of the present invention, the alkene is octene.
According to the preferred embodiment of the present invention, the rhodium complex catalyst is shown in formula (I):
Rh(L1)x(L2)y(L3)zFormula (I)
Wherein, L1Selected from carbonyl, acetylacetone,2,4-pentanedione, diphenylphosphine, cyclo-octadiene, norbornene and triphenylphosphine, L2And L3Phase
It is same or different, it is independently selected from hydrogen, carbonyl, chlorine, bromine, acetylacetone,2,4-pentanedione, diphenylphosphine, cyclo-octadiene, norbornene and three
Phenylphosphine;
X is the integer of 1-3, and y and z are independently selected from the integer of 0-4, x+y+z≤5.
According to the preferred embodiment of the present invention, the rhodium complex catalyst is organophosphine modified Rhodium Complexes Catalyzed
Agent, including rhodium complex catalyst and organic phosphorus compound.Had using the catalyst of organophosphine modified rhodium complex more preferable
Effect, the possible reason is due to organic phosphine compound can with rhodium formed complex, rhodium complex catalyst can be prevented
The separation of middle complex and rhodium helps to stablize rhodium complex, improves the stability of catalyst.
According to the preferred embodiment of the present invention, the organic phosphine compound is the organic phosphine compound containing phenyl, is contained
There is the organic phosphine compound of phenyl to be selected from substituted or unsubstituted triphenylphosphine oxide, substituted or unsubstituted triphenylphosphine and take
Generation or unsubstituted diphenylphosphine, preferably substituted or unsubstituted triphenylphosphine or substituted or unsubstituted diphenylphosphine.
According to the preferred embodiment of the present invention, the substituted triphenylphosphine refers to deposits on the phenyl ring in triphenylphosphine
In the triphenylphosphine of substituent group, substituent group can replace any one hydrogen of any one phenyl ring, it is preferable that described substituted three
Shown in Phenylphosphine such as formula (II):
Wherein, R1、R2And R3It is independently selected from C1-C5Alkyl or alkoxy, it is preferable that R1、R2And R3It is independent
Selected from methyl, ethyl, n-propyl, isopropyl or C1-C5Alkoxy;
According to the preferred embodiment of the present invention, the substituted diphenylphosphine refers to exist on phenyl ring in diphenylphosphine and take
The diphenylphosphine compound of Dai Ji, substituent group can replace any one hydrogen of any one phenyl ring, it is preferable that described substituted
Shown in diphenylphosphine such as formula (III):
Wherein, R4Selected from hexamethylene or cycloheptane;
R5And R6It is independently selected from C1-C5Alkyl or alkoxy, it is preferable that R5And R6Be independently selected from methyl,
Ethyl, n-propyl, isopropyl or C1-C5Alkoxy.
According to the preferred embodiment of the present invention, the molar ratio of the organic phosphine compound and rhodium in rhodium complex catalyst
Example is (0.5-200): 1, preferably (12-200): 1, more preferably (40-150): 1.
According to the preferred embodiment of the present invention, in the hydroformylation reaction, alkene and rhodium complex catalyst rub
Your ratio is (500-100000): 1, the molar ratio of preferred alkenes and rhodium complex catalyst is (1000-10000): and 1, more
Preferably (2000-8000): 1.
According to the preferred embodiment of the present invention, the molar ratio of hydrogen and carbon monoxide is (0.1- in the synthesis gas
20): 1, it is preferable that the molar ratio of hydrogen and carbon monoxide is (1-10): 1, more preferable 1:1 in the synthetic gas.
According to the preferred embodiment of the present invention, the hydroformylation reaction carries out in a solvent, it is preferable that the solvent
For organic solvent, it is preferably selected from C4-C10Aldehyde, C4-C10Ketone, C4-C10Alkane, aromatic compound and substituted aromatic series
One of compound is a variety of.The solvent citing of hydroformylation reaction can be butyraldehyde, valeral, hexanal, enanthaldehyde, octanal, nonyl
One of aldehyde, methyl iso-butyl ketone (MIBK), acetyl benzene,toluene,xylene, chlorobenzene and enanthaldehyde are a variety of.
According to the preferred embodiment of the present invention, in hydroformylation reaction, before the alkene is contacted with synthetic gas,
Alkene and catalyst premixing close, it is preferable that the premixing time be less than 10min, e.g., 0.1-10min, preferably smaller than 5min, such as
0.1-5min, more preferable 1-3min.
The present invention passes through the reaction temperature that two stages of setting are different, control first segment reaction temperature in hydroformylation reaction
At least 5 DEG C lower than second segment reaction temperature are spent, using the method increase the activity of catalyst and stability, and then improves rhodium
The service efficiency of catalyst, reduces production cost.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the present invention is not limited by following embodiments.
In an embodiment of the present invention, chromatography: Agilent 7890A, carrier gas are nitrogen.
31PNMR analysis: Brooker AV400D, with CDCl3For solvent.
Embodiment 1
In glove box under an inert atmosphere, the molar ratio according to rhodium in 1- octene and rhodium complex catalyst is 4000:
1, the 1- octene for measuring 12.14mL is dissolved in 12.86mL toluene, and is added in glass syringe.Weigh tri- (triphen of 17.50mg
Base phosphine) carbonyl hydrogenation Rh (catalyst of structure shown in formula I, wherein L1For H, L2For CO, L3For triphenylphosphine, x=y=1, z=3) and
630mg triphenylphosphine (compound of II structure of formula, wherein R1、R2And R3It is hydrogen) (molar ratio of triphenylphosphine and rhodium is for mixing
It 126:1) is dissolved in 10mL toluene, is added in another glass syringe, is taken out from glove box after syringe is sealed.
Hydroformylation reaction device uses 50mL autoclave reaction unit.Autoclave is heated to 80 DEG C, is used after vacuumizing
Synthetic gas (CO:H2=1:1) it replaces for several times, blow valve is opened, then rapidly by the toluene solution ((triphenyl of catalyst
Phosphine) carbonyl hydrogenation Rh and triphenylphosphine toluene solution) be added in reaction kettle, then the toluene solution of 1- octene is added to
In reaction kettle.Blow valve is closed, premixing stirring 2min sets pressure as 2MPa, is passed through synthetic gas (CO:H thereto2
=1:1) it is reacted, reaction time 20min, autoclave is heated to 100 DEG C using the speed of 5 DEG C/min later, is continued
React 100min.After the reaction was completed, it collects reaction solution and separates and recovers catalyst.Color is carried out to the liquid product for removing catalyst
Spectrum analysis the results are shown in Table 1 (fresh catalyst).
The color of the toluene solution of the catalyst of recycling with react before have no significant change, illustrate that rhodium is not oxidized.Together
When pass through31PNMR analysis finds that its chemical environment is not after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It substantially change, shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalysis of recycling
Agent carries out above-mentioned reaction using the catalyst of recycling without reprocessing again, after the reaction was completed, collects reaction solution and carries out chromatography point
Analysis, the results are shown in Table 1.
Embodiment 2
With embodiment 1, difference is for the additional amount of triphenylphosphine to be changed to 450mg (mole of organic phosphine compound and rhodium
Than for 90:1).Test result is shown in Table 1.
The color of the toluene solution of the catalyst of recycling with react before have no significant change, illustrate that rhodium is not oxidized.Together
When pass through31PNMR analysis finds that its chemical environment is not after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It substantially change, shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalysis of recycling
Agent carries out above-mentioned reaction using the catalyst of recycling without reprocessing again, after the reaction was completed, collects reaction solution and carries out chromatography
Analysis, the results are shown in Table 1.
Embodiment 3
With embodiment 1, difference is for the additional amount of triphenylphosphine to be changed to 200mg (mole of organic phosphine compound and rhodium
Than for 40:1).Test result is shown in Table 1.
The color of the toluene solution of the catalyst of recycling with react before slightly deepen, illustrate there is a small amount of rhodium to be oxidized.Simultaneously
Pass through31Its chemical environment is not sent out after discovery reaction when the chemical environment variation of P atom in ligand in conjunction with rhodium for PNMR analysis
Life is substantially change, and shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalyst of recycling
Without reprocessing, above-mentioned reaction is carried out again using the catalyst of recycling, after the reaction was completed, is collected reaction solution and is carried out chromatography point
Analysis, the results are shown in Table 1.
Embodiment 4
With embodiment 1, difference is, organic phosphine compound is replaced with equimolar triphenylphosphine oxide by triphenylphosphine
(molar ratio of organic phosphine compound and rhodium is 126:1), remaining experiment condition is constant, and test result is shown in Table 1.
The color of the toluene solution of the catalyst of recycling with react before have no significant change, illustrate that rhodium is not oxidized.Together
When pass through31PNMR analysis finds that its chemical environment is not after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It substantially change, shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalysis of recycling
Agent carries out above-mentioned reaction using the catalyst of recycling without reprocessing again, after the reaction was completed, collects reaction solution and carries out chromatography
Analysis, the results are shown in Table 1.
Embodiment 5
With embodiment 1, difference is, the rhodium complex catalyst used is triphenylphosphine acetylacetone,2,4-pentanedione rhodium carbonyl.Test
It the results are shown in Table 1.
The color of the toluene solution of the catalyst of recycling with react before have no significant change, illustrate that rhodium is not oxidized.Together
When pass through31PNMR analysis finds that its chemical environment is not after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It substantially change, shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalysis of recycling
Agent carries out above-mentioned reaction using the catalyst of recycling without reprocessing again, after the reaction was completed, collects reaction solution and carries out chromatography
Analysis, the results are shown in Table 1.
Embodiment 6
With embodiment 1, difference is, the temperature of first segment reaction is 95 DEG C, and the temperature of second segment reaction is 100 DEG C.It surveys
Test result is shown in Table 1.
The solution colour of the toluene of the catalyst of recycling illustrates have a small amount of rhodium to be oxidized than slightly deepening before reaction.Pass through31P goes out peak position and does not occur obviously after discovery is reacted when PNMR analyzes the chemical environment variation of P atom in the ligand in conjunction with rhodium
Change, shows the Phosphine ligands in conjunction with catalyst without departing from catalyst structure does not destroy.The catalyst of recycling no longer needs to locate
Reason, carries out above-mentioned reaction using the catalyst of recycling again, after the reaction was completed, collects reaction solution and carries out chromatography, as a result
It is shown in Table 1.
Embodiment 7
With embodiment 1, difference is, the temperature of first segment reaction is 90 DEG C, and the temperature of second segment reaction is 100 DEG C.It surveys
Test result is shown in Table 1.
The toluene solution color of the catalyst of recycling illustrates have a small amount of rhodium to be oxidized than slightly deepening before reaction.Pass through31PNMR analysis finds that its chemical environment does not occur bright after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It is aobvious to change, show the Phosphine ligands in conjunction with catalyst without departing from catalyst structure does not destroy.The catalyst of recycling no longer needs to
Processing carries out the above reaction using the catalyst of recycling again, after the reaction was completed, collects reaction solution and simultaneously carries out chromatography, tie
Fruit is shown in Table 1.
Embodiment 8
With embodiment 1, difference is, the temperature of first segment reaction is 85 DEG C, and the temperature of second segment reaction is 100 DEG C.It surveys
Test result is shown in Table 1.
The toluene solution color of the catalyst of recycling illustrates have a small amount of rhodium to be oxidized than slightly deepening before reaction.Pass through31PNMR analysis finds that its chemical environment does not occur bright after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It is aobvious to change, show the Phosphine ligands in conjunction with catalyst without departing from catalyst structure does not destroy.The catalyst of recycling no longer needs to
Processing carries out the above reaction using the catalyst of recycling again, after the reaction was completed, collects reaction solution and simultaneously carries out chromatography, tie
Fruit is shown in Table 1.
Embodiment 9
With embodiment 1, difference is, the temperature of first segment reaction is 70 DEG C, and the temperature of second segment reaction is 100 DEG C.It surveys
Test result is shown in Table 1.
The toluene solution color of the catalyst of recycling has no significant change, illustrates that rhodium is not oxidized.Pass through31PNMR analysis
Its chemical environment is not substantially change after discovery reaction when the chemical environment variation of P atom in ligand in conjunction with rhodium, table
The bright Phosphine ligands in conjunction with catalyst are without departing from catalyst structure does not destroy.The catalyst of recycling is without reprocessing, application
The catalyst of recycling carries out the above reaction again, after the reaction was completed, collects reaction solution and simultaneously carries out chromatography, the results are shown in Table 1.
Embodiment 10
With embodiment 1, difference is, the temperature of first segment reaction is 60 DEG C, and the temperature of second segment reaction is 100 DEG C.It surveys
Test result is shown in Table 1.
The toluene solution color of the catalyst of recycling has no significant change, illustrates that rhodium is not oxidized.Pass through31PNMR analysis
Its chemical environment is not substantially change after discovery reaction when the chemical environment variation of P atom in ligand in conjunction with rhodium, table
The bright Phosphine ligands in conjunction with catalyst are without departing from catalyst structure does not destroy.The catalyst of recycling is without reprocessing, application
The catalyst of recycling carries out the above reaction again, after the reaction was completed, collects reaction solution and simultaneously carries out chromatography, the results are shown in Table 1.
Embodiment 11
With embodiment 1, difference is, the temperature of first segment reaction is 70 DEG C, and the temperature of second segment reaction is 90 DEG C.Test
It the results are shown in Table 1.
The color of the toluene solution of the catalyst of recycling with react before have no significant change, illustrate that rhodium is not oxidized.Together
When pass through31PNMR analysis finds that its chemical environment is not after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It substantially change, shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalysis of recycling
Agent carries out above-mentioned reaction using the catalyst of recycling without reprocessing again, after the reaction was completed, collects reaction solution and carries out chromatography
Analysis, the results are shown in Table 1.
Embodiment 12
With embodiment 1, difference is, the temperature of first segment reaction is 60 DEG C, and the temperature of second segment reaction is 80 DEG C.Test
It the results are shown in Table 1.
The toluene solution color of the catalyst of recycling has no significant change, illustrates that rhodium is not oxidized.Pass through31PNMR analysis
Its chemical environment is not substantially change after discovery reaction when the chemical environment variation of P atom in ligand in conjunction with rhodium, table
The bright Phosphine ligands in conjunction with catalyst are without departing from catalyst structure does not destroy.The catalyst of recycling is without reprocessing, application
The catalyst of recycling carries out the above reaction again, after the reaction was completed, collects reaction solution and simultaneously carries out chromatography, the results are shown in Table 1.
Embodiment 13
With embodiment 1, difference is, the temperature of first segment reaction is 90 DEG C, and the temperature of second segment reaction is 110 DEG C.It surveys
Test result is shown in Table 1.
The toluene solution color of the catalyst of recycling illustrates have a small amount of rhodium to be oxidized than slightly deepening before reaction.Pass through31PNMR analysis finds that its chemical environment does not occur bright after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It is aobvious to change, show the Phosphine ligands in conjunction with catalyst without departing from catalyst structure does not destroy.The catalyst of recycling no longer needs to
Processing carries out the above reaction using the catalyst of recycling again, after the reaction was completed, collects reaction solution and simultaneously carries out chromatography, tie
Fruit is shown in Table 1.
Embodiment 14
With embodiment 1, difference is, the time of first segment reaction is 5min, and the time of second segment reaction is 115min.It surveys
Test result is shown in Table 1.
The toluene solution color of the catalyst of recycling illustrates have a small amount of rhodium to be oxidized than slightly deepening before reaction.Pass through31PNMR analysis finds that its chemical environment does not occur bright after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It is aobvious to change, show the Phosphine ligands in conjunction with catalyst without departing from catalyst structure does not destroy.The catalyst of recycling no longer needs to
Processing carries out the above reaction using the catalyst of recycling again, after the reaction was completed, collects reaction solution and simultaneously carries out chromatography, tie
Fruit is shown in Table 1.
Embodiment 15
With embodiment 1, difference is, the time of first segment reaction is 10min, and the time of second segment reaction is 110min.
Test result is shown in Table 1.
The toluene solution color of the catalyst of recycling illustrates have a small amount of rhodium to be oxidized than slightly deepening before reaction.Pass through31PNMR analysis finds that its chemical environment does not occur bright after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It is aobvious to change, show the Phosphine ligands in conjunction with catalyst without departing from catalyst structure does not destroy.The catalyst of recycling no longer needs to
Processing carries out the above reaction using the catalyst of recycling again, after the reaction was completed, collects reaction solution and simultaneously carries out chromatography, tie
Fruit is shown in Table 1.
Embodiment 16
With embodiment 1, difference is, the time of first segment reaction is 15min, and the time of second segment reaction is 105min.
Test result is shown in Table 1.
The toluene solution color of the catalyst of recycling has no significant change, illustrates that rhodium is not oxidized.Pass through31PNMR analysis
Its chemical environment is not substantially change after discovery reaction when the chemical environment variation of P atom in ligand in conjunction with rhodium, table
The bright Phosphine ligands in conjunction with catalyst are without departing from catalyst structure does not destroy.The catalyst of recycling is without reprocessing, application
The catalyst of recycling carries out the above reaction again, after the reaction was completed, collects reaction solution and simultaneously carries out chromatography, the results are shown in Table 1.
Embodiment 17
With embodiment 1, difference is, the time of first segment reaction is 40min, and the time of second segment reaction is 80min.It surveys
Test result is shown in Table 1.
The color of the toluene solution of the catalyst of recycling with react before have no significant change, illustrate that rhodium is not oxidized.Together
When pass through31PNMR analysis finds that its chemical environment is not after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It substantially change, shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalysis of recycling
Agent carries out above-mentioned reaction using the catalyst of recycling without reprocessing again, after the reaction was completed, collects reaction solution and carries out chromatography
Analysis, the results are shown in Table 1.
Embodiment 18
With embodiment 1, difference is, the molar ratio of rhodium is 2000:1 in 1- octene and rhodium complex catalyst.Test knot
Fruit is shown in Table 1.
The color of the toluene solution of the catalyst of recycling with react before have no significant change, illustrate that rhodium is not oxidized.Together
When pass through31PNMR analysis finds that its chemical environment is not after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It substantially change, shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalysis of recycling
Agent carries out above-mentioned reaction using the catalyst of recycling without reprocessing again, after the reaction was completed, collects reaction solution and carries out chromatography
Analysis, the results are shown in Table 1.
Embodiment 19
With embodiment 1, difference is, the molar ratio of 1- octene and rhodium complex catalyst is 8000:1.Test result is shown in
Table 1.
The color of the toluene solution of the catalyst of recycling with react before have no significant change, illustrate that rhodium is not oxidized.Together
When pass through31PNMR analysis finds that its chemical environment is not after reacting when the chemical environment variation of P atom in the ligand in conjunction with rhodium
It substantially change, shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalysis of recycling
Agent carries out above-mentioned reaction using the catalyst of recycling without reprocessing again, after the reaction was completed, collects reaction solution and carries out chromatography
Analysis, the results are shown in Table 1.
Embodiment 20
With embodiment 1, difference is, the molar ratio of 1- octene and rhodium complex catalyst is 10000:1.Test result is shown in
Table 1.
The color of the toluene solution of the catalyst of recycling with react before be slightly changed, illustrate there is a small amount of rhodium to be oxidized.Simultaneously
Pass through31Its chemical environment is not sent out after discovery reaction when the chemical environment variation of P atom in ligand in conjunction with rhodium for PNMR analysis
Life is substantially change, and shows the Phosphine ligands in conjunction with catalyst without departing from the structure of catalyst is not destroyed.The catalyst of recycling
Without reprocessing, above-mentioned reaction is carried out again using the catalyst of recycling, after the reaction was completed, is collected reaction solution and is carried out chromatography point
Analysis, the results are shown in Table 1.
Comparative example 1
With embodiment 1, difference is, wherein autoclave is directly heated to 100 DEG C, reacts 120min, remaining experiment item
Part is constant, and test result is shown in Table 1.
Light yellow from before reacting of the solution colour of the toluene of the catalyst of recycling becomes brown, and catalyst is oxidized.It is logical
It crosses31P goes out peak position and substantially change after discovery is reacted when PNMR analyzes the chemical environment variation of P atom in the ligand in conjunction with rhodium,
Show catalyst structure destroyed.
Comparative example 2
With embodiment 4, difference is, wherein autoclave is directly heated to 100 DEG C, reacts 120min, remaining experiment item
Part is constant, and test result is shown in Table 1.
Light yellow from before reacting of the solution colour of the toluene of the catalyst of recycling becomes brown, and catalyst is oxidized.It is logical
It crosses31P goes out peak position and substantially change after discovery is reacted when PNMR analyzes the chemical environment variation of P atom in the ligand in conjunction with rhodium,
Show catalyst structure destroyed.
Comparative example 3
With embodiment 1, difference is, wherein 1- octene is not added when reacting in the stage 1, reaction time 0.5h is anti-in the stage 2
Seasonable that 1- octene is added, reaction time 120min, remaining experiment condition is constant, and test result is shown in Table 1.
Table 1
" --- " indicates not detect.
It can be seen that the reaction temperature different by two stages of setting, the conversion ratio and product of raw material from the data of table 1
Yield increase significantly compared to being reacted at single temperature.From comparative example 1 and embodiment 1 and comparative example 2 and embodiment 4
Comparison can be seen that and directly reacted at high temperature using catalyst, catalyst activity and selectivity are lower.From comparative example 3
Comparison with embodiment 1 can be seen that individually by catalyst system carry out pre-reaction after, catalyst activity and selectivity compared with
It is low.
Using method provided by the invention, catalyst recycling still has good catalytic effect when reusing, and obtains
The conversion ratio of octene and the selectivity of aldehyde C-9 be held in higher level.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (10)
1. a kind of hydroformylation of olefin method, is included in the presence of rhodium complex catalyst, alkene and synthesis gas are through
One section of reaction and second segment reaction generate aldehyde, and wherein the temperature of first segment reaction is at least 5 DEG C lower than the temperature that second segment reacts, excellent
The temperature for selecting first segment to react is at least 10 DEG C lower than the temperature that second segment reacts, and the temperature of more preferable first segment reaction compares second segment
The temperature of reaction is at least 15 DEG C low.
2. the method according to claim 1, wherein the temperature of first segment reaction is 50-135 DEG C, preferably
It is 60-80 DEG C, more preferable 70-80 DEG C;And/or the pressure of reaction is 0-8MPa, preferably 1-6MPa, more preferably 1-3MPa;
And/or reaction time within 50min, preferably 10-25min, more preferably 10-20min.
3. method according to claim 1 or 2, which is characterized in that the temperature of the second segment reaction is 55-140 DEG C, excellent
It is selected as 80-110 DEG C, more preferably 90-100 DEG C;And/or the pressure of reaction is 0-8MPa, preferably 1-6MPa, more preferably 1-
3MPa;And/or the time of reaction is 1-8h, preferably 1-5h, more preferably 1-3h.
4. method according to any one of claim 1-3, which is characterized in that the alkene is C2-C12Alkene, preferably
C5-C12Alkene, more preferably C6-C10Alkene.
5. method according to any of claims 1-4, which is characterized in that the rhodium complex catalyst is formula (I)
It is shown:
Rh(L1)x(L2)y(L3)zFormula (I)
Wherein, L1Selected from carbonyl, acetylacetone,2,4-pentanedione, diphenylphosphine, cyclo-octadiene, norbornene and triphenylphosphine, L2And L3It is identical or
Difference is independently selected from hydrogen, carbonyl, chlorine, bromine, acetylacetone,2,4-pentanedione, diphenylphosphine, cyclo-octadiene, norbornene and triphenyl
Phosphine;
X is the integer of 1-3, and y and z are independently selected from the integer of 0-4, x+y+z≤5.
6. method according to any one of claims 1-5, which is characterized in that the rhodium complex catalyst is organic phosphine
Compound modified rhodium complex catalyst;Preferably, the organic phosphine compound is the organic phosphine compound containing phenyl, excellent
Choosing is selected from substituted or unsubstituted triphenylphosphine oxide, substituted or unsubstituted triphenylphosphine and substituted or unsubstituted diphenyl
Phosphine,
Preferably, shown in the substituted triphenylphosphine such as formula (II):
Wherein, R1、R2And R3It is independently selected from C1-C5Alkyl or alkoxy, it is preferable that R1、R2And R3It is independently selected from
Methyl, ethyl, n-propyl, isopropyl or C1-C5Alkoxy;
Preferably, shown in the substituted diphenylphosphine such as formula (III):
Wherein, R4Selected from hexamethylene or cycloheptane;
R5And R6It is independently selected from C1-C5Alkyl or alkoxy, it is preferable that R5And R6Be independently selected from methyl, ethyl,
N-propyl, isopropyl or C1-C5Alkoxy.
7. according to the method described in claim 6, it is characterized in that, the organic phosphine compound and rhodium in rhodium complex catalyst
Molar ratio be (0.5-200): 1, preferably (12-200): 1, more preferably (40-150): 1.
8. method according to any one of claims 1-7, which is characterized in that rhodium in alkene and rhodium complex catalyst
Molar ratio is (500-100000): 1, preferably (1000-10000): 1, more preferably (2000-8000): 1;And/or it is described
The molar ratio of hydrogen and carbon monoxide is (0.1-20): 1, preferably (1-10): 1 in synthetic gas.
9. method according to claim 1 to 8, which is characterized in that the hydroformylation reaction is in solvent
It carries out, it is preferable that the solvent is organic solvent, is preferably selected from C4-C10Aldehyde, C4-C10Ketone, C4-C10Alkane, acetyl
At least one of benzene,toluene,xylene and chlorobenzene.
10. method according to claim 1 to 9, which is characterized in that in hydroformylation reaction, the alkene
Before contacting with synthetic gas, alkene and catalyst premixing are closed, it is preferable that the premixing time is less than 10min, preferably smaller than
5min, more preferable 1-3min.
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