CN106607093A - Catalyst composition and use thereof - Google Patents
Catalyst composition and use thereof Download PDFInfo
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- CN106607093A CN106607093A CN201510690505.XA CN201510690505A CN106607093A CN 106607093 A CN106607093 A CN 106607093A CN 201510690505 A CN201510690505 A CN 201510690505A CN 106607093 A CN106607093 A CN 106607093A
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Abstract
The invention relates to a catalyst composition and a hydroformylation technology for preparing pentanal. According to the technology, butene is subjected to hydroformylation in the presence of the catalyst composition. The catalyst composition comprises a rhodium-containing compound selected from highly priced metallocene cationic bisphosphine compounds and metal or ammonium salt-containing promoters having different valences. The technology is used for hydroformylation of butene and its analogues into pentanal, has a high pentanal conversion rate and high pentanal selectivity and can be used for industrial preparation of pentanal.
Description
Technical field
The present invention relates to a kind of carbon monoxide-olefin polymeric, more particularly to a kind of carbon monoxide-olefin polymeric for preparing valeral.
Background technology
Valeral is novel environment-friendly, the crucial synthesis material of nontoxic plasticizer DPHP, while it can also be used as lubrication
The synthesis material of the chemicals closely related with people's life such as oil additive, metal flotation agent and cosmetic perfumes.Therefore,
This area exist to by butylene effectively, efficiently demand of the hydroformylation into the technique of its corresponding valeral.It is especially in the presence of to aobvious
Show the demand of high reaction rate and the selective technique of sound response.Present invention achieves this demand and by read hereafter
Other demands that will be apparent to those skilled in the art with appended claims.
CN200810038223.1 is related to a kind of butene hydroformylation catalyst composition, especially with rhodium-triaryl phosphine network
Compound and at least one diphosphite ester additive synthesize as the catalyst of butene hydroformylation for valeral.The present invention is logical
Cross and use additive, such as bis-phosphite, the just different ratio of valeral in the activity and product of Rh (I)/triaryl phosphine catalyst can be improved,
Make the mol ratio of valeraldehyde/isovaleral>50, and the significant service life for extending bisphosphite ligands, reduce triaryl phosphine
Consumption, reduces the cost of butene hydroformylation industrialized production.
CN200910058201.6 the invention discloses a kind of method of preparing aldehyde by hydroformylation of light olefins, be characterized in by
The weight portion of rhodium complex 0.1～2, the weight portion of bidentate phosphine ligandses 0.3～10, the weight portion of surfactant 0.001～0.1 goes
The weight portion of ionized water 100～500, in adding the autoclave with agitator and thermometer, is allowed to be completely dissolved, in autoclave
With hydrogen: carbon monoxide=1: the synthesis gas of 1 volume ratio is replaced 3～5 times, added needed for low-carbon alkene hydroformylation by pressurization
0.8～1.9MPA of pressure, then increases synthesis atmospheric pressure to 2～6MPA, and in temperature, 60～150 DEG C are reacted 1～4 hour, cold
But reactant is taken out afterwards, aqueous catalyst solution layer is isolated, and obtains product aldehyde.
A kind of methods of preparing aldehyde by alkene hydroformylation of CN200810045977.X, are characterized in the weight portion of rhodium complex 1～10,
The weight portion of Phosphine ligands 10～1000, the weight portion of double Longer-chain surfactants 0.01～1, the weight portion of deionized water 500～5000,
In adding the reactor with agitator and thermocouple, it is allowed to be completely dissolved, hydrogen: carbon monoxide=1: 1 body is used in reactor
The synthesis gas of product ratio is replaced 3～5 times, and by pressurization 100～2000 parts of alkene is added, and then adds synthesis atmospheric pressure to 1～6MPA,
In temperature, 50～150 DEG C are reacted 2～8 hours, and reactant is taken out after cooling, separated, obtain product aldehyde.
The content of the invention
One of the technical problem to be solved is that valeraldehyde selectivity present in prior art is low, yield is low asks
A kind of topic, there is provided new carbon monoxide-olefin polymeric, when the carbon monoxide-olefin polymeric is used to prepare valeraldehyde, selects with valeraldehyde
Property the high, advantage of high income；The two of technical problem solved by the invention are to provide a kind of relative with one of technical problem is solved
The purposes of the catalyst answered.
For technology above-mentioned technical problem, technical scheme is as follows：A kind of carbon monoxide-olefin polymeric, including rhodium complex and
High price metallocene cation diphosphine compound.
In above-mentioned technical proposal, it is preferred that the mol ratio of rhodium complex and high price metallocene cation diphosphine compound is
0.01～100；It is furthermore preferred that the mol ratio of rhodium complex and high price metallocene cation diphosphine compound is 0.1～10.
In above-mentioned technical proposal, it is preferred that the mol ratio of rhodium complex and high price metallocene cation diphosphine compound is
0.2～2；It is furthermore preferred that the mol ratio of rhodium complex and high price metallocene cation diphosphine compound is 0.5～1.
In above-mentioned technical proposal, it is preferred that the valence state of high price metallocene is more than divalent；It is furthermore preferred that the valency of high price metallocene
State is more than 2.5 valencys；Most preferably, the valence state of high price metallocene is more than 2.8 valencys.
In above-mentioned technical proposal, it is preferred that the valence state of high price metallocene is trivalent.
In above-mentioned technical proposal, it is preferred that catalyst also includes accelerator, and it is selected from slaine or ammonium salt；It is furthermore preferred that
Accelerator is selected from ammonium hexafluorophosphate, ammonium tetrafluoroborate, potassium bromide, potassium chloride, Tetrafluoroboric acid tetramethyl-ammonium, potassium carbonate, sulfur
At least one in sour aluminum, sodium bicarbonate.
In above-mentioned technical proposal, it is preferred that accelerator selected from ammonium hexafluorophosphate, ammonium tetrafluoroborate, potassium bromide, potassium chloride,
One kind in Tetrafluoroboric acid tetramethyl-ammonium, potassium carbonate, aluminum sulfate, sodium bicarbonate；It is furthermore preferred that accelerator is selected from hexafluoro phosphorus
Sour ammonium or ammonium tetrafluoroborate；Most preferably, accelerator is selected from ammonium hexafluorophosphate.
In above-mentioned technical proposal, it is preferred that rhodium complex is selected from rhodium chloride, rhodium acetate, dicarbonyl rhodium acetylacetonate, (second
Acyl acetone) (norbornadiene) rhodium, double (1,5- cyclo-octadiene) Tetrafluoroboric acid rhodiums, double (dicyclopentadiene) Tetrafluoroboric acid rhodiums, carbonyl
Double (triphen phosphino-) radium chlorides, three (triphenylphosphine) carbonyl hydrogenation Rhs, double (1,5- cyclo-octadiene) dichloride rhodiums, four (triphenylphosphines)
Hydrogenation Rh, three (triphenylphosphine) radium chlorides, rhodium phosphine complex or its mixture；It is furthermore preferred that rhodium complex is selected from tri-chlorination
Rhodium, rhodium acetate, dicarbonyl rhodium acetylacetonate, (acetylacetone,2,4-pentanedione) (norbornadiene) rhodium, double (1,5- cyclo-octadiene) Tetrafluoroboric acids
It is double (triphen phosphino-) radium chloride of rhodium, double (dicyclopentadiene) Tetrafluoroboric acid rhodiums, carbonyl, three (triphenylphosphine) carbonyl hydrogenation Rhs, double
In (1,5- cyclo-octadiene) dichloride rhodium, four (triphenylphosphine) hydrogenation Rhs, three (triphenylphosphine) radium chlorides, rhodium phosphine complex one
Kind.
In above-mentioned technical proposal, it is preferred that rhodium complex is selected from dicarbonyl rhodium acetylacetonate.
In above-mentioned technical proposal, it is preferred that metal cation is at least one metal sun in the race of the periodic table of elements the VIIIth
Ion；It is furthermore preferred that metal cation is the one kind in Fe, Co, Ni and Rh.
In above-mentioned technical proposal, it is preferred that high price metallocene cation diphosphine compound includes that trivalent ferrocene cation is double
(diaryl) phosphine tetrafluoroborate or double (diaryl) the phosphine hexafluorophosphates of trivalent ferrocene cation；It is furthermore preferred that high
Valency metallocene cation diphosphine compound includes double (diphenyl) the phosphine tetrafluoroborates of trivalent ferrocene cation or trivalent two
Double (diphenyl) the phosphine hexafluorophosphates of luxuriant ferrum cation.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of preparation method of valeral, in hydrogen
In the presence of formylation condition and above-mentioned carbon monoxide-olefin polymeric, butylene and hydrogen and carbon monoxide haptoreaction are obtained into valeral.
In above-mentioned technical proposal, it is preferred that hydroformylation conditions are as follows：25 DEG C～150 DEG C of reaction temperature, reaction pressure
0.1MPa～2MPa, butylene is 1～10000 with the mol ratio of carbon monoxide-olefin polymeric.
In above-mentioned technical proposal, it is preferred that 90 DEG C～130 DEG C；Reaction pressure 0.1MPa～2MPa.
In above-mentioned technical proposal, valeral includes valeraldehyde, 3- methylbutyraldehyds or their mixture；Butylene include 1-butylene,
Carbon four or their mixture after cis-2-butene, Trans-2-butene, ether.
In above-mentioned technical proposal, carbon monoxide-olefin polymeric is dissolved in organic solvent；Preferably, it is not additional organic molten in reaction system
Agent；It is furthermore preferred that the content of organic solvent is less than 1 weight %.
In above-mentioned technical proposal, the organic solvent is selected from alcohol, ether, hydroformylation raw material and hydroformylation reaction product；It is excellent
Selection of land, the organic solvent selected from benzene, toluene, xylol, tetrahydrofuran, 3- methyltetrahydrofurans, methanol, propanol,
Dichloromethane, chloroform, 1,2- dichloroethanes, ether, liquefied butane, pentane, hexamethylene, valeraldehyde, 3- methyl
Butyraldehyde and their mixture or solvent-free.
In above-mentioned technical proposal, it is preferred that the organic solvent includes toluene, tetrahydrofuran, liquefied butane, pentane, ring
Hexane, valeraldehyde, 3- methylbutyraldehyds and their mixture.
In above-mentioned technical proposal, it is preferred that technological process also includes from the catalytic component isolating valeral, and will
The contact procedure that the catalyst component is recycled to continues to react.
Using technical scheme, by getting up and can make reaction condition, phosphine and rhodium component, accelerator and solvent combination
The hydroformylation for obtaining butylene is easy to carry out, such as by n-butene with cis/trans -2-butylene hydroformylation into valeral.Particularly
It was found that rhodium system catalyst system and catalyzing is to effective into the reaction of valeral by butene hydroformylation.The catalyst of the present invention overcomes other people and reports
The low catalytic selectivity in road, and give valeraldehyde in high yield and high selectivity.
Rhodium compound is not particularly limited.It can be the rhodium resource that can be arbitrarily dissolved in organic solvent.Compound of Example includes ruthenium
Salt, hydrogen complex (hydride complex), carbonyl compound, halogenide, oxide, phosphine composition (phosphinecomplex)
With their mixture.Suitable rhodium salt includes dicarbonyl rhodium acetylacetonate.
High price phosphine compound is selected from the double aryl phosphonium salts of trivalent metallocene cation.Metal finger transition metal, some are representational
Material examples are ferrum, cobalt, zirconium, nickel, titanium, vanadium etc..Some representative examples of substituted aryl be phenyl, halogenophenyl,
Such as 4- fluorophenyls, 2,6- difluorophenyls, 2,5- Dichlorobenzene base, 3,4- Dichlorobenzene base, 3- chlorphenyls, 3- bromophenyls,
4- bromophenyls, 3,4- dibromo phenyls, 2- fluorophenyls etc.；Single or two (methyl) aryl, such as 4- aminomethyl phenyls, 3- methylbenzene
Base, 2,4- 3,5-dimethylphenyls, 3,5- 3,5-dimethylphenyls etc.；Methoxyl group aryl, such as 3- or 4- methoxyphenyls.Anion
Refer to tetrafluoride boron and four (3,5- bis- (trifluoromethyl) phenyl) borates.In one embodiment, for example, high price phosphine chemical combination
Thing may be selected from the double aryl phosphonium salts of trivalent metallocene cation.In another embodiment, rhodium compound may be selected from ruthenium salt, hydrogen and coordinate
Thing, carbonyl compound, halogenide, oxide, phosphine composition and their mixture；And trivalent phosphine compound may be selected from
The double aryl phosphonium salts of trivalent metallocene cation.Useful especially trivalent phosphine compound is the double (hexichol of trivalent ferrocene cation
Base) phosphine hexafluorophosphonate.
Reaction rate and selectivity are accelerated by adding accelerator, the accelerator may be selected from ammonium hexafluorophosphate, Tetrafluoroboric acid
Ammonium and their mixture.
Organic solvent can be selected from multiple compounds, the mixture of compound or the thing being in a liquid state under the pressure of implementing process
Matter.The main standard of solvent is its energy catalyst-solvent component and reactant, and does not play a part of to poison catalyst.It is suitable
The organic solvent of conjunction includes alcohol, ether, hydroformylation raw material and hydroformylation reaction product.The concrete reality of suitable organic solvent
Example includes benzene, toluene, xylol, tetrahydrofuran, 3- methyltetrahydrofurans, methanol, propanol, dichloromethane, trichlorine
Methane, 1,2- dichloroethanes, ether, liquefied butane, pentane, hexamethylene, valeraldehyde, 3- methylbutyraldehyds and theirs is mixed
Compound is solvent-free.
Rhodium and trivalent phosphine coordinate the concentration of base to change in a wide range in organic solvent or reactant mixture.It is, in general, that
Ke Moer is kept to coordinate base in reactant mixture:The ratio of gram rhodium atom is at least 1:1.More generally, the proportion
For 1:1—20:1 or 3:1—5:1.
The absolute concentration of rhodium metal can be from 1mg/L changes up to more than 5000mg/L in reactant mixture or solution.When
When technique is operated in the physical condition of the present invention, the concentration of the rhodium metal in reaction solution is typically about 20-600mg/L.
Accelerator content is typically larger than rhodium content.The scope of the amount of accelerator is 0.5-50 molar equivalents.It is, in general, that
The scope of the amount of accelerator is 3-50 molar equivalents.The usage amount of organic solvent is not particularly limited.It is, in general, that
All of catalytic component is dissolved using enough solvents.
The catalyst system and catalyzing and solution for preparing the present invention does not need special or unique technology, but in order to obtain highly active catalysis
Agent, preferably carries out in an inert atmosphere rhodium and phosphine coordinates the operation of base, and inert atmosphere is nitrogen, argon etc..Will be the desired amount of
Suitable rhodium compound and cooperation base is added in the solvent being adapted in reactor.Various carbon monoxide-olefin polymerics or reactant are added
Order in reactor can be different.
Embodiment to being not added with accelerator is analyzed and shown, the conversion ratio of butylene is less than 40%, the selectivity to valeraldehyde
Less than 80%.On the other hand, the operating added with accelerator shows that the conversion of butylene is higher than 50%, and the selectivity of valeraldehyde is high
In 90%, accelerator is added to data display the actively impact in catalytic mixing thing.
Reaction pressure has strong influence to reaction result.Lower pressure typically results in lower reaction rate.Therefore, most
Preferably pressure limit is more than 0.1Mpa.Higher pressure normally results in faster reaction rate, but this is operated
The more high cost of higher pressure is offset.Preferably pressure limit is 0.1-10Mpa, preferred 0.1-2Mpa.
Technological temperature can change in a wide range.Preferably temperature range is 20 DEG C -150 DEG C.The preferred temperature of this technique
Scope is 90 DEG C -130 DEG C.
The amount of butylene can change in a wide range in reactant mixture.In practice, the raw material of higher concentration is favourable in reactor
In reaction rate.
Any of reactor design and structure can be adopted to the technique for carrying out offer of the present invention.For example, the technique can be with
It is carried out as follows in a batch manner in autoclave：By in the presence of carbon monoxide-olefin polymeric described herein, by butylene and hydrogen,
Carbon monoxide is contacted.Skilled in the art realises that the present invention can use other reactor schemes.
An embodiment of the invention is the technique for preparing valeral, and it is included in hydroformylation conditions and carbon monoxide-olefin polymeric
In the presence of, butylene is contacted with hydrogen, carbon monoxide to prepare valeral, the carbon monoxide-olefin polymeric is included：
(a) rhodium complex；
B () trivalent diphosphine compound, it is selected from a class high price metallocene cation diphosphine compound；With
(c) accelerator, its be selected from different valence state containing metal or ammonium class salt accelerator；
Wherein, catalyst combination (a)～(c) is dissolved in organic solvent, and the solvent is selected from benzene, toluene, to two
Toluene, tetrahydrofuran, 3- methyltetrahydrofurans, methanol, propanol, dichloromethane, chloroform, 1,2- dichloroethanes,
Ether, liquefied butane, pentane, hexamethylene, valeraldehyde, 3- methylbutyraldehyds and their mixture or solvent-free.
Above-mentioned technique should be read to include appointing for single accelerator listed above, rhodium compound, initial butylene and solvent
Meaning combination.For example, rhodium compound includes dicarbapentaborane acetyl acetone rhodium.In another example, rhodium compound may include dicarbapentaborane
Acetyl acetone rhodium, accelerator may include ammonium hexafluorophosphate, ammonium tetrafluoroborate and their mixture and solvent may include positive penta
Aldehyde.In another example, accelerator may include four (3,5- bis- (trifluoromethyl) phenyl) sodium borate.In yet another embodiment, rhodium compound
Dicarbapentaborane acetyl acetone rhodium is may include, accelerator may include ammonium hexafluorophosphate, and solvent includes liquefied butane.Yet another embodiment
In, ruthenium compound may include dicarbapentaborane acetyl acetone rhodium, and accelerator may include ammonium tetrafluoroborate, and be not added with any solvent.
In yet another embodiment, ruthenium compound may include dicarbapentaborane acetyl acetone rhodium, and accelerator may include ammonium hexafluorophosphate, Tetrafluoroboric acid
Ammonium and their mixture.Another embodiment of the present invention is the technique for preparing valeral, its be included in hydroformylation conditions and
In the presence of carbon monoxide-olefin polymeric, butylene is contacted with hydrogen, carbon monoxide to prepare valeral, the carbon monoxide-olefin polymeric bag
Contain：
(a) dicarbonyl rhodium acetylacetonate；
Double (diphenyl) the phosphine hexafluorophosphonates of (b) trivalent ferrocene cation；With
(c) accelerator, ammonium hexafluorophosphate, ammonium tetrafluoroborate and their mixture；
Wherein, catalyst combination (a)～(c) be dissolved in toluene, tetrahydrofuran, liquefied butane, pentane, hexamethylene,
Valeraldehyde, 3- methylbutyraldehyds and their mixture.
The hydroformylation process of the present invention is also included and separates such as valeral product from carbon monoxide-olefin polymeric, and will be described
Catalyst component is recycled to hydroformylation contact procedure.Can be used for the separation for separating catalytic component from reactant mixture
The example of technology includes steam stripping, flash distillation and liquid-liquid extraction.One separates catalyst from product, it is possible to again
It is secondary to be added in reactor to recycle.Or, catalyst solution can be used the reaction of such as toluene solvant or such as valeraldehyde
Product dilution, then recycles.Then, valeral product just can be reclaimed from water phase through simple distillation, and will be organic
Mutually it is then added to be recycled in reactor.It should be appreciated that above-mentioned separating technology can with invented technology described herein appoint
One different embodiments are applied in combination.
Below by the embodiment more detailed description present invention of embodiment of the present invention, although it should be understood that these embodiments are only
Add and be not intended to limit the scope of the invention to illustrate purpose.Unless otherwise indicated, all percents are all the amount percentage of material
Than.
Specific embodiment
【Embodiment 1～8】
By butene hydroformylation into valeral in toluene
Load dicarbonyl rhodium acetylacetonate (0.05mmol), trivalent ferrocene cation double (two in 150 milliliters of autoclaves
Phenyl) specified quantitative shown in phosphine hexafluorophosphonate (0.10mmol) and table accelerator.Add toluene (25mL) and butylene
(50mmol), then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 120 DEG C are heated to.
Agitated autoclave, and maintain 120 DEG C of state to amount to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, is returned
Receive content.With the presence of the valeraldehyde in internal standard gas chromatography analysis content and 3- methylbutyraldehyds.As a result see the table below 1.
Table 1
【Comparative example 1】
By butene hydroformylation into valeral in toluene
Load dicarbonyl rhodium acetylacetonate (0.05mmol), trivalent ferrocene cation double (two in 150 milliliters of autoclaves
Phenyl) phosphine hexafluorophosphonate (0.10mmol).Toluene (25mL) and butylene (50mmol) are added, then in N2Displacement is anti-
Answer device.Use H2Reactor is pressurized to into 2.0MPa with CO and 120 DEG C are heated to.Agitated autoclave, and maintain 120 DEG C
State amount to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, content is reclaimed.Use internal standard gas chromatography
The presence of valeraldehyde and 3- methylbutyraldehyds in contents analysed.The results are shown in Table 1.
【Embodiment 9】
By butene hydroformylation into valeral in toluene
Load double (diphenyl) phosphines of rhodium chloride (0.05mmol), trivalent ferrocene cation in 150 milliliters of autoclaves
Hexafluorophosphonate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Toluene (25mL) and butylene (50mmol) are added,
Then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 120 DEG C are heated to.Stirring high pressure
Kettle, and maintain 120 DEG C of state to amount to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, content is reclaimed.
With internal standard gas chromatography analysis content, it is 79.5% to show butene conversion, and valeraldehyde selectivity is 91.0%.
【Comparative example 2】
By butene hydroformylation into valeral in toluene
Load the double (hexichol of carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), bivalence ferrocene cation in 150 milliliters of autoclaves
Base) phosphine hexafluorophosphonate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add toluene (25mL) and butylene (50
Mmol), then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 120 DEG C are heated to.
Agitated autoclave, and maintain 120 DEG C of state to amount to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, is returned
Receive content.With internal standard gas chromatography analysis content, it is 35.7% to show butene conversion, and valeraldehyde selectivity is
64.3%.
【Embodiment 10】
By butene hydroformylation into valeral in toluene
Load the double (hexichol of carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), trivalent ferrocene cation in 150 milliliters of autoclaves
Base) phosphine hexafluorophosphate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add butylene (50mmol), Ran Hou
N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 90 DEG C are heated to.Agitated autoclave, and tie up
The state for holding 90 DEG C is amounted to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, content is reclaimed.Use interior gas
GC headspace analysis content, it is 68.8% to show butene conversion, and valeraldehyde selectivity is 91.0%.
【Embodiment 11】
By butene hydroformylation into valeral in toluene
Load the double (hexichol of carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), trivalent cobaltocene cation in 150 milliliters of autoclaves
Base) phosphine tetrafluoroborate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add toluene (25mL) and butylene (50
Mmol), then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 120 DEG C are heated to.
Agitated autoclave, and maintain 120 DEG C of state to amount to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, is returned
Receive content.With internal standard gas chromatography analysis content, it is 84.3% to show butene conversion, and valeraldehyde selectivity is
90.9%.
【Embodiment 12】
By butene hydroformylation into valeral in toluene
Load the double (hexichol of carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), trivalent dicyclopentadienyl nickel cation in 150 milliliters of autoclaves
Base) phosphine tetrafluoroborate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add toluene (25mL) and butylene (50
Mmol), then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 130 DEG C are heated to.
Agitated autoclave, and maintain 130 DEG C of state to amount to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, is returned
Receive content.With internal standard gas chromatography analysis content, it is 82.1% to show butene conversion, and valeraldehyde selectivity is
91.1%.
【Embodiment 13】
By butene hydroformylation into valeral in toluene
Load the double (dinaphthyls of carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), trivalent cobaltocene cation in 150 milliliters of autoclaves
Base) phosphine hexafluorophosphate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add toluene (25mL) and butylene (50
Mmol), then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 120 DEG C are heated to.
Agitated autoclave, and maintain 120 DEG C of state to amount to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, is returned
Receive content.With internal standard gas chromatography analysis content, it is 75.3% to show butene conversion, and valeraldehyde selectivity is
88.7%.
【Embodiment 14】
By butene hydroformylation into valeral
Load dicarbonyl rhodium acetylacetonate (0.05mmol), trivalent ferrocene cation double (two in 150 milliliters of autoclaves
Phenyl) phosphine hexafluorophosphate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add butylene (50mmol), Ran Hou
N2Metathesis reactor.Reactor is pressurized to into 2MPa with synthesis gas and nitrogen and 120 DEG C are heated to.Agitated autoclave,
And maintain 120 DEG C of state to amount to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, content is reclaimed.With
Internal standard gas chromatography analysis content, it is 91.5% to show butene conversion, and valeraldehyde selectivity is 96.0%.
【Embodiment 15】
By butene hydroformylation into valeral in tetrahydrofuran
Load dicarbonyl rhodium acetylacetonate (0.05mmol), trivalent ferrocene cation double (two in 150 milliliters of autoclaves
Phenyl) phosphine hexafluorophosphate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add tetrahydrofuran (25mL) and fourth
Alkene (50mmol), then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and is heated to
120℃.Agitated autoclave, and maintain 120 DEG C of state to amount to 3 hours.Then autoclave is cooled down, it is unnecessary to discharge
Gas, reclaims content.With internal standard gas chromatography analysis content, it is 81.0% to show butene conversion, valeraldehyde
Selectivity is 90.4%.
【Embodiment 16】
By cis/trans -2-butylene hydroformylation into valeral in toluene
Load dicarbonyl rhodium acetylacetonate (0.05mmol), trivalent ferrocene cation double (two in 150 milliliters of autoclaves
Phenyl) phosphine hexafluorophosphate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add toluene (25mL) and cis/trans
- 2-butylene (50mmol), then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and is heated
To 120 DEG C.Agitated autoclave, and maintain 120 DEG C of state to amount to 3 hours.Then autoclave is cooled down, it is unnecessary to discharge
Gas, reclaim content.With internal standard gas chromatography analysis content, butene conversion is shown for 65.0%, positive penta
Aldehyde selectivity is 87.1%.
Claims (10)
1. a kind of carbon monoxide-olefin polymeric, including rhodium complex and high price metallocene cation diphosphine compound.
2. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that rhodium complex and high price metallocene sun from
The mol ratio of sub- diphosphine compound is 0.01～100.
3. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the valence state of the high price metallocene is more than 2
Valency.
4. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the valence state of the high price metallocene is more than 2.5
Valency.
5. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that catalyst also includes accelerator, and it is selected from
Slaine or ammonium salt.
6. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that rhodium complex is selected from rhodium chloride, acetic acid
It is rhodium, dicarbonyl rhodium acetylacetonate, (acetylacetone,2,4-pentanedione) (norbornadiene) rhodium, double (1,5- cyclo-octadiene) Tetrafluoroboric acid rhodiums, double (double
Cyclopentadiene) Tetrafluoroboric acid rhodium, carbonyl double (triphen phosphino-) radium chloride, three (triphenylphosphine) carbonyl hydrogenation Rhs, double (1,5- rings are pungent
Diene) dichloride rhodium, four (triphenylphosphine) hydrogenation Rhs, three (triphenylphosphine) radium chlorides, rhodium phosphine complex or its mixture.
7. carbon monoxide-olefin polymeric according to claim 6, it is characterised in that rhodium complex includes dicarbapentaborane acetylacetone,2,4-pentanedione
Rhodium.
8. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that metal cation is selected from the periodic table of elements
At least one metal cation in VIIIth race.
9. a kind of preparation method of valeral, in hydroformylation conditions and carbon monoxide-olefin polymeric described in any one of claim 1～8
In the presence of, butylene and hydrogen and carbon monoxide haptoreaction are obtained into valeral.
10. the preparation method of valeral according to claim 9, wherein the hydroformylation conditions are as follows：Reaction temperature
25 DEG C～150 DEG C, reaction pressure 0.01MPa～10MPa, butylene is 1～10000 with the mol ratio of carbon monoxide-olefin polymeric.
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| CN109092366A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The preparation method of carbon monoxide-olefin polymeric and 2- butenoic acid |
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