CN106608816A - Method for preparing C4-C8 aldehydes - Google Patents
Method for preparing C4-C8 aldehydes Download PDFInfo
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- CN106608816A CN106608816A CN201510689826.8A CN201510689826A CN106608816A CN 106608816 A CN106608816 A CN 106608816A CN 201510689826 A CN201510689826 A CN 201510689826A CN 106608816 A CN106608816 A CN 106608816A
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- rhodium
- aldehyde
- carbon monoxide
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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Abstract
The present invention relates to a catalyst composition and a hydroformylation process for preparation of C4-C8 aldehydes, wherein in the presence of the catalyst composition, C3-C7 olefins are subjected to hydroformylation, and the composition comprises a rhodium compound and a compound selected from high-valent metallocene cationic bisphosphine compounds. According to the present invention, the process can be used for the hydroformylation of C3-C7 olefins into C4-C8 aldehydes, has advantages of high C3-C7 olefin conversion rate and high C4-C8 aldehyde selectivity, and can be used for the industrial applications of preparation of C4-C8 aldehydes.
Description
Technical field
The present invention relates to a kind of method for preparing aldehyde, more particularly to a kind of to be used to prepare C4～C8The method of aldehyde.
Background technology
Hydroformylation reaction refers to alkene and CO/H2The process of aldehyde is generated in the presence of catalyst, is important industry side
Method, alkene can be readily synthesized aldehyde by hydroformylation reaction.Aldehyde compound is very valuable fine chemicals,
It is important synthetic intermediate.It further can easily be converted into into alcohol, acid, ester, Aldol condensation products, acetal
Deng chemicals.These chemicals are that the high added values such as the various detergent of synthesis, surfactant, medicine, spices must become more meticulous
The primary raw material of product.Because end group aldehyde has bigger industrial applicability, it is desirable to optimize technique method, turns so as to high
Rate and high selectivity obtain end group aldehyde.For example, the end position aldehyde product valeraldehyde of butene hydroformylation be novel environment-friendly,
The crucial synthesis material of nontoxic plasticizer DPHP, at the same its can also as lube oil additive, metal flotation agent and
The synthesis material of the chemicals closely related with people's life such as cosmetic perfumes.But when the hydrogen first for using end position selectively not enough
During acylation catalyst, product easily forms unwanted non-end position aldehyde, and this adversely affects the economic feasibility of whole technique.
CN 201110046422.9 is the present invention relates to a kind of alkene method for passing through hydroformylation, mainly solves in conventional art
During hydroformylation of olefin, reaction conversion ratio is low, the selectively low technical problem of purpose product.The present invention passes through
Adopt with the alkene of C2～C8, CO and hydrogen as raw material, with rhodium-containing liquid solution as catalyst, reaction temperature 40～
160 DEG C, 0.5～5.0MPa of reaction pressure, the mol ratio of alkene and rhodium is under conditions of 0.5～30: 1, raw material and rhodium-containing
Liquid solution catalyst enters haptoreaction in rotary packed bed reactor, generates the technical scheme of the liquid efflunent containing aldehyde,
The problem is preferably solved, in can be used for the industrial production of preparing aldehyde by hydro formylating defin.
CN 200780050606.4 is the present invention relates to a kind of prepare hydroformylation product from the alkene with least four carbon atoms
The method of thing.By the contained a high proportion of straight chain C with terminal double bond in the charging of olefin-containingIAlkene and a high proportion of tool
There is the C of internal double bondIAlkene all changes into hydroformylation products.In addition, the present invention relates to a kind of side for preparing 2- propyl enanthols
Method, the method includes above-mentioned hydroformylation process.
A kind of hydroformylation of olefin of CN 201110163685.8 prepares aldehyde method, belongs to the preparation field of aldehyde.Including
C2～C4 alkene prepares aldehyde to Jing hydroformylation reaction serializations with carbon monoxide and hydrogen under rhodium-phosphine catalyst effect, its
Feature is to increase the stagnation pressure of reaction system, makes the partial pressure sum of inert fraction not less than the partial pressure sum of active ingredient, the present invention
The stagnation pressure of the system of selection of reaction pressure when also providing a kind of hydroformylation reaction, specially reaction system is arranged according to hydrogen formyl
Change inert component in the gaseous stream discharged after reaction to determine with the partial pressure of active ingredient.The technical side provided using the present invention
Case can reduce the quantity of the active ingredient lost because inert gas is discharged during continuous hydroformylation, and especially reducing has
The loss amount of alkene in effect composition.Under this programme optimum condition, olefin loss amount can be made to reduce 10-50%, this will bring
Considerable economic benefit.
CN 200910058201.6 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, deionization
The weight portion of water 100～500, in adding the autoclave with agitator and thermometer, is allowed to be completely dissolved, and uses hydrogen in autoclave:
Carbon monoxide=1: the synthesis gas of 1 volume ratio is replaced 3～5 times, by pressurization low-carbon alkene hydroformylation desirable pressure is added
0.8～1.9MPA, then increases synthesis atmospheric pressure to 2～6MPA, and in temperature, 60～150 DEG C are reacted 1～4 hour, are taken after cooling
Go out reactant, isolate aqueous catalyst solution layer, obtain product aldehyde.
A kind of methods of preparing aldehyde by alkene hydroformylation of CN 200810045977.X, are characterized in the weight of rhodium complex 1～10
Part, 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, then plus 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 end position C present in prior art4～C8Aldehyde is selectively low, yield is low
Problem, there is provided a kind of new carbon monoxide-olefin polymeric, the carbon monoxide-olefin polymeric be used for prepare end position C4～C8During aldehyde, have
End position C4～C8The selective high, advantage of high income of aldehyde；The two of technical problem solved by the invention are to provide a kind of and solve
The purposes of the corresponding catalyst of one of technical problem.
To solve above-mentioned technical problem, technical scheme is as follows：One kind prepares C4～C8The method of aldehyde, with C3～C7
Alkene and synthesis gas are raw material, make C3～C7Under conditions of olefin conversion is more than 60%, raw material is through carbon monoxide-olefin polymeric
Reaction obtains C4～C8Aldehyde；The carbon monoxide-olefin polymeric includes rhodium complex and high price metallocene cation diphosphine compound.
In above-mentioned technical proposal, it is preferred that reaction condition is as follows：25 DEG C～200 DEG C, reaction pressure 0.01MPa～10MPa,
C3～C7Alkene is 1～10000 with the mol ratio of carbon monoxide-olefin polymeric.
In above-mentioned technical proposal, it is furthermore preferred that reaction condition is as follows：60 DEG C～150 DEG C, reaction pressure 0.1MPa～2MPa,
C3～C7Alkene is 1～10 with the mol ratio of carbon monoxide-olefin polymeric.
In above-mentioned technical proposal, it is preferred that C3～C7Alkene is included in propylene, butylene, amylene, hexene and heptene at least
It is a kind of.
In above-mentioned technical proposal, it is preferred that catalyst also includes accelerator, and it is selected from slaine or ammonium salt.
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, KBr, potassium chloride, tetrafluoro boric acid tetramethyl-ammonium, potassium carbonate, sulphur
At least one in sour aluminium, sodium acid carbonate.
In above-mentioned technical proposal, it is preferred that accelerator selected from ammonium hexafluorophosphate, ammonium tetrafluoroborate, KBr, potassium chloride,
One kind in tetrafluoro boric acid tetramethyl-ammonium, potassium carbonate, aluminum sulfate, sodium acid carbonate；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) tetrafluoro boric acid rhodiums, double (dicyclopentadiene) tetrafluoro boric 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) tetrafluoro boric acids
It is double (triphen phosphino-) radium chloride of rhodium, double (dicyclopentadiene) tetrafluoro boric 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 iron cation.
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, paraxylene, tetrahydrofuran, 3- methyltetrahydrofurans, methyl alcohol, propyl alcohol,
Dichloromethane, chloroform, 1,2- dichloroethanes, ether, liquefied butane, pentane, hexamethylene, C3～C7Alkene, C4~
C8Aldehyde 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, C3～C7Alkene, C4～C8Aldehyde and their mixture or solvent-free.
In above-mentioned technical proposal, it is preferred that technological process also includes isolating C from the catalytic component4～C8Aldehyde,
And the catalyst component is recycled to into contact procedure to continue to react.
Using technical scheme, by getting up and can make reaction condition, phosphine and rhodium component, accelerator and solvent combination
Obtain C3～C7The hydroformylation of alkene is easy to carry out, such as by n-butene with cis/trans -2- butene hydroformylations into valeral.Especially
It is to have been found that rhodium system catalyst system and catalyzing to butene hydroformylation is effective into the reaction of valeral.The catalyst of the present invention overcomes it
The low catalytic selectivity that other people report, and give end position C4～C8Aldehyde is 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), carbonyls, halide, 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 iron, cobalt, zirconium, nickel, titanium, vanadium etc..Some representative examples of substituted aryl be phenyl, halogenophenyl,
Such as 4- fluorophenyls, 2,6- difluorophenyls, 2,5- dichlorophenyls, 3,4- dichlorophenyls, 3- chlorphenyls, 3- bromophenyls,
4- bromophenyls, 3,4- dibromo phenyls, 2- fluorophenyls etc.；Single or two (methyl) aryl, such as 4- aminomethyl phenyls, 3- methylbenzenes
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, carbonyls, halide, 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, tetrafluoro boric 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, paraxylene, tetrahydrofuran, 3- methyltetrahydrofurans, methyl alcohol, propyl alcohol, dichloromethane, trichlorine
Methane, 1,2- dichloroethanes, ether, liquefied butane, pentane, hexamethylene, C3～C7Alkene, C4～C8Aldehyde and they
Mixture 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 equivalent.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 gas 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.
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 -200 DEG C.The preferred temperature of this technique
Scope is 60 DEG C -150 DEG C.
C in reactant mixture3～C7The amount of alkene can change in a wide range.In practice, higher concentration in reactor
Raw material is conducive to 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 C3～C7Alkene
Hydrocarbon is contacted with hydrogen, carbon monoxide.Skilled in the art realises that the present invention can use other reactor schemes.
An embodiment of the invention is to prepare end position C4～C8The technique of aldehyde, it is included in hydroformylation conditions and catalysis
In the presence of agent composition, by C3～C7Alkene contacts to prepare end position C with hydrogen, carbon monoxide4～C8Aldehyde, it is described to urge
Agent composition 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, methyl alcohol, propyl alcohol, dichloromethane, chloroform, 1,2- dichloroethanes,
Ether, liquefied butane, pentane, hexamethylene, C3～C7Alkene, C4～C8Aldehyde and their mixture or solvent-free.
Above-mentioned technique should be read to include single accelerator listed above, rhodium compound, starting C3～C7Alkene and
Any combination of solvent.For example, rhodium compound includes dicarbapentaborane acetyl acetone rhodium.In another example, rhodium compound can be wrapped
Dicarbapentaborane acetyl acetone rhodium is included, accelerator may include ammonium hexafluorophosphate, ammonium tetrafluoroborate and their mixture and solvent can
Including valeraldehyde.In another example, accelerator may include four (3,5- bis- (trifluoromethyl) phenyl) Boratexes.In yet another embodiment,
Rhodium compound may include dicarbapentaborane acetyl acetone rhodium, and accelerator may include ammonium hexafluorophosphate, and solvent includes liquefied butane.
In yet another embodiment, ruthenium compound may include dicarbapentaborane acetyl acetone rhodium, and accelerator may include ammonium tetrafluoroborate, and be not added with appointing
What solvent.In yet another embodiment, ruthenium compound may include dicarbapentaborane acetyl acetone rhodium, accelerator may include ammonium hexafluorophosphate,
Ammonium tetrafluoroborate and their mixture.Another embodiment of the present invention is the technique for preparing valeral, and it is included in hydrogen formyl
In the presence of change condition and carbon monoxide-olefin polymeric, butylene is contacted with hydrogen, carbon monoxide to prepare valeral, the catalyst
Composition is included：
(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, just C can be reclaimed from water phase through simple distillation4～C8Aldehyde product, and
Organic phase is then added to recycle in reactor.It should be appreciated that above-mentioned separating technology can be with invention work described herein
Arbitrary different embodiments of skill 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 percentages are all the amount percentage of material
Than.
Specific embodiment
【Embodiment 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) and with ammonium hexafluorophosphate (0.05mmol).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 internal standard gas chromatography analysis content, it is 81.6% to show butene conversion, and valeraldehyde is selectively
91.4%.
【Embodiment 2】
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 is selectively 91.0%.
【Embodiment 3】
By amylene hydroformylation into hexanal in toluene
Load dicarbonyl rhodium acetylacetonate (0.05mmol), trivalent ferrocene cation double (two in 150 milliliters of autoclaves
Phenyl) phosphine hexafluorophosphonate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add toluene (25mL) and amylene (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 83.6% to show pentene conversion, and n-hexyl aldehyde is selectively
93.7%.
【Embodiment 4】
Amylene hydroformylation will be mixed in toluene into hexanal
Load the double (hexichol of carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), trivalent ferrocene cation in 150 milliliters of autoclaves
Base) phosphine hexafluorophosphonate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add toluene (25mL) and mixing amylene
(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 internal standard gas chromatography analysis content, it is 79.4% to show pentene conversion, and n-hexyl aldehyde is selectively
98.3%.
【Embodiment 5】
By amylene hydroformylation into hexanal 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 amylene (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
Contents analysed, it is 37.6% to show pentene conversion, and n-hexyl aldehyde is selectively 76.3%.
【Embodiment 6】
By amylene hydroformylation into hexanal in toluene
Load dicarbonyl rhodium acetylacetonate (0.05mmol), trivalent ferrocene cation double (two in 150 milliliters of autoclaves
Phenyl) phosphine hexafluorophosphonate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add amylene (50mmol), Ran Hou
N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 120 DEG C are heated to.Agitated autoclave, and
The state for maintaining 120 DEG C is amounted to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, content is reclaimed.With interior
Gas GC headspace analysis content, it is 91.0% to show pentene conversion, and n-hexyl aldehyde is selectively 95.8%.
【Embodiment 7】
By hexene hydroformylation into enanthaldehyde 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 hexafluorophosphonate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add toluene (25mL) and hexene (50
Mmol), then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 60 DEG C are heated to.Stir
Autoclave is mixed, and maintains 60 DEG C of state to amount to 3 hours.Then autoclave is cooled down, unnecessary gas is discharged, reclaims interior
It is tolerant.With internal standard gas chromatography analysis content, it is 55.3% to show hexene conversion ratio, and n-Heptaldehyde is selectively 91.1%.
【Embodiment 8】
By hexene hydroformylation into enanthaldehyde in toluene
Load carbonyl acetylacetone,2,4-pentanedione rhodium (0.05mmol), trivalent ferrocene cation in 150 milliliters of autoclaves double (diphenyl)
Phosphine hexafluorophosphonate (0.10mmol) and ammonium hexafluorophosphate (0.05mmol).Add toluene (25mL) and hexene (50
Mmol), then in N2Metathesis reactor.Use H2Reactor is pressurized to into 2.0MPa with CO and 150 DEG C are heated to.
Agitated autoclave, and maintain 150 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 95.4% to show hexene conversion ratio, and n-Heptaldehyde is selectively
90.0%.
【Embodiment 9】
By heptene hydroformylation into octanal 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 heptene (50
Mmol), then in N2Metathesis reactor.Reactor is pressurized to into 0.1MPa 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, is returned
Receive content.With internal standard gas chromatography analysis content, it is 51.4% to show heptene conversion ratio, and n-octaldehyde is selectively
87.6%.
【Embodiment 10】
In toluene by propylene with heptene mixture hydroformylation into butyraldehyde and octanal
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 propylene with
Heptene mixture (each 25mmol), then in N2Metathesis reactor.Reactor is pressurized to into 2MPa with synthesis gas and nitrogen
And it 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, is arranged
Unnecessary gas is put, content is reclaimed.With internal standard gas chromatography analysis content, it is 83.9% to show propylene conversion,
Hutanal is selectively 99.1%；It is 79.2% to show heptene conversion ratio, and n-octaldehyde is selectively 90.3%.
Claims (8)
1. one kind prepares C4～C8The method of aldehyde, with C3～C7Alkene and synthesis gas are raw material, make C3～C7Alkene turns
Under conditions of rate is more than 60%, raw material obtains C through carbon monoxide-olefin polymeric reaction4～C8Aldehyde；The carbon monoxide-olefin polymeric
Including rhodium complex and high price metallocene cation diphosphine compound.
2. preparation C according to claim 14～C8The method of aldehyde, it is characterised in that reaction condition is as follows：25 DEG C～
200 DEG C, reaction pressure 0.01MPa～10MPa, C3～C7Alkene is 1～10000 with the mol ratio of carbon monoxide-olefin polymeric.
3. preparation C according to claim 24～C8The method of aldehyde, it is characterised in that reaction condition is as follows：60 DEG C～
150 DEG C, reaction pressure 0.1MPa～2MPa, C3～C7Alkene is 1～10 with the mol ratio of carbon monoxide-olefin polymeric.
4. preparation C according to claim 14～C8The method of aldehyde, it is characterised in that C3～C7Alkene comprising propylene,
At least one in butylene, amylene, hexene and heptene.
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) tetrafluoro boric acid rhodiums, double (double
Cyclopentadiene) tetrafluoro boric 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.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096070A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The production method of m-trifluoromethyl benzenepropanal |
| CN109096071A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The preparation method of 3-phenylpropion aldehyde |
| 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 |
| CN113372206A (en) * | 2021-05-12 | 2021-09-10 | 上海簇睿低碳能源技术有限公司 | Method for synthesizing high-carbon aldehyde by using microchannel reaction device |
| CN114426469A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing alcohol and aldehyde by olefin hydroformylation |
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| CN1193955A (en) * | 1995-08-25 | 1998-09-23 | 纳幕尔杜邦公司 | Hydroformylation process |
| CN102649715A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing aldehyde through olefin hydrogen formylation |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193955A (en) * | 1995-08-25 | 1998-09-23 | 纳幕尔杜邦公司 | Hydroformylation process |
| CN102649715A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing aldehyde through olefin hydrogen formylation |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096070A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The production method of m-trifluoromethyl benzenepropanal |
| CN109096071A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The preparation method of 3-phenylpropion aldehyde |
| 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 |
| CN109096070B (en) * | 2017-06-21 | 2021-10-01 | 中国石油化工股份有限公司 | Method for producing m-trifluoromethyl phenylpropyl aldehyde |
| CN109096071B (en) * | 2017-06-21 | 2021-10-01 | 中国石油化工股份有限公司 | Preparation method of 3-phenylpropylaldehyde |
| CN114426469A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing alcohol and aldehyde by olefin hydroformylation |
| CN113372206A (en) * | 2021-05-12 | 2021-09-10 | 上海簇睿低碳能源技术有限公司 | Method for synthesizing high-carbon aldehyde by using microchannel reaction device |
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