CN100469748C - Production and separation of alkyl aromatic aldehyde - Google Patents
Production and separation of alkyl aromatic aldehyde Download PDFInfo
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- CN100469748C CN100469748C CNB2005101305525A CN200510130552A CN100469748C CN 100469748 C CN100469748 C CN 100469748C CN B2005101305525 A CNB2005101305525 A CN B2005101305525A CN 200510130552 A CN200510130552 A CN 200510130552A CN 100469748 C CN100469748 C CN 100469748C
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Abstract
Separation and production of alkyl-aromatic aldehyde are disclosed. The separation is carried out by adding diluting agent into reactant mixture, adding extracting agent into reactant mixture, and separating various isomers of alkyl-aromatic aldehyde from extract. It's easy and has more extract percent.
Description
Technical field
The invention relates to the preparation method and the separation method of alkyl aromatic aldehyde, more particularly, is the separation method about the alkyl aromatic aldehyde of carbonyl process preparation, and the preparation method who comprises the alkyl aromatic aldehyde of this separation method.
Background technology
Aromatic aldehyde, especially p-tolyl aldehyde (PTAL) is the important organism of synthetic many fine chemicals, as can be used for compound perfume and food flavor(ing)s such as synthetic cloves, lily, the oxide compound terephthalic acid (PTA) of p-tolyl aldehyde is an important monomer of producing polyester (PET).
The production method of alkyl aromatic aldehyde is divided into two kinds at present: high-temperature oxidation and carbonyl process.High-temperature oxidation is under hot conditions the alkyl of Alkylaromatics (the alkyl number on the phenyl ring is more than or equal to 2) to be oxidized to aldehyde radical, obtains alkyl aromatic aldehyde.Carbonyl process is that carbonylation reaction generation alkyl aromatic aldehyde is taken place under catalyst action for Alkylaromatics and carbon monoxide.There is the low problem of Alkylaromatics utilization ratio in high-temperature oxidation; In carbonyl process, therefore Alkylaromatics, carbon monoxide aboundresources and relatively inexpensive, and Alkylaromatics utilization ratio height more and more cause people's attention.
For example, US6320083 discloses a kind of method of using ionic liquid to be prepared alkyl aromatic aldehyde by carbonyl process, this method is included under the pressure of 0-100 ℃ temperature and 1.47-19.6 MPa, in the presence of acidic ion liquid, with Alkylaromatics and reaction of carbon monoxide, form the alkyl aromatic aldehyde mixture of reaction products.Wherein, Alkylaromatics comprises toluene, dimethylbenzene, 1 and 1,2,5-Three methyl Benzene.Described acidic ion liquid is made up of Organohalogen compounds and metal halide.The various isomerss that in the alkyl aromatic aldehyde mixture of reaction products that obtains, contain acidic ion liquid and alkyl aromatic aldehyde.Wherein, alkyl aromatic aldehyde is in complex status, is not unbound state, and catalyzer is that acidic ion liquid also participates in forming complex compound.In order to separate from the alkyl aromatic aldehyde mixture of reaction products, US6320083 proposes to use selectivity volatilization method and liquid-liquid extraction method.Wherein, liquid-liquid extraction method comprises insoluble solvent is joined in the described mixture of reaction products, this insoluble solvent and acidic ion liquid layering, the alkyl aromatic aldehyde reaction product is transferred in this insoluble solvent, and then adopts conventional method that the alkyl aromatic aldehyde reaction product is separated from insoluble solvent.Described insoluble solvent comprises benzene and toluene.The selectivity volatilization method is meant aldehyde product is changed into gaseous form, and ionic liquid is not converted to gaseous form, thereby the two is separated.The temperature that the selectivity volatilization method is carried out is at least 90 ℃, is preferably 100-350 ℃, and preferably carries out under decompression or vacuum condition.
Because in the alkyl aromatic aldehyde mixture of reaction products that obtains, there is very strong complexing action power between the alkyl aromatic aldehyde reaction product and between catalyzer and the alkyl aromatic aldehyde reaction product, when therefore using the selectivity volatilization method to separate, need the more energy of loss, and solution causes the polymerization of aldehyde; Percentage extraction is not high when using liquid-liquid extraction method to separate, and needs to use a large amount of organic solvents, so the existing method for preparing alkyl aromatic aldehyde by carbonyl process exists aldehyde product and catalyzer to be difficult to isolating problem.
Summary of the invention
The objective of the invention is to overcome existing aldehyde product and the catalyzer for preparing the method existence of alkyl aromatic aldehyde and be difficult to isolating problem, a kind of separation method of alkyl aromatic aldehyde is provided, uses this separation method easily the alkyl aromatic aldehyde reaction product to be separated from the alkyl aromatic aldehyde mixture of reaction products.
Another object of the present invention provides the preparation method of the alkyl aromatic aldehyde that uses this separation method.
The invention provides a kind of separation method of alkyl aromatic aldehyde, this method is included in the alkyl aromatic aldehyde mixture of reaction products of carbonyl process preparation and adds extraction agent, from extraction liquid, isolate the various isomerss of alkyl aromatic aldehyde, wherein, this method also is included in the mixture of reaction products and adds before the extraction agent, adds thinner in mixture of reaction products.
The present invention also provides a kind of preparation method of aromatic aldehyde, and this method is included in acidic ion liquid and exists down, with alkyl aromatic compound and carbon monoxide contact reacts, obtains mixture of reaction products; Isolate the various isomerss of alkyl aromatic aldehyde, described acidic ion liquid contains metal halide and Organohalogen compounds, wherein, isolating method is included in the alkyl aromatic aldehyde mixture of reaction products of carbonyl process preparation and adds thinner, add extraction agent then, from extraction liquid, isolate the various isomerss of alkyl aromatic aldehyde.
In the separation method of alkyl aromatic aldehyde provided by the invention, owing in described mixture of reaction products, added thinner, thinner can reduce the interaction between the ionic liquid intermediate ion, help making the aldehyde product of complex status to be transformed into unbound state, therefore improved the percentage extraction of alkyl aromatic aldehyde reaction product, made the easy and catalyst separating of alkyl aromatic aldehyde reaction product.
Embodiment
The separation method of alkyl aromatic aldehyde provided by the invention is included in the alkyl aromatic aldehyde mixture of reaction products of carbonyl process preparation and adds extraction agent, from extraction liquid, isolate the various isomerss of alkyl aromatic aldehyde, wherein, this method also is included in the mixture of reaction products and adds before the extraction agent, adds thinner in mixture of reaction products.
According to separation method provided by the invention, described thinner can use the organic solvent that dissolves each other with above-mentioned acidic ion liquid, for example can be selected from furans, halohydrocarbon, carboxylicesters, the ether one or more.
The example of described furans comprises tetrahydrofuran (THF) and 2-methyl furan.
Described halohydrocarbon can use under the existing normal temperature and pressure and to be liquid various halohydrocarbon, is the halohydrocarbon that obtains after one or more hydrogen atoms of the alkane of 1-8 are replaced by halogen as carbonatoms.Described halogen can be fluorine, chlorine, bromine or iodine.Halohydrocarbon is preferably one or more in methylene dichloride, trichloromethane, ethylene dichloride, propylene dichloride, chlorobutane, butyl iodide and the bromooctane.
Described carboxylicesters can use and be liquid various organic carboxylic esters under the existing normal temperature and pressure, as carbonatoms is that the monobasic of 1-10 or polyvalent alcohol and carbonatoms are the monobasic of 1-10 or the organic carboxylic ester that polycarboxylic acid generation esterification obtains, being preferably monobasic that carbonatoms is 1-6 or polyvalent alcohol and carbonatoms is the monobasic of 1-6 or the organic carboxylic ester that polycarboxylic acid generation esterification obtains, more preferably one or more in methyl-formiate, methyl acetate, ethyl acetate, propyl acetate, butylacetate and the pentyl acetate.
Described ether can use and be liquid various ethers under the existing normal temperature and pressure, as carbonatoms is that the monobasic of 1-10 or polyvalent alcohol and carbonatoms are the monobasic of 1-10 or the ether that polyvalent alcohol generation etherificate obtains, being preferably monobasic that carbonatoms is 1-6 or polyvalent alcohol and carbonatoms is the monobasic of 1-6 or the ether that polyvalent alcohol generation etherificate obtains, more preferably one or more in methyl ether, methyl ethyl ether, ether and the n-butyl ether.
Thinner can reduce the interaction between the ionic liquid intermediate ion, help making the alkyl aromatic aldehyde product of complex status to be transformed into unbound state, helped improving the percentage extraction of alkyl aromatic aldehyde, make alkyl aromatic aldehyde easily with from mixture of reaction products, separate.
The volume ratio of employed thinner and mixture of reaction products is 0.1-3, is preferably 0.2-2.0.
Wherein, mixture of reaction products contains alkyl aromatic aldehyde and acidic ion liquid.
Alkyl aromatic aldehyde can be in tolyl aldehyde, dimethylbenzaldehyde and the trimethylbenzaldehyde one or more.Alkyl aromatic aldehyde is preferably p-tolyl aldehyde, o-methyl-benzene formaldehyde and a tolyl aldehyde.
The kind of described extraction agent has been that those skilled in the art are in common knowledge, and the present invention is preferably the alkane that contains 5-16 carbon atom and in the aromatic hydrocarbon one or more, more preferably contains the alkane of 6-10 carbon atom and in the aromatic hydrocarbon one or more.Described alkane can be paraffinic hydrocarbons or naphthenic hydrocarbon.Extraction agent is preferably pentamethylene, normal hexane, hexanaphthene, octane, octane-iso, sherwood oil and/or toluene.
The temperature of extraction is 10-60 ℃, preferred 20-40 ℃.
Described extraction can realize by multi-stage countercurrent, multistage cross flow or continuous countercurrent mode, and total overall reaction product such as p-tolyl aldehyde, o-methyl-benzene formaldehyde, a tolyl aldehyde are transferred in the extraction agent.
Described extraction can be carried out one or many, and repeatedly extraction can make more reaction product such as p-tolyl aldehyde, o-methyl-benzene formaldehyde, a tolyl aldehyde transfer in the extraction agent.
The volume ratio of described extraction agent and mixture of reaction products is 0.2-5.0, is preferably 0.5-4.5.
In mixture of reaction products, add after the extraction agent, be divided into immiscible two-layer.Alkyl aromatic aldehyde is transferred in the extraction agent, is called extraction liquid; Acidic ion liquid and thinner mix, and are called the acidic ionic liquid liquid solution.
Can use ordinary method and instrument that extraction liquid and acidic ionic liquid liquid solution are separated, for example use separating funnel.
Can use method well known in the art to isolate the various isomerss of alkyl aromatic aldehyde from extraction liquid, the present invention preferably uses the method for freezing and crystallizing.Wherein, the temperature of freezing and crystallizing is preferably-6 ℃ to-100 ℃, more preferably-20 ℃ to-60 ℃.Be-56.8 ℃ because the zero pour of p-tolyl aldehyde be-6.2 ℃, the zero pour of o-methyl-benzene formaldehyde for the zero pour of-35.5 ℃, tolyl aldehydes, thus under different temperature freezing and crystallizing, these three kinds of isomerss can be separated.Extraction agent can recycle through after the drying treatment.
Wherein, before carrying out freezing and crystallizing, can also wash extraction agent solution with water, the ion component in the extraction agent solution is transferred in the water, help the separation of aldehydes reaction product.Wash extraction agent solution with water and can adopt the intermittent mode operation, also can adopt the operating method of continuously feeding, discharging.The volume ratio of washing employed water and extraction agent solution is 0.01-0.1.
The acidic ionic liquid liquid solution can be carried out underpressure distillation, obtain acidic ion liquid and thinner respectively, thereby reach the purpose that recirculation is utilized acidic ion liquid and thinner.Wherein, the temperature of underpressure distillation is 50-200 ℃, is preferably 60-150 ℃; Pressure (absolute pressure) is the 0.0005-0.03 MPa, is preferably the 0.001-0.01 MPa.
The preparation method of alkyl aromatic aldehyde provided by the invention is included in acidic ion liquid and exists down, with alkyl aromatic compound and carbon monoxide contact reacts, obtains mixture of reaction products; Isolate the various isomerss of alkyl aromatic aldehyde, described acidic ion liquid contains metal halide and Organohalogen compounds, and wherein, isolating method adopts separation method provided by the invention.
According to the preparation method of alkyl aromatic aldehyde provided by the invention, except isolating method adopted separation method provided by the invention, other step and condition can adopt step of the prior art and condition.
According to the preparation method of alkyl aromatic aldehyde provided by the invention, wherein, described acidic ion liquid contains metal halide and Organohalogen compounds.
Described metal halide can be selected from one or more in aluminum chloride, aluminum bromide, aluminum iodide and the iron trichloride, is preferably aluminum chloride.Molar fraction in ionic liquid is greater than 50% the time when metal halide such as aluminum chloride, and ionic liquid presents Louis (Lewis) acidity, and the anionic form that exists is with AlCl
3The molar fraction difference can be AlCl
4 -, Al
2Cl
7 -, Al
3Cl
10 -Deng, acidic ion liquid plays catalyzer, because acidic ion liquid is in a liquid state, more helps lock out operation and recycles.
Described Organohalogen compounds are the Organohalogen compounds of being made up of organic cation and halide anion.The positively charged ion of Organohalogen compounds can be selected from by alkyl imidazole positively charged ion (C
3H
0-4N
2R
1-5 +, 1-5 alkyl substituent, wherein R of 1-5 position promptly can be arranged on the imidazole ring
1-5Can be the identical or different carbonatomss alkyl that is 1-16), alkyl pyridine positively charged ion (C
5H
5NR
+, wherein R is that carbonatoms is the alkyl of 1-16), quaternary ammonium salt cationic (R
1R
2R
3R
4N
+, R wherein
1, R
2, R
3, R
4Can be the identical or different carbonatomss alkyl that is 1-16), quaternary alkylphosphonium salt positively charged ion (R
1R
2R
3R
4P
+, R wherein
1, R
2, R
3, R
4Can be the identical or different carbonatomss alkyl that is 1-16) and above-mentioned cationic derivative or with the similar organic cation of above-mentioned cationic structural in one or more.The negatively charged ion of Organohalogen compounds can be selected from Cl
-, Br
-Or I
-, be preferably Cl
-
In acidic ion liquid, the mol ratio of metal halide and Organohalogen compounds is 1.2-2.5, is preferably 1.8-2.2.
The Organohalogen compounds in the described acidic ion liquid and the mol ratio of alkyl aromatic compound are 1.2-5.0, are preferably 1.2-2.0.
Described alkyl aromatic compound can be selected from toluene, dimethylbenzene, 1 and 1,2, in the group that the 5-Three methyl Benzene is formed.Dimethylbenzene comprises o-Xylol, m-xylene and p-Xylol.Described alkyl aromatic compound is preferably toluene.
The catalytic temperature of alkyl aromatic compound and carbon monoxide is 0-60 ℃, is preferably 20-40 ℃; Time is 0.5-8 hour, is preferably 2-4 hour.Wherein the dividing potential drop of carbon monoxide is the 1.0-8.0 MPa, is preferably the 2.5-4.0 MPa.
The present invention will be described in more detail below in conjunction with embodiment.
Preparation embodiment 1
This preparation embodiment is used to prepare the alkyl aromatic aldehyde mixture of reaction products.
In 300 milliliters of zirconium material autoclaves, add 100 gram [bmim] Cl-AlCl
3Ionic liquid (AlCl
3Molar fraction be 0.67, i.e. [bmim] Cl and AlCl
3Mol ratio be 1:2, [bmim] Cl represents chloro 1-butyl-3-Methylimidazole, 0.227 mole of [bmim] Cl) and 17 milliliters of (0.160 mole) toluene, with behind the air in the nitrogen replacement still dividing potential drop of carbon monoxide being risen to 3.0 MPas, low whipping speed is that 750 rev/mins, temperature are under 40 ℃ the condition, reacted 5.0 hours, and obtained mixture of reaction products.Gas chromatographic analysis shows that the transformation efficiency of toluene is 51.2%, and the selectivity of p-tolyl aldehyde is 86.3%, and the selectivity of o-methyl-benzene formaldehyde is 11.5%, and the selectivity of a tolyl aldehyde is 2.2%.
Preparation embodiment 2
This preparation embodiment is used to prepare the alkyl aromatic aldehyde mixture of reaction products.
In 300 milliliters zirconium material autoclave, add 100 gram [bupy] Cl-AlCl
3(AlCl
3Molar fraction be 0.64, i.e. [bupy] Cl and AlCl
3Mol ratio be 1:1.8, [bupy] Cl represents chloro 1-butyl-pyridinium, 0.243 mole of [bupy] Cl) and 17.8 milliliters of (0.168 mole) toluene, with behind the air in the nitrogen replacement still carbon monoxide pressure of tension being risen to 3.8 MPas, low whipping speed is that 750 rev/mins, temperature are under 25 ℃ the condition, reacted 2.0 hours, and obtained mixture of reaction products.Gas chromatographic analysis shows that the transformation efficiency of toluene is 41.2%, and the selectivity of p-tolyl aldehyde is 86.6%, and the selectivity of o-methyl-benzene formaldehyde is 11.4%, and the selectivity of a tolyl aldehyde is 1.9%.
Embodiment 1
This embodiment is used to illustrate separation method provided by the invention.
Add mixture of reaction products A and 6 milliliters of methylene dichloride that 30 milliliters of preparation embodiment 1 obtain in 100 milliliters triangular flask, 25 ℃ were stirred 5 minutes down.Add 6 milliliters of octanes then, mixed 5 minutes, static phase-splitting uses separating funnel two-layerly up and down to separate.With 1.0 ml waters washing upper strata octane phase, analyze octane solution with marker method then.The result shows that the percentage extraction of tolyl aldehyde is 24%.
At last, the octane solution that obtains is carried out freezing and crystallizing under-20 ℃ ,-45 ℃ ,-60 ℃, obtain p-tolyl aldehyde, o-methyl-benzene formaldehyde and a tolyl aldehyde respectively.
Comparative Examples 1
This Comparative Examples is used to illustrate the method for separating alkyl aromatic aldehyde when not adding thinner.
Add mixture of reaction products and 6 milliliters of octanes that 30 milliliters of preparation embodiment 1 obtain in 100 milliliters triangular flask, 25 ℃ were stirred 5 minutes down, and static phase-splitting is analyzed octane solution with marker method.The result shows that the percentage extraction of tolyl aldehyde is 0%.
Embodiment 2
This embodiment is used to illustrate separation method provided by the invention.
Add mixture of reaction products and 20 milliliters of tetrahydrofuran (THF)s that 20 milliliters of preparation embodiment 1 obtain in 100 milliliters triangular flask, 25 ℃ were stirred 5 minutes down.Add 20 ml n-hexanes then, mixed 5 minutes, static phase-splitting uses separating funnel two-layerly up and down to separate.With 0.5 ml water washing upper strata normal hexane phase, analyze hexane solution with marker method then.The result shows that the percentage extraction of tolyl aldehyde is 35%.
Add 20 ml n-hexanes in the extracting phase (solution that contains acidic ion liquid and tetrahydrofuran (THF)) of single extraction, mixed then 5 minutes, static phase-splitting uses separating funnel two-layerly up and down to separate.With 0.5 ml water washing upper strata hexane solution, analyze hexane solution with marker method then, the result shows that the percentage extraction of p-tolyl aldehyde is 33.4%.Through twice extraction, about 56.7% tolyl aldehyde is transferred in the hexane solution.
At last, the hexane solution that obtains for twice is mixed, under-16 ℃ ,-42 ℃ ,-100 ℃, carry out freezing and crystallizing, obtain p-tolyl aldehyde, o-methyl-benzene formaldehyde and a tolyl aldehyde respectively.
Embodiment 3
This embodiment is used to illustrate separation method provided by the invention.
In 100 milliliters triangular flask, add mixture of reaction products and 20 milliliters of ether that 20 milliliters of preparation embodiment 1 obtain, stirred 5 minutes down at 10 ℃, add 20 milliliters of toluene then, mixed 15 minutes, static phase-splitting uses separating funnel two-layerly up and down to separate.With 1 ml water washing upper toluene phase, analyze toluene solution with marker method then.The result shows that the percentage extraction of tolyl aldehyde is 36%.
At last, the toluene solution that obtains is carried out freezing and crystallizing under-18 ℃ ,-40 ℃ ,-58 ℃, obtain p-tolyl aldehyde, o-methyl-benzene formaldehyde and a tolyl aldehyde respectively.
Comparative Examples 2
This Comparative Examples is used to illustrate the method for separating alkyl aromatic aldehyde when not adding thinner.
20 milliliters of preparations of adding embodiment 1 obtain in 100 milliliters triangular flask mixture of reaction products and 20 milliliters of toluene mixed 15 minutes, and static phase-splitting uses separating funnel two-layerly up and down to separate.Analyze toluene solution with marker method then.The result shows that the percentage extraction of tolyl aldehyde is 9%.
At last, the toluene solution that obtains is carried out freezing and crystallizing under-10 ℃ ,-40 ℃ ,-65 ℃, obtain p-tolyl aldehyde, o-methyl-benzene formaldehyde and a tolyl aldehyde respectively.
Embodiment 4
This embodiment is used to illustrate separation method provided by the invention.
Add mixture of reaction products and 40 milliliters of trichloromethanes that 20 milliliters of preparation embodiment 2 obtain at 250 milliliters triangular flasks, stirred 5 minutes down at 25 ℃.Add 100 milliliters of hexanaphthenes then, mixed 5 minutes, static phase-splitting uses separating funnel two-layerly up and down to separate.With 1.0 ml waters washing upper strata hexanaphthene phase, analyze cyclohexane solution with marker method then.The result shows that the percentage extraction of tolyl aldehyde is 38%.
At last, the cyclohexane solution that obtains is carried out freezing and crystallizing under-20 ℃ ,-45 ℃ ,-60 ℃, obtain p-tolyl aldehyde, o-methyl-benzene formaldehyde and a tolyl aldehyde respectively.
Embodiment 5
This embodiment is used to illustrate separation method provided by the invention.
In 100 milliliters triangular flask, add mixture of reaction products and 30 milliliters of butylacetates that 20 milliliters of preparation embodiment 2 obtain, stirred 5 minutes down at 25 ℃.Add 70 milliliters of n-hexadecanes then, mixed 5 minutes, static phase-splitting uses separating funnel two-layerly up and down to separate.With 1.5 ml waters washing upper strata n-hexadecane phase, analyze n-hexadecane solution with marker method then.The result shows that the percentage extraction of tolyl aldehyde is 25%.
At last, the n-hexadecane solution that obtains is carried out freezing and crystallizing under-19 ℃ ,-35 ℃ ,-60 ℃, obtain p-tolyl aldehyde, o-methyl-benzene formaldehyde and a tolyl aldehyde respectively.
Claims (19)
1, a kind of separation method of alkyl aromatic aldehyde, this method is included in the alkyl aromatic aldehyde mixture of reaction products of carbonyl process preparation and adds extraction agent, from extraction liquid, isolate the various isomerss of alkyl aromatic aldehyde, described mixture of reaction products contains alkyl aromatic aldehyde and acidic ion liquid, it is characterized in that, this method also is included in and adds before the extraction agent in the mixture of reaction products, in mixture of reaction products, add thinner, this thinner is the organic solvent that dissolves each other with described acidic ion liquid, and this thinner is selected from halohydrocarbon, in carboxylicesters and the ether one or more.
2, method according to claim 1, wherein, described halohydrocarbon comprises one or more in methylene dichloride, trichloromethane, ethylene dichloride, propylene dichloride, chlorobutane, butyl iodide and the bromooctane; Described carboxylicesters comprises one or more in methyl-formiate, methyl acetate, ethyl acetate, propyl acetate, butylacetate and the pentyl acetate; Described ether comprises one or more in methyl ether, methyl ethyl ether, ether, n-butyl ether, tetrahydrofuran (THF) and the 2-methyl furan.
3, method according to claim 1, wherein, the volume ratio of described thinner and mixture of reaction products is 0.1-3.
4, method according to claim 3, wherein, the volume ratio of described thinner and mixture of reaction products is 0.2-2.0.
5, method according to claim 1, wherein, described extraction agent is selected from the alkane that contains 5-16 carbon atom and in the aromatic hydrocarbon one or more; The volume ratio of extraction agent and mixture of reaction products is 0.2-5.0.
6, method according to claim 5, wherein, described extraction agent is selected from the alkane that contains 6-10 carbon atom and in the aromatic hydrocarbon one or more; The volume ratio of extraction agent and mixture of reaction products is 0.5-4.5.
7, method according to claim 1, wherein, alkyl aromatic aldehyde is one or more in tolyl aldehyde, dimethylbenzaldehyde, the trimethylbenzaldehyde.
8, method according to claim 7, wherein, alkyl aromatic aldehyde is p-tolyl aldehyde, o-methyl-benzene formaldehyde and a tolyl aldehyde.
9, method according to claim 1, wherein, the method for various isomerss of isolating alkyl aromatic aldehyde is for to carry out freezing and crystallizing at-6 ℃ to-100 ℃ to extraction liquid.
10, method according to claim 9 wherein, before carrying out freezing and crystallizing, washes extraction liquid with water; The volume ratio of washing employed water and extraction liquid is 0.01-0.1.
11, a kind of preparation method of alkyl aromatic aldehyde, this method are included in acidic ion liquid and exist down, with Alkylaromatics and carbon monoxide contact reacts, obtain mixture of reaction products; Isolate the various isomerss of alkyl aromatic aldehyde, described acidic ion liquid is made up of metal halide and Organohalogen compounds, it is characterized in that, isolating method is any described method among the claim 1-10.
12, method according to claim 11, wherein, the mol ratio of metal halide and Organohalogen compounds is 1.2-2.5.
13, method according to claim 12, wherein, metal halide is selected from one or more in aluminum chloride, aluminum bromide, aluminum iodide and the iron trichloride.
14, method according to claim 12, wherein, described Organohalogen compounds are the Organohalogen compounds of being made up of organic cation and halide anion.
15, method according to claim 14, wherein, the positively charged ion of Organohalogen compounds is selected from a kind of in the quaternary ammonium salt cationic, quaternary alkylphosphonium salt positively charged ion; The negatively charged ion of Organohalogen compounds is Cl
-, Br
-Or I
-
16, method according to claim 15, wherein, described quaternary ammonium salt cationic is alkyl imidazole positively charged ion or alkyl pyridine positively charged ion.
17, method according to claim 11, wherein, the Organohalogen compounds in the described acidic ion liquid and the mol ratio of Alkylaromatics are 1.2-5.0.
18, method according to claim 11, wherein, described Alkylaromatics is a toluene.
19, method according to claim 11, wherein, the catalytic condition of described Alkylaromatics and carbon monoxide is that temperature is that 0-60 ℃, time are that 0.5-8 hour, the dividing potential drop of carbon monoxide are the 1.0-8.0 MPa.
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