CN1833774A - Prepn. of high carbon aldehyde by formylating high carbon olefinic hydrogen in temp ion liquid two-phase system - Google Patents
Prepn. of high carbon aldehyde by formylating high carbon olefinic hydrogen in temp ion liquid two-phase system Download PDFInfo
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- CN1833774A CN1833774A CN 200610046355 CN200610046355A CN1833774A CN 1833774 A CN1833774 A CN 1833774A CN 200610046355 CN200610046355 CN 200610046355 CN 200610046355 A CN200610046355 A CN 200610046355A CN 1833774 A CN1833774 A CN 1833774A
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Abstract
A process for preparing high-C aldehyde from high-C olefin by hydroformylation in a two-phase system consisting of the quaternary ammonium salt ion liquid containing ethoxy chain and the non-polar (or weak-polar) organic solvent features high-temp mixing and dissolving, ordinary-temp phase separation, temp control, homogeneous reaction and two-phase separation. Its advantages are high catalytic activity, selectivity and output rate, and long cyclic life of catalyst (at least 9 cycles).
Description
Technical field
The present invention relates to a kind of reaction system of transition metal-catalyzed using hydroformylation of higher olefins reaction and process for separating and recovering of homogeneous phase complex catalyst of being used for.
Background technology
Effective separation by " homogeneous reaction, two is separated " realization transition metal homogeneous catalyst is reclaimed, and is " reaction-isolation integral " method that closely grows up during the last ten years.Utilize existing fluorine two-phase (the Flurous biphasis system of reaction system of " homogeneous reaction, two is separated " of regulating and controlling temperature enforcement, FBS) (Science, 1994,266,72) and other is by ethylene (third) alkene ester (Chem.Eng.Technol.2000,23 (2), 122) and polyethylene glycol (Chem.Commun., 1998,787; CN 1559685A) liquid/liquid two-phase system that to be polarity form with nonpolar organic facies.Since 1972, report not rarely seen (J.Am.Chem.Soc., 1972,94:8716～8719 of hydroformylation of olefin in ionic liquid, have been carried out; J.Mol.Catal.A:Chem., 2000,164:61～67; J.Mol.Catal.A:Chem., 2001,146:128-134; Chem.Commun., 1998,2341～2342; Chem.Commun., 2001:451～452; EP1400504).Existing document (Can.J.Chem.2001 79:705-708) has reported that a kind of high temperature is miscible, the two-phase system that the fluoride ion fluid/water of low temperature phase-splitting is formed, and this system can be carried out catalytic hydrogenation reaction to water miscible substrate.But the ionic liquid two-phase system that will have function of temperature control is applied to the hydroformylation reaction of higher olefins and yet there are no all documents.
Inventor's gold woods etc. has reported that the phosphine part that contains the PEG chain shows the characteristic (Catal.Lett. of " temperature control is separated " in some organic solvent, 2002,79 (1-4): 55～57), PEG is introduced quaternary ammonium salt structure, the novel ion liquid that a synthetic class has function of temperature control, and then the new design of proposition temperature controlled ionic liquid liquid/liquid biphasic catalysis.The novel ion liquid two-phase system that this class has function of temperature control is not applied in the hydroformylation reaction of higher olefins as yet.
The purpose of this invention is to provide the catalysis new technology that a kind of homogeneous reaction catalyst that is used for transition metal-catalyzed using hydroformylation of higher olefins reaction is easy to separate recovery.
Summary of the invention
The invention provides a class and have the temperature controlled ionic liquid biphasic catalysis reaction system of " high temperature is miscible, the low temperature phase-splitting " function.Ionic liquid in the two-phase system is the quaternary ammonium salt that contains oxyethyl chain mutually, and its structure is shown in (1):
[(C
2H
5)
3N(CH
2CH
2O)
nCH
3]
+[CH
3SO
3]
- (1)
n＝7～16
Another is organic solvent single or that mix mutually, and they are selected from the C of nonpolar or low pole
6-C
10Linear paraffin, toluene, ethylbenzene, dimethylbenzene etc.
When n=16, in the two-phase system of forming by ionic liquid (1) and toluene/n-heptane, ionic liquid: toluene: the percentage by weight of normal heptane is 25.4～31.6: 46.7～57.2:, can obtain consolute temperature and be 35～130 ℃ two-phase system at 17.4～21.7 o'clock; When surpassing consolute temperature, two-phase system is miscible to be homogeneous phase, and when being lower than consolute temperature, system is divided into two-phase; The organic facies that contains product separates product and catalyst with the ionic liquid that contains catalyst by simply being separated.
In the temperature controlled ionic liquid two-phase system of forming by ionic liquid (1), toluene, aliphatic hydrocarbon; can carry out using hydroformylation of higher olefins and prepare high-carbon aldehyde; this is reflected under the higher reaction temperature and carries out in homogeneous system; after reaction finishes cooling; system is divided into two-phase automatically, and the ionic liquid that can will contain catalyst so easily and effectively separates with the organic facies that contains product and recycles.
Prepare high-carbon aldehyde with using hydroformylation of higher olefins in the temperature controlled ionic liquid two-phase system, method is quaternary ammonium salt ionic liquid, organic solvent toluene/n-heptane, the C that will contain oxyethyl chain
6～C
14Linear alpha-olefin or cyclohexene, rhodium-containing catalyst are added in the stainless steel autoclave, make C
6～C
14The mol ratio of linear alpha-olefin or cyclohexene and rhodium-containing catalyst is 1500: 1, the mol ratio of TPPTS and rhodium is 13～16: 1, toluene: normal heptane: ion liquid mol ratio is 18.85: 8.89: 1.05, and the nitrogen replacement of usefulness 2.0Mpa four times charges into CO and H then
2Volume ratio be 1: 1 synthesis gas, under 2.0～8.0Mpa pressure, 80～140 ℃ of reaction temperatures, reacted 1-10 hour, be cooled to room temperature, under nitrogen protection, make the phosphine/rhodium complex catalyst that is dissolved in the ionic liquid phase and contain the organic facies of product through simply being separated, tell upper organic phase, the conversion ratio that obtains higher olefins be 93～99% and yield be 95～99% high-carbon aldehyde; The ionic liquid that contains catalyst can be recycled 9 times mutually, and activity remains unchanged, and is lost to the rhodium average out to 0.5% of upper strata product phase.
Prepare high-carbon aldehyde with using hydroformylation of higher olefins in the temperature controlled ionic liquid two-phase system, alkene is C
6～C
14Linear alpha-olefin or cyclohexene.
Prepare high-carbon aldehyde with using hydroformylation of higher olefins in the temperature controlled ionic liquid two-phase system, catalyst is the phosphine/rhodium complex of TPPTS and phosphine part TMPGP, the PETPP that contains oxyethyl chain or OPGPP and rhodium dicarbonyl acetylacetonate or the formation of three rhodium trichloride hydrate original positions; Wherein the phosphine part is:
TMPGP PETPP
OPGPP TPPTS
Prepare high-carbon aldehyde with using hydroformylation of higher olefins in the temperature controlled ionic liquid two-phase system, the temperature control effect of system can be by the complex-catalyzed cyclohexene hydroformylation reaction explanation of TPPTS/Rh.Successively with ionic liquid, the Rh (CO) of following mol ratio
2Acac, TPPTS, organic solvent toluene and normal heptane, cyclohexene, interior mark decane add in the 75mL stainless steel autoclave.Tighten still and leak detection, use 2.0MPa nitrogen replacement four times, charge into the required pressure synthesis gas (CO/H of reaction then
2=1: 1).At pressure is 5.0MPa; [C=C]/Rh=1500 (mol ratio); TPPTS/Rh=13 (mol ratio); toluene: normal heptane: during ionic liquid=18.85: 8.89: 1.05 (mol ratio); through reaction in 8 hours, take out reactor and be cooled to room temperature, under the nitrogen protection; tell upper organic phase, analyze with gas chromatograph.The result shows that there is significantly influence in reaction temperature to the cyclohexene hydroformylation reaction.In the reaction time is under the condition of 8h, when reaction temperature is 100 ℃, the cyclohexene conversion ratio only is 30%, when temperature is 110 ℃, conversion ratio has rapid increase, reach 88%, when temperature was elevated to 120 ℃, conversion ratio rose to 93%, here temperature rises to 110 ℃ increasing degree scope by 100 ℃ in, conversion ratio has risen to 58%, and when temperature rose to 120 ℃ by 110 ℃, conversion ratio had only risen 5%, occurred the huge difference of reaction conversion ratio amplification under same 10 ℃ of increasing degrees, this is that promptly reaction system exists by the transformation of two-phase to homogeneous phase between 100 ℃～120 ℃ owing to exist the temperature control process in the system.This is that 110 ℃ result is consistent with the consolute temperature of this system that records.
The temperature controlled ionic liquid two-phase system can be used as transition metal-catalyzed reaction system; reclaim with the easy separation that realizes the homogeneous catalytic reaction catalyst; with transient metal complexes such as Rh is that the temperature controlled ionic liquid two-phase using hydroformylation of higher olefins reaction result of catalyst shows; reaction not only can be carried out in the temperature controlled ionic liquid two-phase system smoothly; and catalyst can be by simply being separated conveniently, separating effectively and reclaim; through directly recycling repeatedly, activity of such catalysts remains unchanged.
The preparation method of quaternary ammonium salt ionic liquid (1) who contains oxyethyl chain is easy, with low cost, also has difficult combustion, not quick-fried, nontoxic characteristic.Compare with the fluorine two-phase system, the temperature controlled ionic liquid two-phase system is a kind of more economic and eco-friendly non-water liquid/liquid two-phase reaction system.
The specific embodiment
Embodiment 1
The temperature controlled ionic liquid of TPPTS/Rh catalysis/organic two-phase cyclohexene hydroformylation reaction
Successively with ionic liquid, the Rh (CO) of following mol ratio
2Acac, TPPTS, organic solvent toluene and normal heptane, cyclohexene, interior mark decane add in the 75mL stainless steel autoclave.Tighten still and leak detection, use 2.0MPa nitrogen replacement four times, charge into the required pressure synthesis gas (CO/H of reaction then
2=1: 1).In temperature is 120 ℃; pressure is 5.0MPa; [C=C]/Rh=1500 (mol ratio), TPPTS/Rh=13 (mol ratio), toluene: normal heptane: ion liquid mol ratio is 18.85: 8.89: 1.05; through reaction in 4-10 hour; take out reactor and be cooled to room temperature, under the nitrogen protection, tell upper organic phase; the GC analytical reactions can obtain 93% conversion ratio and 95% aldehyde selectivity.
Embodiment 2
The temperature controlled ionic liquid of TPPTS/Rh catalysis/organic two-phase 1-laurylene hydroformylation reaction
Successively with ionic liquid, the RhCl of following mol ratio
33H
2O, TPPTS, toluene and normal heptane, decane (interior mark), 1-laurylene add in the 75mL stainless steel autoclave.Tighten still and leak detection, use 2.0MPa nitrogen replacement four times, charge into the required pressure synthesis gas (CO/H of reaction then
2=1: 1).In temperature is 110 ℃; pressure is 5.0MPa; [C=C]/Rh=1500 (mol ratio), TPPTS/Rh=16 (mol ratio), toluene: normal heptane: ion liquid mol ratio is 18.85: 8.89: 1.05; through reaction in 4-10 hour; take out reactor and be cooled to room temperature, under the nitrogen protection, tell upper organic phase; the GC analytical reactions can obtain 99% conversion ratio and 98% aldehyde selectivity.
Embodiment 3
The complex-catalyzed cyclohexene hydroformylation reaction of TMPGP/Rh
Successively with ionic liquid, the Rh (CO) of following mol ratio
2Acac, TMPGP, organic solvent toluene and normal heptane, cyclohexene, interior mark decane add in the 75mL stainless steel autoclave.Tighten still and leak detection, use 2.0MPa nitrogen replacement four times, charge into the required pressure synthesis gas (CO/H of reaction then
2=1: 1).In temperature is 120 ℃; pressure is 5.0MPa; [C=C]/Rh=1500 (mol ratio), TPPTS/Rh=13 (mol ratio), toluene: normal heptane: ion liquid mol ratio is 18.85: 8.89: 1.05; through reaction in 4-10 hour; take out reactor and be cooled to room temperature, under the nitrogen protection, tell upper organic phase; the GC analytical reactions can obtain 99% conversion ratio and 99% aldehyde selectivity.
Embodiment 4
The temperature controlled ionic liquid of TPPTS/Rh catalysis/organic two-phase 1-laurylene hydroformylation reaction catalyst circulation result of use is investigated
Successively with ionic liquid, the RhCl of following mol ratio
33H
2O, TPPTS, toluene and normal heptane, decane (interior mark), 1-laurylene add in the 75mL stainless steel autoclave.Tighten still and leak detection, use 2.0MPa nitrogen replacement four times, charge into the required pressure synthesis gas (CO/H of reaction then
2=1: 1).In temperature is 110 ℃; pressure is 5.0MPa; [C=C]/Rh=1500 (mol ratio), TPPTS/Rh=16 (mol ratio), toluene: normal heptane: ion liquid mol ratio is 18.85: 8.89: 1.05; through reaction in 6 hours; take out reactor and be cooled to room temperature, under the nitrogen protection, tell upper organic phase; lower floor's ionic liquid is retained in mutually to prepare against in the still and recycles, and organic facies is analyzed with gas chromatograph.The results are shown in Table 1.
The temperature controlled ionic liquid of table 1 TPPTS/Rh catalysis/organic two-phase 1-laurylene hydroformylation reaction catalyst circulation
Result of use is investigated
| run | Conversion ratio (%) | Alkane+internal olefin yield (%) | Aldehyde yield (%) |
| 0 1 2 3 4 5 6 7 8 9 | 98 97 99 97 99 98 98 97 99 98 | 1.60 1.59 1.59 1.63 1.72 1.63 1.13 1.02 1.12 1.21 | 96 96 97 96 97 96 97 97 98 97 |
As seen from Table 1, by the generated in-situ catalyst of TPPTS/Rh the hydroformylation reaction of 1-laurylene is shown good catalytic activity.The conversion ratio of first set reaction and aldehyde yield are respectively 98% and 96%.Catalyst is constant substantially through 9 circulation activity.Reaction finishes to be cooled to room temperature, and the ionic liquid that contains catalyst is divided into two-phase automatically with the organic facies that contains product aldehyde mutually, can realize separating of catalyst and product by simply being separated.In above-mentioned process of carrying out 9 circular responses, respectively the Rh content in the isolated organic facies in each reaction back is measured, the result shows that rhodium runs off and keeps stable, and keeps about 0.5%.
Claims (5)
1. a class has the temperature controlled ionic liquid biphasic catalysis reaction system that makes the homogeneous phase complex be easy to separate recovery of " high temperature is miscible; the low temperature phase-splitting " function, it is characterized in that ionic liquid in the two-phase system is to use the quaternary ammonium salt that contains oxyethyl chain shown in structure (1) mutually:
[(C
2H
5)
3N(CH
2CH
2O)
nCH
3]
+[CH
3SO
3]
- (1)
n＝7～16
Another is the C that is selected from nonpolar or low pole mutually
6-C
101～2 kind organic solvent in linear paraffin, toluene, ethylbenzene or the dimethylbenzene by the different proportioning of two-phase, constitutes the biphasic catalysis reaction system of a series of different blended solubility temperatures.
2. according to the described temperature controlled ionic liquid biphasic catalysis of claim 1 reaction system, it is characterized in that when n=16, in the two-phase system of forming by ionic liquid (1) and toluene/n-heptane, ionic liquid (1): toluene: the percentage by weight of normal heptane is 25.4～31.6: 46.7～57.2:, can obtain consolute temperature and be 35～130 ℃ two-phase system at 17.4～21.7 o'clock; When surpassing consolute temperature, two-phase system is miscible to be homogeneous phase, and when being lower than consolute temperature, system is divided into two-phase; The organic facies that contains product separates product and catalyst with the ionic liquid that contains catalyst by simply being separated.
3. one kind according to the method for preparing high-carbon aldehyde in the described temperature controlled ionic liquid two-phase system of claim 1 with using hydroformylation of higher olefins, it is characterized in that this method is quaternary ammonium salt ionic liquid, organic solvent toluene/n-heptane, the C that will contain oxyethyl chain
6～C
14Linear alpha-olefin or cyclohexene, catalyst are added in the stainless steel autoclave, make C
6～C
14The mol ratio of linear alpha-olefin or cyclohexene and rhodium-containing catalyst is 1500: 1, the mol ratio of TPPTS and rhodium is 13～16: 1, toluene: normal heptane: ion liquid mol ratio is 18.85: 8.89: 1.05, and the nitrogen replacement of usefulness 2.0Mpa four times charges into CO and H then
2Volume ratio be 1: 1 synthesis gas; under 2.0～8.0Mpa pressure; 80～140 ℃ of reaction temperatures; reacted 1-10 hour; be cooled to room temperature, under nitrogen protection, make the phosphine/rhodium complex catalyst that is dissolved in the ionic liquid phase and contain the organic facies of product through simply being separated; tell upper organic phase, obtain C
6～C
14The conversion ratio of linear alpha-olefin or cyclohexene be 93～99% and yield be 95～99% high-carbon aldehyde; The ionic liquid that contains catalyst can be recycled 9 times mutually, and activity remains unchanged, and is lost to the rhodium average out to 0.5% of upper strata product phase.
4. prepare the method for high-carbon aldehyde according to claim 3 is described with using hydroformylation of higher olefins, it is characterized in that used higher olefins is C
6～C
14Linear alpha-olefin or cyclohexene.
5. prepare the method for high-carbon aldehyde according to claim 3 is described with using hydroformylation of higher olefins, it is characterized in that used catalyst is phosphine/rhodium complex that TPPTS and phosphine part TMPGP, the PETPP that contains oxyethyl chain or OPGPP and rhodium dicarbonyl acetylacetonate or three rhodium trichloride hydrate original positions form; Wherein the phosphine part is:
TMPGP PETPP
OPGPP TPPTS。
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| CN102617308A (en) * | 2012-03-13 | 2012-08-01 | 青岛科技大学 | Olefin two-phase hydroformylation method |
| CN103570514A (en) * | 2013-10-07 | 2014-02-12 | 青岛科技大学 | Olefin hydroformylation method by homogeneous catalysis-biphase separation |
| CN103965102A (en) * | 2014-05-22 | 2014-08-06 | 四川大学 | Preparation method of novel quinoline thermo-sensitive ionic liquid and method for catalyzing methyl esterification of long-chain fatty acid by adopting novel quinoline thermo-sensitive ionic liquid |
| CN105017314A (en) * | 2015-05-16 | 2015-11-04 | 青岛科技大学 | Phosphine-functionalized polyether piperidine salt ionic liquid and application thereof in the hydroformylation of olefins |
| CN105693485A (en) * | 2016-03-19 | 2016-06-22 | 青岛科技大学 | Method for preparing normal aldehyde on basis of high selectivity of olefin two-phase hydroformylation of phosphine functionalized polyether piperidine salt ionic liquid |
| CN111470960A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Composition and method for preparing aldehyde by two-phase catalytic 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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| CN114534795A (en) * | 2020-11-27 | 2022-05-27 | 中国石油天然气股份有限公司 | Catalyst for preparing valeraldehyde through butene hydroformylation, preparation method of catalyst and preparation method of valeraldehyde |
| CN116063162A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Method for hydroformylation of high-carbon olefin and application thereof |
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| CN102617308B (en) * | 2012-03-13 | 2013-11-27 | 青岛科技大学 | Olefin two-phase hydroformylation method |
| CN102617308A (en) * | 2012-03-13 | 2012-08-01 | 青岛科技大学 | Olefin two-phase hydroformylation method |
| CN103570514A (en) * | 2013-10-07 | 2014-02-12 | 青岛科技大学 | Olefin hydroformylation method by homogeneous catalysis-biphase separation |
| CN103570514B (en) * | 2013-10-07 | 2015-11-18 | 青岛科技大学 | The method of a kind of homogeneous catalysis-two-phase laminated flow olefin hydroformylation |
| CN103965102A (en) * | 2014-05-22 | 2014-08-06 | 四川大学 | Preparation method of novel quinoline thermo-sensitive ionic liquid and method for catalyzing methyl esterification of long-chain fatty acid by adopting novel quinoline thermo-sensitive ionic liquid |
| CN105017314B (en) * | 2015-05-16 | 2017-11-03 | 青岛科技大学 | One class phosphine functionalization polyethers piperidinium salt ionic liquid and its application in hydroformylation of olefin |
| CN105017314A (en) * | 2015-05-16 | 2015-11-04 | 青岛科技大学 | Phosphine-functionalized polyether piperidine salt ionic liquid and application thereof in the hydroformylation of olefins |
| CN105693485A (en) * | 2016-03-19 | 2016-06-22 | 青岛科技大学 | Method for preparing normal aldehyde on basis of high selectivity of olefin two-phase hydroformylation of phosphine functionalized polyether piperidine salt ionic liquid |
| CN111470960A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation |
| CN111470960B (en) * | 2019-01-23 | 2023-01-17 | 中国石油化工股份有限公司 | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation |
| CN114534795A (en) * | 2020-11-27 | 2022-05-27 | 中国石油天然气股份有限公司 | Catalyst for preparing valeraldehyde through butene hydroformylation, preparation method of catalyst and preparation method of valeraldehyde |
| 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 |
| CN116063162A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Method for hydroformylation of high-carbon olefin and application thereof |
| CN114456041A (en) * | 2022-02-21 | 2022-05-10 | 广东仁康达材料科技有限公司 | Preparation method of isomeric tridecanol |
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