CN1736602A - Supported catalyst for preparing aldehyde by olefin hydroformylation - Google Patents
Supported catalyst for preparing aldehyde by olefin hydroformylation Download PDFInfo
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- CN1736602A CN1736602A CN 200510089265 CN200510089265A CN1736602A CN 1736602 A CN1736602 A CN 1736602A CN 200510089265 CN200510089265 CN 200510089265 CN 200510089265 A CN200510089265 A CN 200510089265A CN 1736602 A CN1736602 A CN 1736602A
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- rhodium
- catalyst
- ionic liquid
- rhodium complex
- triphenylphosphine
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Abstract
Disclosed is a supported catalyst mainly containing sulfonated triphenylphosphine- rhodium complex and is used for preparing aldehyde by hydroformylation of olefin, and relates to an ionic liquid catalyst. It contains solid oxide, sulfonated triphenylphosphine- rhodium complex, sulfonated triphenylphosphine ligand and ionic liquid. The solid oxide is one from hole molecular sieve, SiO2, TiO2, gamma- Al2O3; sulfonated triphenylphosphine- rhodium complex is single-sulfonated triphenylphosphine- rhodium complex, di- sulfonated triphenylphosphine- rhodium complex and tri- sulfonated triphenylphosphine- rhodium complex; and the ionic liquid is 1, 1, 3, 3, - tetramethyl guanidine lactate, 1- butyl- 3- methyl imidazolium tetrafluorborate and 1- butyl- 3- methyl imidazolium hexafluorophosphate. By mass ratio, the solid oxide is among 50%- 90%, the ionic liquid 8%- 49%, and rhodium 0.05%- 2%, and by molecular ratio phosphine to rhodium is 3- 200.
Description
Technical field
The present invention relates to a kind of ionic-liquid catalyst, especially relate to a kind of load-type ion liquid complex compound catalyst that is used for preparing aldehyde by hydro formylating defin.
Background technology
The hydroformylation method for making of all useful cobalt of the technology of existing production aldehyde, rhodium (as Wilkinson homogeneous phase phosphine-rhodium catalyst) catalyzed alkene.The condition harshness of Co catalysts requires reaction under high pressure; The function admirable of phosphine-rhodium complex catalyst, aldehyde selectivity height, the reaction condition gentleness, but cause rhodium to run off easily and part destruction, thus cause the service life of catalyst short.
France Phone-Polenc and the (FR of Ruhrchemie company; Pat.; 2478078) adopting water soluble sulfonated triphenylphosphine is the pressure hydrogen formylated industrial process that the rhodium catalyst of part is used for the propylene producing butyladehyde; its advantage is that part solubility in water is very big; and almost insoluble in organic facies, hydroformylation only need divide dried up/organic facies just to reach the purpose of complete separated product and catalyst simply.DE, Pat., 3546123; US, Pat., 4248802; FR, Pat., 2561650; DE, Pat., 3447030 and EP, Pat., 0133410 discloses the relevant research in this field.Industrialization is the result show, adopting this method propylene linear chain aldehyde selectivity of hydroformylation under 5.1MPa is that 95%[sees Hydrocarbon Processing, 11,153 (1985)].But, influence the space-time yield [Catal.Lett., 6,43 (1990)] of using hydroformylation of higher olefins owing to the poor solubility of organic facies in water.
The space-time yield of the sulfonated triphenylphosphine-using rhodium complex catalysts of existing preparing aldehyde by hydro formylating defin is not high, though some be used in that the catalyst of two phase reaction has increase productive rate with consisting of phase-transferring agent.U.S. Pat 953016 and German patent DE 19632503 disclose adds certain promoter in aqueous phase catalyst, can obtain good catalytic performance.Promoter commonly used comprises surfactant, quaternary ammonium salt, organic solvent and inorganic/organic salt, though improved catalyst activity to a certain extent, but a series of other problems have also been brought,, reaction back complicated as catalytic component produces emulsion, make product/catalyst separation difficulty, and the structural stability of some additives is bad.
[Nature, 339,454, (1989) such as M.E.Davis; J.Catal., 121,327 (1990); 129,94 (1991); 100 (1991); J.Oganometal.Chem.; 403; 221 (1991)] priority has been delivered the result of study of the support type sulfonated triphenylphosphine-rhodium catalyst that is used for olefin hydroformylation; I.T Horvath[Catal.Lett.; 6,43 (1990)] reported that this catalyst uses the result of study that still kept activity in 38 hours continuously.But existing research and patent (EP, Pat., 372615) show the n-alkanal content low (less than 75%) of this catalyst products therefrom, and the space-time yield of reaction is not high.As the CO/H of 1-octene at 5.1MPa
2Reaction is 5 hours under (1: 1, volume ratio), 70 ℃ the condition, conversion ratio 62.5%, the selectivity 73% of n-alkanal.And because wayward optimum moisture content in actual applications, thereby less stable.
A.Riisager etc. [Angew Chem Int Ed, 43,2～6 (2004)] have reported highly stable olefin hydroformylation load-type ion liquid catalyst, and they are with water-soluble bidentate phosphine ligands sulfoxantphos and not halogen-containing ionic liquid BMIn-C
8H
17OSO
3Load on the Bio-sil, be used for continuous propene hydroformylation reaction, the rhodium atom of seeing than=10 condition under, catalyst used after 60 hours still has very high activity, the positive isomery of product aldehyde is than greater than 20.But this class catalyst does not adopt molecular sieve as carrier, and its part is expensive, and catalytic activity also remains further to be improved.
Chinese patent ZL93100802.6 and ZL01132718.9 have introduced a kind of alkali metal salt promoted type load water-soluble catalyst of preparing aldehyde by hydro formylating and the preparation method of slurry-type catalyst respectively, do not mention and adopt ionic liquid and mesopore molecular sieve carrier.
Summary of the invention
The object of the present invention is to provide a kind of preparing aldehyde by hydro formylating defin loaded catalyst based on sulfonated triphenylphosphine-rhodium complex.
The present invention includes soild oxide, sulfonated triphenylphosphine-rhodium complex, sulfonated triphenylphosphine part and ionic liquid.Said soild oxide can be mesopore molecular sieve, SiO
2, TiO
2, γ-Al
2O
3In a kind of, mesopore molecular sieve particularly; Said sulfonated triphenylphosphine-rhodium complex can be one sulfonated triphenylphosphine-rhodium complex, two sulfonated triphenylphosphines-rhodium complex and trisulfonated triphenylphosphine-rhodium complex, particularly trisulfonated triphenylphosphine-rhodium complex.Said ionic liquid is 1,1,3,3, and-TMG lactate (being called for short TMGL), 1-butyl-3-methyl imidazolium tetrafluoroborate (are called for short BMIBF
4), 1-butyl-3-methylimidazole hexafluorophosphate (is called for short BMIPF
6).Each component is soild oxide 50%～90%, ionic liquid 8%～49%, rhodium 0.05%～2% by the content of mass ratio in the catalyst, calculating phosphine rhodium ratio in molar ratio is 3～200, in the catalyst each component by the preferred soild oxide 60%～80% of the content of mass ratio, ionic liquid 10%～30%, rhodium 0.1%～1.5%, to calculate phosphine rhodium ratio in molar ratio be 10～100.
The said Preparation of catalysts of the present invention is by said ratio the sulfonated triphenylphosphine-rhodium complex and the sulfonated triphenylphosphine part of metering to be dissolved with methyl alcohol, the ionic liquid that adds metering mixes, the soild oxide that adds metering again, mix, vacuum is taken out the methyl alcohol that desolvates, obtain powder catalyst, and at CO/H
2Preserve standby under the synthetic atmosphere.
Above-mentioned soild oxide can be the commercial grade product, and mesopore molecular sieve is according to literature method synthetic [Catal.Lett., 91,243 (2003)].
Evaluating catalyst is to carry out in the strong magnetic agitation autoclave of 100mL.Earlier catalyst and alkene are added in the still, use CO/H
2(1: 1, the V/V) air of flush away the inside was with the CO/H of 1～4.0MPa
2(1: 1, V/V) be synthesis gas reaction.Reaction temperature is between 60～200 ℃, and 80～150 ℃ better, is preferably between 80～110 ℃.Catalyst activity is with 1-hexene conversion ratio (%) and aldehyde space-time yield (mmolh
-1G-Rh
-1) expression.Said alkene is preferably C
2Above terminal olefine.
The said loaded catalyst of the present invention has good olefin hydroformylation performance, can improve the space-time yield of higher olefins reaction, does not change the ratio of positive isomery aldehyde in the product simultaneously and significantly reduces hydrogenation and the isomerization accessory substance must generate.Catalyst contains ionic liquid scale of construction claimed range broad and is difficult for running off, and is convenient to control.Alkene reacts in autoclave reactor, and is easy and simple to handle, separate automatically after the reaction of catalyst and product, and the reaction condition gentleness.This catalyst is reusable, and stable performance is suitable for the production technology of various carbon number terminal olefine hydroformylations.In sum, the major advantage of the said catalyst of the present invention is, does not contain surfactant in the catalyst, forms simply; The catalytic activity height; After reaction finished, catalyst and product can and can be reused through standing separation, operate very simple.
The specific embodiment
The present invention is further illustrated by embodiment below.
Embodiment 1:
Under argon atmospher, the rhodium dicarbonyl acetylacetonate (about 0.0772mmol) of 20mg and the trisulfonated triphenylphosphine (TPPTS) of 243.7mg are dissolved in the 20mL absolute methanol, the ionic liquid 1 that adds the 50mg drying again, 1,3,3,-TMG lactate (TMGL), after mixing, add mesopore molecular sieve MCM-41 (the about 3nm of particle diameter, the specific area 1041m of 1.0g
2G
-1), mix and stir 2h, take out methanol solvate under the normal temperature vacuum, get pale yellow powder shape loaded catalyst.In this catalyst system, phosphine rhodium mol ratio is about 5/1, and rhodium-containing is 0.8% (wt), and ionic liquid content is 5% (wt).Above-mentioned catalyst is transferred in the autoclave, added 1-hexene/toluene that 8mL contains hexene 25% (wt), at the CO/H of 2.0MPa
2React 4h in the synthesis gas, 100 ℃ of temperature.Evaluation result is shown in table 1.
Comparative Examples 1～3:
(1) adopts SiO
2(particle diameter is 3～10nm, specific area 315m
2G
-1) be carrier;
(2) adopt catalyst to consist of the ionic liquid TMGL of 4.0mL and the rhodium dicarbonyl acetylacetonate of 0.0064mmol;
(3) adopt catalyst to consist of the rhodium dicarbonyl acetylacetonate of ionic liquid TMGL, 0.0064mmol of 4.0mL and the trisulfonated triphenylphosphine (phosphine rhodium mol ratio is about 5/1) of 20mg.All the other conditions are with embodiment 1.Reaction result sees Table 1.
The 1-hexene hydroformylation activity comparing result of several catalyst of table 1
| Project | Catalyst | 1-hexene conversion ratio (%) | Space-time yield (mmolh -1·g-Rh -1) | Selectivity (%) | N-alkanal (%) |
| Embodiment Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 | TMGL-TPPTS-Rh/MCM-41 TMGL-TPPTS-Rh/SiO 2 TMGL-Rh TMGL-TPPTS-Rh | 55.6 12.4 5.0 3.7 | 3381 719 311 224 | 98 98 98 98 | 73.0 72.2 76.2 70.6 |
Embodiment 2～5
As the catalyst system of embodiment 1, but ionic liquid content is 10% (wt) and adopt different phosphine rhodium ratios, and other reaction condition is with embodiment 1.The results are shown in Table 2.
The table 2 difference evaluation result of rhodium of seeing than catalyst
| Project | Phosphine rhodium ratio (mol ratio) | 1-hexene conversion ratio (%) | Space-time yield (mmolh -1·g-Rh -1) | Product aldehyde selectivity (%) | N-alkanal selectivity (%) |
| Embodiment 2 embodiment 3 embodiment 4 embodiment 5 | 0 10 15 20 | 16.2 67.5 47.2 29.4 | 1031 4596 3216 2002 | 98 98 98 98 | 68.8 74.3 77.3 79.6 |
Embodiment 6
As catalyst system and the reaction condition of embodiment 1, but adopt ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate (BMIPF
6), content is 10% (wt), other reaction condition is with embodiment 1.The conversion ratio 55.1% of 1-hexene, the selectivity of enanthaldehyde are 98%, and n-alkanal is 62.9%, and space-time yield is 3518mmolh
-1G-Rh
-1
Embodiment 7
As catalyst system and the reaction condition of embodiment 1, but adopt ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate (BMIBF
4), content is 10% (wt), other reaction condition is with embodiment 1.The conversion ratio 76.2% of 1-hexene, the selectivity of enanthaldehyde are 98%, and n-alkanal is 61.5%, and space-time yield is 4859mmolh
-1G-Rh
-1
Embodiment 8
As the catalyst system of embodiment 1, be 10% (wt) but adopt ionic liquid content, after each reaction finishes, adopt and remove by filter reactant and solvent, catalyst is added autoclave react next time, other reaction condition is with embodiment 1.Instead
Should the results are shown in Table 3.
The evaluation result of table 3 catalyst stability
| Recycle number of times | 1-hexene conversion ratio (%) | Space-time yield (mmolh -1·g-Rh -1) | Selectivity (%) | N-alkanal (%) |
| 1 2 3 4 5 6 7 8 9 10 11 | 53.0 49.0 48.7 48.6 48.0 50.0 49.9 50.7 49.0 48.5 48.0 | 3015 2787 2770 2764 2730 2844 2839 2884 2787 2759 2730 | 98 98 98 98 98 98 98 98 98 98 98 | 72.2 71.4 71.4 72.2 72.2 72.2 71.4 71.4 71.4 71.4 71.4 |
Embodiment 9～12:
As the catalyst system of embodiment 1, but adopt different ionic liquid TMGL content in catalyst, other reaction condition is with embodiment 1.Reaction result sees Table 4.
The evaluation result of table 4 ionic liquid different content catalyst
| Project | Ionic liquid content (%, wt) | 1-hexene conversion ratio (%) | Space-time yield (mmolh -1·g-Rh -1) | Selectivity (%) | N-alkanal (%) |
| Embodiment 9 embodiment 10 embodiment 11 embodiment 12 | 0 15 25 49 | 55.0 56.5 36.0 27.9 | 3129 3780 2623 1914 | 98 98 98 98 | 41.2 75.0 77.8 71.4 |
Embodiment 13～15:
Similar with the catalyst system of embodiment 1, its difference is that the ionic liquid that is adopted is selected from 1,1,3,3 respectively, a kind of in-TMG lactate, 1-butyl-3-methyl imidazolium tetrafluoroborate, the 1-butyl-3-methylimidazole hexafluorophosphate.
Claims (5)
1, a kind of loaded catalyst that is used for preparing aldehyde by hydro formylating defin is characterized in that comprising soild oxide, sulfonated triphenylphosphine-rhodium complex, sulfonated triphenylphosphine part and ionic liquid; Said soild oxide is selected from mesopore molecular sieve, SiO
2, TiO
2, γ-Al
2O
3In a kind of; Said sulfonated triphenylphosphine-rhodium complex is selected from a kind of in one sulfonated triphenylphosphine-rhodium complex, two sulfonated triphenylphosphines-rhodium complex, the trisulfonated triphenylphosphine-rhodium complex; Each component is soild oxide 50%～90%, ionic liquid 8%～49%, rhodium 0.05%～2% by the content of mass ratio in the catalyst, and calculating phosphine rhodium ratio in molar ratio is 3～200.
2, a kind of loaded catalyst that is used for preparing aldehyde by hydro formylating defin as claimed in claim 1 is characterized in that said soild oxide is selected from mesopore molecular sieve.
3, a kind of loaded catalyst that is used for preparing aldehyde by hydro formylating defin as claimed in claim 1 is characterized in that said sulfonated triphenylphosphine-rhodium complex is selected from trisulfonated triphenylphosphine-rhodium complex.
4, a kind of loaded catalyst that is used for preparing aldehyde by hydro formylating defin as claimed in claim 1; it is characterized in that said ionic liquid is selected from 1,1,3; 3, a kind of in-TMG lactate, 1-butyl-3-methyl imidazolium tetrafluoroborate, the 1-butyl-3-methylimidazole hexafluorophosphate.
5, as claim 1 or 2 or 3 or 4 described a kind of loaded catalysts that are used for preparing aldehyde by hydro formylating defin, it is characterized in that each component in the catalyst by the content of mass ratio be soild oxide 60%～80%, ionic liquid 10%～30%, rhodium 0.1%～1.5%, to calculate phosphine rhodium ratio in molar ratio be 10～100.
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| CN100430139C (en) * | 2006-06-09 | 2008-11-05 | 中国科学院上海有机化学研究所 | Application of substituted bidentate amido phosphite ligand on binaphthol skeleton in hydroformylation of olefin |
| CN102260147A (en) * | 2011-06-01 | 2011-11-30 | 中国科学院过程工程研究所 | Method for hydroformylation of olefins in ionic liquid solvent |
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| CN102260147A (en) * | 2011-06-01 | 2011-11-30 | 中国科学院过程工程研究所 | Method for hydroformylation of olefins in ionic liquid solvent |
| CN102260147B (en) * | 2011-06-01 | 2013-11-06 | 中国科学院过程工程研究所 | Method for hydroformylation of olefins in ionic liquid solvent |
| CN102617308A (en) * | 2012-03-13 | 2012-08-01 | 青岛科技大学 | Olefin two-phase hydroformylation method |
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| CN103483381A (en) * | 2013-08-22 | 2014-01-01 | 青岛科技大学 | Preparation method of first-class phosphorus functionalized ionic liquid and application of ionic liquid in hydroformylation |
| CN103483381B (en) * | 2013-08-22 | 2016-08-17 | 青岛科技大学 | The preparation of one class phosphine functionalized ion liquid and the application in hydroformylation reaction thereof |
| 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 |
| CN103570514A (en) * | 2013-10-07 | 2014-02-12 | 青岛科技大学 | Olefin hydroformylation method by homogeneous catalysis-biphase separation |
| CN105017317B (en) * | 2014-12-25 | 2018-09-11 | 青岛科技大学 | A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers ionic liquid of alkyl guanidine salt |
| CN105017317A (en) * | 2014-12-25 | 2015-11-04 | 青岛科技大学 | Method for biphasic hydroformaylation of olefins based on phosphine-functionalized polyether alkyl guanidine salt ionic liquid |
| CN105037421A (en) * | 2015-04-02 | 2015-11-11 | 青岛科技大学 | Phosphine-functionalized polyether quaternary ammonium salt ionic liquid and application thereof in hydroformylation reaction of olefins |
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| CN105017316B (en) * | 2015-05-16 | 2018-03-20 | 青岛科技大学 | A kind of phosphine functionalization polyethers pyridiniujm ionic liquid and its application in hydroformylation of olefin |
| CN105001260B (en) * | 2015-05-16 | 2018-03-20 | 青岛科技大学 | A kind of phosphine functionalization polyethers alkylbenzyldimethylasaltsum saltsum ionic liquid and its application in hydroformylation of olefin |
| CN105001260A (en) * | 2015-05-16 | 2015-10-28 | 青岛科技大学 | Phosphine functional polyether morpholine salt ionic liquid and application thereof in olefin hydroformylation reaction |
| 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 |
| CN111056933A (en) * | 2019-12-24 | 2020-04-24 | 万华化学集团股份有限公司 | Method for preparing optically active citronellal and catalyst system used in method |
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