CN1035543C - Water soluble catalyst loaded on high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine - Google Patents
Water soluble catalyst loaded on high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine Download PDFInfo
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- CN1035543C CN1035543C CN93100802A CN93100802A CN1035543C CN 1035543 C CN1035543 C CN 1035543C CN 93100802 A CN93100802 A CN 93100802A CN 93100802 A CN93100802 A CN 93100802A CN 1035543 C CN1035543 C CN 1035543C
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Abstract
The present invention provides a supported water-soluble catalyst for preparing high-carbon aldehyde from high-carbon number terminal olefine by hydroformylation, which comprises sulfonated triphenylphosphine-rhodium complexes as main components and accelerated by alkali metal or alkaline earth metal chloride. The supported water-soluble catalyst contains water-soluble sulfonated triphenylphosphine-rhodium complexes and alkali metal chloride or alkaline earth metal chloride, wherein the content of the utility model metal chloride is from 5 to 1000 times (molar ratio) of the content of rhodium in the catalyst. When high-carbon number terminal olefine is continuously treated by hydroformylation reaction on a flow reactor of a fixed bed under the mild reaction condition, the space-time yield is approximately increased by 2 times by adding the alkali metal chloride or the alkaline earth metal chloride to the catalyst, the selectivity of product normal aldehyde is also increased, and the catalyst performance is stable.
Description
It is water soluble catalyst loaded to the present invention relates to a kind of high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine.
The hydroformylation method of all useful cobalt of the technology of existing production aldehyde, rhodium (as Wilkinson homogeneous phase phosphine-rhodium catalyst) catalyzed alkene.The Co catalysts condition is harsh, requires reaction under high pressure; The function admirable of phosphine-rhodium complex catalyst, aldehyde selectivity height, reaction condition gentleness, this catalyst is mainly used in system low-carbon (LC) aldehyde, and when olefin carbon number was higher, it is loaded down with trivial details that reaction finishes separating of rear catalyst and product, causes rhodium to run off easily and part destruction; On the other hand; high carbon number alkene obtains senior aldehyde through the hydroformylation synthetic method; be important meticulous and specialty chemicals synthetic intermediate, or promptly get higher alcohol through catalytic hydrogenation again, these higher alcohols can be used for making surfactant, plasticizer, synthetic lubricant fluid and petroleum additive etc.Therefore, the research of high carbon number alkene carbon aldehyde by hydrogen formylating high is not only to the improvement of cobalt, rhodium Catalytic processes, and to meticulous and the specialty chemicals industrial expansion is all significant.
France Phone-Polenc and Ruhrchemie company (seeing FR, Pat., 2478078) the water soluble sulfonated triphenyl phasphine of employing are 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 dissolving hardly in organic facies only need divide dried up/organic facies just to reach the purpose of complete separated product and catalyst behind the hydroformylation reaction simply.DE, Pat., 3546123; US, Pat., 4248802; FR, Pat., 2561650; DE, Pat., 3447030 and EP, Pat., 0133410 discloses relevant research.Industrialization is the result show, adopting this method propylene linear chain aldehyde selectivity of hydroformylation under 5.1MPa is 95% (seeing Hydrocarbon Processing, 11,153 (1985)).But report is arranged owing to organic facies poor solubility in water, influence the space-time yield (Catal.Lett., 6,43 (1990)) of the higher olefin hydroformylation of carbon number.(petrochemical industry, 16 (10), 691 (1987) such as Zhou Qizhao; Petrochemical industry, 20 (2), 79 (1991)) the biphasic catalysis technology that adopts ethanol etc. to make phase transfer catalyst has prepared a series of aldehyde such as enanthaldehyde to ten seven carbon aldehyde, and catalyst that is adopted and Phone-Polenc company is similar substantially.Result of study (Nature, 339,454 (1989) that M.E.Davis etc. have successively delivered the support type sulfonated triphenylphosphine-rhodium catalyst that is used for olefin hydroformylation recently; J.Catal., 121,327 (1990); 129,94 (1991); 100 (1991); J.Oganometal.Chem., 403,221 (1991)), I.T.Horvath has reported that this catalyst uses the result of study (Catal.Lett., 6,43 (1990)) 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
2(1: 1, V/V), reaction 5 hours under 70 ℃ the condition, reaction conversion ratio 62.5%, the selectivity 73% of n-alkanal.
In a word, the catalyst of existing high carbon number alkene carbon aldehyde by hydrogen formylating high all is rhodium, the cobalt complex of phosphine modulation basically, and some useful consisting of phase-transferring agent of catalyst that are used in two phase reaction increase productive rate.Support type sulfonated triphenylphosphine-the rhodium catalyst of existing olefin hydroformylation is not seen so far the report that adds promoter.
The object of the present invention is to provide a kind of that promote with metal chloride, water soluble catalyst loaded based on the high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine of sulfonated triphenylphosphine-rhodium complex.
Of the present invention water soluble catalyst loaded for loading on the water-soluble phosphine-rhodium complex on the solid, carrier can be SiO
2, γ-Al
2O
3, cellular glass ball, particularly SiO
2Water-soluble phosphine-rhodium complex such as sulfonation triphenyl phasphine-rhodium complex, particularly trisulfonated triphenylphosphine-rhodium complex; The present invention also contains alkali metal chloride or alkaline earth metal chloride, and the content of metal chloride in catalyst is 5～1000 times (mol ratios) of rhodium content, and the best is 20～200 times.
Said alkali metal chloride is the chloride of Li, Na, K preferably.Said alkaline earth metal chloride is the chloride of Ca, Mg, Ba, Sr preferably.
Above-mentioned metal chloride can be used the commercial grade product.
The carbon number of said high carbon number alkene is C
6Above terminal olefine.
Said catalyst is that the rhodium dicarbonyl acetylacetonate of metering is dissolved in the cyclohexane, and equi-volume process is impregnated on the carrier, drains in vacuum under the normal temperature; It is even the more water-soluble liquid phase of the trisulfonated triphenylphosphine of metering and metal ion to be mixed, and equivalent impregnation is to above-mentioned solid, and vacuum is drained under the normal temperature, at CO/H
2Preserve standby under the synthetic atmosphere.
Evaluating catalyst is in fixed bed stainless steel tube reactor, with the CO/H of 2.0～5.0MPa
2(1: 1, V/V) be synthesis gas, gas flow rate 10～30ml/min is for well.High carbon number alkene is pressed into reaction tube with high pressure pump.Between 60～200 ℃ of the reaction temperatures, 80～150 ℃ better, is preferably between 80～100 ℃.The yield of aldehyde is between 40%～100%.N-alkanal is between 65%～86%.
Catalyst of the present invention has good high carbon number end alkene hydroformylation catalytic performance; after adding alkali metal or alkaline earth metal chloride in the catalyst, the space-time yield of reaction is improved greatly; the ratio of n-alkanal in the product is improved; high carbon number end alkene carries out hydroformylation reaction on fixed bed reaction; easy and simple to handle; the difficulty that catalyst-free separates with product, and reaction condition is gentle.C
6During above high carbon number end alkene reaction, aldehyde selectivity height.
The present invention is further illustrated by embodiment below
Embodiment 1
0.02mol the rhodium dicarbonyl acetylacetonate of concentration/thiacyclohexane solution 1.0ml loads to the SiO of 1.0g
2On, vacuum is taken out the decyclization hexane; 113.8mg trisulfonated triphenylphosphine and after the LiCl aqueous solution 2.0ml of 1.00N is mixed into uniform solution, load to above-mentioned SiO
2On, drain under the normal temperature vacuum.1-octene/cyclohexane with 20% (wt) is a raw material, and flow is 2.0ml/h, at the CO/H of 3.0MPa
2Gas flow rate is 15ml/min, the 1.0g catalyst, and during 100 ℃ of temperature, the conversion ratio 63.1% of 1-octene generates the selectivity 100% of aldehyde C-9, n-alkanal 75%, space-time yield 165.1g/h.l.
When not adding LiCl, under the same condition, the conversion ratio 46.5% of 1-octene, the selectivity 100% of generation aldehyde C-9, n-alkanal 71%, space-time yield 113.8g/h.l.
Embodiment 2
0.02mol the rhodium dicarbonyl acetylacetonate of concentration/cyclohexane solution 3.0ml loads to the SiO of 3.0g
2On, vacuum is taken out the decyclization hexane; After the LiCl aqueous solution 6.0ml of trisulfonated triphenylphosphine 525mg and 1.00N makes homogeneous solution, load to above-mentioned SiO
2On, drain under the normal temperature vacuum.With 20% (wt) methyl undecylenate/cyclohexane is raw material, and flow is 6.8ml/h, 3.0g catalyst, CO/H
2Synthesis gas 4.0MPa, gas flow rate are 10ml/min, and space-time yield 87.8g/h.l generates the selectivity 98.6% of 12 carbon aldehyde, n-alkanal 82.0%.
Embodiment 3
The load trisulfonated triphenylphosphine is to SiO
2On preparation condition other condition except that not adding LiCl with example 2, under the same reaction condition, space-time yield 35.8g/h.l generates the selectivity 98.0% of 12 carbon aldehyde, n-alkanal 80%.
Embodiment 4
The KCl aqueous solution 6.0ml of trisulfonated triphenylphosphine 525mg and 1.00N makes homogeneous solution, other condition is with example 1, with 20% methyl undecylenate/cyclohexane is raw material, flow is 6.3ml/h, 3.0g catalyst, other reaction condition is with example 1, space-time yield 82.8g/h.l, the selectivity 99.1% of 12 carbon aldehyde, n-alkanal 85.0%.
When not adding KCl, under the similarity condition, space-time yield 35.8g/h.l, the selectivity 98.0% of 12 carbon aldehyde, n-alkanal 80%.
Embodiment 5
Removing institute, to add alkali metal chloride as shown in the table, and all the other conditions are all with embodiment 1.Alkali metal chloride addition 1-octene conversion ratio space-time yield selectivity n-alkanal
(%) (g/h.l) (%) (%) 1.0 N-NaCl 0.2ml 55.6 145.5 100 72.01.0 N-NaCl 4.0ml 60.3 157.8 100 75.21.0 N-NaCl 10.0ml 57.7 151.0 100 74.3 embodiment 6
Removing institute, to add alkaline earth metal chloride as shown in the table, and all the other conditions are all with embodiment 1.Alkaline earth metal chloride addition 1-octene conversion ratio space-time yield selectivity n-alkanal
(％) (g/h.l) (％) (％)1.0?N-CaCl
2 2.0ml 50.3 131.6 100 76.01.0?N-MgCl
2 2.0ml 60.1 157.2 100 74.21.0?N-BaCl
2 2.0ml 48.6 127.2 100 77.31.0?N-SrCl
2 2.0ml 57.4 150.1 100 73.7
Claims (5)
1. a high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine is water soluble catalyst loaded, is made up of carrier and the catalyst component that carries thereon, and described carrier is selected from by SiO
2, γ-Al
2O
3, the component formed of cellular glass ball, described catalyst component is sulfonated triphenylphosphine-rhodium complex and alkali metal and/or alkaline earth metal chloride, the mol ratio of metal chloride and rhodium is 5～1000 times in the catalyst.
2. catalyst as claimed in claim 1 is characterized in that said alkali metal chloride is Li, Na, the chloride of K.
3. catalyst as claimed in claim 1 is characterized in that said alkaline earth metal chloride is Ca, Mg, Ba, the chloride of Sr.
4. as the described catalyst of one of claim 1～3, it is characterized in that the content of metal chloride in catalyst is 2～200 times (mol ratios) of rhodium content.
5. catalyst as claimed in claim 1 is characterized in that the carbon number of said high carbon number end alkene is C
6Above terminal olefine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93100802A CN1035543C (en) | 1993-01-09 | 1993-01-09 | Water soluble catalyst loaded on high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93100802A CN1035543C (en) | 1993-01-09 | 1993-01-09 | Water soluble catalyst loaded on high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine |
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| CN1075902A CN1075902A (en) | 1993-09-08 |
| CN1035543C true CN1035543C (en) | 1997-08-06 |
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| CN93100802A Expired - Fee Related CN1035543C (en) | 1993-01-09 | 1993-01-09 | Water soluble catalyst loaded on high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine |
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| CN103084192B (en) * | 2011-10-28 | 2015-05-27 | 中国科学院大连化学物理研究所 | Cobalt phosphide catalyst for preparing 3-pentanone and propanal from hydrogen, carbon monoxide and ethylene |
| CN103071534B (en) * | 2012-12-31 | 2015-02-11 | 浙江江山化工股份有限公司 | Catalyst for catalytically synthesizing N-methyl ethanol amine compound and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989001467A1 (en) * | 1987-08-10 | 1989-02-23 | Eastman Kodak Company | Low pressure rhodium catalyzed hydroformylation of olefins |
| EP0372615A2 (en) * | 1988-11-28 | 1990-06-13 | Virginia Tech Intellectual Properties, Inc. | Hydroformylation process |
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1993
- 1993-01-09 CN CN93100802A patent/CN1035543C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989001467A1 (en) * | 1987-08-10 | 1989-02-23 | Eastman Kodak Company | Low pressure rhodium catalyzed hydroformylation of olefins |
| EP0372615A2 (en) * | 1988-11-28 | 1990-06-13 | Virginia Tech Intellectual Properties, Inc. | Hydroformylation process |
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