CN100366343C - Organic rhodium catalyst and application - Google Patents
Organic rhodium catalyst and application Download PDFInfo
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- CN100366343C CN100366343C CNB2005100573235A CN200510057323A CN100366343C CN 100366343 C CN100366343 C CN 100366343C CN B2005100573235 A CNB2005100573235 A CN B2005100573235A CN 200510057323 A CN200510057323 A CN 200510057323A CN 100366343 C CN100366343 C CN 100366343C
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Abstract
The present invention relates to an organic rhodium catalyst and an application thereof as a catalyst of hydroformylation reaction. The present invention discloses of a complex catalyst mainly prepared from dichloro-nitrosyl (ditriphenylphosphoric) rhodium and an application of a composite catalyst prepared from the complex catalyst and organic cobalt by mix as a catalyst of C2-C4 hydroformylation reaction. Compared with other organic rhodium compounds, the organic rhodium catalyst has more obvious catalytic activity and obvious superiority to no matter of reaction speed, product positive-passive ratio and activity decay.
Description
Technical field
The present invention relates to a kind of organic rhodium catalyst and as the Application of Catalyst of hydroformylation reaction.
Background technology
In the hydroformylation reaction of C2-C4, organic metal rhodium type catalyst commonly used comes catalytic reaction to finish.For the reaction of this class, selection of catalysts is crucial, such as being in the hydroformylation reaction of feedstock production isopentyl aldehyde with the isobutene; no matter high-pressure process (organic cobalt method) and low-pressure process (UCC method); its catalyst all is very crucial, and particularly isobutene contains Alpha-Methyl owing on its structure; the space bit resistance is big; the conventional used organic rhodium catalyst of hydroformylation is applied in the preparation of isopentyl aldehyde, and reaction speed is slower; catalysqt deactivation is very fast, several no industrial production meanings.Even use the n-butene used catalyst similar to isobutene to be applied on the hydroformylation reaction of isobutene, reactivity is also quite low.
The phosphorous acid organic ester modification rhodium type catalyst of Union Carbide company exploitation, though improved reaction speed, can be directly used in the preparation of isopentyl aldehyde, but that the part that catalyst is selected prepares difficulty is bigger, more complicated has increased the cost of catalyst.Chinese patent application CN1569790A also discloses a kind of " isobutene prepares the method for isopentyl aldehyde ", wherein employed catalyst, and its consumption is big, and cost is higher.
In organic rhodium compound, two chloro-nitrosyl (two triphen phosphorus) close rhodium (RhCl
2(NO) (P (C
6H
5)
3)
2) be a kind of organic rhodium compound that is of little use, at present, it is believed that it is almost without any industrial value.
Summary of the invention
The object of the present invention is to provide a kind of novel organic rhodium catalyst, its part is easy to get, and is applicable to suitability for industrialized production.
Another object of the present invention be with catalyst of the present invention as Application of Catalyst at the C2-C4 hydroformylation reaction, particularly be applied to isobutene and prepare in the isopentyl aldehyde method as Application of Catalyst.
Organic rhodium catalyst provided by the present invention mainly closes rhodium (RhCl by major catalyst two chloro-nitrosyl (two triphen phosphorus)
2(NO) (P (C
6H
5)
3)
2), and the complex catalyst of part triphenyl phasphine or its analog 1-phenyl dibenzo phosphine or triphenylmethyl methacrylate phosphine composition is formed.
As everyone knows, the organic metal rhodium costs an arm and a leg, and in order to reduce cost, the acetylacetone cobalt cocatalyst that can also add the 1-5 weight portion in the organic rhodium catalyst provided by the present invention obtains a kind of composite catalyst, and this composite catalyst activity is not seen obvious decline.
The present invention closes rhodium with two chloro-nitrosyl (two triphen phosphorus) first and uses as C2-C4 hydrogen formyl catalyst; composite catalyst that itself and organic cobalt the are mixed Application of Catalyst as the C2-C4 hydroformylation reaction also is provided simultaneously, has particularly prepared in the isopentyl aldehyde method as Application of Catalyst at isobutene.It is greatly improved than other organic rhodium catalysts commonly used in the past.
The present invention also further provides and has adopted the concrete grammar of organic rhodium catalyst of the present invention at the preparation isopentyl aldehyde, and the ratio of described organic rhodium catalyst and initiation material isobutene is 30-500ppm.
Said method, the mixing ratio of carbon monoxide and hydrogen is 1 in the synthesis gas: 1-1.5, reaction temperature is 90 ℃-140 ℃, and pressure is 1.5-9MPa, and the reaction time is 6-10 hour.
The present invention closes rhodium to a kind of organic rhodium compound that is of little use two chloro-nitrosyl (two triphen phosphorus), when the complex catalyst that select for use suitably, appropriate amount of ligands generates is used for isobutene and prepares isopentyl aldehyde, compare with other organic rhodium compound, it is much obvious that its catalytic activity is wanted, no matter in reaction speed, the just different ratio of product, decay of activity all has obvious superiority, and this catalyst does not find yet that after applying mechanically 50 batch reactions continuously its catalytic activity has tangible decay.Simultaneously, this catalyst hydroformylation reaction of being applied in ethene, propylene also has better activity.In a word, organic rhodium catalyst of the present invention, its part is easy to get, after adding cocatalyst, cost obviously reduces, and the catalyst system therefor amount is little, unit consumption is low, using method is simple, and reaction speed is fast, and catalyst is stable, can repeatedly reuse, the product selectivity height does not particularly almost have isomers to generate when the preparation isopentyl aldehyde, is suitable for suitability for industrialized production.In a word, it has overcome the deficiency that catalyst exists in the existing low-pressure process preparation.
The specific embodiment
To help people further to understand the present invention from following illustrative embodiment, but be not limited in this.
Embodiment 1: the preparation of major catalyst
1g three rhodium trichloride hydrates (3.8mmol) are dissolved in the mixed solvent of 250ml ethanol and 2.1gN-methyl-N-nitroso-sulfonyloxy methyl amine, the 10g triphenyl phasphine is dissolved in the 300ml hot ethanol, and join fast in the above-mentioned mixed liquor, reflux and be cooled to room temperature in 10 minutes, brown precipitate is filtered, water, ethanol, ether washing successively, dry that two chloro-nitrosyl (two triphen phosphorus) close rhodium 2.35g, yield is 85%.
The major catalyst that obtains like this adds suitable part and can obtain complex catalyst of the present invention.These parts can be selected triphenyl phasphine and homologue or triphenylmethyl methacrylate phosphine and homologue thereof, and wherein rhodium phosphorus ratio is 1: 3-50.
Embodiment 2-1: a kind of preparation of organic rhodium catalyst
With the major catalyst 0.2g of embodiment 1 gained, mix promptly to get composite catalyst of the present invention with cocatalyst acetylacetone cobalt 0.5g and part triphenyl phasphine 1g.
Embodiment 2-2: a kind of preparation of organic rhodium catalyst
With the major catalyst 0.2g of embodiment 1 gained, mix promptly to get composite catalyst of the present invention with cocatalyst acetylacetone cobalt 1g and part triphenyl phosphite 3g.
Embodiment 2-3: a kind of preparation of organic rhodium catalyst
With the major catalyst 0.2g of embodiment 1 gained, mix promptly to get composite catalyst of the present invention with cocatalyst acetylacetone cobalt 0.5g and ligand 1-phenyl dibenzo phosphine 1g.
Embodiment 3:
In the 1000ml autoclave, add the major catalyst two chloro-nitrosyl (two triphen phosphorus) that embodiment 1 makes respectively and close rhodium 0.7g, part triphenyl phasphine 3g, respectively after hydrogen and synthesis gas displacement, add initiation material isobutene 150g (2.67mol), feed 1: 1.15 carbon monoxide and hydrogen synthesis gas, make pressure reach 3MPa, be warming up to 100 ℃, after pressure reduces, constantly replenish synthesis gas, to guarantee reaction pressure, the pressure decrease speed slows down after about 6 hours, inhale pressure drop and be about 28MP, stop reaction, cooling, sampling is checked through gas chromatographic analysis, the reactant liquor production concentration is 96%, and unstripped gas is 3.5%, obtains isopentyl aldehyde 212g through distillation, yield is 92%, and content is 99%.
Embodiment 4:
The composite catalyst that adding embodiment 2-1 makes in the 1000ml autoclave is after hydrogen and synthesis gas displacement, add initiation material isobutene 150g (2.67mol), feed 1: 1.15 carbon monoxide and hydrogen synthesis gas, make pressure reach 3MPa, be warming up to 120 ℃, after pressure reduces, constantly replenish synthesis gas, to guarantee reaction pressure, the pressure decrease speed slows down after about 6 hours, inhale pressure drop and be about 28MP, stop reaction, cooling, sampling is checked through gas chromatographic analysis, the reactant liquor production concentration is 94%, and unstripped gas is 4.5%, obtains isopentyl aldehyde 208g through distillation, yield is 90%, and content is 98%.
Embodiment 5:
The composite catalyst that in the 1000ml autoclave, adds embodiment 2-3 gained, after hydrogen and synthesis gas displacement, add initiation material isobutene 150g (2.67mol), feed 1: 1.15 carbon monoxide and hydrogen synthesis gas, make pressure reach 3MPa, be warming up to 110 ℃, after reducing, constantly replenishes pressure synthesis gas, to guarantee reaction pressure, the pressure decrease speed slows down after about 6 hours, inhales pressure drop and is about 28MP, stop reaction, cooling, sampling is through the gas chromatographic analysis check, and the reactant liquor production concentration is 94.5%, unstripped gas is 4.5%, obtain isopentyl aldehyde 208g through distillation, yield is 90%, and content is 98%.
Embodiment 6:
In the 1000ml autoclave, add major catalyst two chloro-nitrosyl (two triphen phosphorus) respectively and close rhodium 0.2g, cocatalyst acetylacetone cobalt 1g and part triphenyl phasphine 10g, respectively after hydrogen and synthesis gas displacement, add initiation material isobutene 150g (2.67mol), feed 1: 1.15 carbon monoxide and hydrogen synthesis gas, make pressure reach 3MPa, be warming up to 110 ℃, after reducing, constantly replenishes pressure synthesis gas, to guarantee reaction pressure, the pressure decrease speed slows down after about 10 hours, inhales pressure drop and is about 28MP, stop reaction, cooling, sampling is through the gas chromatographic analysis check, and the reactant liquor production concentration is 93%, unstripped gas is 5.5%, obtain isopentyl aldehyde 205g through distillation, yield is 89%, and content is 98%.
Embodiment 7: catalyst of the present invention prepares application in the isopentyl aldehyde method at isobutene.
In the 1000ml autoclave, add major catalyst two chloro-nitrosyl (two triphen phosphorus) respectively and close rhodium 0.2g, cocatalyst acetylacetone cobalt 0.5g and part triphenyl phosphite 0.6g, respectively after hydrogen and synthesis gas displacement, add initiation material isobutene 150g (2.67mol), feed 1: 1.15 carbon monoxide and hydrogen synthesis gas, make pressure reach 3MPa, be warming up to 110 ℃, after reducing, constantly replenishes pressure synthesis gas, to guarantee reaction pressure, the pressure decrease speed slows down after about 6 hours, inhales pressure drop and is about 28MP, stop reaction, cooling, sampling is through the gas chromatographic analysis check, and the reactant liquor production concentration is 95%, unstripped gas is 4.5%, obtain isopentyl aldehyde 207g through distillation, yield is 90%, and content is 98%.
Embodiment 8: the application of catalyst of the present invention in the hydroformylation reaction of ethene.
In the 1000ml autoclave, add two chloro-nitrosyl (two triphen phosphorus) respectively and close rhodium 0.2g, cocatalyst acetylacetone cobalt 0.5g and part triphenyl phasphine 1g, respectively after hydrogen and synthesis gas displacement, add initiation material ethene 25g (0.89mol), feed 1: 1.15 carbon monoxide and hydrogen synthesis gas, make pressure reach 3MPa, be warming up to 110 ℃, after reducing, constantly replenishes pressure synthesis gas, to guarantee reaction pressure, the pressure decrease speed slows down after about 7 hours, inhales pressure drop and is about 8MP, stop reaction, cooling, sampling is through the gas chromatographic analysis check, and the reactant liquor production concentration is 96%, unstripped gas is 3.5%, obtain propionic aldehyde 46g through distillation, yield is 90%, and content is 98%.
Embodiment 9: the application of catalyst of the present invention in the hydroformylation reaction of propylene.
In the 1000ml autoclave, add major catalyst two chloro-nitrosyl (two triphen phosphorus) respectively and close rhodium 0.2g, cocatalyst acetylacetone cobalt 0.5g and part triphenyl phasphine 1g, respectively after hydrogen and synthesis gas displacement, add initiation material propylene 50g (1.2mol), feed 1: 1.15 carbon monoxide and hydrogen synthesis gas, make pressure reach 3MPa, be warming up to 110 ℃, constantly replenish synthesis gas after pressure reduces, to guarantee reaction pressure, the pressure decrease speed slows down after about 7 hours, inhale pressure drop and be about 13MP, stop reaction, cooling, sampling is checked through gas chromatographic analysis, the reactant liquor production concentration is 83% just different from (85: 15), and unstripped gas is 16.5%.
Embodiment 10: the application of catalyst of the present invention in the hydroformylation reaction of n-butene.
In the 1000ml autoclave, add major catalyst two chloro-nitrosyl (two triphen phosphorus) respectively and close rhodium 0.2g, cocatalyst acetylacetone cobalt 0.5g and part triphenyl phasphine 1g, after hydrogen and synthesis gas displacement, add initiation material n-butene 50g (0.86mol), feed 1: 1.15 carbon monoxide and hydrogen synthesis gas, make pressure reach 3MPa, be warming up to 110 ℃, constantly replenish synthesis gas after pressure reduces, to guarantee reaction pressure, the pressure decrease speed slows down after about 8 hours, inhale pressure drop and be about 9MP, stop reaction, cooling, sampling is checked through gas chromatographic analysis, the reactant liquor production concentration is 91% (just different ratio 84: 16), and unstripped gas is 8.5%.
Claims (8)
1. organic rhodium catalyst, it is characterized in that: this organic rhodium catalyst mainly closes rhodium (RhCl by major catalyst two chloro-nitrosyl (two triphen phosphorus)
2(NO) (P (C
6H
5)
3)
2), and the complex catalyst of part triphenyl phasphine or 1-phenyl dibenzo phosphine or triphenylmethyl methacrylate phosphine composition is formed.
2. organic rhodium catalyst as claimed in claim 1 is characterized in that: this organic rhodium catalyst is made up of described major catalyst, described part and acetylacetone cobalt, and this organic rhodium catalyst is a kind of composite catalyst.
3. organic rhodium catalyst as claimed in claim 1 is characterized in that: rhodium phosphorus ratio is 1 in the described complex catalyst: 3-50, and in weight portion.
Two chloro-nitrosyl (two triphen phosphorus) close rhodium in the hydroformylation reaction of C2-C4 as Application of Catalyst.
As claim 1,2 or 3 described organic rhodium catalysts in the hydroformylation reaction of C2-C4 as Application of Catalyst.
6. prepare in the isopentyl aldehyde method as Application of Catalyst at isobutene as claim 1,2 or 3 described organic rhodium catalysts.
7. one kind prepares the method for isopentyl aldehyde with claim 1,2 or 3 described organic rhodium catalysts, and it is characterized in that: the ratio of described organic rhodium catalyst and initiation material isobutene is 30-500ppm.
8. organic rhodium catalyst as claimed in claim 7 prepares the method for isopentyl aldehyde, it is characterized in that: carbon monoxide in the synthesis gas of feeding: the mixing ratio of hydrogen is 1: 1-1.5, reaction temperature is 90 ℃-140 ℃, and pressure is 1.5-9MPa, and the reaction time is 6-10 hour.
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|---|---|---|---|
| CNB2005100573235A CN100366343C (en) | 2005-10-13 | 2005-10-13 | Organic rhodium catalyst and application |
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|---|---|---|---|
| CNB2005100573235A CN100366343C (en) | 2005-10-13 | 2005-10-13 | Organic rhodium catalyst and application |
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| CN1765506A CN1765506A (en) | 2006-05-03 |
| CN100366343C true CN100366343C (en) | 2008-02-06 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0372313A2 (en) * | 1988-12-02 | 1990-06-13 | Hoechst Aktiengesellschaft | Sulfonated phenyl phosphine-containing complexes |
| CN1241995A (en) * | 1996-11-04 | 2000-01-19 | Dsm有限公司 | Process for the continuous preparation of an alkyl 5-formylvalerate compound |
| US6290926B1 (en) * | 1996-12-17 | 2001-09-18 | Studiengesellschaft Kohle Mbh | Catalysts made from transition metal compounds and 4, 5-diphosphinoacridine-ligands |
| CN1333201A (en) * | 2000-07-14 | 2002-01-30 | 奥克森诺奥勒芬化学股份有限公司 | Multi-stage preparation process of carbonyl synthesizing aldehyde and/or alcohol |
-
2005
- 2005-10-13 CN CNB2005100573235A patent/CN100366343C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0372313A2 (en) * | 1988-12-02 | 1990-06-13 | Hoechst Aktiengesellschaft | Sulfonated phenyl phosphine-containing complexes |
| CN1241995A (en) * | 1996-11-04 | 2000-01-19 | Dsm有限公司 | Process for the continuous preparation of an alkyl 5-formylvalerate compound |
| US6290926B1 (en) * | 1996-12-17 | 2001-09-18 | Studiengesellschaft Kohle Mbh | Catalysts made from transition metal compounds and 4, 5-diphosphinoacridine-ligands |
| CN1333201A (en) * | 2000-07-14 | 2002-01-30 | 奥克森诺奥勒芬化学股份有限公司 | Multi-stage preparation process of carbonyl synthesizing aldehyde and/or alcohol |
Non-Patent Citations (2)
| Title |
|---|
| Perhalocarboxylato complexes of the platinum group metals.Facile fragmentation reactions. Esther B.Boyar et al.Inorganica Chimica Acta,Vol.76 . 1983 * |
| 均相体系中含氮双齿膦配体对1－十二烯氢甲酰化反应的影响。. 黄雪原等。.西南民族大学学报·自然科学版，第31卷第2期. 2005 * |
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Effective date of registration: 20090925 Address after: Chongqing Chongqing southwest synthesis Pharmaceutical Co, Ltd of Pearl River mouth, Jiangbei District, postcode: 400025 Co-patentee after: PKU International Healthcare Group Co., Ltd. Patentee after: Chongqing southwest Synthetic Pharmaceutical Co., Ltd. Address before: Chongqing Chongqing southwest synthesis Pharmaceutical Co, Ltd of Pearl River mouth, Jiangbei District, postcode: 400025 Patentee before: Chongqing Southwest Synthetic Pharmaceutical Co., Ltd. |
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Granted publication date: 20080206 Termination date: 20091113 |