CN112121864A - Hydroformylation catalyst and hydroformylation method of long-chain olefin - Google Patents
Hydroformylation catalyst and hydroformylation method of long-chain olefin Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
Abstract
The hydroformylation catalyst comprises a ligand and a transition metal catalyst, wherein the ligand is 2, 2 '-bis (diphenylphosphinomethyl) -1, 1' -biphenyl (BISBI), and the transition metal catalyst is selected from one or more of cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) and osmium (Os). The hydroformylation catalyst provided by the invention has good activity and stability and low cost, widens the proportion of normal high-carbon aldehyde and alcohol products and isomeric high-carbon aldehyde and alcohol products, and meets the market demand better.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a hydroformylation catalyst and a hydroformylation method of long-chain olefin.
Background
Hydroformylation of olefins is a commercially important homogeneous catalytic reaction process in which olefins are reacted with synthesis gas (carbon monoxide and hydrogen) in the presence of a homogeneous organometallic catalyst and a ligand to produce linear (normal) aldehydes and branched (iso) aldehydes with an increase in carbon number of 1. Various aldehydes synthesized by olefin through hydroformylation reaction can be directly hydrogenated to prepare alcohol, and can also be condensed and hydrogenated to prepare alcohol products. Industrially, straight-chain (normal) alcohols produced by hydroformylation are widely used in solvents, additives, raw materials for various plasticizers, synthetic lubricating oils, detergents, and the like.
Most of research on hydroformylation of olefins focuses on increasing the proportion of normal products, however, recently, the development of isovaleric acid, 2, 4-trimethyl-1, 3-pentanediol, neopentyl glycol (NPG), etc. using isoaldehyde as a raw material has attracted much attention, and the demand for isoaldehyde is increasing, so that it is necessary to improve the existing proportion range of normal products and isoproducts for hydroformylation of olefins, to make the structure of the products flexible and adjustable, and to better meet the market demand.
Although there are many processes for preparing aldehydes by hydroformylation of olefins in the prior art, the hydroformylation process studied is mainly focused on increasing the proportion of normal products as much as possible by improving catalysts, process parameters, reactors, and the like.
The normal isomeric distribution ratio of the olefin hydroformylation products is of great interest. Taking propylene hydroformylation as an example, the liquid phase circulation process using rhodium-TPP as a catalyst is most widely applied at present, and mainly comprises a Davy-Dow process, a Mitsubishi process and a BASF process. Wherein the normal isomerization ratio of the butyraldehyde which is a product of the Davy-Dow process is 7-10; 8-10 of Mitsubishi technology; the normal isomerization ratio of butyraldehyde which is a product of the BASF process is 8-9. As can be seen, the normal isomerization proportion distribution range of the product aldehyde in the existing mainstream process is narrow and is concentrated in the range of 7-10: 1.
In the prior art, the normal-to-iso ratio range of hydroformylation products of aldehyde is narrow, isomeric aldehyde products are few, particularly, the normal-to-iso ratio range of aldehyde and alcohol products prepared by hydroformylation of long-chain olefin (C10-C18) is narrow, and the market competitiveness of the products is poor.
Disclosure of Invention
The invention provides a hydroformylation catalyst and a method for performing olefin hydroformylation reaction by using the same, in particular to a catalyst and a method for C10-C18 long-chain olefin, which can reduce the cost of the catalyst, enlarge the proportion range of a long-chain olefin hydroformylation normal product and an isomeric product, and flexibly adjust the hydroformylation product structure according to market demands.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydroformylation catalyst of long-chain olefin comprises a ligand and a transition metal catalyst, wherein the ligand is 2, 2 '-bis (diphenylphosphinomethyl) -1, 1' -biphenyl (BISBI), and the transition metal catalyst is selected from one or more of cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) and osmium (Os); the transition metal catalyst is selected from cobalt carbonyl [ Co ]2(CO)8]Rhodium dicarbonyl acetylacetonate [ Rh (AcAc) (CO)2]Rhodium acetylacetonate carbonyltriphenylphosphine [ Rh (AcAc) ((CO) (TPP))]Carbonyl tris (triphenylphosphine) rhodium hydride [ HRh (CO) (TPP)3]Iridium dicarbonyl acetylacetonate [ Ir (AcAc) (CO)2]And carbonyltris (triphenylphosphine) iridium hydride [ HIr (CO) (TPP)3]One or more ofThe molar ratio of the ligand to the transition metal catalyst is 1-100: 1 (e.g., 10: 1, 20: 1, 30: 1, 40: 1, 50: 1, 60: 1, 70: 1, 80: 1, 90: 1, etc.).
In some embodiments, the transition metal catalyst has a transition metal content of 50ppm to 1% (e.g., 100ppm, 200ppm, 500ppm, 0.1%, 0.2%, 0.5%, 0.8%).
A process for the hydroformylation of long chain olefins comprising: adding the hydroformylation catalyst and long-chain olefin into a high-pressure reaction kettle, wherein the long-chain olefin is C10-C20 olefin, and is preferably C10-C18 olefin;
introducing synthesis gas into the high reaction kettle, and performing hydroformylation reaction under the conditions that the pressure is 1-7 MPa and the temperature is 80-198 ℃;
after the reaction is finished, the product is separated from the hydroformylation catalyst.
In some embodiments, the hydroformylation reaction is at a pressure of 2MPa, 3MPa, 4MPa, 5MPa or 6MPa and a temperature of 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 1700 deg.C, 180 deg.C or 190 deg.C.
In some embodiments, the molar ratio of the long chain olefin to the transition metal catalyst is 1000 to 10000: 1, such as 2000: 1, 3000: 1, 4000: 1, 5000: 1, 6000: 1, 7000: 1, 8000: 1, 9000: 1.
In some embodiments, the hydroformylation catalyst is dissolved in a solvent that is polybutyral, a C4 to C8 aldehyde, toluene, naphtha, kerosene, cyclohexane, xylene, acetophenone, or benzonitrile.
In some embodiments, the molar ratio of hydrogen to carbon monoxide in the syngas is from 1: 1 to 2: 1.
In some embodiments, the product is separated from the hydroformylation catalyst by salt precipitation, rectification under high vacuum, pervaporation.
In some embodiments, the method further comprises returning the separated hydroformylation catalyst to the autoclave for reuse.
In some embodiments, the method further comprises replacing 3-5 times the air in the autoclave with syngas prior to reacting.
Compared with the prior art, the invention has the advantages that the hydroformylation catalyst has good activity and stability and low cost, and the ratio of C10-C18 olefin hydroformylation normal products to isomeric products is 1: 1 when the ligand BISBI is combined with the transition metal cobalt (Co); the ligand BISBI combined with transition metal rhodium (Rh) can make C10-C18 olefin hydroformylation normal product and isomerate product ratio in 40: 1, thereby widening the proportion of normal high carbon aldehyde and alcohol products and isomeric high carbon aldehyde and alcohol products and meeting the market demand better.
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FIG. 1 is a schematic view of a reaction apparatus in an embodiment of the present invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention provides a hydroformylation catalyst and a method for performing an olefin hydroformylation reaction by using the same, in particular to a hydroformylation catalyst and a hydroformylation method for C10-C18 long-chain olefin.
A catalyst for hydroformylation of long chain olefins, which comprises a bidentate phosphine ligand 2, 2 '-bis (diphenylphosphinomethyl) -1, 1' -biphenyl (BISBI) represented by the following formula 1 and a transition metal catalyst.
The transition metal catalyst is selected from one or more of cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) and osmium (Os); the transition metal catalyst is selected from cobalt carbonyl [ Co ]2(CO)8]Rhodium dicarbonyl acetylacetonate [ Rh (AcAc) (CO)2]Rhodium acetylacetonate carbonyltriphenylphosphine [ Rh (AcAc) ((CO) (TPP))]Carbonyl tris (triphenylphosphine) rhodium hydride [ HRh (CO) (TPP)3]Acetyl acetone dicarbonylIridium [ Ir (AcAc) ((CO))2]And carbonyltris (triphenylphosphine) iridium hydride [ HIr (CO) (TPP)3]One or more of (a).
The olefin is selected from C10-C20 olefins, preferably C10-C18 olefins.
As shown in fig. 1, the reaction apparatus in the embodiment of the present invention includes a synthesis gas storage container 1, a synthesis gas buffer tank 2, a synthesis gas buffer tank 3, a quantitative pipe 4 for quantitatively weighing hydroformylation reaction raw material olefin, an autoclave 5, a temperature control device 6, and a nitrogen storage container 7 (for providing nitrogen for purging the system).
The hydroformylation method comprises the following specific steps:
firstly, preparing a transition metal catalyst with the transition metal content of 50 ppm-1%, a BISBI ligand with the transition metal catalyst in a molar ratio of 1-100: 1 (such as 10: 1, 20: 1, 30: 1, 40: 1, 50: 1, 60: 1, 70: 1, 80: 1, 90: 1) and dissolving the transition metal catalyst in a solvent of polybutyral, C4-C8 aldehyde, toluene, naphtha, kerosene, cyclohexane, xylene, acetophenone, benzonitrile and the like, and adding one of C10-C18 olefins to ensure that the molar ratio of the olefins to the transition metal catalyst is 1000-10000 (such as 2000: 1, 3000: 1, 4000: 1, 5000: 1, 6000: 1, 7000: 1, 8000: 1 and 9000: 1). Adding the prepared mixed solution into a high-pressure reaction kettle, wherein the high-pressure reaction kettle is provided with a heating oil bath (containing a temperature control device), a pressure sensor and stirring equipment;
secondly, introducing synthesis gas with the molar ratio of hydrogen to carbon monoxide of 1: 1-2: 1 into the high reaction kettle, and replacing air in the kettle for 3-5 times;
thirdly, adding the synthesis gas into an autoclave, keeping the total pressure in the autoclave at 1-7 MPa (such as 2MPa, 3MPa, 4MPa, 5MPa or 6MPa), and reacting at 80-198 ℃ (such as 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 1700 ℃, 180 ℃ or 190 ℃);
fourthly, after the reaction is stopped, cooling the mixture solution in the high-pressure reaction kettle to room temperature, sampling and analyzing, and separating the product from the catalyst by the reaction mixture solution through a salt precipitation method, rectification under high vacuum, pervaporation and other methods; when the product is separated from the catalyst, the catalyst solution can be returned to the autoclave for reuse.
The content of the product was determined by gas chromatography: the conversion rate of C10-C18 olefin is 60-100%, and the ratio of normal products to isomeric products can be adjusted between 1-40.
Example 1
50g of toluene, cobalt carbonyl [ Co ] having a cobalt concentration of 500ppm2(CO)8]Catalyst, and cobalt carbonyl [ Co ]2(CO)8]BISBI ligand in a molar ratio of 1: 1 to cobalt carbonyl [ Co ]2(CO)8]C10 olefin with the molar ratio of 1000: 1 is dissolved and then is added into a high-pressure reaction kettle which is provided with a heating oil bath (containing a temperature control device), a pressure sensor and stirring equipment; introducing synthesis gas with the molar ratio of hydrogen to carbon monoxide of 1: 1 into the high reaction kettle, and replacing air in the kettle for 3-5 times; adding the synthetic gas into an autoclave, keeping the total pressure in the autoclave at 5MPa, and reacting at the temperature of 180 ℃.
After the reaction is finished, the content of the product is measured by gas chromatography, and the result shows that the conversion rate of C10 is 65%, and the ratio of the normal product to the isomeric product is 1: 1.
Example 2
50g of toluene, cobalt carbonyl [ Co ] having a cobalt concentration of 1000ppm2(CO)8]Catalyst, and cobalt carbonyl [ Co ]2(CO)8]BISBI ligand in a molar ratio of 10: 1 to cobalt carbonyl [ Co ]2(CO)8]C10 olefin with the molar ratio of 1000: 1 is dissolved and then is added into a high-pressure reaction kettle which is provided with a heating oil bath (containing a temperature control device), a pressure sensor and stirring equipment; introducing synthesis gas with the molar ratio of hydrogen to carbon monoxide of 1: 1 into the high reaction kettle, and replacing air in the kettle for 3-5 times; adding the synthetic gas into an autoclave, keeping the total pressure in the autoclave at 5MPa, and reacting at the temperature of 180 ℃.
After the reaction is finished, the content of the product is measured by gas chromatography, and the result shows that the conversion rate of C10 is 75%, and the ratio of the normal product to the isomeric product is 2: 1.
Example 3
50g of toluene, rhodium acetylacetonate dicarbonyl [ Rh (AcAc) (CO) ] having a rhodium concentration of 200ppm2]Catalyst, rhodium dicarbonyl acetylacetonate [ Rh (AcAc) ((CO))2]BISBI ligand in a molar ratio of 10: 1 to rhodium dicarbonyl acetylacetonate [ Rh (AcAc) (CO ]2]C14 olefin with the molar ratio of 1000: 1 is dissolved and then is added into a high-pressure reaction kettle which is provided with a heating oil bath (containing a temperature control device), a pressure sensor and stirring equipment; introducing synthesis gas with the molar ratio of hydrogen to carbon monoxide of 1: 1 into the high reaction kettle, and replacing air in the kettle for 3-5 times; adding the synthesis gas into an autoclave, keeping the total pressure in the autoclave at 2.7MPa, and reacting at the temperature of 104 ℃.
After the reaction is finished, the content of the product is measured by gas chromatography, and the result shows that the conversion rate of C14 olefin is 85 percent, and the ratio of the normal product to the isomeric product is 22: 1.
Example 4
50g of toluene, rhodium acetylacetonate dicarbonyl [ Rh (AcAc) (CO) ] having a rhodium concentration of 200ppm2]Catalyst, rhodium dicarbonyl acetylacetonate [ Rh (AcAc) ((CO))2]BISBI ligand in a molar ratio of 20: 1 to rhodium dicarbonyl acetylacetonate [ Rh (AcAc) (CO ]2]C14 olefin with the molar ratio of 1000: 1 is dissolved and then is added into a high-pressure reaction kettle which is provided with a heating oil bath (containing a temperature control device), a pressure sensor and stirring equipment; introducing synthesis gas with the molar ratio of hydrogen to carbon monoxide of 1: 1 into the high reaction kettle, and replacing air in the kettle for 3-5 times; adding the synthesis gas into an autoclave, keeping the total pressure in the autoclave at 2.7MPa, and reacting at the temperature of 104 ℃.
After the reaction is finished, the content of the product is measured by gas chromatography, and the result shows that the conversion rate of C14 olefin is 77%, and the ratio of the normal product to the isomeric product is 28: 1.
Example 5
50g of toluene, rhodium acetylacetonate dicarbonyl [ Rh (AcAc) (CO) ] having a rhodium concentration of 200ppm2]Catalyst, rhodium dicarbonyl acetylacetonate [ Rh (AcAc) ((CO))2]BISBI ligand in a 30: 1 molar ratio with rhodium acetylacetonate dicarbonyl [ Rh (AcAc) (CO ]2]C14 olefin with the molar ratio of 1000: 1 is dissolved and then is added into a high-pressure reaction kettle which is provided with a heating oil bath (containing a temperature control device), a pressure sensor and stirring equipment; introducing hydrogen and carbon monoxide in a molar ratio of 1: 1 into the autoclaveReplacing air in the kettle for 3-5 times by using synthesis gas; adding the synthesis gas into an autoclave, keeping the total pressure in the autoclave at 2.7MPa, and reacting at the temperature of 104 ℃.
After the reaction is finished, the content of the product is measured by gas chromatography, and the result shows that the conversion rate of C14 olefin is 71 percent, and the ratio of the normal product to the isomeric product is 33: 1.
Example 6
50g of toluene, rhodium acetylacetonate dicarbonyl [ Rh (AcAc) (CO) ] having a rhodium concentration of 200ppm2]Catalyst, rhodium dicarbonyl acetylacetonate [ Rh (AcAc) ((CO))2]BISBI ligand in a 40: 1 molar ratio with rhodium acetylacetonate dicarbonyl [ Rh (AcAc) (CO ]2]C14 olefin with the molar ratio of 1000: 1 is dissolved and then is added into a high-pressure reaction kettle which is provided with a heating oil bath (containing a temperature control device), a pressure sensor and stirring equipment; introducing synthesis gas with the molar ratio of hydrogen to carbon monoxide of 1: 1 into the high reaction kettle, and replacing air in the kettle for 3-5 times; adding the synthesis gas into an autoclave, keeping the total pressure in the autoclave at 2.7MPa, and reacting at the temperature of 104 ℃.
After the reaction is finished, the content of the product is measured by gas chromatography, and the result shows that the conversion rate of C14 olefin is 60 percent, and the ratio of the normal product to the isomeric product is 37: 1.
Example 7
50g of toluene, rhodium acetylacetonate dicarbonyl [ Rh (AcAc) (CO) ] having a rhodium concentration of 200ppm2]Catalyst, rhodium dicarbonyl acetylacetonate [ Rh (AcAc) ((CO))2]BISBI ligand in a 40: 1 molar ratio with rhodium acetylacetonate dicarbonyl [ Rh (AcAc) (CO ]2]C14 olefin with the molar ratio of 1000: 1 is dissolved and then is added into a high-pressure reaction kettle which is provided with a heating oil bath (containing a temperature control device), a pressure sensor and stirring equipment; introducing synthesis gas with the molar ratio of hydrogen to carbon monoxide of 1: 1 into the high reaction kettle, and replacing air in the kettle for 3-5 times; adding the synthesis gas into an autoclave, keeping the total pressure in the autoclave at 2.7MPa, and reacting at the temperature of 104 ℃.
After the reaction is finished, the content of the product is measured by gas chromatography, and the result shows that the conversion rate of C14 olefin is 60 percent, and the ratio of the normal product to the isomeric product is 40: 1.
The invention can greatly widen the normal-isomerization proportion range of high-carbon-number aldehyde and alcohol products, and simultaneously the catalyst has good activity and stability and can reduce the cost of the catalyst.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A hydroformylation catalyst of long-chain olefin comprises a ligand and a transition metal catalyst, wherein the ligand is 2, 2 '-bis (diphenylphosphinomethyl) -1, 1' -biphenyl (BISBI), and the transition metal catalyst is selected from one or more of cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) and osmium (Os); the transition metal catalyst is selected from cobalt carbonyl [ Co ]2(CO)8]Rhodium dicarbonyl acetylacetonate [ Rh (AcAc) (CO)2]Rhodium acetylacetonate carbonyltriphenylphosphine [ Rh (AcAc) ((CO) (TPP))]Carbonyl tris (triphenylphosphine) rhodium hydride [ HRh (CO) (TPP)3]Iridium dicarbonyl acetylacetonate [ Ir (AcAc) (CO)2]And carbonyltris (triphenylphosphine) iridium hydride [ HIr (CO) (TPP)3]In a molar ratio of 1 to 100: 1 (e.g., 10: 1, 20: 1, 30: 1, 40: 1, 50: 1, 60: 1, 70: 1, 80: 1, or 90: 1).
2. The hydroformylation catalyst of claim 1, wherein the transition metal catalyst has a transition metal content of 50ppm to 1% (e.g., 100ppm, 200ppm, 500ppm, 0.1%, 0.2%, 0.5%, 0.8%).
3. A process for the hydroformylation of long chain olefins comprising: adding the hydroformylation catalyst of claim 1 or 2 and a long chain olefin, which is a C10-C20 olefin, preferably a C10-C18 olefin, to an autoclave;
introducing synthesis gas into the high reaction kettle, and performing hydroformylation reaction under the conditions that the pressure is 1-7 MPa and the temperature is 80-198 ℃;
after the reaction is finished, the product is separated from the hydroformylation catalyst.
4. The hydroformylation process according to claim 3, wherein the pressure of the hydroformylation reaction is 2MPa, 3MPa, 4MPa, 5MPa or 6MPa, and the temperature is 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 1700 ℃, 180 ℃ or 190 ℃.
5. A hydroformylation process according to claim 3, wherein the molar ratio of the long chain olefin to the transition metal catalyst is from 1000 to 10000: 1, for example 2000: 1, 3000: 1, 4000: 1, 5000: 1, 6000: 1, 7000: 1, 8000: 1, 9000: 1.
6. The hydroformylation process of claim 3, wherein the hydroformylation catalyst is dissolved in a solvent which is polybutyral, a C4-C8 aldehyde, toluene, naphtha, kerosene, cyclohexane, xylene, acetophenone or benzonitrile.
7. The hydroformylation process of claim 3, wherein the molar ratio of hydrogen to carbon monoxide in the synthesis gas is from 1: 1 to 2: 1.
8. The hydroformylation process of claim 3, wherein the product is separated from the hydroformylation catalyst by salt precipitation, rectification under high vacuum, pervaporation.
9. The hydroformylation process of claim 3, wherein the process further comprises returning the separated hydroformylation catalyst to the autoclave for reuse.
10. The hydroformylation process of claim 3, wherein the process further comprises replacing the air in the autoclave with synthesis gas 3 to 5 times prior to the reaction.
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| CN113304780A (en) * | 2021-06-16 | 2021-08-27 | 上海华谊（集团）公司 | Use of branched olefin hydroformylation catalyst composition and hydroformylation process |
| CN113385236A (en) * | 2021-06-16 | 2021-09-14 | 上海华谊（集团）公司 | Olefin hydroformylation catalyst composition and hydroformylation method |
| CN114085247A (en) * | 2021-12-02 | 2022-02-25 | 万华化学集团股份有限公司 | Bidentate phosphine type ligand, hydroformylation catalyst and method for preparing linear dihydric alcohol from unsaturated fatty acid |
| CN114716306A (en) * | 2021-11-30 | 2022-07-08 | 国家能源集团宁夏煤业有限责任公司 | Method for hydroformylation of fischer-tropsch products |
| CN115646493A (en) * | 2022-11-03 | 2023-01-31 | 包头市中君科技有限公司 | Cobalt-iron bimetallic catalyst with core-shell structure and preparation method and application thereof |
| CN115701418A (en) * | 2021-08-02 | 2023-02-10 | 中国石油化工股份有限公司 | Aldehyde-alcohol composition, preparation method thereof, and method for continuously preparing aldehyde and alcohol |
| CN116063168A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Method for hydroformylation of olefins |
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