CN113996347A - Hydroformylation catalyst composition and method for preparing hydroxy butyraldehyde by allyl alcohol hydroformylation reaction - Google Patents
Hydroformylation catalyst composition and method for preparing hydroxy butyraldehyde by allyl alcohol hydroformylation reaction Download PDFInfo
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- CN113996347A CN113996347A CN202111511391.XA CN202111511391A CN113996347A CN 113996347 A CN113996347 A CN 113996347A CN 202111511391 A CN202111511391 A CN 202111511391A CN 113996347 A CN113996347 A CN 113996347A
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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
- 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
- B01J31/2414—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 comprising aliphatic or saturated rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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- 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
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
Abstract
The invention discloses a hydroformylation catalyst composition and a method for preparing hydroxy butyraldehyde by allyl alcohol hydroformylation. The catalyst composition comprises a solvent and a complex formed in the solvent and containing a first ligand, a second ligand and a metal active component; wherein the metal active component is rhodium; the first ligand is a composition of one or more of the phosphine-containing ligands of formula I.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a hydroformylation catalyst composition and application thereof in preparation of hydroxybutyraldehyde through allyl alcohol hydroformylation.
Background
The hydroformylation of allyl alcohol is of great industrial interest, with the reaction products including 4-hydroxybutyraldehyde and 2-methyl-3-hydroxypropanal. The 4-hydroxybutyraldehyde can be used for producing 1, 4-butanediol by hydrogenation, the 1, 4-butanediol is an important basic organic chemical and fine chemical raw material, the application is wide, and various fine chemical products with high added values can be derived by taking the 4-hydroxybutyraldehyde as the raw material; the 2-methyl-3-hydroxypropionaldehyde is taken as a reaction byproduct, generally enters a subsequent hydrogenation process together, exists as a 1, 4-butanediol hydrogenation byproduct 2-methyl-1, 3-propanediol, and is low in industrial importance degree. However, with the rise of the mask market in recent years, the demand for moisturizers is increasing, and 2-methyl-1, 3-propanediol is widely used in personal care products as a transparent colorless liquid with low viscosity, no odor and no irritation, and the selling price of the 2-methyl-1, 3-butanediol is increased to about 20000 yuan/ton in 2021 as a main substitute of 1, 3-butanediol, and the mask has begun to show unique market value and prospect.
In the prior art, a catalyst formed by triphenylphosphine and rhodium catalytic active components is widely applied to hydroformylation of allyl alcohol. The carbonyl synthesis process by using a low-pressure rhodium method has the reaction conditions of 75-95 ℃, 0.8-2.0MPa, the conversion rate of allyl alcohol of 97-99 percent, the selectivity of 96-98 percent and the positive-to-differential ratio of the product of 7-10. But the product positive-to-differential ratio is designed to be 7-10, the lower level is difficult to maintain in actual operation, the actual adjustment amplitude is limited, and flexible production is not enough to meet the market demand.
In addition, for the example of an oil soluble rhodium carbonyl phosphine catalyst with triphenylphosphine as ligand, this type of catalyst also has the following drawbacks: the rhodium catalyst has poor high-temperature performance and cannot be used for the carbonylation of high-grade olefin; secondly, the existing rhodium catalyst has good catalytic effect on terminal olefin, but has poor activity on internal olefin; thirdly, in order to improve the normal isomerization ratio of the product, the addition amount of triphenylphosphine needs to be greatly excessive; the catalyst is oil-soluble and the separation of products is difficult, so that the post-treatment is complicated; rhodium is rare as a precious metal resource, is expensive, and has high recycling cost.
The method for preparing the hydroxy butyraldehyde by the hydroformylation of the allyl alcohol described in the patent CN102428062A has low product yield and poor economical efficiency; while patents CN101522602A and CN101652179A describe a catalytic reaction system for producing 4-hydroxybutyraldehyde, the product yield is improved, but the obtained product has very high 4-hydroxybutyraldehyde: the proportion of 2-methyl-3-hydroxypropionaldehyde is difficult to realize stable product proportion modulation, and the high-efficiency production of 2-methyl-3-hydroxypropionaldehyde cannot be realized.
Therefore, the development of the catalyst for synthesizing rhodium by allyl alcohol carbonyl can start from a novel high-efficiency phosphine ligand, the performance of the corresponding rhodium catalyst is improved, the using amount of the noble metal rhodium catalyst is reduced, the selectivity and the stability of the catalyst are improved, and meanwhile, a product with a low positive-to-differential ratio is produced efficiently and stably, so that the continuously changing market demand is met.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a catalyst composition and application thereof in allyl alcohol hydroformylation, the catalyst composition can realize large adjustment range of normal-to-iso ratio of products in the process of producing aldehyde by allyl alcohol hydroformylation, lower normal-to-iso ratio is realized, and the selectivity and stability of the catalyst under the working condition of low normal-to-iso ratio are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydroformylation catalyst composition comprising a solvent and a complex formed in the solvent comprising a first ligand, a second ligand and a metal active component; wherein the metal active component is rhodium;
the first ligand is one or more of phosphine-containing ligands having the following structural formula I;
wherein R is1、R2Each independently selected from-H, methyl and isobutyl;
the second ligand has the following structural formula II:
in particular embodiments, R of the first ligand is1Is methyl, R2is-H, or R1And R2Are both methyl or R1And R2Are all isobutyl; or a combination of the first ligands of the above-described structures.
According to the catalyst composition of the present invention, the mass concentration of the first ligand in the catalyst composition is 0.1 to 10%, and further preferably 4 to 6%.
According to the catalyst composition of the present invention, the mass concentration of the second ligand in the catalyst composition is 1 to 5%, and more preferably 0.9 to 1.1%.
The preferred mass concentrations of the first and second ligands help to obtain the preferred product positive-to-differential ratio and reactivity.
According to the catalyst composition of the present invention, the solvent is preferably toluene.
Further, the preparation method of the first ligand of the invention comprises the following steps: dissolving 2-hydroxybenzyl alcohol or derivatives thereof in a solvent, reacting under the catalysis of organic acid anhydride to obtain a quinone intermediate, and carrying out cyclization reaction on the quinone intermediate and triethyl phosphite under the catalysis of organic acid anhydride to generate oxygen-containing heterocyclic phosphate, namely a first ligand.
The structural formula of the 2-hydroxybenzyl alcohol or the derivative thereof is as follows:
wherein R is1，R2Each independently selected from-H, methyl or isobutyl; preferably, R of the first ligand1Is methyl, R2is-H, or R1And R2Are both methyl or R1And R2Are all isobutyl.
Preferably, in the method for preparing the first ligand, the solvent is selected from one or more of dichloromethane, chloroform and benzene.
Preferably, in the method for preparing the first ligand, the organic anhydride is selected from acetic anhydride and/or propionic anhydride, preferably acetic anhydride.
Preferably, in the preparation method of the first ligand, the molar ratio of the quinone intermediate to triethyl phosphite is 1: (0.8-1.2), preferably 1: 1.
preferably, in the preparation method of the first ligand, the molar ratio of the quinone intermediate to the organic acid anhydride is 1: (0.04-0.06), preferably 1: 0.05.
preferably, in the preparation method of the first ligand, the reaction temperature of the cyclization reaction is 50-70 ℃, and preferably 60 ℃.
Preferably, in the preparation method of the first ligand, the reaction time of the cyclization reaction is 10h-20h, preferably 12 h.
In the catalyst composition of the present invention, the catalytic metal active component is rhodium, and the rhodium source used includes rhodium salt, dicarbonyl acetylacetone rhodium, acetylacetone triphenylphosphine carbonyl rhodium (rhodium park), etc., preferably acetylacetone triphenylphosphine carbonyl rhodium (namely rhodium park).
The mass concentration of the metal active component in the catalyst composition is 200-300ppm calculated by rhodium element, and preferably, the mass concentration of the metal active component in the catalyst composition is 250 ppm. The higher the concentration of the active component, the more active it is in catalyzing the reaction, and the relative positive-to-differential ratio will be reduced (because the ratio of ligand to active component is lower).
The second aspect of the present invention is directed to a method for preparing the above catalyst composition, comprising the steps of: the rhodium source, the first ligand and the second ligand are dissolved in a solvent and then are mixed evenly.
In the catalyst composition of the present invention, the first ligand is a phosphine-containing alkyl ligand, which has low steric hindrance. After the first ligand is added into the catalyst system, a stable complex is formed with the active component rhodium, which can provide lower steric hindrance, and thus lower positive difference ratio of aldehyde products can be formed when the catalyst is applied. Meanwhile, the introduction of the first ligand enables the catalyst system to be used for preparing aldehyde by allyl alcohol hydroformylation, and the problem of rapid catalyst deactivation caused by CO partial pressure adjustment is avoided.
In order to improve the reaction efficiency, a second ligand is introduced in the invention. The second ligand has a similar structure compared with the first ligand, the ligand has stronger pi electron accepting capacity, a catalyst system obtained after the second ligand is coordinated with rhodium has stronger catalytic activity and stability, and the conversion rate of allyl alcohol can be obviously improved under the condition of a small amount of catalyst complex. The second ligand can also reduce the dosage of the first ligand, has stronger electron accepting capability and can inhibit the defect that rhodium is easy to agglomerate and inactivate under the working condition of low positive-to-differential ratio.
The object of the third aspect of the present invention is to provide the use of the above catalyst composition in the hydroformylation of allyl alcohol.
A method for preparing hydroxy butyraldehyde by allyl alcohol hydroformylation reaction comprises the following steps: adding the catalyst composition into a reactor, and continuously introducing allyl alcohol, hydrogen and carbon monoxide synthesis gas into the reactor in a gas phase form for reaction to obtain 4-hydroxybutyraldehyde and 2-methyl-3-hydroxypropionaldehyde.
The hydroformylation reaction temperature is 55-95 ℃, more preferably 85 ℃, the pressure is 1.4-2.0MPa, preferably 1.7MPa, and the mass ratio of allyl alcohol to synthesis gas is 0.5-2. The synthesis gas is prepared by mixing hydrogen and carbon monoxide in a molar ratio of 1-1.05: 1, in the presence of a catalyst. Other reaction conditions are similar to conventional allyl alcohol hydroformylation reactions, for example: the reaction can be carried out in a tank reactor with a stirring paddle, and the reaction process is that allyl alcohol and synthesis gas are continuously introduced from the bottom of the reaction tank in a gas phase form. Other processes such as drying, separation, washing or purification, etc. will not be described in detail.
The above pressures are gauge pressures.
The technical scheme provided by the invention has the following beneficial effects:
(1) in the catalyst composition, the first ligand has lower steric hindrance, forms a stable complex with rhodium, and can provide lower steric hindrance and form a lower positive-to-differential ratio of a hydroxy butyraldehyde product which can reach 2 at least under the same reaction condition as the prior art. The low normal-iso ratio product can realize the production of 3-hydroxy-2-methylpropionaldehyde in more quantity on the premise of no major adjustment of the total yield of the device, and realize the production of methyl propylene glycol in more quantity after hydrogenation so as to adapt to the change of the requirements of the humectant raw materials in the field of moisturizing humectants.
(2) In the catalyst composition, the second ligand has stronger pi electron accepting capacity, and a catalyst system obtained after the ligand is coordinated with rhodium has stronger catalytic activity and stability, so that the catalytic conversion rate and the conversion rate of allyl alcohol can be obviously improved under the condition of not increasing the dosage of the catalyst composition.
(3) The invention uses the combination of the first ligand and the second ligand, ensures high reaction activity, and obtains large adjustment range of the normal-to-iso ratio, especially low adjustment of the normal-to-iso ratio, namely realizes the adjustment and control of the normal-to-iso ratio of the product of the allyl alcohol hydroformylation reaction within the range of 2-10.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
In the examples, the analytical method of the normal-to-iso ratio is Agilent chromatography, and the specific measurement method of the hydroxybutyraldehyde is as follows: sample introduction amount: 0.2 mu L; column temperature: keeping the temperature at 50 ℃ for 4min, heating to 60 ℃ at3 ℃/min, heating to 150 ℃ at 10 ℃/min, heating to 230 ℃ at 20 ℃/min, and keeping the temperature for 8 min; sample inlet temperature: at 250 ℃ to obtain a mixture. Flow rate of spacer purge gas: 3.0 mL/min; flow rate of chromatography column (N)2): 1 mL/min; split-flow sample injection, split ratio 30: 1; a detector: 280 ℃; hydrogen flow rate: 30 mL/min; air flow rate: 400 mL/min; tail gas blowing flow: 25 mL/min.
The raw material sources are as follows:
toluene: the purity of the Aladdin reagent is more than 99.5 percent;
ligand: the purity of the atratin reagent is more than 99.0 percent;
hetero-benzene ligand: (2R, 3R) - (-) -1, 4- (bis-diphenylphosphino) -2, 3-O-isopropylidene-2, 3-butanediol (DIOP) with the purity of more than 98.0 percent.
Rhodium park: and (3) an avastin reagent.
Examples 1-3 are preparation examples of the first ligand
Example 1
179g of 2-hydroxybenzyl alcohol derivative (1mol) (the structure is shown as the following formula 1-1) is added into 600ml of dichloromethane and evenly mixed, 5.1045g of acetic anhydride (0.05mol) is added into the system at room temperature and 25 ℃ for catalytic reaction, after stirring for 2h, quinone intermediate is obtained, 166.16g of triethyl phosphite (1mol) is added into the system, the cyclization reaction is carried out at 60 ℃ overnight (12h), and the reaction progress is monitored by a dot-and-plate method. After the reaction was completed, methylene chloride was removed therefrom by rotary distillation, and elution by column chromatography was carried out to obtain 168g of an oxygen-containing heterocyclic phosphate. First ligand A for short1The structure is shown in the following formula 1-2.
The yield thereof was found to be 80%. Nuclear magnetic data support the following:
1H NMR(400MHz,CDCl3,TMS):δ0.89(t,J＝8Hz,3H),2.28(s,3H),3.41-3.72(m,1H),3.87-4.14(m,1H),7.06-7.12(m,3H),7.16-7.19(m,2H),7.21-7.28(m,3H),7.33-7.41(m,4H),7.52(d,J＝8Hz,1H).13C NMR(100MHz,CDCl3,TMS):δ15.92(t,J＝6Hz),21.01(d,J＝11Hz),59.41(d,J＝206Hz),64.37(dd,J＝8,5Hz),114.03(d,J＝11,1Hz),123.84(d,J＝2Hz),127.52(d,J＝3Hz),128.21(d,J＝7Hz),128.35(d,J＝6Hz),128.89(d,J＝13Hz),128.98(d,J＝16Hz),129.59(d,J＝6Hz),129.63(d,J＝16Hz),132.53(d,J＝6Hz),134.47(d,J＝8Hz),137.33(d,J＝3Hz),137.77(d,J＝8Hz),138.55(d,J＝1Hz).
example 2
193g of a 2-phenolic hydroxybenzyl alcohol derivative (1mol) (the structure is shown in the following formula 2-1) as a raw material is added into 500ml of chloroform to be uniformly mixed, 5.1045g of acetic anhydride (0.05mol) is added into the system at the room temperature of 25 ℃ for catalytic reaction, after stirring for 2h, 166.16g of triethyl phosphite (1mol) is added into the system, the reaction is carried out overnight (20h) at the temperature of 50 ℃, and the reaction progress is monitored by a dot-and-matrix method. After the reaction is finished, removing chloroform as a solvent by rotary distillation, and eluting by column chromatography to obtain 183.68g of oxygen-containing heterocyclic phosphate, namely a first ligand A2The structure is shown in the following formula 2-2.
The yield thereof was found to be 82%. Nuclear magnetic data support the following:
1H NMR(400MHz,CDCl3,TMS):δ0.90(td,J＝8,0.48Hz,3H),2.34(s,3H),2.27(s,3H),3.39-3,49(m,1H),3.86-3.94(m,1H),6.91(d,J＝8Hz,1H),6.95(s,1H),7.06(d,J＝8Hz,1H),7.19(t,J＝8Hz,1H),7.26(t,J＝8Hz,2H),7.33-7.40(m,5H),7.52(d,J＝8Hz,2H).13C NMR (100MHz,CDCl3,TMS):15.90(d,J＝6Hz),21.56,21.59,55.55(d,J＝118Hz),64.34(d,J＝7Hz),114.58(d,J＝11Hz),124.73,127.10,127.51(d,J＝3Hz),127.87(d,J＝13Hz),128.34(d,J＝3Hz),128.41,128.91(d,J＝8Hz),129.18(d,J＝6Hz),129.69(d,J＝5Hz),137.80(d,J＝8Hz),140.83(d,J＝218Hz),151.44(d,J＝10Hz).
example 3
277g of a derivative (1mol) of 2-phenolic hydroxybenzyl alcohol (the structure is shown in the following formula 3-1) serving as a raw material is added into 800ml of benzene to be uniformly mixed, 5.1045g of acetic anhydride (0.05mol) is added into the system at the room temperature of 20 ℃ for catalytic reaction, after stirring for 2 hours, 166.16g of triethyl phosphite (1mol) is added into the system, the reaction is carried out overnight (10 hours) at the temperature of 70 ℃, and the reaction progress is monitored by a dot-and-plate method. After the reaction, the solvent benzene was removed by rotary distillation, and the product was eluted by column chromatography to obtain 249.48g of an oxygen-containing heterocyclic phosphate. First ligand A for short3The structure is shown in the following formula 3-2.
The yield thereof was found to be 81%. Nuclear magnetic data support the following:
1H NMR(400MHz,CDCl3,TMS):δ1.35(td,J＝8,0.56Hz,3H),2.27(s,3H),2.30(s,3H),3.38-3.48(m,1H),3.85-3.95(m,1H),7.00(t,J＝8Hz,2H),7.08(d,J＝8Hz,1H),7.21(t,J＝8Hz,1H),7.27(t,J＝8Hz,2H),7.32-7.38(m,5H),7.53(d,J＝8Hz,2H).13C NMR(100MHz,CDCl3,TMS):15.90(d,J＝6Hz),21.20,21.59,55.85(d,J＝118Hz),64.30(d,J＝8Hz),113.71(d,J＝10Hz),127.13(d,J＝1Hz),127.52(d,J＝3Hz),128.43,128.98(d,J＝8Hz),129.73(d,J＝6Hz),129.81,131.93(d,J＝7Hz),133.43,137.74(d,J＝7Hz),141.84,149.43(d,J＝10Hz).
examples 4-19 are preparation of catalyst compositions and their use in making hydroxybutyraldehyde
Example 4
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)1)37.27g and 7.45g of second ligand (DIOP), heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 1-2.
Test rhodium content about 250ppm, first ligand A1The mass concentration in the catalyst composition was 5%, and the mass concentration of the second ligand in the catalyst composition was 1%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT1-2 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 2, and the yield of the hydroxybutyraldehyde is 87.1%.
Example 5
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)1)74.54g of second ligand (DIOP) and 7.45g of second ligand (DIOP) were heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 1-3.
Test rhodium content about 250ppm, first ligand A1The mass concentration in the catalyst composition was 10%, and the mass concentration of the second ligand in the catalyst composition was 1%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT1-3 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 4, and the yield of the hydroxybutyraldehyde is 84.4%.
Example 6
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)1)0.74g of the second ligand (DIOP) and 7.45g of the second ligand (DIOP) were heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 1-4.
Test rhodium content about 250ppm, first ligand A1The mass concentration in the catalyst composition was 0.1%, and the mass concentration of the second ligand in the catalyst composition was 1%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT1-4 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 6, and the yield of the hydroxybutyraldehyde is 90.1%.
Example 7
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)1)37.27g and 37.25g of second ligand (DIOP), heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 1-4.
Test rhodium content about 250ppm, first ligand A1The mass concentration in the catalyst composition was 5%, and the mass concentration of the second ligand in the catalyst composition was 5%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT1-4 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 3, and the yield of the hydroxy butyraldehyde is 88.6%.
Example 8
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)2)37.27g and 7.45g of second ligand (DIOP), heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 2-2.
Rhodium content of about 250 was testedppm, first ligand A2The mass concentration in the catalyst composition was 5%, and the mass concentration of the second ligand in the catalyst composition was 1%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT2-2 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 3, and the yield of the hydroxy butyraldehyde is 85.2%.
Example 9
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)2)74.54g of second ligand (DIOP) and 7.45g of second ligand (DIOP) were heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 2-3.
Test rhodium content about 250ppm, first ligand A2The mass concentration in the catalyst composition was 10%, and the mass concentration of the second ligand in the catalyst composition was 1%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT2-3 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 4, and the yield of the hydroxybutyraldehyde is 85.2%.
Example 10
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)2)0.74g of the second ligand (DIOP) and 7.45g of the second ligand (DIOP) were heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 2-4.
Test rhodium content about 250ppm, first ligand A2The mass concentration in the catalyst composition was 0.1%, and the mass concentration of the second ligand in the catalyst composition was 1%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT2-4 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 4, and the yield of the hydroxybutyraldehyde is 89.1%.
Example 11
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)2)37.27g and 37.25g of second ligand (DIOP), heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 2-4.
Test rhodium content about 250ppm, first ligand A2The mass concentration in the catalyst composition was 5%, and the mass concentration of the second ligand in the catalyst composition was 5%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT2-4 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 4, and the yield of the hydroxybutyraldehyde is 87.1%.
Example 12
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)3)37.27g and 7.45g of second ligand (DIOP), heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 3-2.
Test rhodium content about 250ppm, first ligand A3The mass concentration in the catalyst composition was 5%, and the mass concentration of the second ligand in the catalyst composition was 1%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT3-2 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 4, and the yield of the hydroxybutyraldehyde is 80.3%.
Example 13
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)3)74.54g of second ligand (DIOP) and 7.45g of second ligand (DIOP) were heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 3-3.
Test rhodium content about 250ppm, first ligand A3The mass concentration of the second ligand in the catalyst composition is 10%, and the mass concentration of the second ligand in the catalyst composition is1％。
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT3-3 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 5, and the yield of the hydroxybutyraldehyde is 77.3%.
Example 14
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.66g of rhodium park, and a first ligand (A)3)0.74g of the second ligand (DIOP) and 7.45g of the second ligand (DIOP) were heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 3-4.
Test rhodium content about 250ppm, first ligand A3The mass concentration in the catalyst composition was 0.1%, and the mass concentration of the second ligand in the catalyst composition was 1%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT3-4 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 5, and the yield of the hydroxybutyraldehyde is 88.9%.
Example 15
Replacing the catalyst preparation tank with nitrogen until the oxygen content is 0.05%, and sequentially adding into the preparation tank700g of toluene, 0.66g of rhodium park, the first ligand (A)3)37.27g and 37.25g of second ligand (DIOP), heated to 50 ℃ and stirred for 120min to obtain a homogeneous catalyst composition CAT 3-4.
Test rhodium content about 250ppm, first ligand A3The mass concentration in the catalyst composition was 5%, and the mass concentration of the second ligand in the catalyst composition was 5%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT3-4 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 5, and the yield of the hydroxybutyraldehyde is 89.7%.
Comparative example 1
The catalyst preparation tank is replaced by nitrogen until the oxygen content is 0.05 percent, 700g of toluene, 0.67g of rhodium park and 36.88g of triphenylphosphine are sequentially added into the preparation tank, the mixture is heated to 50 ℃, and the mixture is stirred for 120min, so that the catalyst CAT4-1 is obtained.
The rhodium content was tested to be about 250ppm and the triphenylphosphine was present in the catalyst composition at a concentration of 5% by mass.
The above catalytic system was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT4-1 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 8, and the yield of the hydroxybutyraldehyde is 44.2%.
Comparative example 2
The catalyst preparation tank is replaced by nitrogen until the oxygen content is 0.05 percent, 700g of toluene, 0.66g of rhodium park, 37.27g of auxiliary triphenylphosphine and 7.45g of second ligand (DIOP) are sequentially added into the preparation tank, the mixture is heated to 50 ℃, and the mixture is stirred for 120min, so that the catalyst CAT4-2 is obtained.
The rhodium content was tested to be about 250ppm and the triphenylphosphine was present in the catalyst composition at a concentration of 5% by mass. The mass concentration of triphenylphosphine in the catalyst composition was 1%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor with stirring paddles (stirred tank volume 0.5L, stirring rate 200r/min), and 50g of the prepared catalyst CAT4-2 was added in advance to the reactor. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 8, and the yield of the hydroxy butyraldehyde is 70.2%.
Comparative example 3
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.67g of rhodium park, and a first ligand (A)1)36.88g was heated to 50 ℃ and stirred for 120min to give CAT1-1, a homogeneous catalyst composition.
The rhodium content was found to be about 250ppm, the first ligand A1The mass concentration in the catalyst composition was 5%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT1-1 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 2, and the yield of the hydroxy butyraldehyde is 50.2%.
Comparative example 4
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.67g of rhodium park, and a first ligand (A)2)36.88g was heated to 50 ℃ and stirred for 120min to give CAT2-1, a homogeneous catalyst composition.
The rhodium content was found to be about 250ppm, the first ligand A2The mass concentration in the catalyst composition was 5%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT2-1 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 3, and the yield of the hydroxybutyraldehyde is 48.4%.
Comparative example 5
The catalyst preparation tank was replaced with nitrogen gas until the oxygen content was 0.05%, and to the preparation tank were added in the order of 700g of toluene, 0.67g of rhodium park, and a first ligand (A)3)36.88g was heated to 50 ℃ and stirred for 120min to give CAT3-1, a homogeneous catalyst composition.
The rhodium content was found to be about 250ppm, the first ligand A3The mass concentration in the catalyst composition was 5%.
The catalytic system of the invention was evaluated by means of allylic hydroformylation:
the reaction was carried out in a stirred tank reactor (stirred tank volume 0.5L, stirring rate 200r/min) equipped with a stirring paddle, to which 50g of the prepared catalyst composition CAT3-1 was previously added. Allyl alcohol and synthesis gas (the molar ratio of hydrogen to carbon monoxide is 1.05: 1) are continuously introduced from the bottom of the reaction kettle in a gas phase mode, the reaction temperature is 85 ℃, and the pressure is 1.7 MPa. Allyl alcohol feed rate of 0.35g/min, syngas feed rate of 200ml/min, homogeneous catalyst feed rate of 0.55 g/min. After reacting for 40h, the experiment is stopped, the sample is taken, the reaction product positive-to-differential ratio is determined to be 4, and the yield of the hydroxybutyraldehyde is 45.1%.
By comparing the above examples with the comparative examples, it can be seen that when the catalyst composition of the embodiment of the present invention is used for preparing hydroxybutyraldehyde by allyl alcohol hydroformylation, a low normal-to-iso ratio range can be achieved, and the yield of hydroxybutyraldehyde is greatly improved.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes or modifications of the technical solution of the present invention are within the spirit of the present invention.
Claims (10)
1. A hydroformylation catalyst composition comprising a solvent and a complex formed in the solvent comprising a first ligand, a second ligand and a metal active component; wherein the metal active component is rhodium;
the first ligand is one or more of phosphine-containing ligands having the following structural formula I;
wherein R is1、R2Each independently selected from-H, methyl and isobutyl;
the second ligand has the following structural formula II:
2. the catalyst composition of claim 1, wherein R of the first ligand is1Is methyl, R2is-H, or R1And R2Are both methyl, or R1And R2Are all isobutyl.
3. Catalyst composition according to claim 1 or 2, characterized in that the mass concentration of the first ligand in the catalyst composition is between 0.1 and 10%, preferably between 4 and 6%; the mass concentration of the second ligand in the catalyst composition is 1-5%, preferably 0.9-1.1%.
4. A catalyst composition according to any one of claims 1 to 3, wherein the first ligand is prepared by a process comprising the steps of: dissolving 2-hydroxybenzyl alcohol or derivatives thereof in a solvent, reacting under the catalysis of organic acid anhydride to obtain a quinone intermediate, and carrying out cyclization reaction on the quinone intermediate and triethyl phosphite under the catalysis of organic acid anhydride to generate oxygen-containing heterocyclic phosphate, namely a first ligand.
5. The catalyst composition of claim 4, wherein the structural formula of the 2-hydroxybenzyl alcohol or derivative thereof is as follows:
wherein R is1，R2Each independently selected from-H, methyl or isobutyl; preferably, R of the first ligand1Is methyl, R2is-H, or R1And R2Are both methyl, or R1And R2Are all isobutyl.
6. The catalyst composition according to claim 4, characterized in that the organic anhydride is selected from acetic anhydride and/or propionic anhydride, preferably acetic anhydride; the molar use ratio of the quinone intermediate to triethyl phosphite is 1: (0.8-1.2); the molar ratio of the quinone intermediate to the organic acid anhydride is 1: (0.04-0.06).
7. The catalyst composition of claim 4, wherein the reaction temperature of the cyclization reaction is between 50 ℃ and 70 ℃; the reaction time of the cyclization reaction is 10-20 h.
8. The catalyst composition of any of claims 1-7, characterized in that: the rhodium source includes rhodium salts, dicarbonyl acetylacetone rhodium, acetylacetone triphenylphosphine carbonyl rhodium.
9. A method for preparing hydroxy butyraldehyde by allyl alcohol hydroformylation reaction comprises the following steps: charging a reactor with a catalyst composition as defined in any one of claims 1 to 8, continuously introducing allyl alcohol and a synthesis gas of hydrogen and carbon monoxide into the reactor in the gas phase, and reacting to obtain 4-hydroxybutyraldehyde and 2-methyl-3-hydroxypropanal.
10. The process of claim 9 wherein the hydroformylation reaction temperature is from 55 to 95 ℃, the pressure is from 1.4 to 2.0MPa, and the allyl alcohol to syngas feed mass ratio is from 0.5 to 2.
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| US4215077A (en) * | 1978-02-09 | 1980-07-29 | Kuraray Co., Ltd. | Hydroformylation of olefins |
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| CN108212150A (en) * | 2017-12-27 | 2018-06-29 | 南京工业大学 | A kind of load rhodium liquid metallic solutions catalyst and its preparation and application |
| CN111686818A (en) * | 2020-07-10 | 2020-09-22 | 万华化学集团股份有限公司 | Catalyst composition and application thereof in propylene hydroformylation reaction |
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| US4215077A (en) * | 1978-02-09 | 1980-07-29 | Kuraray Co., Ltd. | Hydroformylation of olefins |
| US4960949A (en) * | 1988-12-22 | 1990-10-02 | Eastman Kodak Company | Low pressure rhodium catalyzed hydroformylation of olefins |
| CN101610843A (en) * | 2006-12-21 | 2009-12-23 | 伊士曼化工公司 | The catalyst that contains phosphinate that is used for hydroformylation process |
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