CN115254195A - Catalytic system for olefin hydroformylation reaction - Google Patents

Catalytic system for olefin hydroformylation reaction Download PDF

Info

Publication number
CN115254195A
CN115254195A CN202210904568.0A CN202210904568A CN115254195A CN 115254195 A CN115254195 A CN 115254195A CN 202210904568 A CN202210904568 A CN 202210904568A CN 115254195 A CN115254195 A CN 115254195A
Authority
CN
China
Prior art keywords
reaction
olefin
acetylacetonate
catalyst system
hydroformylation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210904568.0A
Other languages
Chinese (zh)
Inventor
朱博源
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Meryer Technologies Co Ltd
Original Assignee
Meryer Technologies Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Meryer Technologies Co Ltd filed Critical Meryer Technologies Co Ltd
Priority to CN202210904568.0A priority Critical patent/CN115254195A/en
Publication of CN115254195A publication Critical patent/CN115254195A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • 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
    • C07C45/505—Asymmetric hydroformylation
    • 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
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/17—Silver
    • 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
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a catalytic system for olefin hydroformylation reaction, which comprises the following steps: adding aldehyde or olefin into a reaction kettle, then adding acetylacetone dicarbonyl rhodium, phosphine ligand and acetylacetone metal salt, and adding H2Reacting with the synthesis gas of CO; and after the reaction is finished, cooling, and taking out reaction liquid, namely the catalytic system for the hydroformylation of the olefin. The invention mainly adds a certain amount of acetylacetone metal salt into a reaction system to form a new catalyst system with high catalytic efficiency, and after the ionic liquid is added to interact with the original catalyst system, the conversion rate and the selectivity are improved compared with the prior catalyst system. In addition, repeated tests prove that the stability of the catalyst system is improved, and the attenuation of the catalytic activity is delayed to different degrees.

Description

Catalytic system for olefin hydroformylation reaction
Technical Field
The invention relates to a catalytic system for olefin hydroformylation reaction, belonging to the field of metal organic catalysis.
Background
Hydroformylation is the reaction of an olefin with hydrogen and carbon monoxide to form an aldehyde with an additional carbon atom: RCH = CH2+H2+CO─→RCH2CH2In the CHO formula, R is alkyl, the reaction is completed under the catalysis of cobalt carbonyl or rhodium, and the total reaction is as follows: one molecule of olefin consumes one molecule of hydrogen and one molecule of carbon monoxide.
The hydroformylation is a process for producing high-carbon aldehydes from olefins, and thus, has been widely used industrially. Olefin feedstocks commercially suitable for hydroformylation processes include straight and branched chain C2-C17A mono-olefin. Where the linear olefins are mainly ethylene, propylene, 1-butene and 2-butene, and alpha-olefins and internal olefins (the double bond not being at the end of the chain) A mixture of (a). The branched olefins being predominantly isopentenes, consisting of C3、C4Hexene, octene, nonene, dodecene obtained by oligomerization of olefins, octene obtained by dimerization and copolymerization of isobutylene, 1-butene and 2-butene, and the like. The main product routes are as follows: producing 1-butanol and 2-ethylhexanol from propylene; producing octanol from heptene; synthesis of C for production of plasticizers and synthetic detergents from Mixed olefins8-C10Alcohol and C12-C16An alcohol; propionaldehyde is produced from ethylene (the main raw material for synthesizing 1-propanol and propionic acid); and pentanol and the like from 1-butene and 2-butene.
The catalyst used in the hydroformylation reaction in industrial production is generally a cobalt (Co) based or rhodium (Rh) based catalyst, i.e. a catalyst having cobalt or rhodium as the active center of the metal. The cobalt-based catalyst is limited in application due to harsh reaction conditions, more side reactions, poor product selectivity, high energy consumption, complex cobalt recovery process and the like, and most of the catalysts used in the existing hydroformylation reaction are rhodium-based catalysts. The activity of rhodium-based catalysts embodied in hydroformylation processes, as well as the selectivity to aldehydes, depends on the combination of catalyst precursor and ligand. In the process of catalyzing the olefin formylation reaction by the rhodium-based catalyst, the catalyst is easy to deactivate because the complex catalyst formed by rhodium and other substances is very sensitive to the change of the state in the reaction process, thereby influencing the conversion rate of the olefin and the selectivity of the product.
A great deal of research work has been carried out on the technical process for preparing the aldehyde by the hydroformylation of the olefin in China, and the obvious progress is achieved at present. Chinese patent CN103814006 discloses a hydroformylation method with improved catalyst stability in the reaction, which adds a special α, β -unsaturated carbonyl compound to inhibit the decomposition of ligand and catalyst in the hydroformylation reaction, and this method increases the stability of catalyst to some extent, but also increases the reaction cost. Chinese patent CN102123978 in examples 8 to 14 uses a rhodium complex of calixarene bisphosphite as a catalyst to hydroformylate 1-octene with two or more aldehydes by varying the partial pressure of carbon monoxide. Chinese patent CN 113856720A provides a method for treating heterogeneous diseasesPhase hydroformylation catalyst and its preparation method and application. The catalyst is prepared from rhodium (Rh)/(CoO-CuO) -N-CNTs by the process steps of oxidizing roasting, catalytic carbonization and the like. Chinese patent CN 112679327B discloses a method for preparing aldehyde compounds by olefin two-phase hydroformylation, which belongs to the technical field of aldehyde synthesis, a catalytic system is formed by water-soluble phosphine ligand and rhodium catalyst, cheap and easily-obtained nonpolar formamide, N-methyl formamide, N-dimethyl formamide and the like are used as solvents, so that olefin and H are reacted with each other2The reaction activity of the/CO synthetic gas is greatly improved compared with that of water-oil two-phase hydroformylation because the solubility of olefin in a large-polarity organic solvent is far higher than that of the olefin in water; after the reaction is finished, the system automatically separates phases, the upper layer is a low-polarity product aldehyde, the lower layer is a high-polarity solvent phase, the water-soluble catalyst is dissolved in the high-polarity solvent phase, and the catalyst can be recycled for multiple times through liquid separation operation. Chinese patent CN 111825542A provides a method for hydroformylating high-carbon olefin with carbon number more than or equal to 8, which takes the high-carbon olefin with carbon number more than or equal to 8 as a raw material, one or more metals and compounds of cobalt, rhodium, ruthenium, iron and manganese as catalysts, water as a solvent and a novel cationic phosphine ligand to catalyze hydroformylation reaction of the olefin, after the reaction is finished, two phases of water and oil are layered, an upper hydroformylation product is separated, a lower hydroformylation product is a catalyst aqueous solution, the addition of the phosphine ligand obviously improves the solubility of the olefin, and the activity of the catalyst is greatly improved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a method for improving the conversion rate of hydroformylation reaction and increasing the stability of a catalyst system.
In order to solve the problems, the invention adds acetylacetone metal salt, acetylacetone dicarbonyl rhodium and ligand to form a new catalyst system, and compared with the original catalyst system, the catalyst system has the advantages of improved hydroformylation reaction conversion rate and increased catalyst system stability. The adding mode is realized by the following technical scheme:
the method comprises the following steps: when the olefin is C2-C4The olefin (b) of (a): aldehyde (hydroformylation reaction product of olefin as a reaction raw material used in the reaction) was charged in a reaction vessel, followed by using H2Replacing gas in the reaction kettle with the synthesis gas of CO, adding acetylacetonatodicarbonylrhodium, phosphine ligand and acetylacetonato metal salt, stirring, heating, and adding olefin (preferably in a molar ratio of olefin to H) under the condition of constant reaction pressure2: CO = 1.05); cooling after the reaction is finished, and weighing to calculate the reaction yield;
the second method comprises the following steps: when the olefin is C5-C8The olefin (b) of (a): adding olefin, rhodium acetylacetonate dicarbonyl, phosphine ligand and acetylacetone metal salt into a reaction kettle, starting stirring, and adding H2Reacting with the synthesis gas of CO under the controlled reaction pressure; and (3) cooling after the reaction is finished, taking out the reaction liquid, measuring the content of aldehyde and olefin in the reaction liquid by using gas chromatography, and calculating the conversion rate.
Preferably, in the first method and the second method, the reaction kettle replaces the internal gas with nitrogen more than three times before use.
Preferably, the acetylacetone metal salt in the first and second methods is a mixture of any one or more of iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, and silver acetylacetonate; the dosage of the acetylacetone metal salt is 1 to 10 percent of the molar weight of the acetylacetone dicarbonyl rhodium.
Preferably, in the first and second methods, H2With H in the synthesis gas of CO2The molar ratio to CO is 1.0 to 1.05.
Preferably, in the first method, the molar ratio of the rhodium acetylacetonate dicarbonyl to the phosphine ligand is 1.
Preferably, in the first method, the molar ratio of CO in the synthesis gas added during the reaction to the olefin serving as the reaction raw material is 1:1.
preferably, in the first method, the reaction pressure is controlled to be 2.0Mpa, the temperature is 65-95 ℃, and the time is 0.5-2 hours.
Preferably, in the second method, the molar ratio of the rhodium acetylacetonate dicarbonyl, the phosphine ligand and the acetylacetone metal salt is 1; the weight ratio of rhodium acetylacetonate dicarbonyl to olefin is 80-200ppm.
Preferably, in the second method, the reaction pressure is 1.0-4.0Mpa, the temperature is 70-100 ℃, and the reaction time is 4-7 hours.
The invention mainly adds a certain amount of acetylacetone metal salt into a reaction system to form a new catalyst system with high catalytic efficiency, and after the ionic liquid is added to interact with the original catalyst system, the conversion rate and the selectivity are both improved compared with the prior art. In addition, repeated tests prove that the stability of the catalyst system is improved, and the attenuation of the catalytic activity is delayed to different degrees.
Detailed Description
In order that the invention may be more readily understood, preferred embodiments will now be described in detail.
Example 1
Replacing the 2L pressure reaction kettle with nitrogen for more than three times, adding 0.4kg propionaldehyde, and then using synthesis gas (H)2: CO =1.0 (molar ratio)) was displaced once, 0.10g of rhodium acetylacetonate dicarbonyl, 1g of triphenylphosphine ligand and 8.0mg of iron acetylacetonate were added, stirring was started and the molar ratio was varied according to the ethylene: h2: adding CO = 1.05.
Comparative example 1
This comparative example differs from example 1 in that no iron acetylacetonate was added. The activity of the resulting catalyst system was 5280 g/g.h.
Example 2
Replacing the 2L pressure reaction kettle with nitrogen for more than three times, adding 0.4kg of propionaldehyde, and then using synthesis gas (H)2: CO =1.0 (molar ratio)) was displaced once, 0.10g of rhodium acetylacetonate dicarbonyl, 0.8g of complex ligand (triphenylphosphine and triphenylphosphine oxide molar ratio 7, 3), 13.0mg of iron acetylacetonate and 12.0mg of cobalt acetylacetonate were added, stirring was started, and the molar ratio of ethylene: h2: CO =1.05 (molar ratio) was added to the reaction kettle and the reaction was controlledThe reaction pressure is 0.9MPa, the reaction temperature is 70 ℃, the reaction is carried out for 0.5 hour, the temperature is reduced, the reaction liquid is taken out and weighed, the reaction product propionaldehyde is 420.6g, and the activity of the obtained catalytic system is 8412 g/g.h.
Comparative example 2
This comparative example differs from example 2 in that no iron acetylacetonate or cobalt acetylacetonate was added. The activity of the resulting catalyst system was 7033 g/g.h.
Example 3
Replacing the 2L pressure reaction kettle with nitrogen for more than three times, adding 0.4kg propionaldehyde, and then using synthesis gas (H)2: CO =1.0 (molar ratio)) was substituted once, and 0.10g of rhodium acetylacetonate dicarbonyl and 1.2g of a complex ligand (triphenylphosphine, triphenylphosphine oxide and tris [ 2.4-di-tert-butylphenyl ] were added]Phosphite mole ratio of 4): h2: adding CO = 1.05.
Comparative example 3
This comparative example differs from example 3 in that no iron acetylacetonate and no cobalt acetylacetonate were added. The activity of the obtained catalytic system is 9051 g/g.h.
Example 4
Replacing the 2L pressure reaction kettle with nitrogen for more than three times, adding 0.4kg of propionaldehyde, and then using synthesis gas (H)2: CO =1.0 (molar ratio)) was replaced once, and 0.10g of rhodium acetylacetonate dicarbonyl and 0.6g of a complex ligand (triphenylphosphine oxide and tris [ 2.4-di-tert-butylphenyl ]]Phosphite molar ratio of 2: h2: the method comprises the following steps of adding CO = 1.05.
Comparative example 4
This comparative example differs from example 4 in that no iron acetylacetonate and no cobalt acetylacetonate were added. The activity of the resulting catalytic system was 8911 g/g.h.
Example 5
The 2L autoclave was replaced with nitrogen for three or more times, 0.4kg of butylaldehyde was added, and then synthesis gas (H) was used2: CO =1.0 (molar ratio)) was replaced once, 0.10g of rhodium acetylacetonate dicarbonyl, 0.8g of triphenylphosphine, 66.0mg of ferrous acetylacetonate and 55.0mg of copper acetylacetonate were added, and stirring was started in accordance with the ratio of propylene: h2: adding CO = 1.05.
Comparative example 5
This comparative example differs from example 5 in that no iron acetylacetonate and no cobalt acetylacetonate were added. The activity of the obtained catalytic system was 8041 g/g.h.
Example 6
The 2L autoclave was replaced with nitrogen for three or more times, 0.4kg of butylaldehyde was added, and then synthesis gas (H) was used2: CO =1.0 (molar ratio)) was displaced once, 0.10g of rhodium acetylacetonate dicarbonyl, 1.2g of complex ligand (triphenylphosphine and triphenylphosphine oxide ratio 8, 2), 60.0mg of cobalt acetylacetonate and 30.0mg of copper acetylacetonate were added, stirring was started, and the molar ratio of propylene: h2: adding CO = 1.05.
Comparative example 6
This comparative example differs from example 6 in that copper acetylacetonate and cobalt acetylacetonate are not added. The activity of the resulting catalyst system was 6140 g/g.h.
Example 7
The 2L autoclave was replaced with nitrogen for three or more times, 0.4kg of butylaldehyde was added, and then synthesis gas (H) was used2: CO =1.0 (molar ratio)) was substituted once, and 0.10g of rhodium acetylacetonate dicarbonyl and 1.3g of a complex ligand (triphenylphosphine, palladium, etc.) were added,The ratio of triphenylphosphine oxide to bis (2, 4-di-tert-butylphenol) pentaerythritol and diphosphite was 4: h2: adding CO = 1.05.
Comparative example 7
This comparative example differs from example 7 in that copper acetylacetonate and cobalt acetylacetonate are not added. The activity of the resulting catalytic system was 7500 g/g.h.
Example 8
The 2L autoclave was replaced with nitrogen for three or more times, 0.4kg of butylaldehyde was added, and then synthesis gas (H) was used2: CO =1.0 (molar ratio)) was substituted once, and 0.10g of rhodium acetylacetonate dicarbonyl and 0.8g of a complex ligand (triphenylphosphine oxide and tris [ 2.4-di-tert-butylphenyl ] were added]Phosphite), 50.0mg cobalt acetylacetonate, 28mg cobalt acetylacetonate, and 38.0mg silver acetylacetonate, stirring was started, according to the ratio of propylene: h2: adding CO = 1.05.
Comparative example 8
This comparative example differs from example 8 in that copper acetylacetonate, cobalt acetylacetonate, and silver acetylacetonate were not added. The activity of the resulting catalyst system was 8210 g/g.h.
Example 9
The 2L autoclave was replaced with nitrogen three times or more, 0.4kg of n-valeraldehyde was added, and then synthesis gas (H) was used2: CO =1.0 (molar ratio)) was replaced once, 0.10g of rhodium acetylacetonate dicarbonyl, 0.5g of triphenylphosphine, 5.0mg of ferrous acetylacetonate, 5.0mg of cobalt acetylacetonate, 5mg of cobalt acetylacetonate and 5.0mg of silver acetylacetonate were added, stirring was started, and the ratio of butene-1: h2: CO =1.05 (molar ratio) was added to the reaction kettle, and the reaction pressure was controlledReacting for 0.5 hour at the reaction temperature of 90 ℃ under the pressure of 1.4MPa, cooling, taking out reaction liquid, weighing, obtaining 365g of n-valeraldehyde as a reaction product, and obtaining the catalytic system with the activity of 7300 g/g.h.
Comparative example 9
This comparative example differs from example 9 in that no ferrous acetylacetonate, no copper acetylacetonate, no cobalt acetylacetonate, and no silver acetylacetonate were added. The activity of the obtained catalytic system was 7210 g/g.h.
Example 10
Replacing the 2L pressure reaction kettle with nitrogen for more than three times, adding 0.4kg of isovaleraldehyde, and then using synthesis gas (H)2: CO =1.0 (molar ratio)) was displaced once, 0.10g of rhodium acetylacetonate dicarbonyl, 1.0g of triphenylphosphine and 0.5g of triphenylphosphine oxide, 30.0mg of ferrous acetylacetonate were added, stirring was started, and the molar ratio of butene-2: h2: adding CO = 1.05.
Comparative example 10
This comparative example differs from example 10 in that no ferrous acetylacetonate, no copper acetylacetonate, no cobalt acetylacetonate, and no silver acetylacetonate were added. The activity of the resulting catalyst system was 5510 g/g.h.
Example 11
Replacing the 2L pressure reaction kettle with nitrogen for more than three times, adding 0.4kg of isovaleraldehyde, and then using synthesis gas (H)2: CO =1.0 (molar ratio)) was replaced once, and 0.10g of rhodium acetylacetonate dicarbonyl, 0.8g of triphenylphosphine, 0.2g of triphenylphosphine oxide and 0.3g of tris [ 2.4-di-tert-butylphenyl ] were added]Phosphite, 100mg cuprous acetylacetonate, stirring was started, and the ratio of butene-2: h2: adding the mixture into a reaction kettle according to the proportion of CO = 1.05.
Comparative example 11
This comparative example differs from example 11 in that no copper acetylacetonate was added. The activity of the obtained catalytic system is 6193 g/g.h.
Example 12
Replacing the 2L pressure reaction kettle with nitrogen for more than three times, adding 0.4kg of isovaleraldehyde, and then using synthesis gas (H)2: CO =1.0 (molar ratio)) was substituted once, and 0.10g of rhodium acetylacetonate dicarbonyl, 1.0g of triphenylphosphine oxide and 1.0g of tris [ 2.4-di-tert-butylphenyl ] were added]Phosphite, 100mg cuprous acetylacetonate, stirring was started, and the ratio of butene-2: h2: adding CO = 1.05.
Comparative example 12
This comparative example differs from example 12 in that no copper acetylacetonate was added. The activity of the resulting catalyst system was 4110 g/g.h.
Example 13
Replacing the 2L polymerization kettle with nitrogen for more than three times; 1.0kg of hexene-1, 0.10g of rhodium acetylacetonate dicarbonyl was added at room temperature, followed by 0.2g of triphenylphosphine, 0.2g of triphenylphosphine oxide and 0.1g of tris [ 2.4-di-tert-butylphenyl ]]Phosphite, 8mg of ferrous acetylacetonate, and synthesis gas (H)2: CO =1.05 to 1.0 (molar ratio)), the reaction was carried out at 80 ℃ and 2.0Mpa for 4 hours, and the reaction mixture was taken out and the hexene-1 conversion was 59.6% by gas chromatography.
Comparative example 13
This comparative example differs from example 13 in that no ferrous acetylacetonate was added. Hexene-1 conversion was 49.3%.
Example 14
Replacing the 2L polymerization kettle with nitrogen for more than three times; 1.0kg of hexene-1, 0.10g of rhodium acetylacetonate dicarbonyl was added at room temperature, followed by 0.2g of triphenylphosphine, 0.2g of triphenylphosphine oxide and 0.1g of bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite, 140mg of silver acetylacetonate, and synthesis gas (H) was passed through2: CO =1.05-1.0 (molar ratio)), reacting at 90 deg.C and 2.0MPa for 4 hr, and taking outLiquid, gas chromatography found hexene-1 conversion to 61.2%.
Comparative example 14
This comparative example differs from example 14 in that no ferrous acetylacetonate was added. Hexene-1 conversion was 54.3%.
The experiment was repeated to examine the catalytic action of the catalytic system, and example 14 was repeated 6 times for deactivation and comparative example 14 was repeated 4 times for deactivation.
Example 15
Replacing the 2L polymerization kettle with nitrogen for more than three times; 1.0kg of diisobutylene and 0.10g of rhodium acetylacetonate dicarbonyl are added at room temperature, 10g of triphenylphosphine, 2g of triphenylphosphine oxide and 5g of bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, 50mg of silver acetylacetonate and 40mg of ferrous acetylacetonate are then added and synthesis gas (H) is passed through2: CO =1.05 to 1.0 (molar ratio)), the reaction was carried out at 90 ℃ and 2.0Mpa for 4 hours, and the reaction mixture was taken out and the conversion of diisobutylene was 56.6% by gas chromatography.
Comparative example 15
This comparative example differs from example 15 in that no ferrous acetylacetonate was added. The conversion of diisobutylene was 42.3%.
The experiment was repeated to examine the catalytic action of the catalytic system, and example 15 was repeated 8 times for deactivation and comparative example 15 was repeated 5 times for deactivation.
Example 16
Replacing the 2L polymerization kettle with nitrogen for more than three times; 1.0kg of octene-1,0.10 g of rhodium acetylacetonate dicarbonyl was added at room temperature, followed by 2g of triphenylphosphine, 2g of triphenylphosphine oxide and 10g of bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, 100mg of silver acetylacetonate, and synthesis gas (H) was passed through2: CO =1.05 to 1.0 (molar ratio)), the reaction was carried out at 100 ℃ and 2.0Mpa for 4 hours, and the reaction mixture was taken out and the octene-1 conversion rate was 51.6% by gas chromatography.
Comparative example 16
This comparative example differs from example 16 in that silver acetylacetonate is not added. Octene-1 conversion was 44.3%.
The experiment was repeated to examine the catalytic action of the catalytic system, and example 16 was repeated 10 times for deactivation and comparative example 16 was repeated 5 times for deactivation.

Claims (9)

1. A catalyst system for olefin hydroformylation is characterized in that acetylacetone metal salt, acetylacetone dicarbonyl rhodium and a ligand are added into the catalyst system, and the specific addition mode is as follows:
the method comprises the following steps: when the olefin is C2-C4The olefin (b) of (a): adding aldehyde, i.e. the hydroformylation reaction product of the reaction raw material olefin used in the reaction, into a reaction kettle, and then using H2Replacing gas in the reaction kettle with synthesis gas of CO, adding acetylacetonatodicarbonylrhodium, phosphine ligand and acetylacetonato metal salt, stirring, heating, adding olefin under the condition of controlling reaction pressure to be constant, and introducing gas for reaction; cooling after the reaction is finished, and weighing to calculate the reaction yield;
the second method comprises the following steps: when the olefin is C5-C8The olefin (b) of (a): adding olefin, rhodium acetylacetonate dicarbonyl, phosphine ligand and acetylacetone metal salt into a reaction kettle, starting stirring, and adding H2Reacting with the synthesis gas of CO under the controlled reaction pressure; and (4) cooling after the reaction is finished, taking out the reaction liquid, measuring the content of aldehyde and olefin in the reaction liquid by using gas chromatography, and calculating the conversion rate.
2. The catalyst system according to claim 1, wherein the nitrogen gas is introduced into the reaction vessel three times or more before use in the first and second processes.
3. The catalyst system according to claim 1, wherein the acetylacetone metal salt in the first and second processes is a mixture of one or more of iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, and silver acetylacetonate; the dosage of the acetylacetone metal salt is 1 to 10 percent of the molar weight of the acetylacetone dicarbonyl rhodium.
4. The catalyst system for hydroformylation of olefins according to claim 1, wherein in the first and second processes, H2With H in the synthesis gas of CO2The molar ratio to CO is 1.0 to 1.05.
5. The catalyst system for the hydroformylation of olefins according to claim 1, wherein the molar ratio of rhodium acetylacetonate dicarbonyl to the phosphine ligand is 1.
6. The catalyst system for olefin hydroformylation according to claim 1, wherein in the first process, the molar ratio of CO in the introduced synthesis gas to the olefin as the reaction raw material is 1:1.
7. the catalyst system for hydroformylation of olefins according to claim 1, wherein in the first process, the reaction pressure is controlled to 2.0MPa, the temperature is 65 to 95 ℃ and the time is 0.5 to 2 hours.
8. The catalytic system for hydroformylation of olefins according to claim 1, wherein in the second process, the molar ratio of acetylacetonatodicarbonylrhodium to the phosphine ligand to the acetylacetonatometal salt is 1;
the weight ratio of rhodium acetylacetonate dicarbonyl to olefin is 80-200ppm.
9. The catalyst system for hydroformylation of olefins according to claim 1, wherein in the second process, the reaction pressure is 1.0 to 4.0MPa, the temperature is 70 to 100 ℃ and the time is 4 to 7 hours.
CN202210904568.0A 2022-07-29 2022-07-29 Catalytic system for olefin hydroformylation reaction Pending CN115254195A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210904568.0A CN115254195A (en) 2022-07-29 2022-07-29 Catalytic system for olefin hydroformylation reaction

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210904568.0A CN115254195A (en) 2022-07-29 2022-07-29 Catalytic system for olefin hydroformylation reaction

Publications (1)

Publication Number Publication Date
CN115254195A true CN115254195A (en) 2022-11-01

Family

ID=83771395

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210904568.0A Pending CN115254195A (en) 2022-07-29 2022-07-29 Catalytic system for olefin hydroformylation reaction

Country Status (1)

Country Link
CN (1) CN115254195A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115521194A (en) * 2022-11-02 2022-12-27 四川大学 Method for regulating catalytic performance of catalyst based on anion-pi action

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107855135A (en) * 2017-11-23 2018-03-30 成都欣华源科技有限责任公司 A kind of preparation method of olefin hydroformylation catalyst
CN110801864A (en) * 2019-10-23 2020-02-18 迈瑞尔实验设备（上海）有限公司 Ethylene tetramerization catalyst composition and application thereof
CN112500431A (en) * 2020-11-26 2021-03-16 上海簇睿低碳能源技术有限公司 Preparation method of olefin hydroformylation catalyst system
CN113087601A (en) * 2019-12-23 2021-07-09 内蒙古伊泰煤基新材料研究院有限公司 High-carbon ether preparation method based on Fischer-Tropsch olefins and high-carbon ether phase change material
CN114163476A (en) * 2021-12-02 2022-03-11 万华化学集团股份有限公司 Monodentate phosphine ligand, hydroformylation catalyst and method for preparing linear aldehyde by olefin hydroformylation
KR20220053229A (en) * 2020-10-22 2022-04-29 주식회사 엘지화학 Catalyst composition for hydroformylation and method for ptrparing aldehyde

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107855135A (en) * 2017-11-23 2018-03-30 成都欣华源科技有限责任公司 A kind of preparation method of olefin hydroformylation catalyst
CN110801864A (en) * 2019-10-23 2020-02-18 迈瑞尔实验设备（上海）有限公司 Ethylene tetramerization catalyst composition and application thereof
CN113087601A (en) * 2019-12-23 2021-07-09 内蒙古伊泰煤基新材料研究院有限公司 High-carbon ether preparation method based on Fischer-Tropsch olefins and high-carbon ether phase change material
KR20220053229A (en) * 2020-10-22 2022-04-29 주식회사 엘지화학 Catalyst composition for hydroformylation and method for ptrparing aldehyde
CN112500431A (en) * 2020-11-26 2021-03-16 上海簇睿低碳能源技术有限公司 Preparation method of olefin hydroformylation catalyst system
CN114163476A (en) * 2021-12-02 2022-03-11 万华化学集团股份有限公司 Monodentate phosphine ligand, hydroformylation catalyst and method for preparing linear aldehyde by olefin hydroformylation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115521194A (en) * 2022-11-02 2022-12-27 四川大学 Method for regulating catalytic performance of catalyst based on anion-pi action
CN115521194B (en) * 2022-11-02 2024-02-06 四川大学 Method for regulating and controlling catalytic performance of catalyst based on anion-pi action

Similar Documents

Publication Publication Date Title
RU2296739C2 (en) Process of multistage hydrofomylation of c6-c24-olefins into aldehydes and/or alcohols
JP5134687B2 (en) Catalyst composition for hydroformylation of phosphorus-containing olefinic compounds and hydroformylation method using the same
EP1863747B1 (en) Hydroformylation process with improved iso-selectivity
KR101587302B1 (en) Method for separating 1-butene from c4-containing hydrocarbon streams by hydroformylation
US20060241324A1 (en) Method for the hydroformylation of olefinically unsaturated compounds, especially olefins,in the presence of cyclic carbonic acid esters
US4201728A (en) Hydroformylation catalyst and process
CN112794796A (en) Method for preparing isononanal by diisobutylene hydroformylation
US4069273A (en) Dimerization of linear alpha-olefins
CN112010906B (en) Bisphosphite and preparation method and application thereof
CN115254195A (en) Catalytic system for olefin hydroformylation reaction
Wiese et al. Hydroformylation
CN106608816A (en) Method for preparing C4-C8 aldehydes
CN101855193B (en) Method for production of aldehydes
US8692027B2 (en) Catalysts and processes for preparing aldehydes
US20050215829A1 (en) Process for the synthesis of alpha-substituted acroleins
Souma et al. Synthesis of tert.-Alkanoic acid catalyzed by Cu (CO) n+ and Ag (CO) 2+ under atmospheric pressure
EP0150943B1 (en) Hydroformylation of allyl alcohol
KR20060118369A (en) A ligand for hydroformylation catalyst, a catalyst system containing the ligand, and hydroformylation method using the catalyst system
CN114534795A (en) Catalyst for preparing valeraldehyde through butene hydroformylation, preparation method of catalyst and preparation method of valeraldehyde
KR100436594B1 (en) A catalyst system for hydroformylation and preparation method of aldehyde using the same catalyst system
KR102610473B1 (en) Preparing method of aldehyde
KR100322616B1 (en) Hydroformylation of olefin with rhodium catalyst/salt co-catalyst system
Ferreira Palladium catalysed hydroformylation of alpha-olefins
JPH03392B2 (en)
KR100676299B1 (en) A ligand for hydroformylation catalyst, a catalyst system containing the ligand, and hydroformylation method using the catalyst system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination