阅读说明：本技术 一种碳原子数≥8的高碳烯烃氢甲酰化的方法 (Method for hydroformylating high-carbon olefin with carbon number not less than 8 ) 是由 黄少峰 袁帅 任亚鹏 许振成 黎源 于 2020-06-24 设计创作，主要内容包括：本发明涉及一种碳原子数≥8的高碳烯烃氢甲酰化的方法,该方法以碳数≥8的高碳烯烃为原料,以钴、铑、钌、铁、锰中的一种或多种金属及其化合物为催化剂,以水为溶剂,加入新型的阳离子型膦配体,催化烯烃氢甲酰化反应,反应结束后水油两相分层,分离上层氢甲酰化产品,下层为催化剂水溶液,膦配体的加入显著提高了烯烃的溶解度,催化剂的活性大幅度提升。(The invention relates to 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, takes one or more metals and compounds of cobalt, rhodium, ruthenium, iron and manganese as a catalyst, takes water as a solvent, adds a novel cationic phosphine ligand to catalyze the hydroformylation reaction of the olefin, stratifies water and oil phases after the reaction is finished, separates an upper-layer hydroformylation product, takes a lower-layer catalyst aqueous solution as a lower layer, and obviously improves the solubility of the olefin and greatly improves the activity of the catalyst.)

1. A method for hydroformylating high-carbon olefin with carbon number more than or equal to 8 is characterized in that the high-carbon olefin with carbon number more than or equal to 8 is used as a raw material, one or more metals and compounds thereof in cobalt, rhodium, ruthenium, iron and manganese are used as catalysts, water is used as a solvent, a cationic phosphine ligand is added to catalyze the hydroformylation reaction of the olefin, after the reaction is finished, two phases of water and oil are layered, the upper oil phase is separated to be a hydroformylation product, and the lower layer is a catalyst aqueous solution.

2. The method according to claim 1, wherein the high carbon olefin having a carbon number of 8 or more is selected from one or more of linear alpha-olefin having a carbon number of 8 or more, linear internal olefin, branched alpha-olefin, and branched internal olefin, preferably one or more of 1-octene, cyclooctene, 1-nonene, 1-decene, tripropylene, tetrapropylene, di-n-butene, tri-n-butene, diisobutylene, and triisobutene.

3. The method of claim 1, wherein the catalyst is selected from one or more of rhodium acetate, rhodium octanoate, rhodium acetylacetonate, rhodium triphenylphosphine, cobalt acetate, cobalt chloride, cobalt carbonyl, cobalt sulfate, ruthenium chloride, ruthenium carbonyl, ruthenium acetate, manganese acetylacetonate, manganese carbonyl, ferric sulfate, ferric carbonyl, ferric nitrate, ferric chloride, and ferric acetylacetonate; and/or the catalyst is used in an amount of 0.1 to 10 wt%, preferably 1 to 5 wt% of the olefin feedstock.

4. The process according to any one of claims 1 to 3, characterized in that the reaction temperature is 100-; and/or the reaction time is 0.5-5h, preferably 1-4 h; and/or the reaction pressure is 8-20MPaG, preferably 10-18 MpaG.

5. A process according to any of claims 1 to 4, characterized in that the phosphine ligand is added in an amount of 0.2 to 20 wt%, preferably 1 to 10 wt%, based on the mass of the olefin feed; and/or the dosage of the solvent water is 10-500% of the mass of the olefin raw material.

6. A method according to any one of claims 1 to 5, wherein the cationic phosphine ligand has the structure:

wherein R 'represents phenyl or cyclohexyl, R' represents saturated alkyl with 8-22 carbons, and X represents chlorine, bromine, iodine.

7. The method of claim 6, wherein the phosphine ligand is synthesized by the steps of: (1) reacting triethanolamine with alkyl lithium, then adding diphenyl phosphine chloride or dicyclohexyl phosphine chloride to generate an intermediate I, (2) carrying out esterification reaction on the intermediate I and fatty acid with 8-22 carbon atoms to generate an intermediate II, and (3) reacting the intermediate II with methyl halide to generate a cationic phosphine ligand product, wherein the structures of the intermediate I and the intermediate II are as follows:

8. the method according to claim 7, wherein in step (1), the alkyl lithium is selected from one of methyl lithium, n-butyl lithium and tert-butyl lithium, and the feeding molar ratio of the alkyl lithium to the triethanolamine is 1:1-1.2:1, preferably 1.05:1-1.1:1, and/or the reaction temperature is-78-30 ℃, preferably-30-0 ℃, and/or the reaction time is 0.5-3h, preferably 1-2 h.

9. The process according to claim 7 or 8, characterized in that in step (1), the molar ratio of the diphenyl phosphonium chloride or dicyclohexyl phosphonium chloride to triethanolamine is 1:1 to 1.2:1, preferably 1.05:1 to 1.1:1, and/or the reaction temperature is 0 to 100 ℃, preferably 20 to 80 ℃, and/or the reaction time is 0.5 to 3 hours, preferably 1 to 2 hours.

10. The method according to any one of claims 7 to 9, wherein in the step (2), the intermediate I is subjected to esterification reaction with fatty acid with 8 to 22 carbon atoms, an acid is used as a catalyst, the amount of the catalyst is 0.1 to 10% of the mass of the intermediate I, preferably the acid used comprises one or more of sulfuric acid, tetrabutyl titanate, an acidic resin and a molecular sieve, and the feeding molar ratio of the intermediate I to the fatty acid with 8 to 22 carbon atoms is 1: 2-1:10, preferably 1:3-1: 5; and/or the reaction temperature is 100-200 ℃, preferably 120-150 ℃; and/or the reaction time is 0.5 to 5h, preferably 2 to 4 h.

11. The process according to any one of claims 7 to 10, wherein in step (3), the intermediate II is reacted with the methyl halide in a molar ratio of 1: 1-1:10, preferably 1:1.2-1: 2; and/or the reaction temperature is 20-100 ℃, preferably 40-80 ℃; and/or the reaction time is 0.5 to 5h, preferably 2 to 4 h.

Technical Field

The invention relates to a method for hydroformylating high-carbon olefin, in particular to a method for hydroformylating high-carbon olefin with carbon atom number more than or equal to 8.

Technical Field

The hydroformylation reaction, also known as OXO reaction, is the reaction of an olefin with synthesis gas (CO + H)₂) A catalytic reaction process for generating aldehyde or alcohol under the action of a catalyst.

Catalysts used in the short-chain olefin hydroformylation industry have undergone a progression from simple cobalt carbonyls to modified cobalt carbonyls, and then from oil-soluble rhodium phosphine complexes to the latest generation of water-soluble rhodium phosphine complexes. The production conditions are improved from complex process to simple process and from harsh condition to mild condition. However, the difficulty for hydroformylation of higher olefins is much greater because the higher alditols have high boiling points, the higher alditols prepared from higher olefins must be separated from the catalyst by flash evaporation at high temperature, and the rhodium catalyst is decomposed and lost at high temperature, so that the separation and recycling processes of the rhodium catalyst for hydroformylation of higher olefins are complicated and costly, in view of the above, the cobalt catalyst is still mostly used in the hydroformylation of higher olefins to prepare higher alditols, and the cobalt catalyst is separated by first converting the catalyst into easily separable substances (reducing into metallic cobalt, centrifugally separating from the solution or chemically converting oil-soluble cobalt complexes into water-soluble cobalt complexes, and separating by liquid separation extraction), so that the separated substances containing metallic cobalt must be regenerated before the catalytic cycle is realized, in addition, the method of separating the catalyst by distilling off the product by distillation under reduced pressure consumes a large amount of energy and causes loss of the expensive transition metal complex catalyst. The cobalt-catalyzed hydroformylation of high-carbon olefin has the disadvantages of harsh reaction conditions, poor selectivity, more side reactions, high energy consumption, complex cobalt recovery process and the like, and has poor comprehensive economic and technical indexes.

The RCH/RP two-phase catalytic process using water-soluble rhodium-phosphine complex catalyst can directly separate and recycle the catalyst after the reaction is finished, and the catalyst is easy and convenient to recover, but the hydroformylation of high-carbon olefin (C >8) is difficult to carry out due to the limitation of mass transfer because the water solubility of the high-carbon olefin is too low. Therefore, it is necessary to develop a new process for improving the solubility of olefin in the two-phase hydroformylation process and improving the hydroformylation efficiency.

Disclosure of Invention

The invention aims to provide a method for hydroformylating high-carbon olefin with carbon atom number more than or equal to 8, which improves the solubility of the high-carbon olefin in a water phase and improves the reaction efficiency of a water-oil two-phase hydroformylation process by developing a brand-new ligand and a production process.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:

a method for hydroformylating high-carbon olefin with carbon number more than or equal to 8 comprises the steps of taking the high-carbon olefin with carbon number more than or equal to 8 as a raw material, taking one or more metals and compounds of cobalt, rhodium, ruthenium, iron and manganese as catalysts, taking water as a solvent, adding a cationic phosphine ligand to catalyze hydroformylation of the olefin, layering two phases of water and oil after the reaction is finished, separating an upper oil phase to obtain a hydroformylation product, and recycling a lower catalyst aqueous solution.

In the invention, the olefin is selected from one or more of linear alpha-olefin, linear internal olefin, branched alpha-olefin and branched internal olefin with the carbon number being more than or equal to 8, including but not limited to one or more of 1-octene, cyclooctene, 1-nonene, 1-decene, tripropylene, tetrapropylene, dimeric n-butene, trimeric n-butene, diisobutylene and triisobutene.

In the invention, the catalyst is selected from one or more of cobalt, rhodium, ruthenium, iron and manganese metals and/or compounds thereof, and comprises one or more of rhodium acetate, rhodium octoate, rhodium acetylacetonate, triphenylphosphine rhodium, cobalt acetate, cobalt chloride, cobalt carbonyl, cobalt sulfate, ruthenium chloride, ruthenium carbonyl, ruthenium acetate, manganese acetylacetonate, manganese carbonyl, ferric sulfate, ferric carbonyl, ferric nitrate, ferric chloride and ferric acetylacetonate. The amount of catalyst used is from 0.1 to 10% by weight, preferably from 1 to 5% by weight, based on the olefin feed. The reaction temperature of the hydroformylation reaction is 100-200 ℃, preferably 120-170 ℃, the reaction time is 0.5-5h, preferably 1-4h, and the reaction pressure is 8-20MPaG, preferably 10-18 MpaG.

In the invention, the dosage of the solvent water is 10-500% of the mass of the olefin raw material.

In the invention, the used cationic phosphine ligand has the following structure:

wherein R 'represents phenyl or cyclohexyl, R' represents saturated alkyl with 8-22 carbons, and X represents chlorine, bromine, iodine.

The synthesis method of the phosphine ligand comprises the following steps of (1) reacting triethanolamine with alkyl lithium, then adding diphenyl phosphine chloride/dicyclohexyl phosphine chloride to generate an intermediate I, (2) esterifying the intermediate I with fatty acid with 8-22 carbon atoms to generate an intermediate II, and (3) reacting the intermediate II with methyl halide to generate a final cationic phosphine ligand product. The reaction process is shown as the following formula:

in the synthesis method of the phosphine ligand, in the step (1), triethanolamine reacts with alkyllithium, wherein the alkyllithium is selected from one of methyllithium, n-butyllithium and tert-butyllithium, and the feeding molar ratio of the alkyllithium to the triethanolamine is 1:1-1.2:1, preferably 1.05:1-1.1: 1. The reaction temperature is-78-30 deg.C, preferably-30-0 deg.C. The reaction time is 0.5-3h, preferably 1-2 h. And (3) continuously adding diphenyl phosphine chloride or dicyclohexyl phosphine chloride after the reaction of the alkyl lithium is finished, wherein the feeding molar ratio of the diphenyl phosphine chloride or the dicyclohexyl phosphine chloride to the triethanolamine is 1:1-1.2:1, and preferably 1.05:1-1.1: 1. The reaction temperature is 0-100 deg.C, preferably 20-80 deg.C. The reaction time is 0.5-3h, preferably 1-2 h. After the reaction is finished, standing at the temperature of-20-10 ℃ for 12-48h, separating out solid in the reaction liquid, and filtering to obtain an intermediate I.

In the step (2) of the synthesis method of the phosphine ligand, the intermediate I and fatty acid with 8-22 carbon atoms are esterified, acid is used as a catalyst, and the dosage of the catalyst is 0.1-10% of the mass of the intermediate I. Preferred acids for use include sulfuric acid, tetrabutyl titanate, acidic resins, molecular sieves, and the like. The feeding molar ratio of the intermediate I to the fatty acid with 8-22 carbon atoms is 1: 2-1:10, preferably 1:3-1: 5. The reaction temperature is 100-200 ℃, preferably 120-150 ℃. The reaction time is 0.5-5h, preferably 2-4h, and after the reaction is finished, the intermediate II is obtained by rectification and separation.

In the synthesis method of the phosphine ligand, in step (3), the intermediate II is reacted with halogenated methane (such as chlorine/bromine/iodomethane) in a feeding molar ratio of 1: 1-1:10, preferably 1:1.2-1: 2. The reaction temperature is 20-100 deg.C, preferably 40-80 deg.C. The reaction time is 0.5-5h, preferably 2-4 h. Adding hexane as a solvent, wherein the adding amount of the hexane is 1-10 times of the mass of the intermediate II, and filtering and separating solid powder after the reaction is finished to obtain the phosphine ligand.

In the present invention, the phosphine ligand is added in an amount of 0.2 to 20% by weight, preferably 1 to 10% by weight, based on the mass of the olefin, in the hydroformylation reaction.

The surfactant is an amphiphilic molecule, namely one part of the molecule has hydrophilic property, the other part of the molecule has lipophilic property and hydrophobic property, and the hydrophobic part of the surfactant is generally composed of hydrocarbon groups, particularly high-carbon hydrophobic groups; the structure of the hydrophilic group is changed in a plurality of ways. When the surfactant reaches a certain concentration, a molecular ordered assembly is formed, so that the properties of the aqueous solution can be obviously changed, such as the reduction of the interfacial tension of an organic phase and an aqueous phase, the increase of the solubility of an oil-soluble substrate in the aqueous phase and the like, and the surfactant is particularly suitable for accelerating the reaction between two immiscible phases.

The cationic phosphine ligand of the invention is essentially a cationic surfactant, and the phosphine ligand can form a micelle structure as shown in figure 1 in aqueous solution. The hydrophobic chains of the surfactant inwardly form a hydrophobic micelle core in which the olefin molecules are solubilized by hydrophobic interactions. The polar ammonium ion head of the surfactant faces the aqueous phase, and the formed micelle interface is a positively charged surface layer. The metal or metal compound added into the water phase is subjected to coordination with one or more phosphine ligands (two phosphine ligands are taken as a schematic diagram in the figure), the metal active center is reduced into a carbonyl metal compound with an active center in a synthesis gas environment, and high-carbon olefin can be solubilized in the micelle core under the action of the phosphine ligands, so that the solubility in water is greatly improved, the olefin diffusion barrier in the reaction microenvironment is remarkably reduced, the olefin diffusion barrier is easy to diffuse and migrate to the metal center, and the coordination insertion reaction is carried out to form the final aldehyde/alcohol product. The micelle is similar to a microreactor, and the olefin and the catalyst are concentrated in the microreactor, so that favorable conditions are created for coordination between the olefin and the catalyst, and the reaction is greatly accelerated.

Compared with the prior art, the invention has the following advantages:

(1) the novel phosphine ligand is adopted, the solubility of high-carbon olefin in water is improved, the hydroformylation reaction efficiency is greatly improved, the reaction time is shortened (taking triisobutene as an example, an RCH/RP two-phase catalytic process is adopted, the conversion rate of 24h is 3%, the conversion rate of 85% can be reached within 4h by adopting the novel phosphine ligand), and the production cost is obviously reduced.

(2) After the reaction is finished, the catalyst can be directly separated and reused, and the activity of the catalyst can still be kept stable after continuous repeated use.

Description of the drawings:

FIG. 1 is a schematic diagram of the reaction mechanism of the cationic phosphine ligands of the present invention participating in hydroformylation, wherein L is a coordinating atom or molecule, including hydrogen, carbon monoxide, olefin, M metal.

The specific implementation mode is as follows:

the present invention is further illustrated by the following examples, which include, but are not limited to, the scope of the present invention.

The analytical instruments and methods used in the examples are as follows:

gas chromatograph: agilent-7820;

gas chromatography column 1: 0.25mm 30m DB-5 capillary column, detector FID, vaporizer temperature 280 deg.C, column box temperature 280 deg.C, FID detector temperature 300 deg.C, argon carrying capacity 2.1mL/min, hydrogen flow 30mL/min, air flow 400mL/min, and sample injection 1.0 μ L. The conversion of the alkene and the selectivity of the product were calculated using area normalization. Temperature rising procedure: preheating to 40 deg.C, holding for 5min, and heating at 15 deg.C/min from 40 deg.C to 280 deg.C, and holding for 2 min.

Gas chromatography column 2: 0.25mm 30m DB-5 capillary column, detector FID, vaporizer temperature 300 deg.C, column box temperature 300 deg.C, FID detector temperature 300 deg.C, argon carrying capacity 2.1mL/min, hydrogen flow 30mL/min, air flow 400mL/min, and sample injection 1.0 μ L. The conversion of the alkene and the selectivity of the product were calculated using area normalization. Temperature rising procedure: preheating to 80 deg.C, maintaining for 5min, and raising the temperature from 80 deg.C to 300 deg.C at 20 deg.C/min, and maintaining for 15 min.

A mass spectrum analyzer: agilent7890B-5977A GC-MS

An element analyzer: euro Vector EA3000

Nuclear magnetic analyzer: bruker AVANCE III 400M 400