CN114433239B - Rhodium nanoparticle dispersion and preparation method and application thereof - Google Patents

Rhodium nanoparticle dispersion and preparation method and application thereof Download PDF

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Publication number
CN114433239B
CN114433239B CN202011112462.4A CN202011112462A CN114433239B CN 114433239 B CN114433239 B CN 114433239B CN 202011112462 A CN202011112462 A CN 202011112462A CN 114433239 B CN114433239 B CN 114433239B
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rhodium
reaction
dispersion
nanoparticle dispersion
diphenylphosphino
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CN114433239A (en
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黄谢君
刘俊涛
孙凤侠
宋海峰
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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
    • B01J31/18—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
    • 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
    • B01J31/18—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
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • 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
    • B01J2531/80—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 rhodium nanoparticle dispersion, a preparation method and application thereof. The dispersion consists of surface grafted rhodium nano-particles and a dispersion medium, wherein the size of the surface grafted rhodium nano-particles is 3-20 nm. The preparation method comprises the following steps: (1) Mixing rhodium salt, grafts, a reducing agent and a solvent to obtain a mixed solution; (2) Heating the mixed solution obtained in the step (1) to a reaction temperature under the protection of inert gas, and carrying out a reaction; (3) And (3) after solid-liquid separation of the product obtained in the step (2), dispersing the solid phase into a dispersing solvent to obtain rhodium nanoparticle dispersion. The rhodium nanoparticle dispersion has the characteristics of high specific surface area, more active sites, high stability and the like, and can be used as a catalyst in a hydroformylation reaction, so that the positive-to-negative ratio of a product can be improved, and the catalyst has high circulating activity.

Description

Rhodium nanoparticle dispersion and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano material dispersoid production. More particularly, it relates to a rhodium nanoparticle dispersion with a catalytic hydroformylation reaction, a preparation method and application thereof.
Background
Rhodium is a precious metal material that can be used as a catalyst for hydrogenation, hydroformylation, carbon monoxide oxidation, etc., and has been recently studied to enhance detection of surface raman spectra. The particle size and morphology of the nano rhodium play an important role in the catalytic reaction process.
At present, researchers regulate the particle size of nano rhodium by a method of templates such as macromolecules, micelles and the like, and a series of research results are obtained. However, the size effect of the nano material determines that the nano material has high surface energy and easy agglomeration under a low scale, and the specific surface area is greatly reduced, so that the catalytic efficiency is reduced. Although grafting of surface macromolecules or micelles can reduce its surface energy to some extent, enhancing dispersibility, it still cannot form monodispersion, and stability tends to be reduced in long-term use. Compared with common nano metal or oxide powder, the dispersion has the advantages of well dispersing nano particles, allowing more active sites to act and approaching monoatomic catalysis theoretically.
CN104549244a prepares rhodium particles with a flake-like multilevel structure through a hydrothermal reaction of reducing rhodium acetylacetonate by formaldehyde, and has the disadvantages of more severe preparation conditions, large product particle size and poorer dispersibility. CN103696000a discloses a solvothermal method for preparing icosahedral rhodium nanocrystals, comprising: rhodium acetylacetonate and polyvinylpyrrolidone are dissolved in benzyl alcohol to obtain a mixed solution, the mixed solution is subjected to hydrothermal reaction for 5-15 hours at 170-200 ℃ to obtain rhodium nanocrystals, the dispersibility of the rhodium nanocrystals obtained by the method cannot reach the degree of dispersion, sufficient active sites cannot be provided for catalytic reaction, and catalytic performance is difficult to develop. CN107597192a discloses a catalyst for hydroformylation reaction, which comprises a rhodium metal compound and a biphosphine ligand having an ethoxy unit, and the catalyst is in an ion complex state in a solvent, and although the activity of the rhodium catalyst can be improved to a certain extent, the positive difference in the obtained hydroformylation reaction product is low, and the catalyst has a complex structure, a difficult preparation process and high cost.
Disclosure of Invention
The inventors have found that when a plurality of phosphine groups are connected to the surface of rhodium nanoparticles in the form of a hard scaffold, on the one hand, the free change space of the conformation is less, and on the other hand, the dispersion of rhodium nanoparticles is facilitated, and the catalyst prepared by the method is beneficial to increasing the positive-to-negative ratio of hydroformylation reaction products. Therefore, the inventor grafts specific phosphine ligand groups on the surface of rhodium nano-particles with rich hydroxyl groups in a covalent bond mode, so that the dispersity of the rhodium nano-particles is high, and rhodium atoms and phosphine on the surface form multi-ligand, and the obtained nano-dispersion is used as a catalyst to be beneficial to improving the selectivity of hydroformylation reaction.
The invention provides a rhodium nanoparticle dispersion, a preparation method thereof and application thereof in hydroformylation reaction. The rhodium nanoparticle dispersion has the characteristics of high specific surface area, more active sites, high stability and the like, and can be used as a catalyst in a hydroformylation reaction, so that the positive-to-negative ratio of a product can be improved, the recycling loss is less, and the recycling activity is high.
In a first aspect, the invention provides a rhodium nanoparticle dispersion comprising surface grafted rhodium nanoparticles and a dispersion medium, the surface grafted rhodium nanoparticles having a size of from 3 to 20nm.
In the technical scheme, the solid content of the dispersion is 1-50 wt%, preferably 10-40 wt%.
In the technical scheme, the dispersion medium is at least one of toluene, n-hexane, cyclohexane, n-heptane, xylene, ethylbenzene and petroleum ether.
In the above technical solution, in the surface grafted rhodium nanoparticle, the graft is at least one selected from methyl 3- (trimethoxysilyl) propyl methylphosphonate, 2- (diphenylphosphino) ethyl triethoxysilane, diphenylphosphinoethyl dimethylethoxysilane, N-bis [ (diphenylphosphino) methyl ] -3- (triethoxysilyl) -1-propylamine, pentaethoxyphosphine, ethanolamine phosphonate, glufosinate, 2- (diphenylphosphino) aniline, 2- (diisopropylphosphine) ethylamine, O- (diphenylphosphino) hydroxylamine, 2- (diphenylphosphino) ethylamine, [ hydroxy (4-phenylbutyl) phosphino ] acetic acid, 3- (diphenylphosphino) propionic acid, preferably at least one selected from 2- (diphenylphosphino) ethyl triethoxysilane, 2- (diphenylphosphino) ethylamine, [ hydroxy (4-phenylbutyl) phosphino ] acetic acid, 3- (diphenylphosphino) propionic acid, pentaethoxyphosphine, methyl 3- (trimethoxy-silyl) propyl methylphosphonate.
In the technical scheme, in the surface grafted rhodium nano-particle, the graft accounts for 5-30wt% of the mass of the surface grafted rhodium nano-particle.
The second aspect of the invention discloses a method for preparing rhodium nanoparticle dispersion, comprising the following steps:
(1) Mixing rhodium salt, grafts, a reducing agent and a solvent to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to a reaction temperature under the protection of inert gas, and carrying out a reaction;
(3) And (3) after solid-liquid separation of the product obtained in the step (2), dispersing the solid phase into a dispersion medium to obtain rhodium nanoparticle dispersion.
In the above technical scheme, the rhodium salt in the step (1) is at least one selected from ammonium chlororhodium, rhodium acetylacetonate dicarbonyl, rhodium dimeric acetate and rhodium chloride.
In the above technical solution, the graft in step (1) is at least one selected from methyl 3- (trimethoxysilyl) propyl methylphosphonate, 2- (diphenylphosphino) ethyl triethoxysilane, diphenylphosphinoethyl dimethylethoxysilane, N-bis [ (diphenylphosphino) methyl ] -3- (triethoxysilyl) -1-propylamine, pentaethoxyphosphine, ethanolamine phosphonate, phosphinic acid, 2- (diphenylphosphino) aniline, 2- (diisopropylphosphine) ethylamine, O- (diphenylphosphino) hydroxylamine, 2- (diphenylphosphino) ethylamine, [ hydroxy (4-phenylbutyl) phosphino ] acetic acid, 3- (diphenylphosphino) propionic acid, preferably at least one selected from 2- (diphenylphosphino) ethyl triethoxysilane, 2- (diphenylphosphino) ethylamine, [ hydroxy (4-phenylbutyl) phosphino ] acetic acid, 3- (diphenylphosphino) propionic acid, pentaethoxyphosphine, methyl 3- (trimethoxysilyl) propyl methylphosphonate.
In the above technical solution, the reducing agent in the step (1) is at least one selected from ascorbic acid, oleylamine, glucose, aniline, ethylene glycol, diethylene glycol and triethylene glycol.
In the above technical scheme, the solvent in the step (1) is at least one selected from oleylamine, oleic acid, octadecylamine, octadecene, ethylene glycol, diethylene glycol and triethylene glycol. The solvent may be the same as or different from the reducing agent.
In the above technical scheme, when the solvent in the step (1) adopts at least one of oleylamine, ethylene glycol, diethylene glycol and triethylene glycol, no other reducing agent may be added into the reaction system, and other reducing agents may also be added. The reducing agent is used in an amount to reduce the rhodium in the higher valence state to zero valence rhodium. The amounts of reducing agent and solvent may be determined by one skilled in the art based on the actual circumstances.
In the above technical scheme, the concentration of rhodium salt in the mixed solution in the step (1) is 5-100 mmol/L, for example, 5mmol/L, 8mmol/L, 10mmol/L, 15mmol/L, 20mmol/L, 30mmol/L, 40mmol/L, 50mmol/L, 60mmol/L, 70mmol/L, 80mmol/L, 90mmol/L, 100mmol/L and the like can be used.
In the above technical scheme, in the mixed solution in step (1), the concentration of the graft is 2-10 g/L, for example, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, etc.
In the above technical solution, the inert gas in step (2) may be N 2 、Ar、He、CO 2 At least one of them.
In the technical scheme, the heating rate of the heating in the step (2) is 3-8 ℃/min.
In the technical scheme, the reaction temperature in the step (2) is 100-250 ℃, the reaction time is 2-4 h, and the reaction is carried out under normal pressure.
In the above technical solution, the dispersion medium in step (3) is at least one selected from toluene, n-hexane, cyclohexane, n-heptane, xylene, ethylbenzene, and petroleum ether.
In the above technical solution, the solid-liquid separation in the step (3) may be a conventional solid-liquid separation method such as centrifugation and filtration.
In the technical scheme, the solid content of the rhodium nanoparticle dispersion obtained in the step (3) is 1-50 wt%.
In the above technical scheme, the solid phase obtained by solid-liquid separation in the step (3) may be washed and then dispersed in a dispersion medium, wherein the washing solvent is at least one selected from acetone, methanol, ethanol, butanone and cyclohexanone.
In the technical scheme, the prepared rhodium nanoparticle dispersion consists of surface grafted rhodium nanoparticles and a dispersion medium, wherein the size of the surface grafted rhodium nanoparticles is 3-20 nm.
In the technical scheme, in the surface grafted rhodium nano-particle, the graft accounts for 5-30wt% of the mass of the surface grafted rhodium nano-particle.
In a third aspect the invention provides a C 4 A process for the hydroformylation of olefins comprising: c is C 4 The olefin is dissolved in a solvent and then reacted in contact with the rhodium nanoparticle dispersion, CO and hydrogen.
In the technical scheme, C 4 The olefin is one or more of butene-1, butene-2, isobutene and 2, 5-dihydrofuran.
In the technical scheme, C 4 The olefin is dissolved in at least one of toluene, n-hexane, cyclohexane, n-heptane, xylene, ethylbenzene and petroleum ether.
In the technical scheme, the concentration of the rhodium nanoparticle dispersion in the reaction system is 0.1-2.0 mmol/L based on rhodium.
In the technical scheme, the reaction conditions are as follows: the reaction temperature is 60-150 ℃, the reaction pressure is 0.1-3.0 MPa, and the reaction time is 0.5-24.0 h; h 2 And CO in a molar ratio of 1 to 5, C 4 The mass fraction of the olefin relative to the solvent is 5-20wt%.
The rhodium nanoparticle dispersion of the invention has the following advantages:
1. in the rhodium nanoparticle dispersion, the special groups containing phosphine grafts are grafted on the surfaces of rhodium nanoparticles in a covalent bond mode, so that the rhodium nanoparticles are highly dispersed in corresponding solvents, rhodium atoms and phosphine on the surfaces form multi-ligand, and the rhodium nanoparticle dispersion has the characteristics of high specific surface area, more active sites, high stability and the like.
2. The rhodium nano-particles and the grafted ligand can not be decomposed and lost in the process of rectifying and separating the product, so that the guarantee is provided for the recycling of the catalyst, and the cost is saved.
3. The rhodium nanoparticle dispersion prepared by the method has high specific surface area, multiple active sites, high stability and is particularly suitable for catalyzing C 4 The olefin hydroformylation reaction has the characteristics of high catalyst recycling activity, small catalyst consumption, easy recovery and the like.
Drawings
FIG. 1 is a transmission electron microscope image of rhodium nanoparticles in example 1 of the present invention;
FIG. 2 is a schematic structural diagram of a surface-grafted rhodium nanoparticle in example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to examples and drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
In the invention, the morphology, the size and the dispersibility of the sample are observed by adopting an HT7700 type transmission electron microscope of Hitachi corporation in Japan. When the nano particles are observed, a sample with proper concentration is dripped on the carbon film, and sample injection is carried out after natural air drying.
Example 1
The present example provides a rhodium nanoparticle dispersion, the preparation method of which comprises:
(1) 15mL of oleylamine, 0.1mmol of rhodium acetylacetonate dicarbonyl, 0.1g of ascorbic acid and 100. Mu.L of 2- (diphenylphosphino) ethylamine were added to a three-necked flask and dissolved by stirring to obtain a mixed solution;
(2) Continuously introducing nitrogen into the mixed solution for 20min, starting oil bath heating to 240 ℃, heating at a heating rate of 6 ℃/min, and then carrying out reaction for 2h;
(3) Stopping heating, cooling the three-neck flask to room temperature in air, centrifuging, washing and centrifuging the obtained solid phase product with acetone for three times, and adding toluene into the washed product to perform ultrasonic dispersion to obtain rhodium nanoparticle dispersion A.
In the dispersion A, the solid content is 20wt%, the dispersion is sealed and kept stand for six months without sedimentation, the one-dimensional size of the dispersed particles is 3-5 nm, and the transmission electron microscope diagram is shown in figure 1.
Example 2
The present example provides a rhodium nanoparticle dispersion, the preparation method of which comprises:
(1) 12mL of ethylene glycol, 0.1mmol of rhodium diacetate dimer and 100 mu L of methyl 3- (trimethoxysilyl) propyl methylphosphonate are added into a three-neck flask and stirred for dissolution, so as to obtain a mixed solution;
(2) Continuously introducing nitrogen into the mixed solution for 20min, starting oil bath heating to 100 ℃, wherein the heating rate is 3 ℃/min, and then carrying out reaction for 2h;
(3) Stopping heating, cooling the three-neck flask to room temperature in air, centrifuging, washing and centrifuging the obtained solid phase product with acetone for three times, and adding xylene into the washed product to perform ultrasonic dispersion to obtain rhodium nanoparticle dispersion B.
In the dispersion B, the solid content is 20wt%, the dispersion is sealed and kept stand for six months without sedimentation, and the one-dimensional size of the dispersed particles is 4.0-5.5 nm.
Example 3
The present example provides a rhodium nanoparticle dispersion, the preparation method of which comprises:
(1) 10mL of oleic acid, 0.1mmol of rhodium diacetate dimer, 0.1g of glucose, 50. Mu.L of 3- (diphenylphosphino) propionic acid and 50. Mu.L of [ hydroxy (4-phenylbutyl) phosphino ] acetic acid were placed in a three-necked flask and dissolved by stirring to obtain a mixed solution;
(2) Continuously introducing nitrogen into the mixed solution for 20min, starting oil bath heating to 150 ℃ at a heating rate of 4 ℃/min, and then carrying out reaction for 4h;
(3) Stopping heating, cooling the three-neck flask to room temperature in air, centrifuging, washing and centrifuging the obtained solid phase product with acetone for three times respectively, and adding cyclohexane into the washed product to perform ultrasonic dispersion to obtain rhodium nanoparticle dispersion C.
In the dispersion C, the solid content is 30wt%, the dispersion C is sealed and kept stand for six months without sedimentation, and the one-dimensional size of the dispersed particles is 10-12 nm.
Example 4
The present example provides a rhodium nanoparticle dispersion, the preparation method of which comprises:
(1) 10mL of octadecene, 0.1mmol of rhodium acetylacetonate, 0.1g of ascorbic acid and 100 mu L of pentaethoxyphosphine are added into a three-neck flask and stirred for dissolution to obtain a mixed solution;
(2) Continuously introducing nitrogen into the mixed solution for 20min, starting oil bath heating to 150 ℃ at a heating rate of 4 ℃/min, and then carrying out reaction for 3h;
(3) Stopping heating, cooling the three-neck flask to room temperature in air, centrifuging, washing and centrifuging the obtained solid phase product with acetone for three times, and adding ethylbenzene into the washed product to perform ultrasonic dispersion to obtain rhodium nanoparticle dispersion D.
In the dispersion D, the solid content is 25wt%, the dispersion D is sealed and kept stand for six months without sedimentation, and the one-dimensional size of the dispersed particles is 9-11 nm.
Example 5
The dispersion A obtained in example 1 was used as a catalyst in the reaction for producing valeraldehyde by catalytic hydrogenation of butene-1, and the catalytic activity and selectivity after single and 5 cycles were compared. The method comprises the following specific steps: butene-1 and catalyst were dissolved in 100mL of toluene to form a liquid phase and introduced into a 500mL autoclave, the mass fraction of butene-1 was 10wt% (relative to solvent), N 2 Replacing air, and introducing synthetic gas with a mixed pressure ratio of carbon monoxide to hydrogen of 1:1 to replace N 2 The pressure is complemented to 1MPa, the preheating temperature of the autoclave type jacketed reactor is set to be 100 ℃, the mixture is fully stirred and reacted for 3 hours, and finally the product enters a separation device to separate aldehydeThe rhodium catalyst is recycled. Different catalyst concentrations (mmol/L in terms of rhodium), calculate C 4 The olefin conversion and the product normal-to-iso ratio are shown in Table 1.
Comparative example 1
The III-generation hydroformylation catalyst is used for the reaction of preparing valeraldehyde by the catalytic hydrogenation of butene-1, and the catalytic activity and the selectivity after single cycle and 5 cycles are compared. The method comprises the following specific steps: the third hydroformylation catalyst is prepared by mixing and dissolving acetylacetone dicarbonyl rhodium catalyst and triphenylphosphine in toluene according to phosphine rhodium mol ratio of 180. Dissolving butene-1 and the catalyst in 100mL of toluene to form a liquid phase, introducing the liquid phase into a 500mL autoclave, wherein the mass fraction of butene-1 is 10wt% (relative to the solvent), N 2 Replacing air, and introducing synthetic gas with a mixed pressure ratio of carbon monoxide to hydrogen of 1:1 to replace N 2 And (3) supplementing the pressure to 1MPa, setting the preheating temperature of the autoclave type jacketed reactor to be 100 ℃, fully stirring and reacting for 3 hours, and finally, enabling the product to enter a separation device for aldehyde separation and recycling the rhodium catalyst. Different catalyst concentrations (mmol/L in terms of rhodium), calculate C 4 The olefin conversion and the product normal-to-iso ratio are shown in Table 1.
Comparative example 2
For comparison with the rhodium nanoparticle dispersion according to the invention, the following catalysts were used: the rhodium acetylacetonate dicarbonyl catalyst and 2- (diphenylphosphino) ethylamine were mixed and dissolved in toluene at a phosphine-rhodium molar ratio of 180 as a catalyst. The catalyst is used for the reaction of preparing valeraldehyde by catalytic hydrogenation of butene-1, and the catalytic activity and the selectivity after single cycle and 5 cycles are compared. The method comprises the following specific steps: dissolving butene-1 and the catalyst in 100mL of toluene to form a liquid phase, introducing the liquid phase into a 500mL autoclave, wherein the mass fraction of butene-1 is 10wt% (relative to the solvent), N 2 Replacing air, and introducing synthetic gas with a mixed pressure ratio of carbon monoxide to hydrogen of 1:1 to replace N 2 And (3) supplementing the pressure to 1MPa, setting the preheating temperature of the autoclave type jacketed reactor to be 100 ℃, fully stirring and reacting for 3 hours, and finally, enabling the product to enter a separation device for aldehyde separation and recycling the rhodium catalyst. Different catalyst concentrations (mmol/L in terms of rhodium), calculate C 4 The olefin conversion and the product normal-to-iso ratio are shown in Table 1.
TABLE 1
As can be seen from Table 1, when the catalyst concentration reached 0.6mmol/L, the highest conversion of both catalysts was close to 99%, and the positive-to-negative ratio was not very different. However, the catalyst of the present invention requires significantly less catalyst than conventional catalysts to achieve the highest conversion. The activity and selectivity of the III-generation catalyst are far lower than those of the catalyst of the invention at low catalyst dosage, because the catalyst of the invention has extremely high specific surface area, higher utilization rate of active sites, less coordination conformation change space and easier formation of normal aldehyde. In addition, after the catalyst is recycled for 5 times, the activity and the selectivity of the rhodium nanoparticle catalyst are basically unchanged, and the activity and the selectivity of the III-generation catalyst are obviously reduced, which is mainly caused by the loss of rhodium salt and phosphine ligand in the catalyst recovery process. To eliminate the difference in results caused by the difference in phosphine ligands, the phosphine ligands of the III-generation Rh catalyst were changed to phosphine ligands used in the preparation of the dispersion A, the rhodium-phosphine ratio was still 180, and the catalytic effect was poorer because 2- (diphenylphosphino) ethylamine was less thermally stable than triphenylphosphine and the loss of phosphine ligands was greater during the separation.
Example 6
The dispersion B obtained in example 2 was used as a catalyst in the reaction for producing valeraldehyde by catalytic hydrogenation of butene-1, and the catalytic activity and selectivity after single and 5 cycles were compared. The method comprises the following specific steps: butene-1 and catalyst were dissolved in 100mL of xylene forming liquid phase and introduced into a 500mL autoclave, the mass fraction of butene-1 was 10wt% (relative to solvent), N 2 Replacing air, and introducing synthetic gas with a mixed pressure ratio of carbon monoxide to hydrogen of 1:1 to replace N 2 And (3) supplementing the pressure to 1MPa, setting the preheating temperature of the autoclave type jacketed reactor to be 100 ℃, fully stirring and reacting for 3 hours, and finally, enabling the product to enter a separation device for aldehyde separation and recycling the rhodium catalyst. Different catalyst concentrations (mmol/L in terms of rhodium), calculate C 4 The olefin conversion and the product normal-to-iso ratio are shown in Table 2.
Example 7
The dispersion C obtained in example 3 was used as a catalyst in the reaction for producing valeraldehyde by catalytic hydrogenation of butene-1, and the catalytic activity and selectivity after single and 5 cycles were compared. The method comprises the following specific steps: butene-1 and catalyst dissolved in 100mL cyclohexane forming liquid phase into a 500mL autoclave, butene-1 mass fraction 10wt% (relative to solvent), N 2 Replacing air, and introducing synthetic gas with a mixed pressure ratio of carbon monoxide to hydrogen of 1:1 to replace N 2 And (3) supplementing the pressure to 1MPa, setting the preheating temperature of the autoclave type jacketed reactor to be 100 ℃, fully stirring and reacting for 3 hours, and finally, enabling the product to enter a separation device for aldehyde separation and recycling the rhodium catalyst. Different catalyst concentrations (mmol/L in terms of rhodium), calculate C 4 The olefin conversion and the product normal-to-iso ratio are shown in Table 2.
Example 8
The dispersion D obtained in example 4 was used as a catalyst in the reaction for producing valeraldehyde by catalytic hydrogenation of butene-1, and the catalytic activity and selectivity after single and 5 cycles were compared. The method comprises the following specific steps: butene-1 and catalyst were dissolved in 100mL of ethylbenzene to form a liquid phase and introduced into a 500mL autoclave, the mass fraction of butene-1 was 10wt% (relative to solvent), N 2 Replacing air, and introducing synthetic gas with a mixed pressure ratio of carbon monoxide to hydrogen of 1:1 to replace N 2 And (3) supplementing the pressure to 1MPa, setting the preheating temperature of the autoclave type jacketed reactor to be 100 ℃, fully stirring and reacting for 3 hours, and finally, enabling the product to enter a separation device for aldehyde separation and recycling the rhodium catalyst. Different catalyst concentrations (mmol/L in terms of rhodium), calculate C 4 The olefin conversion and the product normal-to-iso ratio are shown in Table 2.
TABLE 2
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (11)

1. A rhodium nanoparticle dispersion consisting of surface grafted rhodium nanoparticles and a dispersion medium, the surface grafted rhodium nanoparticles having a size of 3-20 nm;
the graft is selected from at least one of methyl 3- (trimethoxysilyl) propyl methyl phosphonate, 2- (diphenylphosphino) ethyl triethoxysilane, diphenylphosphinoethyl dimethyl ethoxysilane, pentaethoxyphosphine, ethanolamine phosphonate, glufosinate, 2- (diphenylphosphine) aniline, 2- (diisopropylphosphine) ethylamine, O- (diphenylphosphino) hydroxylamine, 2- (diphenylphosphino) ethylamine, [ hydroxy (4-phenylbutyl) phosphino ] acetic acid, 3- (diphenylphosphine) propionic acid;
in the surface grafted rhodium nano-particle, the graft accounts for 5-30wt% of the mass of the surface grafted rhodium nano-particle.
2. The dispersion according to claim 1, wherein the dispersion medium is selected from at least one of toluene, n-hexane, cyclohexane, n-heptane, xylene, ethylbenzene, petroleum ether;
and/or the solids content of the dispersion is 1wt% to 50wt%.
3. The dispersion according to claim 1, wherein the grafts are selected from at least one of 2- (diphenylphosphino) ethyl triethoxysilane, 2- (diphenylphosphino) ethylamine, [ hydroxy (4-phenylbutyl) phosphino ] acetic acid, 3- (diphenylphosphino) propionic acid, pentaethoxyphosphane, methyl 3- (trimethoxysilane) propyl methylphosphonate.
4. A process for the preparation of a rhodium nanoparticle dispersion according to any of claims 1 to 3, comprising the steps of:
(1) Mixing rhodium salt, grafts, a reducing agent and a solvent to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to a reaction temperature under the protection of inert gas, and carrying out a reaction;
(3) And (3) after solid-liquid separation of the product obtained in the step (2), dispersing the solid phase into a dispersion medium to obtain rhodium nanoparticle dispersion.
5. The process according to claim 4, wherein the rhodium salt in the step (1) is at least one selected from the group consisting of ammonium chlororhodium, rhodium acetylacetonate dicarbonyl, rhodium dimeric acetate and rhodium chloride.
6. The method according to claim 4, wherein the reducing agent in the step (1) is at least one selected from the group consisting of ascorbic acid, oleylamine, glucose, aniline, ethylene glycol, diethylene glycol and triethylene glycol.
7. The process according to claim 4, wherein the solvent in the step (1) is at least one selected from the group consisting of oleylamine, oleic acid, octadecylamine, octadecene, ethylene glycol, diethylene glycol and triethylene glycol.
8. The process according to claim 4, wherein the concentration of rhodium salt in the mixed solution in the step (1) is 5 to 100mmol/L;
and/or, in the mixed solution in the step (1), the concentration of the graft is 2-10 g/L.
9. The preparation method according to claim 4, wherein the heating rate of step (2) is 3 to 8 ℃/min;
and/or the reaction temperature in the step (2) is 100-250 ℃, the reaction time is 2-4 h, and the reaction is carried out under normal pressure.
10. C (C) 4 A process for the hydroformylation of olefins comprising: c is C 4 An olefin is dissolved in a solvent and then prepared with a rhodium nanoparticle dispersion according to any one of claims 1 to 3 or a preparation according to any one of claims 4 to 9The rhodium nanoparticle dispersion prepared by the method is contacted with CO and hydrogen for reaction.
11. The method of claim 10, wherein C 4 The olefin is one or more of butene-1, butene-2, isobutene and 2, 5-dihydrofuran;
and/or C 4 The olefin is dissolved in at least one of toluene, n-hexane, cyclohexane, n-heptane, xylene, ethylbenzene and petroleum ether;
and/or the concentration of the rhodium nanoparticle dispersion in the reaction system is 0.1-2.0 mmol/L based on rhodium;
and/or, the reaction conditions are as follows: the reaction temperature is 60-150 ℃, the reaction pressure is 0.1-3.0 MPa, and the reaction time is 0.5-24.0 h; h 2 And CO in a molar ratio of 1 to 5, C 4 The mass fraction of the olefin relative to the solvent is 5-20wt%.
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