CN113813991B - Preparation method and application of phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst - Google Patents
Preparation method and application of phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst Download PDFInfo
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- CN113813991B CN113813991B CN202111156682.1A CN202111156682A CN113813991B CN 113813991 B CN113813991 B CN 113813991B CN 202111156682 A CN202111156682 A CN 202111156682A CN 113813991 B CN113813991 B CN 113813991B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
Abstract
The invention discloses a preparation method and application of a phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst, and Nb coated with different organic phosphonic acid loading amounts is prepared 2 O 5 The load, active component ruthenium loaded by the equal volume impregnation method, prepares the phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst. By deposition of organophosphonic acids on Nb 2 O 5 The electron density of the original carrier is changed on the carrier, the hydrophobicity of the catalyst is adjusted, the carrier and ruthenium are acted together to realize the regulation and control of Lewis acid sites and Bronsted acid sites, and the catalyst has hydrophilic and oleophilic characteristics, so that stable Pickering emulsion is formed in a water phase and an oil phase to serve as a reaction interface, and the ultrahigh cyclohexanol conversion rate is realized. The reaction condition is mild, the cyclohexanol yield is high, and a novel and sustainable method is provided for preparing cyclohexanol.
Description
Technical Field
The invention belongs to the technical field of environmental protection and comprehensive resource utilization of nano catalytic materials, and particularly relates to a preparation method of a phosphonic acid modified ruthenium metal load niobium-based oxide catalyst and application of phenol of a lignin derivative in preparation of cyclohexanol by hydrogenation in a water-oil two-phase solution.
Background
Lignin, one of the main components of lignocellulose, can be catalyzed into biofuels and chemicals through hydrogenation and hydrodeoxygenation reactions due to its unique aromatic polymer structure and chemical properties, and has great application potential. However, the complex chemical structure and high degree of condensation of lignin has led to the production of hundreds of oxygenated bio-oil compounds, of which phenol, one of the representatives of lignin-derived phenols, is the main bio-oil component.
Cyclohexanol, an essential synthetic intermediate for the production of hexamethylenediamine, caprolactam of nylon 6, adipic acid of nylon 66, and the like, is a major commodity of important chemical industries. Phenol hydrogenation is an attractive route to the production of cyclohexanol, the green technology of choice, because such catalytic systems increase atomic efficiency and save energy. In addition, the derived phenol obtained by the catalytic conversion of the lignin is subjected to high-efficiency catalytic hydrogenation to generate cyclohexanol, so that the more promising valence of the lignin is improved, and the lignin-to-chemical cycle is economically and effectively realized.
The reaction of the hydrogenation of phenol to cyclohexanol may be carried out in the gas phase or the liquid phase. The liquid phase hydrogenation of phenol can overcome the limit of easy deactivation of catalyst in the gas phase hydrogenation of phenol to a certain extent, and has attracted great interest of researchers. The challenge of liquid phase hydrogenation of phenol is the design of the catalyst and the improvement of product selectivity. The noble metal catalyst breaks through the limitations that active sites and active metals in the traditional catalyst are easy to sinter and the like, so that the noble metal catalyst is widely applied to hydrogenation reaction of phenol and phenolic compounds thereof. Nevertheless, higher temperature and higher hydrogen pressure are still required in the research of hydrogenation for producing cyclohexanol, so that energy is consumed too much, and sustainable development is not facilitated. Therefore, there is an urgent need to develop a novel catalyst to achieve efficient and green hydrogenation of phenol under mild conditions.
It is reported that ruthenium catalyst among metal-based catalysts is superior to other noble metal catalysts due to moderate cost and high catalytic activity. In addition, emerging niobium-based catalysts exhibit unique reactivity and have received great attention in lignin depolymerization and hydrogenation reactions of lignin derivatives. The catalyst is coated with phosphonic acid, and after the phosphonic acid is deposited on the surface of the catalyst, the phosphonic acid can be combined with an oxide carrier and form a firm chemical bond on the surface, so that the selectivity and the reactivity of the aryl substituted alcohol can be improved, and the deactivation efficiency of the catalyst can be slowed down.
At the same time, the solvent system is also a key factor in determining the catalytic performance. The application of coupling of a two-phase reaction and a separation system in catalytic reaction in-situ separation has received great attention in the aspects of realizing high-efficiency conversion and selectivity. The Pickering emulsion with stable particles and the solid catalyst is used as a dual-phase catalytic system of a reaction interface, so that the contact surface of the reaction can be increased, the oil/water dual-phase system can promote the separation of water-insoluble organic products, and the clean separation of the products and the solvent and the repeated use of the catalyst are realized.
Disclosure of Invention
The invention aims to provide a preparation method and application of a phosphonic acid modified ruthenium metal supported niobium-based oxide catalyst.
The invention provides a preparation method of a phosphonic acid modified ruthenium metal load niobium-based oxide catalyst, which comprises the following specific steps:
(1) Dissolving a ruthenium precursor in methanol to obtain a methanol solution of the ruthenium precursor;
(2) Adding niobium pentoxide into the methanol solution of the ruthenium precursor obtained in the step (1), and continuously stirring to obtain a solid suspension; the mass ratio of the ruthenium to the niobium pentoxide is (0.001-0.05): 1;
(3) Carrying out rotary evaporation on the solid suspension obtained in the step (2) to obtain first solid powder;
(4) Heating the first solid powder obtained in the step (3) in the air, preserving the heat for a period of time, and cooling to room temperature to obtain second solid powder;
(5) Dissolving organic phosphonic acid in methanol, adding the second solid powder obtained in the step (4), and continuously heating and stirring to obtain a mixed suspension; the mass ratio of the second solid powder to the organic phosphonic acid is 1: 0.01-0.5;
(6) Performing rotary evaporation on the mixed suspension obtained in the step (5) to obtain third solid powder;
(7) Heating the third solid powder obtained in the step (6) in the air, preserving the heat for a period of time, and cooling to room temperature; then H is added 2 Heating and preserving heat for a period of time under the environment, and cooling to room temperature to obtain the phosphonic acid modified ruthenium metal supported niobium-based oxide catalyst.
In the present invention, the ruthenium precursor in step (1) includes, but is not limited to, any one of ruthenium chloride, ruthenium oxide, ruthenium nitrate, ruthenium acetate, or ruthenium acetylacetonate.
In the invention, the first solid powder in the step (4) is heated to 100-400 ℃ in the air, and the temperature is kept for 0.5-5 h.
In the present invention, the organic phosphonic acid in step (5) includes, but is not limited to, any organic phosphonic acid with carbon chain length from 1 to 18, such as methyl phosphonic acid, decyl phosphonic acid or octadecyl phosphonic acid, etc.
In the invention, in the step (7), the third solid powder obtained in the step (6) is heated to 100-400 ℃ in the air, and is kept warm for 0.5-5 h and cooled to room temperature; then H is added 2 Heating to 100-400 deg.C in environment, and maintaining for 0.5-5 h.
The application of the phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst in preparation of cyclohexanol by using the preparation method provided by the invention is that the phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst is used for hydrogenation catalysis of phenol two-phase solution containing lignin derivatives to prepare cyclohexanol, and the preparation method comprises the following specific steps:
(1) Adding a phosphonic acid modified ruthenium metal supported niobium-based oxide catalyst into a two-phase system consisting of water containing phenol and an organic solvent to obtain a mixture; the mass ratio of the phosphonic acid modified ruthenium metal loaded niobium-based oxide to phenol is 1-10;
(2) Adding the mixture obtained in the step (1) into a hydrothermal reaction kettle, filling hydrogen pressure, stirring and heating to a certain temperature, and keeping the temperature for a certain reaction time;
(3) After the reaction in the step (2) is finished, cooling;
(4) Filtering and separating the product obtained after cooling in the step (3) to obtain an organic phase;
(5) And (4) carrying out rotary evaporation on the organic phase obtained in the step (4) to remove the organic solvent, so as to obtain cyclohexanol.
In the invention, in the step (2), the mixture obtained in the step (1) is added into a hydrothermal reaction kettle, and 2-20 bar of H is filled into the hydrothermal reaction kettle 2 Stirring and heating to any temperature value of 40-220 ℃, and keeping reaction for 0.5-6 h at the temperature.
In the invention, the organic solvent in the step (1) is any one of 2-methyltetrahydrofuran, toluene, dichloromethane, ethyl acetate, cyclopentyl methyl ether, methyl isobutyl ketone or decalin.
The invention discloses effective preparation conditions of a phosphonic acid modified ruthenium metal load niobium-based oxide catalyst, which are mild and have good effect. The invention relates to a method for preparing cyclohexanol by using phenol containing lignin derivatives as a raw material and hydrogenating in water and oil two phases, in particular to a method for preparing a phosphonic acid modified ruthenium metal loaded niobium-based oxide and a method for preparing cyclohexanol by using a phenol-containing two-phase solution under the hydrogenation catalysis of the phosphonic acid modified ruthenium metal loaded niobium-based oxide. The method has the advantages of mild conditions, low required temperature and hydrogen pressure, high cyclohexanol yield, high catalytic efficiency, greenness and economy, and provides a novel and sustainable method for preparing cyclohexanol. Under mild reaction conditions, the method has positive significance for the development of cyclohexanol industry, biological energy and biological refining industry.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a method for depositing a phosphonic acid on Nb 2 O 5 The electron density of the original carrier is changed on the carrier, and the Brnsted acid site is introduced to act together with ruthenium metal, so that the regulation and control of the Lewis acid site and the Brnsted acid site are realized, and the phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst with stronger catalytic activity is obtained.
(2) In the phosphonic acid modified ruthenium metal load niobium-based oxide catalyst provided by the invention, organic phosphonic acid is deposited on Ru/Nb through an impregnation method 2 O 5 The surface of the carrier. The hydrophilic and oleophilic characteristics of the phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst can be controlled by adjusting the loading amount of the organic phosphonic acid, so that a stable Pickering emulsion is formed in a water phase and an oil phase to serve as a reaction interface, and the ultrahigh cyclohexanol conversion rate is realized.
(3) The phosphonic acid modified ruthenium metal load niobium-based oxide catalyst can be used for catalyzing the hydrogenation reaction of phenol, and the conversion rate is more than 95% and the cyclohexanol yield is more than 90% under the conditions of lower temperature and lower hydrogen pressure; and the target products (benzene, cyclohexanone, cyclohexane) can be selectively adjusted by controlling the reaction temperature and the reaction time.
Drawings
FIG. 1 is a flow chart of the process for preparing a ruthenium metal supported niobium based oxide catalyst according to the present invention.
Fig. 2 is a TEM image of the ruthenium metal supported niobium-based oxide catalyst in example 2 of the present invention.
Detailed Description
The following examples are intended to further illustrate the invention and are not intended to limit the invention.
Example 1
(1) Dissolving 0.0812 g of ruthenium acetylacetonate in 8 mL of methanol to obtain a methanol solution of ruthenium acetylacetonate;
(2) Adding 2.0 g of niobium pentoxide into the methanol solution of ruthenium acetylacetonate obtained in the step (1), and continuously stirring to obtain a solid suspension;
(3) Carrying out rotary evaporation on the solid suspension obtained in the step (2) to obtain solid powder;
(4) Preserving the heat of the solid powder obtained in the step (3) in the air at 200 ℃ for 2 h, and cooling to room temperature to obtain solid powder;
(5) Dissolving 0.0258 g of octadecylphosphonic acid in 5.16 mL of methanol, adding 0.5 g of the solid powder obtained in the step (4), and continuously heating and stirring to obtain a mixed suspension;
(6) Performing rotary evaporation on the mixed suspension obtained in the step (5) to obtain solid powder;
(7) Preserving the temperature of the solid powder obtained in the step (6) in the air at 200 ℃ for 2 h, and cooling to room temperature; then H 2 Keeping the temperature at 200 ℃ for 3 h in the environment, and cooling to room temperature to obtain the phosphonic acid modified ruthenium metal supported niobium-based oxide catalyst;
(8) The application of the phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst in preparing cyclohexanol by catalyzing phenol hydrogenation comprises the following specific steps: adding 0.05 g of phosphonic acid modified ruthenium metal supported niobium-based oxide, 0.05 g of phenol, 7.5 mL of water and 2.5 mL of decalin into a hydrothermal reaction kettle, and filling 10 bar H 2 Stirring and heating to 180 ℃ for reaction for 4 hours, and cooling after the reaction is finished;
(9) The organic phase after filtration and separation of the cooled product was analyzed for cyclohexanol yield by GC-MS and GC-FID, which was about 68%.
Example 2
(1) Dissolving 0.0812 g of ruthenium acetylacetonate in 8 mL of methanol to obtain a methanol solution of ruthenium acetylacetonate;
(2) Adding 2.0 g of niobium pentoxide into the methanol solution of ruthenium acetylacetonate obtained in the step (1), and continuously stirring to obtain a solid suspension;
(3) Carrying out rotary evaporation on the solid suspension obtained in the step (2) to obtain solid powder;
(4) Preserving the heat of the solid powder obtained in the step (3) in the air at 200 ℃ for 2 h, and cooling to room temperature to obtain solid powder;
(5) Dissolving 0.0860 g of octadecylphosphonic acid in 17.20 mL of methanol, adding 0.5 g of the solid powder obtained in the step (4), and continuously heating and stirring to obtain a mixed suspension;
(6) Performing rotary evaporation on the mixed suspension obtained in the step (5) to obtain solid powder;
(7) Keeping the solid powder obtained in the step (6) at 200 ℃ in the air for 2 h, and cooling to room temperature; then H 2 Keeping the temperature at 200 ℃ for 3 h in the environment, and cooling to room temperature to obtain the phosphonic acid modified ruthenium metal supported niobium-based oxide catalyst;
(8) The application of the phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst in preparing cyclohexanol by catalyzing phenol hydrogenation comprises the following specific steps: adding 0.05 g of phosphonic acid modified ruthenium metal-supported niobium-based oxide, 0.05 g of phenol, 7.5 mL of water and 2.5 mL of decalin into a hydrothermal reaction kettle, and filling 10 bar H 2 Stirring and heating to 180 ℃ for reaction for 4 hours, and cooling after the reaction is finished;
(9) The organic phase after filtration and separation of the cooled product was analyzed for cyclohexanol yield by GC-MS and GC-FID, which was about 56%.
Example 3
(1) Dissolving 0.0812 g of ruthenium acetylacetonate in 8 mL of methanol to obtain a methanol solution of ruthenium acetylacetonate;
(2) Adding 2.0 g of niobium pentoxide into the methanol solution of ruthenium acetylacetonate obtained in the step (1), and continuously stirring to obtain a solid suspension;
(3) Carrying out rotary evaporation on the solid suspension obtained in the step (2) to obtain solid powder;
(4) Preserving the heat of the solid powder obtained in the step (3) in the air at 200 ℃ for 2 h, and cooling to room temperature to obtain solid powder;
(5) Dissolving 0.0860 g of octadecylphosphonic acid in 17.20 mL of methanol, adding 0.5 g of solid powder obtained in the step (4), and continuously heating and stirring to obtain a mixed suspension;
(6) Performing rotary evaporation on the mixed suspension obtained in the step (5) to obtain solid powder;
(7) Keeping the solid powder obtained in the step (6) at 200 ℃ in the air for 2 h, and cooling to room temperature; then H 2 Keeping the temperature at 200 ℃ for 3 h in the environment, and cooling to room temperature to obtain the phosphonic acid modified ruthenium metal supported niobium-based oxide catalyst;
(8) The application of the phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst in preparing cyclohexanol by catalyzing phenol hydrogenation comprises the following specific steps: adding 0.05 g of phosphonic acid modified ruthenium metal-supported niobium-based oxide, 0.05 g of phenol, 2.5 mL of water and 7.5 mL of decalin into a hydrothermal reaction kettle, and filling 10 bar H 2 Stirring and heating to 80 ℃ for reaction for 4 h, and cooling after the reaction is finished;
(9) The organic phase after filtration and separation of the cooled product was analyzed for cyclohexanol yield by GC-MS and GC-FID, which was about 93%.
Claims (8)
1. A preparation method of a phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst is characterized by comprising the following specific steps:
(1) Dissolving a ruthenium precursor in methanol to obtain a methanol solution of the ruthenium precursor;
(2) Adding niobium pentoxide into the methanol solution of the ruthenium precursor obtained in the step (1), and continuously stirring to obtain a solid suspension; the mass ratio of the ruthenium to the niobium pentoxide is (0.001-0.05): 1;
(3) Carrying out rotary evaporation on the solid suspension obtained in the step (2) to obtain first solid powder;
(4) Heating the first solid powder obtained in the step (3) in the air, preserving the heat for a period of time, and cooling to room temperature to obtain second solid powder;
(5) Dissolving organic phosphonic acid in methanol, adding the second solid powder obtained in the step (4), and continuously heating and stirring to obtain a mixed suspension; the mass ratio of the second solid powder to the organic phosphonic acid is 1: 0.01-0.5;
(6) Performing rotary evaporation on the mixed suspension obtained in the step (5) to obtain third solid powder;
(7) Heating the third solid powder obtained in the step (6) in the air, preserving the heat for a period of time, and cooling to room temperature; then H is added 2 Heating and preserving heat for a period of time under the environment, and cooling to room temperature to obtain the phosphonic acid modified ruthenium metal supported niobium-based oxide catalyst.
2. The method of claim 1, wherein: (1) The precursor of ruthenium includes, but is not limited to, any one of ruthenium chloride, ruthenium oxide, ruthenium nitrate, ruthenium acetate or ruthenium acetylacetonate.
3. The method of claim 1, wherein: in the step (4), the solid powder is heated to 100-400 ℃ in the air, and the temperature is kept for 0.5-5 h.
4. The method of claim 1, wherein: the organophosphonic acid in step (5) includes, but is not limited to, any of organophosphonic acids having carbon chain lengths of from 1 to 18.
5. The method of claim 1, wherein: in the step (7), the solid powder obtained in the step (6) is heated to 100-400 ℃ in the air, the temperature is kept for 0.5-5 h, and the solid powder is cooled to the room temperature; then H 2 Heating to 100-400 deg.C in environment, and maintaining for 0.5-5 h.
6. Use of a phosphonic acid modified ruthenium metal supported niobium based oxide catalyst obtained by the method of claim 1 in the preparation of cyclohexanol, wherein: the preparation method of cyclohexanol by using phosphonic acid modified ruthenium metal loaded niobium-based oxide as a catalyst to catalyze phenol-containing two-phase solution through hydrogenation comprises the following specific steps:
(1) Adding the phosphonic acid modified ruthenium metal-loaded niobium-based oxide into a two-phase system consisting of water containing phenol and an organic solvent to obtain a mixture; the mass ratio of the phosphonic acid modified ruthenium metal loaded niobium-based oxide to phenol is 1-10;
(2) Adding the mixture obtained in the step (1) into a hydrothermal reaction kettle, filling certain hydrogen pressure, stirring and heating to a certain temperature, and keeping the temperature for a certain reaction time;
(3) After the reaction in the step (2) is finished, cooling;
(4) Filtering and separating the product obtained after cooling in the step (3) to obtain an organic phase;
(5) And (4) carrying out rotary evaporation on the organic phase obtained in the step (4) to remove the solvent, so as to obtain cyclohexanol.
7. Use according to claim 6, characterized in that: in the step (2), the mixture obtained in the step (1) is added into a hydrothermal reaction kettle, and 2-20 bar of H is filled 2 Stirring and heating to any temperature value of 40-220 ℃, and keeping reaction for 0.5-6 h at the temperature.
8. Use according to claim 6, characterized in that: the organic solvent in the step (1) is any one of 2-methyltetrahydrofuran, toluene, dichloromethane, ethyl acetate, cyclopentyl methyl ether, methyl isobutyl ketone or decalin.
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