CN116673022A - Montmorillonite-based furfural hydrogenation catalyst and preparation method thereof - Google Patents

Montmorillonite-based furfural hydrogenation catalyst and preparation method thereof Download PDF

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CN116673022A
CN116673022A CN202310609677.4A CN202310609677A CN116673022A CN 116673022 A CN116673022 A CN 116673022A CN 202310609677 A CN202310609677 A CN 202310609677A CN 116673022 A CN116673022 A CN 116673022A
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montmorillonite
furfural
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catalyst
hydrogenation
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程道建
王天睿
吴登峰
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Beijing University of Chemical Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • B01J37/18—Reducing with gases containing free hydrogen
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract

The invention relates to a montmorillonite-based furfural hydrogenation catalyst and a preparation method thereof, and relates to the technical field of biomass conversion. The catalyst of the invention takes montmorillonite as a carrier and platinum nano particles as an active component, which can obviously improve the conversion rate of furfural hydrogenation and the selectivity of furfuryl alcohol; meanwhile, the preparation method of the catalyst has mild reaction conditions, improves the hydrogenation conversion rate of furfural and the selectivity of furfuryl alcohol, and simultaneously remarkably reduces the production cost.

Description

Montmorillonite-based furfural hydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of biomass conversion, in particular to a montmorillonite-based furfural hydrogenation catalyst and a preparation method thereof.
Background
Furfuryl alcohol is an important chemical intermediate of biomass for the production of many chemical products such as vitamin C, lysine, plasticizers, dispersants, lubricants, resins, and the like. Due to the importance of furfuryl alcohol in the chemical industry and the renewable utilization of furfural, the research on the selective hydrogenation of furfural to furfuryl alcohol has received a great deal of attention.
Noble metal nanoparticles have proven to be effective catalysts in hydrogenation reactions, which have been widely used in industry. Among the various noble metal nanoparticles, platinum nanoparticles are widely used in catalytic hydrogenation reactions due to their unique electrical and chemical properties. Also, platinum-based catalysts exhibit excellent catalytic activity in the hydrogenation of furfural.
The clay mineral has the advantages of environmental friendliness, low cost, rich reserves and the like, and has proved to have wide application scenes. Among them, montmorillonite has ordered lamellar structure, unique swelling property and high ion exchange property, and is an excellent carrier candidate.
It is difficult to control the selectivity of the product because hydrogenolysis and decarboxylation of the c=o bond or hydrogenation of the c=o bond and the furan ring may occur. The catalytic hydrogenation of furfural to furfuryl alcohol is typically carried out in the gas phase or in the liquid phase. Compared with the liquid phase hydrogenation process, the gas phase hydrogenation process of the furfural has more byproducts, and the furfural needs to be gasified, so that the energy consumption is higher. Therefore, the exploration of a high-efficiency catalytic system for preparing furfuryl alcohol by liquid-phase hydrogenation of furfural is of great significance.
Copper-chromium catalysts are the most widely used catalysts in the furfural hydrogenation industry over the last decades. However, strict reaction conditions such as high temperature and high pressure greatly increase the production cost, and meanwhile, the high toxicity of the copper-chromium catalyst has serious influence on the environment, and does not meet the requirement of sustainable development.
Chinese patent publication No. CN112791731A describes a catalyst for preparing furfuryl alcohol by gas phase hydrogenation of furfuraldehyde, and its preparation method and application. The catalyst consists of sepiolite and active components loaded on the sepiolite, wherein the active components are CuO and Cr 2 O 3 And CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the CuO and the Cr 2 O 3 The CeO 2 The content mole ratio of (3) is 1:0.33-0.5:0.008-0.020 and the sepiolite content is 20-80 wt% based on the total weight of the catalyst. The catalyst has excellent catalytic activity in the gas-phase hydrogenation of furfural, but contains heavy metal ions such as copper, chromium and the like, and CuO and Cr 2 O 3 The catalyst has high toxicity, can have serious influence on the environment, and has high reaction temperature and high cost. The Chinese patent with publication number of CN106083775A describes a green synthesis route of furfuryl alcohol, wherein the synthesis route adopts a porous nano silicon carbide loaded platinum catalyst to catalyze the selective hydrogenation reaction of furfural in a water solvent at room temperature, so that the furfuryl alcohol is synthesized with high selectivity; siC is used as a carrier, hexahydrated chloroplatinic acid is used as an active component precursor, the catalyst is prepared by reduction in high-purity hydrogen at 500 ℃ and 99.999% after ultrasonic impregnation and drying, the weight ratio of Pt active metal in the catalyst is 1-5%, the hydrogen pressure is 0.5-2Mpa, the reaction temperature is 25 ℃, the reaction time is 30-240min, the conversion rate of furfural can reach 99%, the selectivity of furfuryl alcohol can reach 98%, but the preparation cost of the catalyst is higher. The Chinese patent with publication number of CN115160266A describes a method for carrying platinum nanoparticle catalyst on the inner wall of carbon nanotube for hydrogenation reaction of furfural, stirring and grinding by external force, and reacting with the surface of open carbon nanotube, and continuously entering the filled metal precursor into the lumen of carbon tube during slow evaporation of solvent. By grinding, the slow drying is controlled, so that enough time is available for more platinum ions to enter the lumen of the carbon tube; under normal temperature and pressure, isopropanol is used as a solvent, and after the MWNT catalyst with 5wt% Pt reacts for 100 hours in a reaction solution with the mass concentration of furfural being 5wt%, the conversion rate of furfural can still reach 90%, and the selectivity of furfuryl alcohol can still reach 95%. However, concentrated nitric acid is needed in the preparation process of the carbon nano tube, and meanwhile, the preparation process is complex, so that the preparation cost of the catalyst is greatly increased.
Disclosure of Invention
The invention aims to provide a montmorillonite-based furfural hydrogenation catalyst and a preparation method thereof, which are used for solving the problems in the prior art, and further preparing the catalyst with excellent furfural selective hydrogenation effect at low cost, so that the efficient conversion of furfural into furfuryl alcohol is realized under the condition of low cost.
In order to achieve the above object, the present invention provides the following solutions:
the invention aims to provide a montmorillonite-based catalyst, which takes montmorillonite as a carrier and platinum nano particles as an active component.
The invention adopts natural clay mineral montmorillonite as catalyst carrier, the purity is more than or equal to 95 percent, and a small amount of impurities are silicon dioxide.
In the invention, the main component of the platinum nano-particles is zero-valent platinum.
In the present invention, the platinum nanoparticles as the active component in the catalyst are derived from chloroplatinic acid hexahydrate.
As a further preferred aspect of the present invention, the weight of the platinum nanoparticles is 0.5% to 5% of the total weight of the montmorillonite-based catalyst; more preferably 1% -3%, most preferably 3%.
The second object of the present invention is to provide a method for preparing the above montmorillonite-based catalyst, comprising the steps of:
mixing montmorillonite dispersion with platinum compound solution, removing solvent from the obtained reaction system, drying the obtained reactant, grinding, calcining, and calcining to obtain H 2 And (3) reducing to obtain the montmorillonite-based catalyst.
Further, the calcination temperature is 300 ℃, and the time is preferably 3 hours;
further, the H 2 The temperature of the reduction is 200-300 ℃, preferably 200 ℃ and 300 ℃; the time is preferably 2 hours.
As a further preferred aspect of the invention, the platinum compound is dissolved as H2PtCl6.
The solution of the platinum compound is preferably ethanol solution; the montmorillonite dispersion liquid is montmorillonite water dispersion liquid.
The more preferred preparation method of the invention comprises the following specific steps:
(1) Taking a certain amount of montmorillonite powder (purity is more than or equal to 95%, and a small amount of impurities are silicon dioxide), and placing the montmorillonite powder into a vacuum drying oven for vacuum drying.
(2) And (3) weighing the montmorillonite powder treated in the step (1) under the condition of continuous stirring, and adding deionized water to uniformly mix the montmorillonite powder and the deionized water. More specifically, 0.5g of the montmorillonite powder treated in step (1) can be prepared by adding it to 15ml of deionized water.
(3) And (3) placing the slurry uniformly stirred in the step (2) into an ultrasonic machine for ultrasonic treatment to uniformly disperse montmorillonite particles in water.
(4) Taking out the slurry after the ultrasonic treatment in the step (3), taking an ethanol solution of H2PtCl6, and dropwise adding the ethanol solution into the montmorillonite solution in a stirring state, wherein the solution gradually turns to light yellow.
(5) And (3) placing the pale yellow solution obtained in the step (4) into an ultrasonic machine for ultrasonic treatment, so that the solution is uniformly mixed.
(6) Stirring the uniform mixed solution obtained in the step (5) after the ultrasonic treatment is completed.
(7) And (3) placing the solution after the stirring in the step (6) into a water bath kettle, heating and stirring until the solvent of the mixed solution is completely evaporated.
(8) And (3) drying the catalyst sample evaporated in the step (7) in an oven to remove residual moisture in the catalyst pore channels.
(9) And (3) grinding the sample obtained in the step (8) in a mortar, passing through a 100-mesh screen after grinding into fine powder, and placing the powder into a porcelain boat after collecting.
(10) And placing the porcelain boat into a tubular furnace, calcining in the air, and introducing hydrogen for reduction to obtain a black catalyst sample.
More preferably, the vacuum drying temperature in step (1) is 80℃and the time is 8 hours.
More preferably, the ethanol solution of H2PtCl6 in step (4) is 1.0g chloroplatinic acid hexahydrate dissolved in 100ml absolute ethanol, wherein the platinum content of the chloroplatinic acid hexahydrate is not less than 37.5%.
More preferably, the water bath temperature in step (7) is set to 70℃and the rotational speed is set to 500rpm.
More preferably, the oven temperature in step (8) is set to 80℃for a period of 4 to 6 hours.
More preferably, the temperature rise rate of the tube furnace for air calcination in the step (10) is 5 ℃/min, the final temperature is 300 ℃, and the calcination time is 3 hours; the heating rate of the tube furnace for hydrogen calcination is 5 ℃/min, the final temperature is 200-300 ℃, preferably 300 ℃, and the hydrogen reduction time is 2h.
The invention further aims to provide an application of the montmorillonite-based furfural hydrogenation catalyst in preparing furfuryl alcohol by selectively hydrogenating furfural.
Further, the temperature of the catalytic reaction is 40-70 ℃, preferably 40 ℃; the time is preferably 3 hours.
Further, the hydrogen pressure of the hydrogenation catalyst is 1.5-2Mpa.
Selection of the vector: the carrier montmorillonite used in the invention is aluminosilicate and consists of two layers of silicon tetrahedrons and one layer of aluminum octahedron, and has the advantages of low price, high mass transfer efficiency, good chemical stability, stronger electrostatic force with metal nanoclusters and the like.
The invention discloses the following technical effects:
the montmorillonite-based catalyst prepared by the method has the remarkable advantages of low preparation cost, mild reaction conditions and high hydrogenation selectivity of the furfural, and the production cost is remarkably reduced while the hydrogenation selectivity of the furfural is provided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a transmission electron microscope image of a sample of a montmorillonite-based furfural hydrogenation catalyst prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a sample of the montmorillonite-based furfural hydrogenation catalyst prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of a sample of the montmorillonite-based furfural hydrogenation catalyst prepared in example 1 of the present invention;
FIG. 4 is a sample N of a montmorillonite-based furfural hydrogenation catalyst prepared in example 1 of the present invention 2 -an adsorption-desorption curve;
fig. 5 is an XPS image of a sample of the montmorillonite-based furfural hydrogenation catalyst prepared in example 1 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The montmorillonite used in the embodiment of the invention is natural mineral montmorillonite, the purity is more than or equal to 95%, and a small amount of impurities are silicon dioxide.
Example 1
Preparing a montmorillonite-based furfural hydrogenation catalyst:
step 1, 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
Step 2, the montmorillonite (vacuum drying for 8h at 80 ℃) is added dropwise with 3.97ml ethanol solution of chloroplatinic acid after 30min ultrasound until the montmorillonite solution becomes light yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
And 3, stirring the obtained solution for 12 hours at normal temperature, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying box for 6 hours after the solvent is completely evaporated, setting the temperature of the drying box to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. Calcining the sample powder for 3 hours in an air atmosphere at 300 ℃, and then reducing the sample powder with hydrogen for 2 hours at 300 ℃ to obtain the montmorillonite-based furfural hydrogenation catalyst with the load of 3 wt%.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfuraldehyde was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 1.5MPa, and the reaction was carried out at 40℃for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
The transmission electron microscope image of the montmorillonite-based furfural hydrogenation catalyst sample is shown in fig. 1, and Pt was observed to be uniform in the state of nanoparticlesDispersing on the surface of montmorillonite; scanning electron microscope images are shown in fig. 2, and it can be found that the layered structure of montmorillonite at this temperature still exists without being destroyed by loading and calcination; the XRD pattern is shown in FIG. 3, and the characteristic peak of Pt at a loading of 3wt% can be clearly observed, demonstrating that Pt has been successfully loaded onto the support surface; n (N) 2 The adsorption and desorption curves are shown in fig. 4, and the type IV isotherm hysteresis loop and the H4 hysteresis loop reveal a dominant slit-like porous structure; the XPS image is shown in FIG. 5, after the interference of Al 2p is eliminated, the XPS of Pt is mainly divided into 0 price and +2 price, wherein the 0 price percentage is higher than the high price state, and the XPS is more beneficial to the reduction of hydrogen.
Example 2
Preparing a montmorillonite-based furfural hydrogenation catalyst:
step 1, 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
Step 2, the montmorillonite (vacuum dried for 8h at 80 ℃) is added dropwise with 0.67ml ethanol solution of chloroplatinic acid after 30min ultrasound until the montmorillonite solution becomes light yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
And 3, stirring the obtained solution for 12 hours at normal temperature, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying box for 6 hours after the solvent is completely evaporated, setting the temperature of the drying box to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. Calcining the sample powder for 3 hours in an air atmosphere at 300 ℃, and then reducing the sample powder with hydrogen for 2 hours at 300 ℃ to obtain the montmorillonite-based furfural hydrogenation catalyst with the load of 0.5 weight percent.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfuraldehyde was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 1.5MPa, and the reaction was carried out at 40 ℃ for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
Example 3
Step 1, 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
Step 2, the montmorillonite (vacuum drying for 8h at 80 ℃) is added dropwise with 1.33ml ethanol solution of chloroplatinic acid after 30min ultrasound until the montmorillonite solution becomes light yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
And 3, stirring the obtained solution for 12 hours at normal temperature, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying box for 6 hours after the solvent is completely evaporated, setting the temperature of the drying box to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. Calcining the sample powder for 3 hours in an air atmosphere at 300 ℃, and then reducing the sample powder with hydrogen for 2 hours at 300 ℃ to obtain the montmorillonite-based furfural hydrogenation catalyst with the load of 1 wt%.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfuraldehyde was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 1.5MPa, and the reaction was carried out at 40 ℃ for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
Example 4
Preparing a montmorillonite-based furfural hydrogenation catalyst:
step 1, 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
Step 2, the montmorillonite (vacuum dried for 8h at 80 ℃) is added dropwise with 6.12ml ethanol solution of chloroplatinic acid after 30min ultrasound until the montmorillonite solution becomes light yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
And 3, stirring the obtained solution for 12 hours at normal temperature, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying box for 6 hours after the solvent is completely evaporated, setting the temperature of the drying box to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. Calcining the sample powder for 3 hours in an air atmosphere at 300 ℃, and then reducing the sample powder with hydrogen for 2 hours at 300 ℃ to obtain the montmorillonite-based furfural hydrogenation catalyst with the load of 5 wt%.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfuraldehyde was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 1.5MPa, and the reaction was carried out at 40 ℃ for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
Example 5
Preparing a montmorillonite-based furfural hydrogenation catalyst:
step 1, 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
Step 2, the montmorillonite (vacuum drying for 8h at 80 ℃) is added dropwise with 3.97ml ethanol solution of chloroplatinic acid after 30min ultrasound until the montmorillonite solution becomes light yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
And 3, stirring the obtained solution for 12 hours at normal temperature, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying box for 6 hours after the solvent is completely evaporated, setting the temperature of the drying box to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. Calcining the sample powder for 3 hours in an air atmosphere at 300 ℃, and then reducing the sample powder with hydrogen for 2 hours at 300 ℃ to obtain the montmorillonite-based furfural hydrogenation catalyst with the load of 3 wt%.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfural was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 1.5MPa, and the reaction was carried out at 50 ℃ for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
Example 6
Preparing a montmorillonite-based furfural hydrogenation catalyst:
step 1, 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
Step 2, the montmorillonite (vacuum drying for 8h at 80 ℃) is added dropwise with 3.97ml ethanol solution of chloroplatinic acid after 30min ultrasound until the montmorillonite solution becomes light yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
And 3, stirring the obtained solution for 12 hours at normal temperature, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying box for 6 hours after the solvent is completely evaporated, setting the temperature of the drying box to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. Calcining the sample powder for 3 hours in an air atmosphere at 300 ℃, and then reducing the sample powder with hydrogen for 2 hours at 300 ℃ to obtain the montmorillonite-based furfural hydrogenation catalyst with the load of 3 wt%.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfural was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 1.5MPa, and the reaction was carried out at 60 ℃ for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
Example 7
Preparing a montmorillonite-based furfural hydrogenation catalyst:
step 1, 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
Step 2, the montmorillonite (vacuum drying for 8h at 80 ℃) is added dropwise with 3.97ml ethanol solution of chloroplatinic acid after 30min ultrasound until the montmorillonite solution becomes light yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
And 3, stirring the obtained solution for 12 hours at normal temperature, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying box for 6 hours after the solvent is completely evaporated, setting the temperature of the drying box to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. Calcining the sample powder for 3 hours in an air atmosphere at 300 ℃, and then reducing the sample powder with hydrogen for 2 hours at 300 ℃ to obtain the montmorillonite-based furfural hydrogenation catalyst with the load of 3 wt%.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfural was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 1.5MPa, and the reaction was carried out at 70 ℃ for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
Example 8
Preparing a montmorillonite-based furfural hydrogenation catalyst:
(1) 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
(2) Montmorillonite (vacuum dried at 80deg.C for 8 hr) was sonicated for 30min, and 3.97ml ethanol solution of chloroplatinic acid was added dropwise until the montmorillonite solution became pale yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
(3) Stirring the obtained solution at normal temperature for 12h, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying oven for 6h after the solvent is completely evaporated, setting the temperature of the drying oven to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. Calcining the sample powder for 3 hours in an air atmosphere at 300 ℃, and then reducing the sample powder with hydrogen for 2 hours at 200 ℃ to obtain the montmorillonite-based furfural hydrogenation catalyst with the load of 3 wt%.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfuraldehyde was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 1.5MPa, and the reaction was carried out at 40 ℃ for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
Example 9
Preparing a montmorillonite-based furfural hydrogenation catalyst:
(1) 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
(2) Montmorillonite (vacuum dried at 80deg.C for 8 hr) was sonicated for 30min, and 3.97ml ethanol solution of chloroplatinic acid was added dropwise until the montmorillonite solution became pale yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
(3) Stirring the obtained solution at normal temperature for 12h, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying oven for 6h after the solvent is completely evaporated, setting the temperature of the drying oven to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. Calcining the sample powder for 3 hours in an air atmosphere at 300 ℃, and then reducing the sample powder with hydrogen for 2 hours at 300 ℃ to obtain the montmorillonite-based furfural hydrogenation catalyst with the load of 3 wt%.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfuraldehyde was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 2.0MPa, and the reaction was carried out at 40℃for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
The furfural conversion and furfuryl alcohol selectivity achieved by the montmorillonite-based furfural hydrogenation catalyst of examples 1-9 of the present invention are shown in Table 1.
TABLE 1
Furfural conversion/% Furfuryl alcohol selectivity/%
Example 1 100 97.5
Example 2 46.2 87.1
Example 3 82.7 95.7
Example 4 100 73.5
Example 5 100 97.2
Example 6 100 88.4
Example 7 100 79.6
Example 8 99.5 81.1
Example 9 100 93.5
Examples 1-4 are the effects of Pt loading on furfural conversion and furfuryl alcohol selectivity, with Pt loading of 0.5wt% to 5wt%, when Pt loading is less than 3wt%, furfural is not fully converted compared to example 1, while furfuryl alcohol selectivity is not high, mainly because the active sites are fewer when the loading is low, which is unfavorable for hydrogenation reaction; examples 5-7 are the effects of temperature on furfural conversion and furfuryl alcohol selectivity, as the temperature increases, which promotes the progress of side reactions, with a portion of the furfural being reacted with solvent to form condensation products; example 8 is that the reduction effect of Pt is reduced due to the reduction temperature being lowered, and the reduction selectivity of furfural is reduced due to the reduction of the zero-valent Pt content being lowered compared with example 1; the decrease in the reaction pressure in example 9 resulted in a major increase in the catalyst selectivity, and thus, the catalyst effect was somewhat affected compared to example 1.
Comparative example 1
Preparing a montmorillonite-based furfural hydrogenation catalyst:
(1) 1g of chloroplatinic acid hexahydrate was dissolved in absolute ethanol to obtain 100ml of an ethanol solution of chloroplatinic acid having a platinum metal content of 3.778mg/ml.
(2) Montmorillonite (vacuum dried at 80deg.C for 8 hr) was sonicated for 30min, and 3.97ml ethanol solution of chloroplatinic acid was added dropwise until the montmorillonite solution became pale yellow. And then putting the pale yellow solution into an ultrasonic machine again for ultrasonic treatment for 30min, so that chloroplatinic acid is uniformly dispersed in the montmorillonite solution.
(3) Stirring the obtained solution at normal temperature for 12h, evaporating the mixed solution in a water bath kettle, setting the temperature of the water bath kettle to be 70 ℃, drying the dried sample in a drying oven for 6h after the solvent is completely evaporated, setting the temperature of the drying oven to be 80 ℃, grinding the dried sample after the moisture in the aperture of the sample is completely evaporated, and sieving the sample with a 100-mesh sieve. And directly reducing the sample powder with hydrogen at 300 ℃ for 2 hours to obtain the montmorillonite-based furfural hydrogenation catalyst.
Selective hydrogenation to make furfuryl alcohol:
100mg of the catalyst was placed in a 100ml autoclave, 30ml of absolute ethanol was added, 0.25g of furfuraldehyde was further added, the air in the vessel was replaced by nitrogen purge for 2 minutes, the nitrogen in the vessel was replaced by hydrogen, and finally the hydrogen reaction pressure was set to 1.5MPa, and the reaction was carried out at 40 ℃ for 3 hours. And (3) carrying out chromatographic analysis on the reacted sample, and collecting to obtain furfuryl alcohol.
The furfural conversion and furfuryl alcohol selectivity comparison data for comparative example 1 and example 1 are shown in table 2:
TABLE 2
Sample number Furfural conversion/% Furfuryl alcohol selectivity/%
Example 1 100 97.5
Comparative example 1 99.1 71.8
Comparative example 1 Pt was not well fixed on montmorillonite due to lack of calcination step, agglomeration of Pt was aggravated in the reduction process, and the selectivity effect of the catalyst was greatly affected.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.

Claims (9)

1. A montmorillonite-based catalyst is characterized in that montmorillonite is used as a carrier, and platinum nano particles are used as active components.
2. The montmorillonite-based catalyst according to claim 1, wherein the weight of the platinum nanoparticles is 0.5% -5% of the total weight of the montmorillonite-based catalyst.
3. A process for the preparation of a montmorillonite-based catalyst according to claim 1 or 2, comprising the steps of:
mixing montmorillonite dispersion with platinum compound solution, removing solvent from the obtained reaction system, drying the obtained reactant, grinding, calcining, and calcining to obtain H 2 And (3) reducing to obtain the montmorillonite-based catalyst.
4. A method according to claim 3, wherein the calcination is carried out at a temperature of 300 ℃ for a period of 3 hours; the H is 2 The reduction temperature is 200-300 ℃ and the time is 2h.
5. The method according to claim 3, wherein the platinum compound is H 2 PtCl 6 。
6. Use of a montmorillonite-based catalyst as claimed in claim 1 or 2 in the selective hydrogenation of furfural to prepare furfuryl alcohol.
7. The use according to claim 6, wherein the hydrogenation reaction process comprises the steps of:
and mixing furfural with a solvent, and carrying out catalytic hydrogenation on the furfural by using the montmorillonite-based catalyst under the condition of hydrogen to obtain furfuryl alcohol.
8. The use according to claim 7, wherein the catalytic reaction is carried out at a temperature of 40-70 ℃.
9. The use according to claim 7, wherein the hydrogen pressure of the hydrogenation is 1.5-2Mpa.
CN202310609677.4A 2023-05-26 2023-05-26 Montmorillonite-based furfural hydrogenation catalyst and preparation method thereof Pending CN116673022A (en)

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